CN115044243A - Color printing ink, color photovoltaic glass, color photovoltaic module and preparation method thereof - Google Patents

Color printing ink, color photovoltaic glass, color photovoltaic module and preparation method thereof Download PDF

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Publication number
CN115044243A
CN115044243A CN202210528179.2A CN202210528179A CN115044243A CN 115044243 A CN115044243 A CN 115044243A CN 202210528179 A CN202210528179 A CN 202210528179A CN 115044243 A CN115044243 A CN 115044243A
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glass
ink
color
colored
pigment
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魏晓虎
谭小春
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Longi Solar Technology Co Ltd
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Longi Solar Technology Co Ltd
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Priority to CN202210528179.2A priority Critical patent/CN115044243A/en
Publication of CN115044243A publication Critical patent/CN115044243A/en
Priority to PCT/CN2023/090514 priority patent/WO2023221749A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0488—Double glass encapsulation, e.g. photovoltaic cells arranged between front and rear glass sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B10/00—Integration of renewable energy sources in buildings
    • Y02B10/10—Photovoltaic [PV]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The application discloses a color ink, including: low-melting-point glass powder, varnish, structural color pigment and inorganic wavelength conversion material. Also disclosed is a method of making a colored ink comprising: dissolving resin and an auxiliary agent in a solvent to obtain varnish; stirring and mixing the low-melting-point glass powder, the varnish and the wavelength conversion material, and grinding the mixture to the fineness of less than 10 microns to obtain transparent ink; and adding the structural color pigment into the transparent ink for mixing and dispersing to obtain the color ink. Also disclosed is a colored photovoltaic glass comprising: a glass body; and a colored ink layer on the surface of the glass body; the color ink layer is formed by applying the color ink on the surface of the glass body. Also discloses a method for preparing the colored photovoltaic glass. Also disclosed is a colored photovoltaic module comprising the colored photovoltaic glass. The color photovoltaic glass prepared by the color ink has higher hardness and better weather resistance, the light transmittance is increased to 60 percent or even more than 70 percent, and the problem of color change of the structural color pigment along with the angle is effectively alleviated.

Description

Colored printing ink, colored photovoltaic glass, colored photovoltaic module and preparation method thereof
Technical Field
The application relates to the technical field of solar photovoltaics, in particular to color printing ink, color photovoltaic glass, a color photovoltaic module and a preparation method thereof.
Background
Solar energy is a renewable clean energy source which is not limited by regions, the photovoltaic power generation cost is rapidly reduced along with the development of the photovoltaic technology in recent years, the photovoltaic power generation technology is used in a wider range, and the combination of photovoltaic and buildings also becomes one of the fields of photovoltaic application. The Building Integrated Photovoltaic (BIPV) is beneficial to realizing the fusion of a Photovoltaic component and a colorful Building environment, accords with the future development trend of assembly type, green and low carbon in the Building industry, and has popularization prospect. The photovoltaic module is added with colors in various forms, such as coloring of a battery antireflection film, a color photoelectric layer, a color packaging adhesive film and color front plate glass. Based on economic and efficiency considerations, the commercial color crystal silicon photovoltaic product at present can obtain the color front plate glass to realize the required color through means such as printing a coating, glass coating and the like.
The coating of the traditional colored coating glass is prepared by compounding common color-absorbing inorganic pigment and low-melting-point glass powder, so that the glass has higher hardness and weather resistance, but the selected pigment color-absorbing principle can convert part of light energy into heat energy, so that the light energy utilization rate is low.
Patent document 1 and patent document 2 select pearlescent pigments based on the interference color rendering principle, so that absorption of the pigments to light energy is reduced, and the light energy utilization rate is improved, but the main body of the ink coating is made of high polymer resin, and the mechanical property of the coating is improved by adding a cross-linking structure, but the coating is still deficient in hardness, wear resistance and weather resistance compared with inorganic materials. In addition, the interference color development pearlescent pigment has certain transmittance to ultraviolet rays, reduces the performance of the packaging adhesive film battery, and brings the effect of color change along with the angle, so that the interference color development pearlescent pigment is not suitable for building curtain walls. Patent document 3 combines ultraviolet curing and high-temperature sintering processes, the light transmittance is improved by mechanical embossing after the UV curing, and the weather resistance of the final inorganic coating can be ensured by high-temperature sintering, but the process is complex and has high requirements on equipment because the ultraviolet curing and the high-temperature sintering are required, defects are easily formed when the high-temperature sintering is performed with the organic matter content of more than 30%, and the impact resistance of glass may be affected by the pores on the coating.
In addition, in order to improve the solar energy utilization efficiency, there are patent reports that light with a wavelength of 400nm or less is converted into light in the visible light range by using a wavelength conversion material, wherein the light wave conversion material is added into an encapsulation adhesive film to improve the utilization rate of the photovoltaic module to light energy in patent documents 4 and 5. Patent document 6 discloses that an organic chromophore is used as a light wave conversion material and is fixed to a glass plate with an organic resin. None of the above patents relate to colored glass and converted wavelength color.
Therefore, there is a need to develop a color ink and a color photovoltaic glass having high weather resistance, which can be applied to a solar cell and can improve the utilization efficiency of light energy through wavelength conversion.
Documents of the prior art
Patent document 1: CN110437676A publication
Patent document 2: CN110606668A publication
Patent document 3: CN113087406A publication
Patent document 4: CN107681015A publication
Patent document 5: CN107154442A publication
Patent document 6: CN104428907A publication
Disclosure of Invention
The color ink has high hardness and strong weather resistance, can reduce the absorption of pigment to light energy, improves the utilization efficiency of the light energy, and reduces the problem of color change along with the angle. The application also aims to provide a preparation method of the color ink, color photovoltaic glass formed by coating the color ink on the surface of ultra-white glass, and a preparation method of the color photovoltaic glass.
The specific technical scheme of the application is as follows:
1. a colored ink, comprising: low-melting-point glass powder, varnish, structural color pigment and inorganic wavelength conversion material.
2. The colored ink according to item 1, comprising, based on the total weight of the colored ink:
60 to 80 percent of low-melting-point glass powder, preferably 65 to 75 percent;
18 to 30 percent of varnish, preferably 22 to 28 percent of varnish;
1 to 10 percent, preferably 1 to 5 percent of structural color pigment; and
1-10%, preferably 1-4% of an inorganic wavelength converting material;
3. the color ink according to item 1 or 2, wherein the low-melting glass frit has a melting onset temperature of 350 to 500 ℃;
preferably, the low-melting glass frit has a linear expansion coefficient of 85 × 10 -7 ～91×10 -7 /℃；
Preferably, the particle size of the low-melting glass powder is less than or equal to 15 μm.
