Mechanoluminescent ink, preparation method and application thereof, intelligent packaging material and preparation method

Abstract

The invention belongs to the technical field of intelligent packaging printing, and particularly relates to mechanoluminescent ink, a preparation method and application thereof, an intelligent packaging material and a preparation method. The piezoelectric material and the light-emitting material are connected through the conductive ink, when the piezoelectric material generates voltage due to pressure, the voltage can be transmitted to the light-emitting material through the conductive ink, so that the light-emitting material emits light, the pressing light-emitting effect is achieved, and the anti-fake and decoration functions are achieved. The invention further provides application of the mechanoluminescent ink obtained by the scheme or the preparation method in the field of intelligent packaging. The mechanoluminescent ink provided by the invention can be used in the field of intelligent packaging to prepare various intelligent packaging products. The invention further provides a mechanoluminescent material, and the mechanoluminescent ink adopting the scheme is coated on the surface of a base material, so that the material is endowed with an interactive function of pressing luminescence or information display, and the user experience is enhanced.

Description

Technical Field

[0001] The present invention belongs to the technical field of intelligent packaging and printing, and specifically relates to a mechanoluminescent ink and a preparation method and application thereof, and an intelligent packaging material and a preparation method thereof. Background Art

[0002] Electronic ink is a rapidly developing field in recent years and is widely used in printed electronic devices such as flexible circuits, sensors and displays. By preparing materials into inks, large-area, low-cost electronic component manufacturing can be achieved using traditional printing processes.

[0003] With the rise of the Internet of Things (IOT) and smart packaging technology, the market demand for interactive packaging materials has increased. How to realize the interactive function of packaging materials is a problem facing the smart packaging field. Summary of the invention

[0004] The object of the present invention is to provide a mechanoluminescent ink and its preparation method, application, intelligent packaging material and preparation method. The material prepared by the mechanoluminescent ink provided by the present invention has an interactive function of pressing to emit light.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] The present invention provides a mechanoluminescent ink, including piezoelectric ink, luminescent ink and conductive ink;

[0007] The piezoelectric ink comprises the following components in parts by mass: 30 to 50 parts of piezoelectric material, 3 to 5 parts of inorganic pigment, 1 to 2 parts of first photoinitiator, 0.5 to 1 part of first adhesive, and 94 to 124 parts of first solvent;

[0008] Based on the mass fraction of the piezoelectric material, the luminescent ink includes the following components in mass fractions: 30 to 50 parts of luminescent material, 3 to 5 parts of dispersant, 1 to 2 parts of second photoinitiator, 0.5 to 0.8 parts of second binder, 0.5 to 1 parts of thickener, 0.1 to 0.5 parts of defoamer, and 78 to 114 parts of second solvent;

[0009] Based on the mass fraction of the piezoelectric material, the conductive ink includes the following components in mass fractions: 10 to 15 parts of conductive material, 1 to 2 parts of a third photoinitiator, 0.5 to 0.8 parts of a third adhesive, and 78 to 108 parts of a third solvent.

[0010] Preferably, the piezoelectric material includes one or more of lead zirconium titanate ceramics, zinc sulfide and strontium fluoride.

[0011] Preferably, the luminescent material includes one or more of zinc sulfide doped with rare earth ions and strontium aluminate doped with europium and dysprosium.

[0012] The present invention also provides a method for preparing the mechanoluminescent ink described in the above scheme, comprising the following steps:

[0013] Mixing a piezoelectric material, an inorganic pigment, a first photoinitiator, a first adhesive, and a first solvent to obtain a piezoelectric ink;

[0014] The luminescent material, the dispersant, the second photoinitiator, the second adhesive, the thickener, the defoamer and the second solvent are mixed and ground to obtain a luminescent ink;

[0015] The conductive material, the third photoinitiator, the third binder and the third solvent are mixed to obtain a conductive ink.

[0016] Preferably, the target particle size of the grinding is 10 to 20 microns.

[0017] Preferably, after the grinding, the viscosity of the luminescent ink is further adjusted; the target viscosity of the viscosity adjustment is 2000-3000 centipoise.

[0018] The present invention also provides the use of the mechanoluminescent ink described in the above scheme or the mechanoluminescent ink obtained by the preparation method described in the above scheme in the field of intelligent packaging.

[0019] The present invention also provides a mechanoluminescent material, comprising a piezoelectric layer, a luminescent layer, and an electrode layer connecting the piezoelectric layer and the luminescent layer; the piezoelectric layer, the luminescent layer or the electrode layer are respectively prepared from the piezoelectric ink, the luminescent ink or the conductive ink in the mechanoluminescent ink described in the above scheme or the mechanoluminescent ink obtained by the preparation method described in the above scheme.

[0020] Preferably, the pattern of the electrode layer is a straight line or a cross grid; the width of the straight line or the cross grid is 0.2 to 0.5 mm, and the resistance is less than 100 ohms; the thickness of the piezoelectric layer is 30 to 50 microns; the thickness of the light-emitting layer is 0.10 to 0.15 mm.

