Transparent colored-glazed panel and colored photovoltaic module

Abstract

Disclosed in the present application are a transparent colored-glazed panel and a colored photovoltaic module. The transparent colored-glazed panel comprises a glass substrate, a transparent colored coating covering the outer surface of the glass substrate, and a transparent glaze layer covering the outer surface of the transparent colored coating; the transparent glaze layer is covalently bonded to the transparent colored coating; and the main component of the transparent glaze layer is silicon dioxide. In the present application, the transparent colored coating of the colored photovoltaic module is located on the outer surface of the glass panel of the photovoltaic module, thus overcoming the defect of glass texture of traditional photovoltaic modules used as building material products; the transparent glaze layer with silicon dioxide as the main component is further arranged as a protective layer outside the transparent colored coating, and has excellent properties comprising high hardness, high transparency, excellent adhesion, super weatherability, acid and alkali resistance, scratch resistance and stain resistance, thus effectively protecting the colored coating from fading, peeling and external corrosion caused by acid rain, ultraviolet, and wind and sand.

Description

Transparent colored glaze panel, colored photovoltaic module

[0001] The present application claims priority to the Chinese patent application No. 202411160048.9, filed on August 22, 2024, and entitled "Colored photovoltaic module", the content of which is incorporated herein by reference in its entirety. TECHNICAL FIELD

[0002] The present application relates to the technical field of solar energy, in particular to a transparent colored glaze panel and a colored photovoltaic module. BACKGROUND

[0003] Colorful photovoltaic building integrated (BIPV) is to integrate photovoltaic power generation function and building decoration, meet the power generation function while meeting the design requirements of building aesthetics, and harmonize with the surrounding environment.

[0004] The existing colored photovoltaic module generally includes a transparent colored panel, a transparent adhesive layer A, a cell layer, an adhesive layer B, and a back plate which are stacked in sequence. The transparent colored panel includes a glass panel and a colored coating layer coated on the surface of the glass panel. There are two mainstream technical routes for the colored coating layer, namely high-temperature tempered colored glaze and low-temperature cured colored coating. For example, CN113087406A discloses a high-temperature tempered colored photovoltaic glass panel and a production method thereof; CN110606668A discloses a production method of a double-cured colored photovoltaic glass panel with a low-temperature cured colored coating. The method coats a color-changing ink on the solar glass panel, preheats it at low temperature, irradiates it with ultraviolet light for photocuring, and finally performs post-curing by IR infrared heating to obtain a color-changing solar glass panel.

[0005] The main component of high-temperature tempered colored glaze is inorganic material (glass powder / inorganic pigment). The glass powder is melted on the surface of the glass by high-temperature (680-720℃) heating to form a high-hardness (≥6H) glaze layer, which is not afraid of sand and hail impact, resistant to UV aging, and the process is mature. The disadvantages are poor acid resistance, difficult color adjustment, low glaze transmittance, reduced glass impact strength, and affected module power generation efficiency, which are determined by the properties of high-temperature glaze material. The glass powder (quartz sand / soda ash) contains alkaline substances. If the tempered coating is placed on the outside of the curtain wall glass, it cannot withstand the long-term (more than 10 years) erosion of acid rain, and the coating is easily discolored and falls off in large areas.

[0006] Low temperature curing process includes low temperature baking and UV light curing, which is the combination of high transparent weather resistant resin and structural color effect pigment such as pearl powder. The low temperature coating has the advantages of high light transmittance, bright color, not easy to fade, easy to adjust color, etc. The disadvantage is that the coating hardness is low (3-4H). The low temperature curing color coating is coated on the outer side of the glass, and the coating cannot resist the long-term mechanical erosion of wind and sand, hail and other external factors.

[0007] In order to avoid the discoloration or peeling of the color coating caused by wind and sun exposure, acid rain erosion, and safety accidents, most color coatings are applied to the inner side of the photovoltaic glass panel. Because the surface of the color photovoltaic module is transparent glass, it lacks the natural texture, three-dimensional effect and metal texture of traditional building materials such as granite, marble and aluminum plate, and the decoration effect is poor. Directly installing photovoltaic modules on building curtain walls or roofs will inevitably cause light pollution, which is also a long-standing defect of traditional glass curtain walls.

[0008] Coating the color coating on the outer surface of the glass panel of the photovoltaic module in contact with the air is the fundamental way to solve the light pollution of glass curtain walls and realize the colorization of solar products. However, it puts forward very strict requirements for the color coating material. It not only needs to meet the requirements of 25 years without fading, peeling, small light transmittance attenuation, and not significantly reducing the power generation efficiency, but also needs to be able to resist the invasion of acid rain and sand. It is equivalent to having the advantages of high temperature inorganic tempered glaze layer with high hardness (more than 6H), impact resistance and long-term ultraviolet aging resistance, and also having the advantages of low temperature coating with high light transmittance, acid rain resistance, rich color, easy color adjustment and other advantages.