4. The color ink according to any one of claims 1 to 3, wherein the varnish comprises a solvent and a resin, and preferably the varnish further comprises an auxiliary agent;
preferably, the varnish comprises, based on the total weight of the varnish: 70-90% of solvent, 9-29% of resin and 0.5-4% of auxiliary agent;
preferably, the solvent is selected from one or two or three of terpineol, turpentine and diethylene glycol;
preferably, the resin is selected from one or two or three of rosin modified phenolic resin, aldehyde ketone resin and ethyl cellulose;
preferably, the auxiliary agent is selected from one or two of an oily dispersant and a defoaming agent.
5. The color ink according to any one of claims 1 to 4, wherein the structural color pigment is one or more selected from a pearlescent pigment, a multilayer metal oxide interference pigment and a photonic crystal pigment;
preferably, the metal oxides of the layers of the multilayer metal oxide interference pigment are respectively selected from one or more than two of metal oxides of titanium, aluminum, silicon, tin, zirconium and zinc.
6. The color ink according to any one of claims 1 to 5, wherein the structural color pigment is a pearlescent pigment, and the pearlescent pigment includes a substrate selected from one of natural mica, synthetic mica and synthetic borosilicate;
preferably, the pearlescent pigment further comprises a coating material for coating the substrate, wherein the coating material is one or two or three of titanium dioxide, ferric oxide and tin oxide;
preferably, the particle size of the pearlescent pigment is 200 μm or less.
7. The color ink according to any one of claims 1 to 6, wherein the wavelength conversion material is a rare earth doped compound;
preferably, the wavelength converting material is selected from one or more of a green wavelength converting material, a red wavelength converting material, a blue wavelength converting material, and a yellow wavelength converting material;
preferably, the green wavelength converting material is selected from CaAlSiN 3 :Eu 2+ 、Ba 2 SiO 4 :Eu 2+ And Lu 3 Al 5 O 12 :Ce 3+ One or two or three of (1);
preferably, the red wavelength converting material is selected from Y 2 MoO 6 :Eu 3+ 、Sr 2 Si 5 N 8 :Eu 2+ And Y 3 Al 5 O 12 :Mn 4+ One or two or three of (1);
preferably, the blue wavelength converting material is selected from LiSrPO 4 :Eu 2+ 、Ba 3 Y 2 B 6 O 15 :Ce 3+ 、SrLu 2 O 4 :Ce 3+ 、Ca 3 ZrSi 2 O 9 :Ce 3+ 、LiCaPO 4 :Eu 2+ And Ca 2 PO 4 Cl:Eu 2+ One or more than two of the above;
preferably, the yellow wavelength converting material is selected from Y 3 Al 5 O 12 :Ce 3+ 、Tb 3 Al 5 O 12 :Ce 3+ And Sr 3 SiO 5 :Eu 2+ One or two or three of them.
8. A method of making a colored ink comprising the steps of:
preparing ink mixing oil: dissolving resin and an auxiliary agent in a solvent to obtain varnish;
preparing transparent ink: mixing the low-melting-point glass powder, the ink adjusting oil and the wavelength conversion material, and grinding the mixture to the fineness of less than 10 mu m to obtain transparent ink;
adding a structural color pigment: and adding the structural color pigment into the transparent ink for mixing and dispersing to obtain the color ink.
9. The method according to item 8,
the low-melting-point glass powder accounts for 60-80 parts by weight, preferably 65-75 parts by weight;
the ink mixing oil accounts for 18-30 parts by weight, and preferably 22-28 parts by weight;
the structural color pigment accounts for 1-10 parts by weight, preferably 1-5 parts by weight;
the inorganic wavelength conversion material is 1 to 10 parts by weight, preferably 1 to 4 parts by weight.
10. The method according to item 8 or 9, wherein the resin, the auxiliary, the low-melting glass frit, the varnish, the wavelength conversion material, and the structural color pigment are any one of the resins, the auxiliary, the low-melting glass frit, the varnish, the wavelength conversion material, and the structural color pigment according to items 1 to 7.
11. A colored photovoltaic glass, comprising:
a glass body; and
a colored ink layer on the surface of the glass body;
wherein the color ink layer comprises the color ink of any one of items 1 to 7 or the color ink prepared by the method of any one of items 8 to 10.
12. Colored photovoltaic glass according to claim 11, characterized in that the glass body is ultra-white glass, preferably ultra-white float glass or ultra-white patterned glass;
preferably, the thickness of the glass body is 2-6 mm.
13. A method of making colored photovoltaic glass comprising the steps of: applying the color ink according to any one of items 1 to 7 or the color ink prepared by the method according to any one of items 8 to 10 to a glass body, and drying, sintering and tempering to obtain the color photovoltaic glass;
preferably, the coloured ink is applied to the glass body by screen printing, roller coating or spraying.
14. The method according to item 13, characterized in that the mesh number of the screen used for screen printing is 100 to 350 meshes;
preferably, the drying temperature is 140-200 ℃, and the drying time is 1-8 min;
preferably, the sintering tempering temperature is 660-720 ℃, and the sintering tempering time is 2-4 min;
preferably, the glass body is ultra-white glass, preferably ultra-white float glass or ultra-white patterned glass;
preferably, the thickness of the glass body is 2-6 mm.
15. A color photovoltaic module, comprising: the solar photovoltaic glass comprises color front plate glass, a first layer of packaging adhesive film, a photovoltaic cell array, a second layer of packaging adhesive film and back plate glass, wherein the color front plate glass is the color photovoltaic glass described in item 11 or 12.
ADVANTAGEOUS EFFECTS OF INVENTION
The low-melting-point glass powder is added into the color ink, so that a compact inorganic coating can be formed on the surface of a glass body after the ink is sintered, and the color ink has higher hardness and better weather resistance compared with a glass coating which takes polymer resin as a substrate.
The color ink is added with the structural color pigment, and the color forming principle is an interference color forming principle, so that the light transmittance of the prepared color photovoltaic glass is increased to more than 60%; and the light transmittance of the traditional colored photovoltaic glass prepared by adding the same amount of chemical pigment is only about 30 percent.