[0021] The present invention also provides a method for preparing the mechanoluminescent material described in the above scheme, comprising the following steps:

[0022] Printing an electrode layer on the screen using conductive ink, printing a piezoelectric layer on the screen using piezoelectric ink, and printing a luminescent layer on the screen using luminescent ink to obtain a mechanoluminescent intermediate;

[0023] The mechanoluminescent intermediate is cured to obtain a mechanoluminescent material.

[0024] The present invention provides a mechanoluminescent ink. Piezoelectric materials generate electric charge (piezoelectric effect) and voltage when subjected to pressure. Luminescent materials are usually electroluminescent materials, which emit light when subjected to voltage. The present invention connects the piezoelectric material and the luminescent material through conductive ink. When the piezoelectric material generates voltage due to pressure, the voltage can be transmitted to the luminescent material through the conductive ink, so that the luminescent material emits light, thereby achieving a press-to-light effect, and having anti-counterfeiting and decorative functions.

[0025] The present invention also provides a method for preparing the mechanoluminescent ink described in the above scheme. The preparation method provided by the present invention has simple steps, convenient operation, high feasibility, and is suitable for industrial production.

[0026] The present invention also provides the use of the mechanoluminescent ink described in the above scheme or the mechanoluminescent ink obtained by the preparation method described in the above scheme in the field of smart packaging. The mechanoluminescent ink provided by the present invention can be used in the field of smart packaging to prepare various smart packaging products.

[0027] The present invention also provides a mechanoluminescent material. The mechanoluminescent material provided by the present invention adopts the mechanoluminescent ink of the above solution, and by coating it on the surface of a base material, the material is given an interactive function of emitting light or displaying information when pressed, thereby enhancing the user experience.

[0028] The present invention also provides a method for preparing the mechanoluminescent material described in the above scheme. The preparation method provided by the present invention has low cost, high production efficiency, and significant economic and social benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0030] Figure 1 A schematic diagram of the luminescence principle of the mechanoluminescent material provided by the present invention;

[0031] Figure 2 A process flow chart of the mechanoluminescent ink and mechanoluminescent material provided by the present invention;

[0032] Figure 3 This is a schematic structural diagram of the mechanoluminescent material provided by the present invention. DETAILED DESCRIPTION

[0033] The present invention provides a mechanoluminescent ink, including piezoelectric ink, luminescent ink and conductive ink;

[0034] The piezoelectric ink comprises the following components in parts by mass: 30 to 50 parts of piezoelectric material, 3 to 5 parts of inorganic pigment, 1 to 2 parts of first photoinitiator, 0.5 to 1 part of first adhesive, and 94 to 124 parts of first solvent;

[0035] Based on the mass fraction of the piezoelectric material, the luminescent ink includes the following components in mass fractions: 30 to 50 parts of luminescent material, 3 to 5 parts of dispersant, 1 to 2 parts of a second photoinitiator, 0.5 to 0.8 parts of a second adhesive, 0.5 to 1 parts of a thickener, 0.1 to 0.5 parts of a defoaming agent, and 78 to 114 parts of a second solvent.

[0036] Based on the mass fraction of the piezoelectric material, the conductive ink includes the following components in mass fractions: 10 to 15 parts of conductive material, 1 to 2 parts of a third photoinitiator, 0.5 to 0.8 parts of a third adhesive, and 78 to 108 parts of a third solvent.

[0037] The mechanoluminescent ink provided by the present invention includes piezoelectric ink, and the piezoelectric ink includes 30 to 50 parts of piezoelectric material, specifically 30 parts, 35 parts, 40 parts, 45 parts or 50 parts.

[0038] In the present invention, the piezoelectric material preferably comprises lead zirconate titanate ceramic (PZT, Pb[Zr x Ti 1-x ]O3), zinc sulfide (ZnS) and strontium fluoride (SrF2) One or more.

[0039] When the piezoelectric material of the present invention is subjected to pressure, mechanical stress is converted into electrical energy, which is expressed as electrical displacement. The calculation method of the electrical displacement is as follows:

[0040] D = d × σ + ∈ × E;

[0041] Among them, D is the electric displacement, d is the piezoelectric constant, σ is the stress, ∈ is the dielectric constant, and E is the electric field.

[0042] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes piezoelectric ink, and the piezoelectric ink includes 3 to 5 parts of inorganic pigments, specifically 3 parts, 3.4 parts, 3.7 parts, 4 parts, 4.3 parts, 4.7 parts or 5 parts.

[0043] In the present invention, the inorganic pigment preferably includes one or more of iron oxide (Fe2O3), silicon dioxide (SiO2) and titanium dioxide (TiO2). The present invention utilizes the inorganic pigment to print the pattern of the pressing area of ​​the packaging material.

[0044] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes piezoelectric ink, and the piezoelectric ink includes 1 to 2 parts of a first photoinitiator, specifically 1 part, 1.2 parts, 1.5 parts, 1.8 parts or 2 parts.