[0009] Therefore, it is of great significance to develop a new material and innovative production process that combines the advantages of high temperature tempered coating and low temperature curing coating, while making up for the quality defects of the two, so that the outer coating of the photovoltaic glass has the same 50-year service life as the building curtain wall. SUMMARY

[0010] Therefore, the present application provides a transparent color glaze panel and a color photovoltaic module. The present application not only solves the defect that the existing color photovoltaic module will produce light pollution, but also has the advantages of high temperature tempered coating and low temperature curing coating. It has high hardness, high transparency, excellent fastness, super weather resistance, acid and alkali resistance, scratch resistance and excellent stain resistance. It effectively protects the color coating from fading and peeling, and is not affected by acid rain, ultraviolet light, wind and sand. It gives the photovoltaic module a super long service life.

[0011] The technical solution of the present application is as follows:

[0012] A color photovoltaic module, comprising a transparent color glaze panel, a transparent adhesive layer A, a cell layer, an adhesive layer B and a back plate which are sequentially laminated and packaged;

[0013] The transparent colored glaze panel comprises a glass substrate, a transparent colored coating layer covering the outer surface of the glass substrate, and a transparent glaze layer covering the outer surface of the transparent colored coating layer; the transparent glaze layer is combined with the transparent colored coating layer by a covalent bond.

[0014] The main component of the transparent glaze layer is silicon dioxide.

[0015] The inner surface of the glass substrate refers to the side adjacent to the transparent adhesive layer A, the outer surface of the glass substrate refers to the side away from the transparent adhesive layer A, and the transparent glaze layer directly contacts the external environment.

[0016] The colored photovoltaic module of the present application has a non-glass texture feature, that is, when viewed from the outer surface of the module, the first thing seen is the pattern of the colored coating layer rather than the transparent glass. The colored coating layer can present a strong metallic texture, and through the combination of pattern design and different printing processes, the colored coating layer can also be endowed with artistic texture and three-dimensional effect, and meanwhile, the defect of light pollution caused by the glass outer surface of the existing photovoltaic module is solved.

[0017] The transparent colored coating layer can be a high-temperature tempered colored glaze layer, a low-temperature cured or UV light cured colored coating layer.

[0018] The main components of the conventional tempered colored glaze are quartz sand (silicon dioxide) and soda ash, which are fused on the surface of the glass at a high temperature (600-720℃). Although the tempered colored glaze has advantages such as high hardness, resistance to washing, and resistance to ultraviolet aging, it cannot withstand long-term acid rain erosion because the acidic components in the acid rain will react with the basic components in the tempered glaze layer, causing the colored glaze layer to discolor or fall off in large areas. The low-temperature cured or UV light cured colored coating layer has high light transmission and excellent acid resistance, but the ultraviolet aging resistance of the coating layer is not as good as that of inorganic colored glaze, and the hardness is relatively low, the washing resistance is poor, and the coating layer cannot resist long-term mechanical impact such as wind and sand, hail, etc.

[0019] The transparent colored coating layer of the colored photovoltaic module of the present application is located on the outer surface of the glass panel of the photovoltaic module, overcoming the glass texture defect of the traditional photovoltaic module as a building material product. A transparent glaze layer with silicon dioxide as the main component is further provided outside the transparent colored coating layer as a protective layer, and the transparent glaze layer is combined with the colored coating layer by a covalent bond, having high adhesion, high hardness, high transparency, super weather resistance, acid and alkali resistance, scratch resistance, and excellent stain resistance, effectively protecting the colored coating layer from discoloration and falling off, and resisting external erosion such as acid rain, ultraviolet light, wind and sand, etc. The colored photovoltaic module not only overcomes the light pollution caused by reflection and refraction of the glass panel of the traditional photovoltaic module, but also can give the photovoltaic module a super-long service life.

[0020] Preferably, the mass percentage of silicon dioxide in the transparent glaze layer is ≥70%.

[0021] Preferably, the hardness of the transparent glaze layer is ≥4H; more preferably, the hardness of the transparent glaze layer is ≥6H; even more preferably, the hardness of the transparent glaze layer is ≥8H.

[0022] Preferably, the transparent glaze layer has a transmittance of ≥80% in the ultraviolet region of 260-380 nm, ≥93% in the visible light region of 380-780 nm, and ≥90% in the infrared light region of 780-2500 nm.