The application adds inorganic wavelength conversion material in the colored printing ink, converts the ultraviolet ray into visible light wave band, utilizes the visible light wave band luminousness of the colored photovoltaic glass prepared by the colored printing ink is increased, and the colored photovoltaic glass is used for the photovoltaic module and can improve the efficiency of the module and prolong the service life of the module. The color ink of the application also has the light-emitting component due to the addition of the wavelength conversion material, so that the problem of angular color change of the structural color pigment is reduced.
Drawings
Fig. 1 is a schematic view of a color photovoltaic module according to an embodiment of the present disclosure.
Description of the symbols
1 colorful front plate glass 2 first layer packaging adhesive film 3 photovoltaic cell array
4 second layer packaging adhesive film, 5 backboard glass 101 glass body
102 color ink layer
Detailed Description
The present application is described in detail below with reference to the embodiments illustrated in the accompanying drawings, wherein like numerals represent like features throughout the drawings. While specific embodiments of the present application are shown in the drawings, it should be understood that the present application may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
It is to be understood that throughout the specification and claims, the terms "including" and "comprising" are used in an open-ended fashion, and thus should be interpreted to mean "including, but not limited to. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.
In one aspect, the present application provides a color ink comprising: low-melting-point glass powder, varnish, structural color pigment and inorganic wavelength conversion material.
The application aims at the problems of low hardness and poor weather resistance of the traditional glass coating taking polymer resin as a substrate, the high-temperature color ink is prepared by adding low-melting-point glass powder, and a compact inorganic coating can be formed on the surface of glass after the ink is sintered, so that the ink has higher hardness and better weather resistance.
This application absorbs the problem that the color development led to the fact the light energy utilization ratio low, absorption to generate heat and reduce battery efficiency to the chemical pigment in traditional glass coating, adopts the structure look pigment preparation color printing ink of the look principle of interference, can reduce the absorption of pigment to the light energy.
Aiming at the problems that a crystalline silicon cell has low photoelectric conversion efficiency on light rays in an ultraviolet band and the cell efficiency is reduced due to long-term ultraviolet irradiation to cause the power attenuation of a component, an inorganic wavelength conversion material is added, the wavelength conversion performance can be kept after high-temperature sintering, ultraviolet rays are converted into a visible light band, the light energy utilization efficiency can be improved, the damage of the ultraviolet rays to a packaging adhesive film and the cell is reduced, and the service life of the photovoltaic cell is prolonged; this application has still decided it to the interference colour forming principle of structure look pigment to have certain angle-dependent discoloration problem to make the printing ink coating have luminescent component through adding wavelength conversion material, with the superposition of structure look pigment reflection colour, can not only promote the saturation of colored photovoltaic glass product colour, can also alleviate its angle-dependent discoloration problem.
In one embodiment, the color ink of the present application is composed of a low melting point glass frit, a varnish, a structural color pigment, and an inorganic wavelength converting material.
In one embodiment, the color ink of the present application comprises, based on the total weight of the color ink:
60 to 80 percent of low-melting-point glass powder;
18 to 30 percent of varnish;
1 to 10 percent of structural color pigment; and
1% -10% of inorganic wavelength conversion material.
For example, the color ink may include 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, etc. of a low melting point glass frit, preferably 65% to 75% of a low melting point glass frit, based on the total weight of the color ink.
For example, the color ink may include 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, etc. of varnish, preferably 22% to 28% of varnish, based on the total weight of the color ink.
For example, the color ink may include 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., of the structural color pigment, preferably 1% to 5%, based on the total weight of the color ink.
For example, the color ink may include 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., of the inorganic wavelength converting material, preferably 1% to 4%, based on the total weight of the color ink.
In one embodiment, the color ink of the present application comprises, based on the total weight of the color ink: 65-75% of low-melting-point glass powder, 22-28% of varnish, 1-5% of structural color pigment and 1-4% of inorganic wavelength conversion material.
The utility model provides a colored printing ink, with low melting glass powder, transfer black ink, structural color pigment and inorganic wavelength conversion material's weight percent control in above-mentioned within range, can further improve the hardness on colored printing ink layer, strengthen the weatherability on colored printing ink layer, reduce the absorption of pigment to the light energy, can also further promote light energy utilization efficiency, promote the photovoltaic cell life-span, also can further reduce the angular dependent discoloration phenomenon of final colored photovoltaic glass product simultaneously.
In one embodiment, the color ink of the present application is a color ink consisting of, based on the total weight of the color ink: 60 to 80 percent of low-melting-point glass powder; 18 to 30 percent of varnish; 1 to 10 percent of structural color pigment; and 1% -10% of inorganic wavelength conversion material.
In one embodiment, in the color ink of the present invention, the low-melting glass frit may have a melting onset temperature of 350 to 500 ℃, for example, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃ and the like. The "melting start temperature of the low-melting-point glass frit" in the present application means a temperature at which the low-melting-point glass frit starts to melt. The initial melting temperature within the range can ensure that the low-melting-point glass powder is completely melted and has certain strength in the glass toughening process.
In one embodiment, in the color ink of the present application, the low melting point glass frit has a linear expansion coefficient of 85 × 10 -7 ～91×10 -7 /. degree.C, may be, for example, 85X 10 -7 /℃、86×10 -7 /℃、87×10 -7 /℃、88×10 -7 /℃、89×10 -7 /℃、90×10 -7 /℃、91×10 -7 /° c, etc. The "linear expansion coefficient" in this application, also called the linear expansion coefficient, is the ratio of the change in length of a solid substance at each 1 ℃ change in temperature to its length at the original temperature (not necessarily 0 ℃), and is expressed in units of 1/DEG C. The linear expansion coefficient in the range is consistent with or similar to that of the photovoltaic front panel glass, and the coating cracks when the coating is prepared or used in an environment with large outdoor temperature difference due to the large linear expansion coefficient difference.
In one embodiment, in the color ink of the present application, the low melting point glass frit has a particle size of 15 μm or less. Here, the particle diameter of the low melting point glass frit means a particle diameter D90, and the "particle diameter D90" means a particle diameter in nanometers, which divides a particle diameter distribution such that 90% of particles have a particle diameter size below this value. In one embodiment, the value of particle size D90 is determined by: the dispersion medium is water, and the laser particle size analyzer is used for testing, and can be, for example, BT-9300ST laser particle size analyzer manufactured by Dandong Baite instruments Co. The glass powder with the particle size of less than or equal to 15 microns can ensure that the grinding time is reduced during the preparation of the printing ink, and the mixing effect of the wavelength conversion material and the glass powder is improved.