[0045] In the present invention, the first photoinitiator preferably includes 1-hydroxycyclohexyl phenyl ketone (C 13 H 12 O2), 2-hydroxy-2-methyl-1-phenyl-1-propanone (C 11 H 12 O2) and 2,2-dimethoxy-2-phenylethanone (C 11 H 14 O3) or more. The present invention uses a photoinitiator to achieve the curing of the raw materials.

[0046] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes piezoelectric ink, and the piezoelectric ink includes 0.5 to 1 part of the first adhesive, specifically 0.5 part, 0.7 part, 0.9 part or 1 part.

[0047] In the present invention, the first adhesive preferably includes one or more of polyvinyl alcohol (PVA, (C2H4O)n), epoxy resin and acrylic resin. The present invention uses an adhesive to bond piezoelectric materials.

[0048] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes piezoelectric ink, and the piezoelectric ink includes 94 to 124 parts of a first solvent, specifically 94 parts, 97 parts, 100 parts, 105 parts, 108 parts, 112 parts, 116 parts, 120 parts or 124 parts.

[0049] In the present invention, the first solvent preferably includes one or more of N,N-dimethylformamide (DMF, C3H7NO), N-methylpyrrolidone (NMP, C5H9NO) and isopropyl alcohol (IPA, C3H8O). The present invention uses the first solvent to adjust the viscosity of the ink, dissolve and disperse solid particles, etc.

[0050] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes luminescent ink, and the luminescent ink includes 30 to 50 parts of luminescent material, specifically 30 parts, 35 parts, 40 parts, 45 parts or 50 parts.

[0051] In the present invention, the luminescent material preferably includes zinc sulfide doped with rare earth ions (ZnS 2+ ) and strontium aluminate doped with europium and dysprosium (SrAl2O4-Eu-Dy). The luminescent material of the present invention emits blue-green fluorescence when subjected to voltage.

[0052] The luminescence mechanism of the luminescent material of the present invention is as follows Figure 1 As shown, the luminescent material, after being subjected to mechanical pressure, transfers from the ground state to the excited state and emits light when returning to the ground state:

[0053] Eu 2+ + Mechanical pressure → Eu 2+* →Eu 2+ +hν(light emission);

[0054] Among them, Eu 2+* represents the excited state of europium ion, and hν represents the emitted photon.

[0055] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes luminescent ink, and the luminescent ink includes 3 to 5 parts of dispersant, specifically 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts.

[0056] In the present invention, the dispersant preferably includes ethylene glycol monobutyl ether (BCS, C6H 14 O2) and sodium polyacrylate ((C3H3NaO2)n). The present invention ensures that the luminescent material is evenly distributed in the ink and prevents the particles from agglomerating by using a dispersant.

[0057] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes luminescent ink, and the luminescent ink includes 1 to 2 parts of a second photoinitiator, specifically 1 part, 1.2 parts, 1.5 parts, 1.8 parts or 2 parts.

[0058] In the present invention, the second photoinitiator preferably includes 1-hydroxycyclohexyl phenyl ketone (C 13 H 12 O2), 2-hydroxy-2-methyl-1-phenyl-1-propanone (C 11 H 12 O2) and 2,2-dimethoxy-2-phenylethanone (C 11 H 14 O3) one or more.

[0059] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes luminescent ink, and the luminescent ink includes 0.5 to 0.8 parts of the second adhesive, specifically 0.5 parts, 0.6 parts, 0.7 parts or 0.8 parts.

[0060] In the present invention, the second adhesive preferably includes one or more of polyvinyl alcohol (PVA, C2H4O), epoxy resin and acrylic resin.

[0061] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes luminescent ink, and the luminescent ink includes 0.5 to 1 part of a thickener, specifically 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part.

[0062] In the present invention, the thickener is preferably hydroxypropyl methylcellulose (HPMC).

[0063] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes luminescent ink, and the luminescent ink includes 0.1 to 0.5 parts of a defoaming agent, specifically 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts or 0.5 parts.

[0064] In the present invention, the defoaming agent is preferably polydimethylsiloxane (PDMS).

[0065] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes luminescent ink, and the luminescent ink includes 78 to 114 parts of the second solvent, specifically 78 parts, 82 parts, 85 parts, 88 parts, 92 parts, 95 parts, 98 parts, 100 parts, 105 parts, 108 parts, 112 parts or 114 parts.

[0066] In the present invention, the second solvent preferably includes one or more of isopropyl alcohol (IPA, C3H8O), ethyl acetate (C4H8O2) and N,N-dimethylformamide (DMF, C3H7NO).

[0067] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes a conductive ink, and the conductive ink includes 10 to 15 parts of the conductive material, specifically 10 parts, 12 parts, 14 parts or 15 parts.

[0068] In the present invention, the conductive material preferably includes one or more of silver nanowires (AgNWs) and copper nanoparticles (Copper).

[0069] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes a conductive ink, and the conductive ink includes 1 to 2 parts of a third photoinitiator, specifically 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts or 2 parts.

[0070] In the present invention, the third photoinitiator preferably includes 1-hydroxycyclohexyl phenyl ketone (C 13 H 12 O2) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (C 11 H 12 O2) one or more.