[0023] Preferably, the transparent color coating and the transparent glaze layer covering the outer surface of the transparent color coating are subjected to 2 atm high-pressure steam cooking for 48 hours, and then tested for their ultraviolet radiation resistance according to the GB / T30984.1-2015 standard, with the transmittance attenuation being ≤1% and the color difference value attenuation being ≤1.0.

[0024] Preferably, the transparent glaze layer has a heat resistance of 400℃.

[0025] Preferably, the transparent glaze layer is formed by curing a glaze coating, and the glaze coating comprises the following raw materials in mass percentage: polysilazane 90-100%; and additives 0-10%.

[0026] The polysilazane molecular chain contains Si-NH-Si polar structure, which can be combined with most substrates (such as glass, metal, ceramic, plastic, etc.) in the form of covalent bond, with excellent adhesion. After curing, the polysilazane forms a three-dimensional cross-linked structure glaze layer with silica as the main component, which is similar to quartz glass or ceramic in that it has high surface hardness and transmittance, and excellent heat resistance, ultraviolet resistance, acid resistance, adhesion, and other physical and chemical properties.

[0027] The additives are transparent particulate fillers; the particle size of the additives is 10 nm-10 μm; further preferably, the particle size of the additives is 100 nm-7 μm, and more preferably 1-5 μm.

[0028] The additives play the roles of anti-glare, anti-diffusion, matte, wear resistance, etc., and can also reduce internal stress during the curing process of the coating and prevent the coating from cracking.

[0029] Preferably, the additives are at least one of silica powder, silicon powder, and glass powder.

[0030] The glaze coating mainly comprises polysilazane resin. Preferably, the molecular weight of the polysilazane is 100-15000 g / mol, and the viscosity is 10-10000 cps / 25℃.

[0031] The polysilazane includes organic polysilazane or inorganic polysilazane, such as Merck organic polysilazane 1500 Rapid Cure and the like. 1500Rapid Cure and the like. 1500Slow Cure, inorganic polysilazane such as AZ NN 120-20 and AZ NAX 120-20; silicone-modified polysilazane (such as XSC-N0701) and hetero-element-modified polysilazane (such as XSC-N0801) of Shin-Etsu, pre-crosslinked polysilazane XSC-N0901; 8024PV211, 8808PV11, 8804PV11 of Shanghai Kuberd, ZG-02, ZG-107 of Zhongsi New Material, and methyl polysilazane resin PSN1 / PSN2 (molecular weight 600-1000 g / mol) of Qiyang Guoshun Company, etc.

[0032] After the polysilazane is coated on the surface of the substrate, it will react violently with the moisture in the air, the resin of the composition, and the active groups on the surface of the substrate. It can be cross-linked and cured at room temperature with the moisture in the air, and it can also be accelerated by heating or ultraviolet light irradiation.

[0033] The higher the degree of conversion of the polysilazane coating into silicon dioxide, the closer the properties of the formed glaze layer to those of quartz glass, the higher the surface hardness and light transmittance of the glaze layer, and the more excellent its physical and chemical properties such as heat resistance, ultraviolet resistance, acid resistance, and adhesion. The degree of conversion of polysilazane into silicon dioxide is closely related to the curing process conditions and sequence, which in turn affects the hardness, adhesion, and other physical and chemical properties of the glaze layer.

[0034] Air humidity and curing temperature have a great influence on the curing effect. The higher the humidity, the faster the curing speed, and at the same time, ammonia gas and other small molecular compounds will be released. Ultraviolet light irradiation will make the glaze layer cure more thoroughly and have higher hardness. The more complete the curing of the polysilazane, the higher the content of silicon dioxide in the coating, the closer the properties to those of quartz, the higher the surface hardness, and the more excellent the physical and chemical properties such as heat resistance and ultraviolet resistance.

[0035] Preferably, the curing method for curing the glaze layer coating into a transparent glaze layer comprises:

[0036] dry curing the glaze layer coating to form a dry-cured glaze layer under the condition of relative humidity ≤55% and temperature 0-350°C, and then wet curing the dry-cured glaze layer.

[0037] The dry curing is to cure the glaze layer coating to form a dry-cured glaze layer under the condition of relative humidity ≤55% and temperature 0-350°C.

[0038] The curing reaction mainly involves the hydrolysis and oxidation of Si-NH-Si, the reaction of Si- of polysilazane with -OH groups on the surface of the substrate to form Si-O bonds, and the reaction of NH- with polar groups on the substrate or water molecules in the air to release NH3, forming a three-dimensionally cross-linked structure glaze layer with silicon dioxide as the main component, which is similar to quartz glass or ceramic.