In one embodiment, the varnish comprises a solvent and a resin, and preferably the varnish further comprises an auxiliary agent.
In one embodiment, the color ink of the present application, the varnish includes, based on the total weight of the varnish: 70-90% of solvent, 9-29% of resin and 0.5-4% of auxiliary agent; for example, the solvent may be 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, etc., the resin may be 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, etc., and the auxiliary agent may be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, etc., for example.
In one embodiment, the color ink of the present application is not particularly limited to the solvent, the resin and the auxiliary agent in the ink-jet ink, and may be selected according to the need. For example, the solvent may be selected from one or two or three of terpineol, turpentine, and diethylene glycol; the resin is selected from one or two or three of rosin modified phenolic resin, aldehyde ketone resin and ethyl cellulose; the auxiliary agent is selected from one or two of an oily dispersant and a defoaming agent.
As used herein, "terpineol" refers to an important fragrance having the formula C 10 H 18 O, which is a colorless, viscous liquid with a boiling point of 217 ℃ and has lilac fragrance. The isomers are generally referred to as alpha-terpineol, beta-terpineol, gamma-terpineol, respectively. Terpineol is low in price, is one of varieties with large yield in synthetic spices, and is widely applied to preparation of daily-use and edible essences.
"turpentine" in this application refers to an essential oil, which is an important industrial raw material. Turpentine is a liquid extracted from resin of plant of Pinaceae by distillation or other method, and contains terpene as main ingredient. Turpentine can be mixed with chloroform, ether or acetic acid at any ratio, but is insoluble in water. Turpentine oil belongs to flammable liquid with high flash point, has volatility and can generate a large amount of dense smoke during combustion.
"diethylene glycol", also known as diethylene glycol, refers to a polyol of formula C 4 H 10 O 3 It is colorless, odorless, transparent, hygroscopic, viscous liquid, has pungent sweet taste, no corrosiveness, and low toxicity.
The rosin modified phenol resin is a resin which is best applied to offset printing oil at present, and is a high molecular product generated by chemical reaction of alkylphenol (phenols used for offset printing ink include phenol, bisphenol A, PTBP p-tert-butyl phenol, POP p-tert-octyl phenol, PNP nonyl phenol and PDDP dodecyl phenol), formaldehyde, polyalcohol and rosin.
The "aldehyde ketone resin" (also referred to as polyketone resin) in the present application is a neutral, nonsaponifiable type cyclohexanone-formaldehyde resin having high brightness and light resistance.
The term "ethylcellulose" as used herein refers to an ethyl ether of cellulose, which is a long-chain polymer having β -anhydroglucose units linked via acetal, and is one of the most widely used water-insoluble cellulose derivatives.
The term "oily dispersant" as used herein refers to a substance capable of uniformly dispersing pigment and filler particles in an organosol, and may be, for example, propylene glycol methyl ether, fatty alcohol-polyoxyethylene ether, fatty alcohol ether phosphate, alkyl ammonium salt copolymer, or amine group-containing block copolymer.
"antifoaming agent" in the present application means a substance that reduces the surface tension of water, solutions, suspensions, etc., prevents the formation of foam, or reduces or eliminates the original foam. The type of the defoaming agent in the present application is not limited, and examples thereof include silicones, mineral oils, and polyethers.
The structural color, also called physical color, refers to the color generated by the interaction between light and a structure with the same wavelength order of light, and the structural color pigment refers to the pigment of which the color is generated by the interaction (such as refraction, diffuse reflection, diffraction or interference) between the light and the microstructure of the pigment.
The color ink of the application is added with the structural color pigment, so that the color ink layer formed by coating the color ink on the surface of a rigid substrate which is not limited to glass and the like can present different colors, such as red, blue, yellow, green, purple and the like and mixed colors thereof. The thickness of the color ink layer and the concentration of the various structural color pigments can be varied to achieve the desired color effect. In particular, a large color range can be achieved by the combination of different concentrations of red, green, yellow and blue structure-color pigments.
The structured color pigments of the present application are preferably red, blue, green or yellow structured color pigments. However, the structural color pigment may also be a structural color pigment of other colors such as gray, white, violet or orange. Other colors of structural color pigments or mixtures thereof may be used to produce specific colors and hues.
The color ink of the present application may contain different kinds of structural color pigments so that a special effect can be obtained, and the respective structural color pigments may be mixed in any ratio.
In one embodiment, the structured color pigment is selected from one or more of pearlescent pigments, multilayer metal oxide interference pigments, and photonic crystal pigments.
The term "pearlescent pigment" as used herein means an optical effect pigment which is also called a non-metallic pigment having a metallic luster because it exhibits a certain metallic luster. The pearl pigment has the flash effect of metal pigment, can produce the soft color of natural pearl, can produce multi-level reflection when being irradiated by sunlight, and the reflected light interacts with each other to present soft and glaring or colorful luster and color.
The "multilayer metal oxide interference pigment" of the present application has a multilayer metal oxide platelet structure in which a high refractive index metal oxide and a low refractive index metal oxide are alternately distributed to generate optical interference.
In one embodiment, the metal oxides of the individual layers of the multilayer metal oxide interference pigment are each selected from one or two or more of the metal oxides of titanium, aluminum, silicon, tin, zirconium, zinc.
The "photonic crystal pigment" herein refers to a pigment that exhibits a color when the crystal itself is completely colorless by utilizing the diffraction effect of the periodic arrangement of the photonic crystals on light.
In a specific embodiment, in the color ink of the present application, the structured color pigment is a pearlescent pigment, and the pearlescent pigment includes a substrate selected from one of natural mica, synthetic mica, and synthetic borosilicate.
In a specific embodiment, in the color ink of the present application, the pearlescent pigment is composed of a substrate selected from one of natural mica, synthetic mica and synthetic borosilicate.
In one embodiment, in the color ink of the present application, the pearlescent pigment includes a substrate and a coating material coating the substrate, wherein the substrate may be selected from one of natural mica, synthetic mica and synthetic borosilicate; the coating material can be one or two or three of titanium dioxide, ferric oxide and tin oxide.
In one embodiment, the pearlescent pigment in the color ink of the present application has a particle size of 200 μm or less, and may be, for example, 5 μm, 10 μm, 20 μm, 40 μm, 60 μm, 80 μm, 100 μm, 120 μm, 140 μm, 160 μm, 180 μm, 200 μm, or the like. The particle size of the pearlescent pigment herein is a particle size D90, and the measurement method is: the dispersion medium is water, and the dispersion medium is measured by a laser particle size analyzer, such as BT-9300ST laser particle size analyzer manufactured by Dandong Baite instruments.