[0071] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes a conductive ink, and the conductive ink includes 0.5 to 0.8 parts of a third adhesive, specifically 0.5 parts, 0.6 parts, 0.7 parts or 0.8 parts.

[0072] In the present invention, the third adhesive preferably includes one or more of polyvinyl alcohol (PVA) and epoxy resin.

[0073] Based on the mass fraction of the piezoelectric material, the mechanoluminescent ink provided by the present invention includes a conductive ink, and the conductive ink includes 78 to 108 parts of a third solvent, specifically 78 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105 parts or 108 parts.

[0074] In the present invention, the third solvent preferably includes one or more of isopropyl alcohol (IPA) and ethyl acetate.

[0075] The present invention also provides a method for preparing the mechanoluminescent ink described in the above scheme, comprising the following steps:

[0076] Mixing a piezoelectric material, an inorganic pigment, a first photoinitiator, a first adhesive, and a first solvent to obtain a piezoelectric ink;

[0077] The luminescent material, the dispersant, the second photoinitiator, the second adhesive, the thickener, the defoamer and the second solvent are mixed and ground to obtain a luminescent ink;

[0078] The conductive material, the third photoinitiator, the third binder and the third solvent are mixed to obtain a conductive ink.

[0079] The present invention mixes a piezoelectric material, an inorganic pigment, a first photoinitiator, a first adhesive and a first solvent (referred to as a first mixture) to obtain a piezoelectric ink. In the present invention, the first mixture is preferably: mixing the piezoelectric material with the inorganic pigment (referred to as mixing A) to obtain a mixed powder, mixing the mixed powder with the first solvent (referred to as mixing B) to obtain a mixture B, mixing the mixture B with the first adhesive (referred to as mixing C) to obtain a mixture C, and mixing the mixture C with the first photoinitiator (referred to as mixing D).

[0080] In the present invention, the mixing B is preferably stirring mixing; the stirring mixing is preferably sequentially performing magnetic stirring and ultrasonic dispersion; the magnetic stirring time is preferably 30 to 50 minutes, specifically 30 minutes, 35 minutes, 40 minutes, 45 minutes or 50 minutes; the ultrasonic dispersion time is preferably 30 to 50 minutes, specifically 30 minutes, 35 minutes, 40 minutes, 45 minutes or 50 minutes.

[0081] In the present invention, the mixing C is preferably stirring mixing.

[0082] In the present invention, the mixing D is preferably stirring mixing.

[0083] In the present invention, the luminescent material, the dispersant, the second photoinitiator, the second adhesive, the thickener, the defoamer and the second solvent are mixed (referred to as the second mixing) and then ground to obtain the luminescent ink. In the present invention, the second mixing is preferably stirring mixing. The present invention ensures that the luminescent material is uniformly dispersed in the solution through the second mixing.

[0084] In the present invention, the grinding equipment is preferably a three-roller grinder; the target particle size of the grinding is preferably 10 to 20 microns, specifically 10 microns, 12 microns, 14 microns, 16 microns, 18 microns or 20 microns. The present invention ensures the uniformity of the ink and a good printing effect through grinding.

[0085] In the present invention, the grinding preferably further includes adjusting the viscosity of the luminescent ink; the reagent used for adjusting the viscosity is preferably a second solvent or a second adhesive; the target viscosity of the viscosity adjustment is preferably 2000 to 3000 centipoise, specifically 2000 centipoise, 2200 centipoise, 2400 centipoise, 2600 centipoise, 2800 centipoise or 3000 centipoise. The present invention can better meet the requirements of screen printing by adjusting the luminescent ink to the target viscosity.

[0086] In the present invention, the luminescent ink is preferably filtered after grinding; the filter element precision of the filter used for filtering is preferably 10 microns. The present invention removes impurities and undispersed particles in the luminescent ink by filtering.

[0087] The present invention mixes a conductive material, a third photoinitiator, a third adhesive and a third solvent (referred to as a third mixture) to obtain a conductive ink. In the present invention, the third mixture is preferably: the conductive material and the third solvent are mixed and then ultrasonically dispersed to obtain a dispersion, the dispersion and the third adhesive are mixed (referred to as a mixture L) to obtain a mixture L, and the mixture L and the third photoinitiator are mixed (referred to as a mixture M).

[0088] In the present invention, the ultrasonic dispersion time is preferably 30 to 50 min, specifically 30 min, 35 min, 40 min, 45 min or 50 min, the power is preferably 100 to 150 W, specifically 100 W, 120 W, 140 W or 150 W, and the frequency is preferably 20 to 40 kHz, specifically 20 kHz, 25 kHz, 30 kHz, 35 kHz or 40 kHz.

[0089] In the present invention, the mixing L is preferably stirring mixing.

[0090] In the present invention, the mixing M is preferably stirring mixing.

[0091] The present invention also provides the use of the mechanoluminescent ink described in the above scheme or the mechanoluminescent ink obtained by the preparation method described in the above scheme in the field of intelligent packaging.

[0092] The mechanoluminescent ink provided by the present invention can be used in the field of intelligent packaging to prepare various intelligent packaging products.