[0039] Preferably, the dry curing time is 1 min-168 h.

[0040] Preferably, the wet curing is: heating the dry cured glaze layer under the condition of relative humidity ≥ 95%, temperature 90-200℃, 0.8-3 atmosphere pressure, to make it further cured, forming a wet cured glaze layer;

[0041] Preferably, the wet curing is followed by or not by light curing; the light curing includes: UV light irradiation of the wet cured glaze layer to make it further cured.

[0042] During the dry curing process, the relative humidity is low, and the reaction of Si- with the -OH group on the surface of the substrate to form Si-O bond is dominant. The polysilazane resin preferentially reacts with the hydroxyl group or other polar groups on the substrate surface, so that the transparent glaze layer and the substrate surface are covalently bonded together, improving the adhesion to the substrate. During the dry curing stage, it is not desirable for a large number of polar groups such as Si-NH-Si in the coating to undergo vigorous hydrolysis and oxidation with water molecules in the air, releasing a large amount of ammonia and other small molecule compounds, which in turn affects the adhesion of the coating to the substrate. The greater the humidity, the more vigorous the reaction, the more ammonia and small molecule compounds are released, and the faster the coating body is cured, which will adversely affect the adhesion of the coating. During the dry curing stage, by controlling the humidity and temperature, the curing reaction is mainly the chemical reaction between the polysilazane and the active groups on the surface of the substrate, so that the formed glaze layer is covalently bonded to the surface of the substrate, enhancing the adhesion of the glaze layer.

[0043] After dry curing, the adhesion of the transparent glaze layer to the substrate surface can reach 100%, but the curing is not complete, and the surface hardness is only 3-4H, the coating scraped off by the blade is soft and strip-shaped, and a distinct ammonia smell can be smelled after dry curing, indicating that there are still a lot of active groups in the coating that have not reacted, and the transparent glaze layer needs to be further wet cured after dry curing.

[0044] During the wet curing stage, high humidity and high pressure are used to facilitate the entry of water into the interior of the cured coating, the reaction of water with NH- to release NH3, and the full conversion of the silicon-containing polymer to silicon dioxide, so that the hardness of the glaze layer can reach 5-6H, and the coating scraped off by the blade is in powder form.

[0045] Further preferably, the wet curing is: water boiling for 5-180min under the condition of relative humidity 100%, temperature 90-180℃, 0.8-3 atmosphere pressure; or water vapor steaming for 1-120min under the condition of relative humidity 100%, temperature 90-180℃, 0.8-3 atmosphere pressure.

[0046] After boiling in open water or pressure steam cooking, water molecules can quickly penetrate into the interior of the glaze layer, and the residual active groups in the polysilazane glaze layer can quickly react with water molecules, so that the product after wet curing basically does not smell ammonia, and the curing is relatively complete.

[0047] Preferably, the photo-curing comprises: irradiating the wet-cured glaze layer with 250-450nm UV light, and the irradiation energy is 250-5000mj / cm 2 .

[0048] The photo-curing is to irradiate the glaze layer with 250-450nm UV light, so that the glaze layer is cured more thoroughly and has higher hardness, thereby obtaining a glaze layer with better performance. The UV light irradiation can cause the ceramic transformation of polysilazane, mainly the cross-linking between silicon-hydrogen bond, double bond and nitrogen-hydrogen bond. The shorter the wavelength of the UV light irradiating the coating layer, the greater the energy, and the faster the ceramic transformation of the glaze layer. The hardness of the glaze layer after photo-curing can reach 7-9H, and the glaze layer scraped off by the blade is in the form of fine powder. The acid resistance, high temperature resistance and ultraviolet yellowing resistance of the glaze layer are optimal. The more complete the hydrolysis of polysilazane, the more complete the release of ammonia gas, the lower the N content in the transparent glaze layer, and the better the acid resistance of the coating layer.

[0049] Preferably, the relative humidity in the photo-curing stage is 20-95%, and the temperature is ≤100℃.

[0050] The higher the temperature and the greater the humidity, the faster the curing reaction of the glaze layer. The polysilazane on the surface of the glaze layer is first hydrolyzed to release ammonia gas and other gases, and then cross-linked and cured. Lower humidity and higher temperature are more conducive to the formation of covalent bonds between silazane and the glass substrate, thereby improving the adhesion. In the later stage of the reaction, increasing the temperature and humidity can promote more complete curing. Increasing the air pressure makes water molecules more easily penetrate into the glaze layer, so that the conversion rate of silicon dioxide in the glaze layer is higher, the residual active groups are fewer, the hardness is greater, and the high temperature resistance and weather resistance are better. Therefore, different humidity, temperature and air pressure should be adopted in different stages to make the polysilazane cure step by step, so that the performance of the glaze layer can be optimal.