The term "wavelength converting material" as used herein refers to a material that converts ultraviolet or infrared light into visible light. In a specific embodiment, in the color ink of the present application, the wavelength converting material is a rare earth doped compound.
In one embodiment, in the color ink of the present application, the wavelength converting material is selected from one or two or three or four of a green wavelength converting material (i.e., a wavelength converting material that emits green light), a red wavelength converting material (i.e., a wavelength converting material that emits red light), a blue wavelength converting material (i.e., a wavelength converting material that emits blue light), and a yellow wavelength converting material (i.e., a wavelength converting material that emits yellow light).
In a specific embodiment, in the color ink of the present application, the green wavelength converting material is selected from CaAlSiN 3 :Eu 2+ 、Ba 2 SiO 4 :Eu 2+ And Lu 3 Al 5 O 12 :Ce 3+ One or two or three of (1); the red wavelength converting material is selected from Y 2 MoO 6 :Eu 3+ 、Sr 2 Si 5 N 8 :Eu 2+ And Y 3 Al 5 O 12 :Mn 4+ One or two or three of (1); the blue wavelength converting material is selected from LiSrPO 4 :Eu 2+ 、Ba 3 Y 2 B 6 O 15 :Ce 3+ 、SrLu 2 O 4 :Ce 3+ 、Ca 3 ZrSi 2 O 9 :Ce 3+ 、LiCaPO 4 :Eu 2+ And Ca 2 PO 4 Cl:Eu 2+ One or more than two of the above; the yellow wavelength converting material is selected from Y 3 Al 5 O 12 :Ce 3+ 、Tb 3 Al 5 O 12 :Ce 3+ And Sr 3 SiO 5 :Eu 2+ One or two or three of them.
In a specific embodiment, in the color ink of the present application, the structural color pigment is a green pigment, the wavelength converting material is a green wavelength converting material, preferably the green wavelength converting material is selected from CaAlSiN 3 :Eu 2+ 、Ba 2 SiO 4 :Eu 2+ And Lu 3 Al 5 O 12 :Ce 3+ One or two or three of them.
In one embodiment, in the color ink of the present application, the structural color pigment is a red pigment, the wavelength converting material is a red wavelength converting material, preferably the red wavelength converting material is selected from Y 2 MoO 6 :Eu 3+ 、Sr 2 Si 5 N 8 :Eu 2+ And Y 3 Al 5 O 12 :Mn 4+ One or two or three of them.
In one embodiment, in the color ink of the present application, the structural color pigment is a blue pigment, the wavelength converting material is a blue wavelength converting material, preferably the blue wavelength converting material is selected from the group consisting of LiSrPO 4 :Eu 2+ 、Ba 3 Y 2 B 6 O 15 :Ce 3+ 、SrLu 2 O 4 :Ce 3+ 、Ca 3 ZrSi 2 O 9 :Ce 3+ 、LiCaPO 4 :Eu 2+ And Ca 2 PO 4 Cl:Eu 2+ One or more than two of them.
In one embodiment, in the color ink of the present application, the structural color pigment is a yellow pigment, the wavelength converting material is a yellow wavelength converting material, preferably the yellow wavelength converting material is selected from Y 3 Al 5 O 12 :Ce 3+ 、Tb 3 Al 5 O 12 :Ce 3+ And Sr 3 SiO 5 :Eu 2+ One or two or three of them.
In another aspect, the present application also provides a method of preparing a color ink, the method comprising the steps of:
(1) preparing ink mixing oil: dissolving resin and an auxiliary agent in a solvent to obtain varnish;
(2) preparing transparent ink: mixing the low-melting-point glass powder, the ink adjusting oil and the wavelength conversion material, and grinding the mixture to the fineness of less than 10 mu m to obtain transparent ink;
(3) adding a structural color pigment: and adding the structural color pigment into the transparent ink for mixing and dispersing to obtain the color ink.
In one embodiment, in the method of preparing a colored ink of the present application,
the low-melting-point glass powder accounts for 60-80 parts by weight, preferably 65-75 parts by weight;
the ink mixing oil accounts for 18-30 parts by weight, and preferably 22-28 parts by weight;
the structural color pigment accounts for 1-10 parts by weight, preferably 1-5 parts by weight;
the inorganic wavelength conversion material is 1 to 10 parts by weight, preferably 1 to 4 parts by weight.
For example, the low melting point glass frit may be 60 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight, or the like; the varnish may be 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, and the like; the structural color pigment may be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, or the like; the inorganic wavelength converting material may be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, or the like.
In one embodiment, in the method of preparing a color ink of the present application,
65-75 parts by weight of low-melting-point glass powder;
the ink mixing oil accounts for 22-28 parts by weight;
1-5 parts by weight of the structural color pigment;
the inorganic wavelength conversion material is 1-4 parts by weight.
In the method for preparing the color ink, the resin, the auxiliary agent, the low-melting-point glass powder, the varnish, the wavelength conversion material and the structural color pigment are any one of the resin, the auxiliary agent, the low-melting-point glass powder, the varnish, the wavelength conversion material and the structural color pigment.
In yet another aspect, the present application also provides a colored photovoltaic glass comprising:
a glass body; and
a colored ink layer on the surface of the glass body;
wherein the colored ink layer comprises any one of the colored inks described above or the colored ink prepared by any one of the methods described above.
In a specific embodiment, in the colored photovoltaic glass of the present application, the glass body is ultra-white glass, and the "ultra-white glass" of the present application refers to an ultra-transparent low-iron glass, which is also called low-iron glass or high-transparent glass. The glass is a high-quality and multifunctional novel high-grade glass variety, has the light transmittance of over 91.5 percent, and is widely applied to the front plate glass of a photovoltaic module at present.
In one embodiment, in the colored photovoltaic glass of the present application, the glass body is preferably ultra-white float glass or ultra-white patterned glass.
In a specific embodiment, in the colored photovoltaic glass of the present application, the thickness of the glass body is 2 to 6mm, and for example, may be 2mm, 3.2mm, 4mm, 5mm, 6mm, and the like.
In a specific embodiment, in the colored photovoltaic glass of the present application, the colored ink layer is formed by applying the colored ink onto the glass body by screen printing, roll coating or spraying, preferably by screen printing.