[0093] In the present invention, the smart packaging product is preferably a smart packaging box.

[0094] The present invention also provides a mechanoluminescent material, comprising a piezoelectric layer, a luminescent layer, and an electrode layer connecting the piezoelectric layer and the luminescent layer; the piezoelectric layer, the luminescent layer or the electrode layer are respectively prepared from the piezoelectric ink, the luminescent ink or the conductive ink in the mechanoluminescent ink described in the above scheme or the mechanoluminescent ink obtained by the preparation method described in the above scheme.

[0095] In the present invention, the pattern of the electrode layer is preferably a straight line or a cross grid; the width of the line in the straight line or cross grid is preferably 0.2-0.5 mm, specifically 0.2 mm, 0.3 mm, 0.4 mm or 0.5 mm, and the resistance is preferably less than 100 ohms, specifically 100 ohms, 80 ohms, 60 ohms, 40 ohms, 20 ohms or 10 ohms.

[0096] In the present invention, the pattern of the piezoelectric layer is preferably circular; the thickness of the piezoelectric layer is preferably 30 to 50 microns, specifically 30 microns, 35 microns, 40 microns, 45 microns or 50 microns.

[0097] In the present invention, the thickness of the light-emitting layer is preferably 0.10-0.15 mm, and specifically can be 0.10 mm, 0.11 mm, 0.12 mm, 0.13 mm, 0.14 mm or 0.15 mm.

[0098] In the present invention, the mechanoluminescent material preferably further includes a protective layer; the protective layer preferably covers the surfaces of the piezoelectric layer, the luminescent layer and the electrode layer; the protective layer is preferably a transparent protective layer; and the transparent protective layer is preferably polyimide.

[0099] The structure of the mechanoluminescent material provided by the present invention is as follows Figure 3 As shown, it includes a piezoelectric layer, a light-emitting layer, and an electrode layer connecting the piezoelectric layer and the light-emitting layer.

[0100] The present invention also provides a method for preparing the mechanoluminescent material described in the above scheme, comprising the following steps:

[0101] Printing an electrode layer on the screen using conductive ink, printing a piezoelectric layer on the screen using piezoelectric ink, and printing a luminescent layer on the screen using luminescent ink to obtain a mechanoluminescent intermediate;

[0102] The mechanoluminescent intermediate is cured to obtain a mechanoluminescent material.

[0103] The present invention uses conductive ink to print an electrode layer on a silk screen, uses piezoelectric ink to print a piezoelectric layer on a silk screen, and uses luminescent ink to print a luminescent layer on a silk screen to obtain a mechanoluminescent intermediate. The present invention connects a piezoelectric material and a luminescent material by printing an electrode layer.

[0104] In the present invention, the speed of printing the piezoelectric layer is preferably 2-3 m / min, specifically 2 m / min, 2.3 m / min, 2.7 m / min or 3 m / min; the pressure of the printed piezoelectric layer is preferably based on uniform transfer of ink.

[0105] After obtaining the mechanoluminescent intermediate, the present invention cures the mechanoluminescent intermediate to obtain a mechanoluminescent material. In the present invention, the curing device is preferably an ultraviolet curing machine; the curing is preferably ultraviolet curing; the UV light intensity of the ultraviolet curing is preferably 30 to 50 W / cm 2 , specifically 30W / cm 2 、35W / cm 2 , 40W / cm 2 , 45W / cm 2 or 50W / cm 2 The UV light wavelength is preferably 365 nm, and the curing time is preferably 30 to 60 seconds, specifically 30 seconds, 40 seconds, 50 seconds or 60 seconds. The present invention ensures that the mechanoluminescent ink is firmly attached by curing.

[0106] In the present invention, the curing preferably further includes coating of a protective layer. The present invention protects the mesoluminescent material from environmental influences by coating the protective layer.

[0107] The present invention provides a mechanoluminescent ink and a mechanoluminescent material, and the overall preparation process of the two is as follows: Figure 2 The present invention mixes raw materials of piezoelectric ink to obtain piezoelectric ink, mixes raw materials of conductive ink to obtain conductive ink, mixes raw materials of luminescent ink, grinds, adjusts viscosity and filters in sequence to obtain luminescent ink, and then uses the three inks (mechloluminescent ink) for screen printing, solidifies after printing, and coats a protective film to obtain a mechloluminescent material.

[0108] In order to further illustrate the present invention, the scheme of the present invention is described in detail below in conjunction with the accompanying drawings and embodiments, but they should not be understood as limiting the protection scope of the present invention.

[0109] Example 1

[0110] 1. Preparation of piezoelectric ink:

[0111] formula:

[0112] 50g zirconium lead titanate ceramics; 3g iron oxide; 110mL N,N-dimethylformamide; 12mL polyvinyl alcohol; 1g 1-hydroxycyclohexyl phenyl ketone.

[0113] Process:

[0114] (1) Lead zirconium titanate ceramic powder is mixed with iron oxide to obtain a mixed powder.

[0115] (2) DMF was added to the mixed powder and stirred with a magnetic stirrer for 40 min to obtain a mixture.