[0051] In this application, after step (1) (dry curing), the semi-cured glaze layer (i.e. the dry-cured glaze layer) is subjected to step (2) (wet curing), or after steps (1) and (2), the semi-cured glaze layer is subjected to step (3) (photo-curing).

[0052] The polysilazane coating layer that has not been subjected to dry curing cannot be immediately subjected to wet curing, otherwise even if the hardness of the glaze layer is increased, the adhesion of the glaze layer to the surface of the substrate is poor.

[0053] The color coating is not suitable for being coated too thick at one time, otherwise, coating cracking, incomplete curing or surface dry and inner not dry phenomenon will occur. The polysilazane resin in contact with the surface of the substrate first reacts with the silicon hydroxyl group on the surface of the substrate to form a silicon-oxygen bond, forming a silica inorganic glaze layer on the surface of the substrate which is covalently bonded. If the glaze layer is coated too thick at one time, the surface of the glaze layer will react with the water vapor in the air to form a shell, which will hinder the further curing of the internal polysilazane resin, resulting in low hardness of the polysilazane glaze layer, poor high temperature resistance and poor ultraviolet aging resistance.

[0054] Preferably, the transparent color coating and the transparent glaze layer each independently have a thickness of 1-150 μm; further preferably 2-50 μm; more preferably 3-20 μm.

[0055] The transparent color coating and the transparent glaze layer can be coated by any one or two common methods, such as spraying, shower coating, slit coating, scraping, screen printing, spin coating, dipping, inkjet printing, roller coating, etc.

[0056] Compared with the prior art, the application has the following beneficial effects:

[0057] (1) The color photovoltaic module of the application applies a color coating to the outer surface of the module glass panel, solves the glass texture defect of the photovoltaic module as a building material product, shields the color difference of the appearance of the module caused by the battery sheet, improves the overall appearance of the product, and also solves the defect of light pollution caused by the glass outer surface of the existing photovoltaic module.

[0058] (2) The color photovoltaic module of the application uses a transparent glaze layer formed by curing polysilazane to cover the surface of the color coating. The transparent glaze layer mainly composed of silicon dioxide has excellent performance of quartz glass or ceramic glaze layer, and is covalently bonded to the polar groups on the surface of the color coating, has high adhesion, high hardness, high transparency, super weather resistance, acid and alkali resistance, scratch resistance, and excellent performance of stain resistance, effectively protects the color coating from fading, falling off, acid rain, ultraviolet light, wind sand and other external erosion, and gives the solar module a super long service life. DETAILED DESCRIPTION

[0059] The application will be further described in detail below in conjunction with the drawings and examples. It should be pointed out that the following examples are intended to facilitate the understanding of the application and do not limit it in any way.

[0060] Example 1

[0061] A golden color tempered color glaze panel, comprising a color glaze layer composed of a golden color bottom layer and a transparent varnish layer, and the production method is as follows:

[0062] A golden color toughening enamel composition, consisting of the following components by weight based on 100 parts: transparent ink oil 7020 (Kunshan Tianling) 20 parts, transparent glass powder (melting point 520-580°C) 75 parts, golden color pearlescent pigment (KC319) 5 parts. Preparation method of the golden color toughening enamel composition: 20 parts of transparent ink oil 7020, 75 parts of transparent glass powder are weighed, and three-roll grinding is performed to less than 10 microns. Finally, 5 parts of golden color pearlescent pigment is added, and the mixture is stirred uniformly and then reserved.

[0063] Transparent varnish layer composition: polysilazane XSC-N0901 95 parts; silica powder (3 microns) 5 parts.

[0064] Preparation method of the transparent varnish layer composition: 95 parts of polysilazane XSC-N0901 and 5 parts of silica powder are weighed in a stirring container, nitrogen is introduced, and the mixture is stirred uniformly and then reserved in a sealed state.

[0065] (1) Enamel coating

[0066] The mixed golden color toughening enamel composition is printed on the surface of 5 mm thick photovoltaic glass through a 200 mesh screen, and a golden color coating with a dry film thickness of 10 microns is formed.

[0067] (2) Enamel layer toughening

[0068] The coated golden color coating is toughened under the conditions of 680-720°C for 180 seconds, and a golden color glass panel is obtained.