In yet another aspect, the present application also provides a method for preparing colored photovoltaic glass, comprising the steps of: the color ink or the color ink prepared by the method is applied to a glass body, and the color photovoltaic glass is obtained after drying, sintering and tempering.
In a particular embodiment, the colored ink is applied to the glass body by screen printing, roll coating or spray coating, preferably by screen printing.
In one embodiment, in the method for manufacturing a colored photovoltaic glass, the colored ink is applied to the glass body by screen printing, and the mesh number of the screen printing plate used for screen printing is 100-350 mesh, for example, 100 mesh, 120 mesh, 140 mesh, 150 mesh, 170 mesh, 190 mesh, 200 mesh, 220 mesh, 250 mesh, 270 mesh, 290 mesh, 300 mesh, 330 mesh, 350 mesh and the like.
In a specific embodiment, in the method for preparing the colored photovoltaic glass, the drying temperature is 140 to 200 ℃, for example, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ and the like, and the drying time is 1 to 8min, for example, 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min and the like; the sintering tempering temperature is 660-720 ℃, for example 660 ℃, 670 ℃, 680 ℃, 690 ℃, 700 ℃, 710 ℃, 720 ℃ and the like, and the sintering tempering time is 2-4 min, for example 2min, 2.5min, 3min, 3.5min, 4min and the like.
In a specific embodiment, in the method for manufacturing a colored photovoltaic glass, the glass body is ultra-white glass, preferably ultra-white float glass or ultra-white embossed glass, and the thickness of the glass body is 2-6 mm, for example, 2mm, 3.2mm, 4mm, 5mm, 6mm, and the like.
In another aspect, the present application further provides a color photovoltaic module, as shown in fig. 1, which includes: the photovoltaic solar panel comprises a colored front panel glass 1, a first layer of packaging adhesive film 2, a photovoltaic cell array 3, a second layer of packaging adhesive film 4 and a back panel glass 5, wherein the colored front panel glass 1 is any one of the colored photovoltaic glass, and the colored front panel glass 1 comprises a glass body 101 and a colored ink layer 102.
In one embodiment, the light transmittance of the colored front glass is 60% or more, preferably 70% or more, and may be, for example, 60%, 65%, 70%, 75%, 80%, 85%, 88%, 90%, or the like.
In a specific embodiment, the material of the first layer of encapsulant film may be selected from one of EVA, POE, and PVB, and the material of the second layer of encapsulant film may be selected from one of EVA, POE, and PVB.
In one embodiment, the cell used in the photovoltaic cell array can be a P-type or N-type cell, and the back plate glass is float glass with a thickness of 2-6 mm.
The color printing ink is applied to the glass body, and the color photovoltaic glass obtained through drying and sintering tempering has high light transmittance and high reflectivity, and the problem of color change along with the angle is effectively relieved. Specifically, the light transmittance of the light-emitting diode is more than 60 percent, even more than 72 percent, even up to 76 percent; meanwhile, the reflectivity is over 17 percent and can even reach 19 percent; the color difference between the 45 DEG visual angle and the 75 DEG visual angle is less than 8 and can be even as low as 6.
Examples
The materials used in the tests and the test methods are generally and/or specifically described in the present application, and in the following examples, the reagents or instruments used are not indicated by manufacturers, but are all conventional reagent products commercially available, and some of the raw material sources in the present application are shown in table 1 below.
TABLE 1
Figure BDA0003645445430000141
Figure BDA0003645445430000151
Preparation of Ba by microwave heating, referenced Chengwei et al 2 SiO 4 :Eu 2+ Method in Green phosphor preparation of Green wavelength converting Material Ba to be used 2 SiO 4 :Eu 2+ 。
The following red wavelength conversion material Y was prepared by referring to Zhang et al, A method in "Sol-gel Synthesis Y2MoO6: Eu3+ fluorescent Material and study of photoluminescence Properties thereof 2 MoO 6 :Eu 3+ 。
Reference is made to the method in "A High Symmetry, Narrow-Emitting Blue Phosphor for Wide-Gamma White Lighting" of AC Duke et al for the preparation of Ba 3 Y 2 B 6 O 15 :Ce 3+ 。
Refer to "Y" of mu Zhong Fei et al 3 Al 5 O 12 :Ce 3+ The method in (1) afterglow and thermoluminescence characteristics 3 Al 5 O 12 :Ce 3+ 。
First, 1080g of aldehyde ketone resin, 120g of ethyl cellulose, 150g of oily dispersant and 30g of antifoaming agent were dissolved in a mixed solvent composed of 4200g of terpineol and 420g of turpentine to prepare 6000g of varnish, which was used in examples 1 to 10 and comparative examples 1 to 2 described below.
Example 1
Preparing raw materials: 1380g of low-melting-point glass powder with the initial melting temperature of 450 ℃, 500g of varnish, 80g of natural mica which is used as a substrate, green pearlescent pigment with the particle size of 45 mu m, and 40g of green wavelength conversion material Ba 2 SiO 4 :Eu 2+ 。
Preparing color printing ink: stirring and mixing the low-melting-point glass powder, the ink adjusting oil and the wavelength conversion material uniformly, and grinding the mixture to the fineness of less than 10 mu m by using a grinder to obtain transparent ink; the transparent ink and the pearlescent pigment are mechanically stirred, mixed and dispersed to obtain the color ink of the embodiment.
Preparing color photovoltaic glass: and printing the prepared color ink on 3.2mm ultra-white float glass by a 300-mesh screen, drying the glass at 160 ℃ for 5min, and toughening the dried glass at 700 ℃ for 2min to obtain the color photovoltaic glass.
Preparing a color photovoltaic module: and laminating and packaging the colored photovoltaic glass, the first EVA packaging adhesive film layer, the N-type battery array, the second EVA packaging adhesive film layer and the 3.2mm float glass to obtain the colored photovoltaic module.
Example 2
Preparing raw materials: 1380g of low-melting-point glass powder with the initial melting temperature of 450 ℃, 500g of varnish, 80g of natural mica which is used as a base material and has the grain diameter of 45 mu m, 40g of red wavelength conversion material Y 2 MoO 6 :Eu 3+ 。
The methods of making the colored ink, colored photovoltaic glass, and colored photovoltaic module are the same as in example 1.
Example 3
Preparing raw materials: 1380g of low-melting-point glass powder with the initial melting temperature of 450 ℃, 500g of varnish, 80g of natural mica which is used as a substrate and has the particle size of 45 mu m, and 40g of blue wavelength conversion material Ba 3 Y 2 B 6 O 15 :Ce 3+ 。
The methods of making the colored ink, colored photovoltaic glass, and colored photovoltaic module are the same as in example 1.