[0116] (3) The mixture was placed in an ultrasonic cleaner for ultrasonic dispersion for 40 min.

[0117] (4) The mixture and PVA are stirred and mixed until dissolved to obtain a mixed solution.

[0118] (5) The mixed solution and 1-hydroxycyclohexyl phenyl ketone are stirred and mixed to obtain a piezoelectric ink.

[0119] 2. Preparation of luminescent ink:

[0120] formula:

[0121] Zinc sulfide doped with rare earth ions 50 g, isopropyl alcohol 100 mL, polyvinyl alcohol 12 mL, ethylene glycol monobutyl ether 5 g, 1-hydroxycyclohexyl phenyl ketone 2 g, polydimethylsiloxane 0.3 g, and hydroxypropyl methylcellulose 1 g.

[0122] Process:

[0123] (1) Zinc sulfide doped with rare earth ion luminescent material, isopropyl alcohol, polyvinyl alcohol, ethylene glycol monobutyl ether, 1-hydroxycyclohexyl phenyl ketone, polydimethylsiloxane and hydroxypropyl methylcellulose are mixed in the above proportions using a high-speed stirrer to obtain a mixture.

[0124] (2) The mixture was poured into a three-roll mill for grinding until the particle size reached 16 μm to obtain a grinding liquid.

[0125] (3) Measure the viscosity of the polishing liquid and add polyvinyl alcohol to adjust the viscosity to 2700 centipoise.

[0126] (4) Filter using a precision filter (filter element accuracy 10 microns) to remove impurities and undispersed particles to obtain luminescent ink.

[0127] 3. Preparation of conductive ink:

[0128] formula:

[0129] Silver nanowires 15 g, isopropyl alcohol 115 mL, polyvinyl alcohol 12 mL, 1-hydroxycyclohexyl phenyl ketone 1 g.

[0130] Process:

[0131] (1) Dispersing silver nanowires in isopropyl alcohol to obtain a mixture.

[0132] (2) The mixture was placed in an ultrasonic cleaner for ultrasonic dispersion for 40 min at a power of 130 W and a frequency of 30 kHz.

[0133] (3) Add polyvinyl alcohol to the mixture and stir until dissolved.

[0134] (4) Add 1-hydroxycyclohexyl phenyl ketone to the mixture and stir to obtain a conductive ink.

[0135] 4. Preparation of mechanoluminescent materials:

[0136] (1) Use conductive ink to print electrode patterns (simple straight lines, such as Figure 3 ), the line width is 0.35mm and the resistance is less than 100 ohms;

[0137] (2) printing the piezoelectric layer using piezoelectric ink at a printing speed of 2 m / min to form a blue-green circular pattern with a thickness of 38 μm;

[0138] (3) Printing the luminescent layer with luminescent ink to a thickness of 0.15 mm;

[0139] (4) Use a UV curing machine to cure the ink, the UV light intensity is 40W / cm 2 , curing time is 60s, UV light wavelength is 365nm;

[0140] (5) A layer of polyimide is coated on the surface of the cured mesoluminescent ink to obtain a mesoluminescent material.

[0141] Example 2

[0142] 1. Preparation of piezoelectric ink:

[0143] formula:

[0144] Zinc sulfide 50g, silicon dioxide 4g, N-methylpyrrolidone 120mL, epoxy resin 13mL, 2-hydroxy-2-methyl-1-phenyl-1-propanone 1g.

[0145] Process:

[0146] (1) Zinc sulfide powder and silicon dioxide are mixed to obtain a mixed powder.

[0147] (2) Add N-methylpyrrolidone to the mixed powder and stir with a magnetic stirrer for 50 minutes to obtain a mixture.

[0148] (3) The mixture was placed in an ultrasonic cleaner for ultrasonic dispersion for 50 min.

[0149] (4) The mixture and epoxy resin are stirred and mixed until dissolved to obtain a mixed solution.

[0150] (5) Add 2-hydroxy-2-methyl-1-phenyl-1-propanone to the mixed solution and stir to obtain a piezoelectric ink.

[0151] 2. Preparation of luminescent ink:

[0152] formula:

[0153] Strontium aluminate doped with europium and dysprosium 50 g, ethyl acetate 110 mL, epoxy resin 11 mL, sodium polyacrylate 4 g, 2-hydroxy-2-methyl-1-phenyl-1-propanone 1 g, polydimethylsiloxane 0.3 g, and hydroxypropyl methylcellulose 1 g.

[0154] Process:

[0155] (1) Strontium aluminate doped with europium dysprosium luminescent material, ethyl acetate, epoxy resin solution, sodium polyacrylate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, polydimethylsiloxane and hydroxypropyl methylcellulose are mixed in the above proportions using a high-speed stirrer to obtain a mixture.

[0156] (2) The mixture was poured into a three-roll mill for grinding until the particle size reached 13 μm to obtain a grinding liquid.

[0157] (3) Measure the viscosity of the polishing liquid and add epoxy resin to adjust the viscosity to 2500 centipoise.