[0069] (3) Varnish coating

[0070] The mixed transparent varnish layer composition is sprayed on the surface of the golden color glass panel, and a transparent coating with a thickness of 10 microns is formed.

[0071] (4) Varnish curing

[0072] Dry curing: the golden color glass panel coated with the transparent varnish layer composition is first cured at a relative humidity of 35% and a temperature of 45°C for 72 hours to preliminarily cure the coating;

[0073] Wet curing: the coating glass is boiled in water at a relative humidity of 100% and a temperature of 100°C for 2 hours to further convert the polysilazane coating into a silica coating. The coating performance is shown in Table 1.

[0074] Example 2

[0075] A white color enamel glass panel, the enamel layer is composed of a low-temperature curing enamel bottom layer and a transparent varnish layer, and the production method is as follows:

[0076] White thermosetting coating composition, consisting of: acrylic copolymer resin 1619 70 parts; isocyanate curing agent H-100 25 parts; white pearlescent pigment (KC8100) 5 parts, based on 100 parts by weight.

[0077] Method for preparing white thermosetting coating composition: 70 parts of acrylic copolymer resin 1619 (hydroxyl content 55 mg KOH / g, molecular weight 4000 g / mol, acid value ≤20 mg KOH / g), 5 parts of isocyanate curing agent H-100 (Wanhua Chemical), and 5 parts of pearlescent pigment (KC8100) were weighed into a stirring container and stirred uniformly for standby use.

[0078] Transparent gloss oil composition, consisting of: polysilazane resin 8024PV211 92 parts; silicon powder (2 microns) 8 parts, based on 100 parts by weight.

[0079] Transparent gloss oil layer composition: 92 parts of polysilazane resin 8024PV211 and 8 parts of silicon powder were weighed into a stirring container, nitrogen was introduced, and stirred uniformly for standby use.

[0080] (1) Glaze coating

[0081] The mixed white thermosetting coating composition was printed on the surface of 5 mm thick photovoltaic glass through a 200 mesh silk screen to form a white coating layer with a dry film thickness of 10 μm.

[0082] (2) Glaze layer curing

[0083] The printed white coating layer was heated and cured at 180°C for 15 minutes to obtain a white glass panel.

[0084] (3) Gloss coating

[0085] The transparent gloss oil composition was sprayed on the surface of the gold white coating layer to form a gloss oil coating layer with a thickness of 10 μm.

[0086] (4) Gloss curing

[0087] Dry curing: the white glass with sprayed transparent gloss oil composition was first cured at a relative humidity of 35% and a temperature of 185°C for 0.2 hours to preliminarily cure the coating layer;

[0088] Wet curing: the gloss oil coating layer glass was steamed in water vapor at a relative humidity of 100% and a temperature of 120°C for 60 minutes to convert the polysilazane coating layer into a silica coating layer. The coating performance is shown in Table 1.

[0089] Example 3

[0090] A red color glaze glass panel, the color glaze layer is composed of a low-temperature curing color glaze bottom layer and a transparent gloss oil layer, and the production method is as follows:

[0091] Red heat-curable coating composition, consisting of the following components, based on 100 parts by weight:

[0092] Red heat-curable coating composition preparation method: Take 65 parts of acrylate resin BS8270 (hydroxyl content 100 mg KOH / g, acid value <10-13 mg KOH / g, solid content 70%), 20 parts of H-100 isocyanate curing agent (Wanhua Chemical), 9 parts of hexafunctional polyurethane acrylate EB220, 1 part of 1173 photosensitizer and 5 parts of pearl pigment (KC8100) in a stirring container, and stir uniformly for standby.

[0093] Transparent varnish composition, consisting of the following components, based on 100 parts by weight: Inorganic polysilazane such as AZ NN 120-20 95 parts; Silicon powder (2 microns) 5 parts.

[0094] Transparent varnish layer composition: Take 95 parts of inorganic polysilazane such as AZ NN 120-20, 5 parts of silicon powder in a stirring container, and stir uniformly under nitrogen atmosphere, and seal for standby.

[0095] (1) Glaze coating

[0096] The mixed red heat-curable coating composition is printed on the surface of 5mm thick photovoltaic glass through a 200 mesh silk screen, forming a red coating layer with a dry film thickness of 10μm.

[0097] (2) Glaze layer curing

[0098] The printed red coating layer is first cured by UV lamp irradiation, energy 1800mj / cm 2 , relative humidity 55%, temperature 60℃, and then cured for 30 minutes at 180℃ under IR heating, to obtain a red glass panel.