Example 4
Preparing raw materials: 1380g of low-melting-point glass powder with the initial melting temperature of 450 ℃, 500g of varnish, 80g of natural mica which is used as a substrate and has the particle size of 45 mu m, and 40g of yellow wavelength conversion material Y 3 Al 5 O 12 :Ce 3+ 。
The methods of making the colored ink, colored photovoltaic glass, and colored photovoltaic module are the same as in example 1.
Example 5
Preparing raw materials: 1300g of low-melting-point glass powder with the initial melting temperature of 450 ℃, 480g of varnish, 140g of natural mica which is used as a base material and has the particle size of 45 mu m, 80g of yellow wavelength conversion material Y 3 Al 5 O 12 :Ce 3+ 。
The methods for preparing the colored ink, the colored photovoltaic glass, and the colored photovoltaic module are the same as in example 1.
Example 6
Preparing raw materials: 1260g of low-melting-point glass powder with an initial melting temperature of 450 ℃, 500g of varnish, 200g of natural mica as a base material, yellow pearlescent pigment with the particle size of 45 mu m, and 40g of yellow wavelength conversion material Y 3 Al 5 O 12 :Ce 3+ 。
The methods of making the colored ink, colored photovoltaic glass, and colored photovoltaic module are the same as in example 1.
Example 7
Preparing raw materials: 1440g of low-melting glass powder with an initial melting temperature of 450 ℃, 500g of varnish, 20g of natural mica as a base material, yellow pearlescent pigment with a particle size of 45 mu m, and 40g of yellow wavelength conversion material Y 3 Al 5 O 12 :Ce 3+ 。
The methods of making the colored ink, colored photovoltaic glass, and colored photovoltaic module are the same as in example 1.
Example 8
Preparing raw materials: 1220g of low-melting-point glass powder with the initial melting temperature of 450 ℃, 500g of varnish,80g of a yellow pearl pigment having a particle diameter of 45 μm and a natural mica as a base, 200g of a yellow wavelength converting material Y 3 Al 5 O 12 :Ce 3+ 。
The methods of making the colored ink, colored photovoltaic glass, and colored photovoltaic module are the same as in example 1.
Example 9
Preparing raw materials: 1200g of low-melting-point glass powder with the initial melting temperature of 450 ℃, 580g of varnish, 20g of natural mica which is used as a base material and has the particle size of 45 mu m, and 200g of yellow wavelength conversion material Y 3 Al 5 O 12 :Ce 3+ 。
The methods of making the colored ink, colored photovoltaic glass, and colored photovoltaic module are the same as in example 1.
Example 10
Preparing raw materials: 1600g of low melting point glass powder with the initial melting temperature of 450 ℃, 360g of varnish, 20g of natural mica which is used as a base material and has the particle size of 45 mu m, and 20g of yellow wavelength conversion material Y 3 Al 5 O 12 :Ce 3+ 。
The methods for preparing the colored ink, the colored photovoltaic glass, and the colored photovoltaic module are the same as in example 1.
Comparative example 1
Preparing raw materials: 1420g of low-melting glass powder with the initial melting temperature of 450 ℃, 500g of varnish and 80g of natural mica which are used as substrates, and the yellow pearlescent pigment with the particle size of 45 mu m.
Preparing color printing ink: stirring and mixing the low-melting-point glass powder and the ink-adjusting oil uniformly, and grinding the mixture to the fineness of less than 10 mu m by using a grinder to obtain transparent ink; and then the transparent ink and the pearlescent pigment are mechanically stirred, mixed and dispersed to obtain the color ink of the comparative example.
The method for preparing the colored photovoltaic glass and the colored photovoltaic module is the same as the example 1.
Comparative example 2
Preparing raw materials: 1420g of low-melting-point glass powder with the initial melting temperature of 450 ℃, 500g of varnish and 80g of absorption color pigment titanium nickel yellow.
Preparing color printing ink: stirring and mixing the low-melting-point glass powder and the ink adjusting oil uniformly, and grinding the mixture by a grinder until the fineness is below 10 mu m to obtain transparent ink; and then mechanically stirring, mixing and dispersing the transparent ink and the titanium-nickel yellow pigment for absorbing color to obtain the color ink of the comparative example.
The method for preparing the colored photovoltaic glass and the colored photovoltaic module is the same as the example 1.
Comparative example 3
Preparing raw materials: 1380g of low-melting-point glass powder with the initial melting temperature of 450 ℃, 500g of varnish, 80g of absorption color pigment titanium nickel yellow and 40g of yellow wavelength conversion material Y 3 Al 5 O 12 :Ce 3+ 。
Preparing color printing ink: stirring and mixing the low-melting-point glass powder, the ink adjusting oil and the wavelength conversion material uniformly, and grinding the mixture to the fineness of less than 10 mu m by using a grinder to obtain transparent ink; and then mechanically stirring, mixing and dispersing the transparent ink and the titanium-nickel yellow pigment for absorbing color to obtain the color ink of the comparative example.
The method for preparing the colored photovoltaic glass and the colored photovoltaic module is the same as the example 1.
The color inks prepared in the examples and the comparative examples are printed on 3.2mm ultra-white float glass through 300-mesh screen printing, the glass is dried for 5min at 160 ℃, the dried glass is tempered and sintered for 2min at 700 ℃ to obtain color photovoltaic glass, and the parameters of each color photovoltaic glass are measured, and the results are shown in table 1.
The light transmittance and the reflectivity are detected by a Perkin Elmer ultraviolet-visible-near infrared spectrophotometer LAMBDA1050, and the detection wavelength range is 380-1100 nm.
The color difference between the 45-degree visual angle and the 75-degree visual angle is tested by a Konika Meinenda multi-angle spectral colorimeter CM-M6, and a black back bottom is padded under the glass during the test.
The viscosity is tested by a rotational viscometer NDJ-8S, and the test conditions are as follows: (23. + -.2). degree.C., rotor # 4, 12 RPM.
TABLE 2
Figure BDA0003645445430000191
The principles and embodiments of the present application have been described with reference to specific embodiments, which are merely provided to assist understanding of the method and the core concept thereof. It will be apparent to those skilled in the art that numerous modifications and variations of certain details of the foregoing may be made without the exercise of inventive faculty. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (15)

1. A colored ink, comprising: low-melting-point glass powder, varnish, structural color pigment and inorganic wavelength conversion material.