[0158] (4) Filter using a precision filter (filter element accuracy 10 microns) to remove impurities and undispersed particles to obtain luminescent ink.

[0159] 3. Preparation of conductive ink:

[0160] formula:

[0161] Copper nanoparticles 15 g, ethyl acetate 120 mL, epoxy resin 10 mL, 2-hydroxy-2-methyl-1-phenyl-1-propanone 1 g.

[0162] Process:

[0163] (1) Copper nanoparticles are dispersed in ethyl acetate to obtain a mixture.

[0164] (2) The mixture was placed in an ultrasonic cleaner for ultrasonic dispersion for 50 min at a power of 130 W and a frequency of 35 kHz.

[0165] (3) Add PVA to the mixture and stir until dissolved.

[0166] (4) Add 1-hydroxycyclohexyl phenyl ketone to the mixture and stir to obtain a conductive ink.

[0167] 4. Preparation of mechanoluminescent materials:

[0168] (1) Use conductive ink to print electrode patterns (simple straight lines, such as Figure 3 ), the line width is 0.35mm and the resistance is less than 100 ohms;

[0169] (2) printing the piezoelectric layer using piezoelectric ink at a printing speed of 2 m / min to form a blue-green circular pattern with a thickness of 50 μm;

[0170] (3) Printing the luminescent layer with luminescent ink to a thickness of 0.15 mm;

[0171] (4) Use a UV curing machine to cure the ink, the UV light intensity is 50W / cm 2 , curing time is 60s, UV light wavelength is 365nm;

[0172] (5) A layer of polyimide is coated on the surface of the cured mesoluminescent ink to obtain a mesoluminescent material.

[0173] Example 3

[0174] 1. Preparation of piezoelectric ink:

[0175] formula:

[0176] 50g strontium fluoride, 4g titanium dioxide, 120mL isopropanol, 13mL acrylic resin, 1g 2,2-dimethoxy-2-phenylethanone.

[0177] Process:

[0178] (1) Strontium fluoride powder and titanium dioxide are mixed to obtain a mixed powder.

[0179] (2) Add isopropyl alcohol to the mixed powder and stir with a magnetic stirrer for 50 minutes to obtain a mixture.

[0180] (3) The mixture was placed in an ultrasonic cleaner for ultrasonic dispersion for 50 min.

[0181] (4) Add acrylic resin to the mixture and stir until dissolved.

[0182] (5) Add 1-hydroxycyclohexyl phenyl ketone to the mixture, stir and mix, and obtain a piezoelectric ink.

[0183] 2. Preparation of luminescent ink:

[0184] formula:

[0185] Zinc sulfide doped with rare earth ions 50 g, N,N-dimethylformamide 110 mL, acrylic resin 10 mL, ethylene glycol monobutyl ether 3 g, 2,2-dimethoxy-2-phenylethanone 1 g, polydimethylsiloxane 0.5 g, hydroxypropyl methylcellulose 1 g.

[0186] Process:

[0187] (1) Zinc sulfide doped with rare earth ion luminescent material, N,N-dimethylformamide, acrylic resin solution, ethylene glycol monobutyl ether, 2,2-dimethoxy-2-phenylethanone, polydimethylsiloxane and hydroxypropyl methylcellulose are mixed in the above proportions using a high-speed stirrer to obtain a mixture.

[0188] (2) The mixture was poured into a three-roll mill for grinding until the particle size was 13 μm to obtain a grinding liquid.

[0189] (3) Measure the viscosity of the polishing liquid and add N,N-dimethylformamide to adjust the viscosity to 2500 centipoise.

[0190] (4) Filter using a precision filter (filter element accuracy 10 microns) to remove impurities and undispersed particles to obtain luminescent ink.

[0191] 3. Preparation of conductive ink:

[0192] formula:

[0193] Silver nanowires 15 g, ethyl acetate 120 mL, polyvinyl alcohol 11 mL, 2-hydroxy-2-methyl-1-phenyl-1-propanone 1 g.

[0194] Process:

[0195] (1) Dispersing silver nanowires in ethyl acetate to obtain a mixture.

[0196] (2) The mixture was placed in an ultrasonic cleaner for ultrasonic dispersion for 50 min at a power of 130 W and a frequency of 40 kHz.

[0197] (3) Add PVA to the mixture and stir until dissolved.

[0198] (4) Add 1-hydroxycyclohexyl phenyl ketone to the mixture and stir to obtain a conductive ink.

[0199] 4. Preparation of mechanoluminescent materials

[0200] (1) Use conductive ink to print the electrode pattern (cross grid) with a line width of 0.35 mm and a resistance of less than 100 ohms;

[0201] (2) printing the piezoelectric layer using piezoelectric ink at a printing speed of 2 m / min to form a blue-green circular pattern with a thickness of 50 μm;

[0202] (3) Printing the luminescent layer with luminescent ink to a thickness of 0.15 mm;

[0203] (4) Use a UV curing machine to cure the ink, the UV light intensity is 50W / cm 2 , curing time is 60s, UV light wavelength is 365nm;

[0204] (5) A layer of polyimide is coated on the surface of the cured mesoluminescent ink to obtain a mesoluminescent material.