[0099] (3) Varnish coating

[0100] The transparent varnish composition is sprayed on the surface of the red coating layer, forming a varnish coating layer with a thickness of 10μm.

[0101] (4) Varnish curing

[0102] Dry curing: The red glass with sprayed transparent varnish composition is first cured at a relative humidity of 45% and a temperature of 175℃ for 10 minutes to preliminarily cure the coating layer;

[0103] Wet curing: The coating glass is boiled in boiling water at a relative humidity of 100% and a temperature of 100℃ for 120 minutes to further cure the polysilazane coating layer and convert it into a silica coating layer;

[0104] Light curing: The wet cured enamel glass was irradiated by UV lamp, energy 2500 mj / cm 2 , relative humidity 55%, temperature 80℃. The performance of the coating after light curing is shown in Table 1.

[0105] Example 4

[0106] A white enamel glass panel, the enamel layer is composed of a low-temperature cured enamel base layer and a transparent light oil layer, the production method is as follows:

[0107] A white thermosetting coating composition, the total weight is 100 parts, and the composition is as follows: acrylic copolymer resin 1619 70 parts; isocyanate curing agent H-100 25 parts; white pearl pigment (KC8100) 5 parts.

[0108] Preparation method of white thermosetting coating composition: 70 parts of acrylic copolymer resin 1619 (hydroxyl content 55 mg KOH / g, molecular weight 4000 g / mol, acid value ≤20 mg KOH / g), 5 parts of H-100 isocyanate curing agent (Wanhua Chemical), and 5 parts of pearl pigment (KC8100) are weighed in a stirring container, and then stirred uniformly for standby.

[0109] Transparent light oil, the total weight is 100 parts, and the composition is as follows: organic polysilazane 1500 Rapid Cure 100 parts.

[0110] (1) Enamel coating

[0111] The mixed white thermosetting coating composition is printed on the surface of 5mm photovoltaic glass through a 200 mesh silk screen, forming a white coating layer with a dry film thickness of 10μm.

[0112] (2) Enamel layer curing

[0113] The printed white coating layer is heated and cured at 180℃ / 15min to obtain a white glass panel.

[0114] (3) Light oil coating

[0115] The transparent light oil is sprayed on the surface of the white coating layer to form a light oil coating layer with a thickness of 10μm.

[0116] (4) Light oil curing

[0117] Dry curing: The white glass with sprayed transparent light oil is naturally cured at a relative humidity of 55% and a temperature of 35℃ for 168 hours to cure the coating, and the performance of the coating is shown in Table 1.

[0118] Comparative examples 1-3

[0119] The colored glaze glasses in Examples 1, 2, and 3 are not sprayed with a transparent varnish composition (only steps (1) and (2) in Examples 1, 2, and 3 are performed, and steps (3) and (4) are not performed), and the remaining conditions are unchanged. The properties of the cured colored glaze are tested, and the coating properties are shown in Table 1.

[0120] Comparative Example 4

[0121] A golden color tempered colored glaze panel, comprising a colored glaze layer composed of a golden color bottom layer and a transparent varnish layer, is produced by the following method:

[0122] A golden color tempered glaze composition, with a total weight of 100 parts, is composed of: transparent ink oil 7020 (Kunshan Tianling) 20 parts; transparent glass powder (melting point 520-580°C) 75 parts; golden color pearl pigment (KC319) 5 parts.

[0123] A preparation method of the golden color tempered glaze composition: 20 parts of transparent ink oil 7020, 75 parts of transparent glass powder, and 5 parts of golden color pearl pigment are weighed and ground to less than 10 microns by a three-roll mill. After stirring uniformly, the mixture is ready for use.

[0124] A transparent varnish layer composition: polysilazane XSC-N0901 95 parts; silica powder (3 microns) 5 parts.

[0125] A preparation method of the transparent varnish layer composition: 95 parts of polysilazane XSC-N0901 and 5 parts of silica powder are weighed in a stirring container, nitrogen is introduced, and the mixture is stirred uniformly and sealed for standby use.

[0126] (1) Glaze coating

[0127] The mixed golden color tempered glaze composition is printed on the surface of a 5mm thick photovoltaic glass through a 200 mesh silk screen to form a golden color coating with a dry film thickness of 10 microns.

[0128] (2) Glaze layer tempering

[0129] The coated golden color coating is tempered under the conditions of 680-720°C for 180 seconds to obtain a golden color glass panel.

[0130] (3) Varnish coating

[0131] The mixed transparent varnish layer composition is sprayed on the surface of the golden color glass panel to form a transparent coating with a thickness of 10 microns.