2. The colored ink of claim 1, wherein the colored ink comprises, based on the total weight of the colored ink:
60 to 80 percent, preferably 65 to 75 percent of low-melting-point glass powder;
18 to 30 percent of varnish, preferably 22 to 28 percent of varnish;
1 to 10 percent, preferably 1 to 5 percent of structural color pigment; and
1% to 10%, preferably 1% to 4% of an inorganic wavelength converting material.
3. The color ink according to claim 1 or 2, wherein the low-melting glass frit has a melting onset temperature of 350 to 500 ℃;
preferably, the linear expansion coefficient of the low-melting-point glass powder is 85 × 10 -7 ～91×10 -7 /℃；
Preferably, the particle size of the low-melting glass powder is less than or equal to 15 μm.
4. A colour ink as claimed in any one of claims 1 to 3, characterised in that the varnish comprises a solvent and a resin, preferably the varnish further comprises an auxiliary agent;
preferably, the varnish comprises, based on the total weight of the varnish: 70-90% of solvent, 9-29% of resin and 0.5-4% of auxiliary agent;
preferably, the solvent is selected from one or two or three of terpineol, turpentine and diethylene glycol;
preferably, the resin is selected from one or two or three of rosin modified phenolic resin, aldehyde ketone resin and ethyl cellulose;
preferably, the auxiliary agent is selected from one or two of an oily dispersant and a defoaming agent.
5. The color ink according to any one of claims 1 to 4, wherein the structural color pigment is one or more selected from a pearlescent pigment, a multilayer metal oxide interference pigment and a photonic crystal pigment;
preferably, the metal oxides of the layers of the multilayer metal oxide interference pigment are respectively selected from one or more than two of metal oxides of titanium, aluminum, silicon, tin, zirconium and zinc.
6. The color ink according to any one of claims 1 to 5, wherein the structural color pigment is a pearlescent pigment, and the pearlescent pigment comprises a substrate selected from one of natural mica, synthetic mica and synthetic borosilicate;
preferably, the pearlescent pigment further comprises a coating material for coating the substrate, wherein the coating material is one or two or three of titanium dioxide, ferric oxide and tin oxide;
preferably, the particle size of the pearlescent pigment is 200 μm or less.
7. The color ink according to any one of claims 1 to 6, wherein the wavelength converting material is a rare earth doped compound;
preferably, the wavelength conversion material is selected from one or more of a green wavelength conversion material, a red wavelength conversion material, a blue wavelength conversion material, and a yellow wavelength conversion material;
preferably, the green wavelength converting material is selected from CaAlSiN 3 :Eu 2+ 、Ba 2 SiO 4 :Eu 2+ And Lu 3 Al 5 O 12 :Ce 3+ One or two or three of (1);
preferably, the red wavelength converting material is selected from Y 2 MoO 6 :Eu 3+ 、Sr 2 Si 5 N 8 :Eu 2+ And Y 3 Al 5 O 12 :Mn 4+ One or two or three of (1);
preferably, the blue wavelength converting material is selected from LiSrPO 4 :Eu 2+ 、Ba 3 Y 2 B 6 O 15 :Ce 3+ 、SrLu 2 O 4 :Ce 3+ 、Ca 3 ZrSi 2 O 9 :Ce 3+ 、LiCaPO 4 :Eu 2+ And Ca 2 PO 4 Cl:Eu 2+ One or more than two of (a);
preferably, the yellow wavelength converting material is selected from Y 3 Al 5 O 12 :Ce 3+ 、Tb 3 Al 5 O 12 :Ce 3+ And Sr 3 SiO 5 :Eu 2+ One or two or three of them.
8. A method of making a colored ink comprising the steps of:
preparing ink mixing oil: dissolving resin and an auxiliary agent in a solvent to obtain varnish;
preparing transparent ink: mixing the low-melting-point glass powder, the ink adjusting oil and the wavelength conversion material, and grinding the mixture to the fineness of less than 10 mu m to obtain transparent ink;
adding a structural color pigment: and adding the structural color pigment into the transparent ink for mixing and dispersing to obtain the color ink.
9. The method of claim 8,
the low-melting-point glass powder accounts for 60-80 parts by weight, preferably 65-75 parts by weight;
the ink mixing oil accounts for 18-30 parts by weight, and preferably 22-28 parts by weight;
the structural color pigment accounts for 1-10 parts by weight, preferably 1-5 parts by weight;
the inorganic wavelength conversion material is 1 to 10 parts by weight, preferably 1 to 4 parts by weight.
10. The method according to claim 8 or 9, wherein the resin, the auxiliary, the low-melting glass frit, the varnish, the wavelength converting material and the structural color pigment are the resin, the auxiliary, the low-melting glass frit, the varnish, the wavelength converting material and the structural color pigment according to any one of claims 1 to 7.
11. A colored photovoltaic glass, comprising:
a glass body; and
a colored ink layer on the surface of the glass body;
wherein the color ink layer comprises the color ink of any one of claims 1 to 7 or the color ink prepared by the method of any one of claims 8 to 10.
12. The colored photovoltaic glass according to claim 11, wherein the glass body is ultra-white glass, preferably ultra-white float glass or ultra-white patterned glass;
preferably, the thickness of the glass body is 2-6 mm.
13. A method of making colored photovoltaic glass comprising the steps of: applying the color ink as defined in any one of claims 1 to 7 or the color ink prepared by the method as defined in any one of claims 8 to 10 onto a glass body, and drying, sintering and tempering to obtain the color photovoltaic glass;
preferably, the coloured ink is applied to the glass body by screen printing, roller coating or spraying.
14. The method according to claim 13, wherein the mesh number of the screen used for screen printing is 100-350 mesh;
preferably, the drying temperature is 140-200 ℃, and the drying time is 1-8 min;
preferably, the sintering tempering temperature is 660-720 ℃, and the sintering tempering time is 2-4 min;
preferably, the glass body is ultra-white glass, preferably ultra-white float glass or ultra-white patterned glass;
preferably, the thickness of the glass body is 2-6 mm.
15. A color photovoltaic module, comprising: the solar cell module comprises colored front glass, a first layer of packaging adhesive film, a photovoltaic cell array, a second layer of packaging adhesive film and back glass, wherein the colored front glass is the colored photovoltaic glass in claim 11 or 12.
CN202210528179.2A 2022-05-16 2022-05-16 Color printing ink, color photovoltaic glass, color photovoltaic module and preparation method thereof Pending CN115044243A (en)

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