[0205] The performance of the mechanoluminescent material prepared in Example 1 was tested, and the results are shown in Table 1.

[0206] Table 1 Performance data of the mechanoluminescent material prepared in Example 1

[0207] Test items Test Method Reference Standards Test results Piezoelectric material dispersion Microscope observation Evenly dispersed 90% particles are evenly dispersed Piezoelectric performance Piezoelectric voltage constant measurement g33>10mV / N g33=12.5mV / N Luminous efficiency of luminescent materials Spectrometer measurement Luminous efficiency>10lm / W 15lm / W Conductive ink conductivity Four-point probe method Resistivity <50Ω·cm Resistivity 40Ω·cm Printing uniformity Visual inspection or microscopic observation Clear printing pattern 95% area printing is good Interlayer bonding strength Cross-cut test Binding strength>4B Binding Strength 5B

[0208] It can be seen from Table 1 that the charge generated by the piezoelectric material can directly and effectively drive the luminescent material to emit light. The mechanoluminescent material provided by the present invention has excellent conductivity and piezoelectric properties, high luminous efficiency, can achieve the effect of pressed light, and has a high degree of bonding and good component uniformity.

[0209] It can be seen from the above embodiments that the mechanoluminescent material provided by the present invention, using the mechanoluminescent ink of the present invention, has the interactive function of emitting light by pressing or displaying information.

[0210] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A mechanoluminescent ink, characterized in that: Including piezoelectric ink, luminescent ink and conductive ink; The piezoelectric ink comprises the following components in parts by mass: 30 to 50 parts of piezoelectric material, 3 to 5 parts of inorganic pigment, 1 to 2 parts of first photoinitiator, 0.5 to 1 part of first adhesive, and 94 to 124 parts of first solvent; Based on the mass fraction of the piezoelectric material, the luminescent ink includes the following components in mass fractions: 30 to 50 parts of luminescent material, 3 to 5 parts of dispersant, 1 to 2 parts of second photoinitiator, 0.5 to 0.8 parts of second binder, 0.5 to 1 parts of thickener, 0.1 to 0.5 parts of defoamer, and 78 to 114 parts of second solvent; Based on the mass fraction of the piezoelectric material, the conductive ink includes the following components in mass fractions: 10 to 15 parts of conductive material, 1 to 2 parts of a third photoinitiator, 0.5 to 0.8 parts of a third adhesive, and 78 to 108 parts of a third solvent.

2. The mechanoluminescent ink according to claim 1, characterized in that: The piezoelectric material includes one or more of zirconium lead titanate ceramics, zinc sulfide and strontium fluoride.

3. The mechanoluminescent ink according to claim 1 or 2, characterized in that: The luminescent material includes one or more of zinc sulfide doped with rare earth ions and strontium aluminate doped with europium and dysprosium.

4. The method for preparing the mechanoluminescent ink according to any one of claims 1 to 3, characterized in that: The following steps are involved: Mixing a piezoelectric material, an inorganic pigment, a first photoinitiator, a first adhesive, and a first solvent to obtain a piezoelectric ink; The luminescent material, the dispersant, the second photoinitiator, the second adhesive, the thickener, the defoamer and the second solvent are mixed and ground to obtain a luminescent ink; The conductive material, the third photoinitiator, the third binder and the third solvent are mixed to obtain a conductive ink.

5. The preparation method according to claim 4, characterized in that: The target particle size of the grinding is 10 to 20 microns.

6. The preparation method according to claim 4 or 5, characterized in that: After the grinding, the viscosity of the luminescent ink is adjusted; the target viscosity of the viscosity adjustment is 2000-3000 centipoise.

7. Use of the mechanoluminescent ink according to any one of claims 1 to 3 or the mechanoluminescent ink obtained by the preparation method according to any one of claims 4 to 6 in the field of smart packaging.

8. A mechanoluminescent material, characterized in that: It includes a piezoelectric layer, a light-emitting layer, and an electrode layer connecting the piezoelectric layer and the light-emitting layer; the piezoelectric layer, the light-emitting layer or the electrode layer are prepared from the piezoelectric ink, the luminescent ink or the conductive ink in the mesoluminescent ink according to any one of claims 1 to 3 or the mesoluminescent ink obtained by the preparation method according to any one of claims 4 to 6.

9. The mechanoluminescent material according to claim 8, characterized in that: The pattern of the electrode layer is a straight line or a cross grid; the width of the straight line or the cross grid is 0.2-0.5 mm, and the resistance is less than 100 ohms; the thickness of the piezoelectric layer is 30-50 microns; the thickness of the light-emitting layer is 0.10-0.15 mm.

10. The method for preparing the mechanoluminescent material according to any one of claims 8 to 9, characterized in that: The following steps are involved: Printing an electrode layer on the screen using conductive ink, printing a piezoelectric layer on the screen using piezoelectric ink, and printing a luminescent layer on the screen using luminescent ink to obtain a mechanoluminescent intermediate; The mechanoluminescent intermediate is cured to obtain a mechanoluminescent material.

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