[0132] (4) Varnish curing

[0133] Wet curing: under the conditions of relative humidity 100% and temperature 100°C, the coating glass is boiled in water for 2 hours to directly convert the polysilazane coating into a silica coating. The coating properties are shown in Table 1.

[0134] Evaluation method:

[0135] According to JC / T-1006-2018-Standard for Tempered and Tempered- toughened Glass with Coating, test the performance of color coating.

[0136] PCT / 48 hours aging test + UV120KW resistance performance:

[0137] First, the color glass coating is placed in a 2 atmosphere pressure cooker (121℃, 100% RH. saturated water vapor) for 48 hours, then according to the 5.21 provisions of GB / T30984.1-2015 standard test coating UV resistance performance, record the initial % of light transmittance, light transmittance after test, calculate the light transmittance attenuation % and the color difference value (△E) before and after illumination.

[0138] The results are shown in Table 1.

[0139] Table 1 Color solar module coating performance

[0140] From the results in Table 1, the hardness of the products coated with varnish layer in Examples 1-4 is significantly higher than that of the color glaze layer in Comparative Examples 2 and 3, and the resistance to washing, acid resistance, color difference value (△E) after PCT48+UV120KW aging test, and light transmittance are much better than those of Comparative Examples 1, 2 and 3, which shows that the varnish layer can significantly improve the performance of the color bottom layer. The coating hardness of Comparative Example 1 is the hardness of tempered glass. Comparative Example 4 does not dry curing but direct wet curing, resulting in a high degree of hydrolysis and oxidation of the polar groups in the polysilazane, such as Si-NH-Si, with water molecules in the air during the curing process, releasing a large amount of ammonia and other small molecule compounds, forming a high degree of silicon dioxide, and the cured varnish layer has high hardness, while the chemical reaction between the polysilazane resin and the hydroxyl or other polar groups on the surface of the substrate is insufficient, resulting in poor adhesion between the cured varnish layer and the substrate, which does not play the expected protective role, resulting in significant color difference and light transmittance attenuation of the color bottom layer.

[0141] The above examples have described the technical solutions and beneficial effects of the present application in detail. It should be understood that the above description is only a specific embodiment of the present application and is not intended to limit the present application. Any modification, supplement and equivalent replacement made within the principle range of the present application shall be included in the protection scope of the present application.

Claims

1. A transparent enameled panel, characterized in that, The transparent enamel layer is combined with the transparent color coating by covalent bond. The transparent enamel layer mainly comprises silicon dioxide.

2. The clear-glazed panel according to claim 1, characterized in that, The mass percentage of silicon dioxide in the transparent enamel layer is greater than or equal to 70%.

3. The clear-glazed panel according to claim 1, characterized in that, The hardness of the transparent enamel layer is greater than or equal to 4H.

4. The transparent glazed panel according to claim 1 or 2, characterized in that, The transparent enamel layer has a transmittance of greater than or equal to 80% in the ultraviolet region of 260-380 nm, greater than or equal to 93% in the visible light region of 380-780 nm, and greater than or equal to 90% in the infrared light region of 780-2500 nm.

5. The clear-glazed panel according to claim 1, wherein The transparent color coating and the transparent enamel layer covering the outer surface of the transparent color coating are subjected to high-pressure water vapor cooking for 48 hours at 2 atmospheres, and then the ultraviolet radiation resistance performance is tested according to the GB / T 30984.1-2015 standard, and the transmittance attenuation is less than or equal to 1%, and the color difference value attenuation is less than or equal to 1.

0.

6. The clear-glazed panel according to claim 1, characterized in that, The transparent enamel layer is formed by curing an enamel coating, and the enamel coating comprises the following raw materials in mass percentage: Polysilazane 90-100%; Auxiliary agent 0-10%.

7. The clear-glazed panel according to claim 6, characterized in that, The molecular weight of the polysilazane is 100-15000 g / mol, and the viscosity is 10-10000 cps / 25 DEG C.

8. The clear glazed panel of claim 6, wherein, The curing method comprises: dry curing the enamel coating and then wet curing; The dry curing is: under the condition of relative humidity less than or equal to 55% and temperature 0-350 DEG C, the coating of the enamel coating is cured to form a dry-cured enamel layer; The wet curing is: under the condition of relative humidity greater than or equal to 95%, temperature 90-200 DEG C and pressure 0.8-3 atmospheres, the dry-cured enamel layer is heated to be further cured to form a wet-cured enamel layer.

9. The clear-glazed panel according to claim 8, characterized in that, The wet curing is followed by or not by light curing; The light curing comprises: UV light irradiation of the wet-cured enamel layer to further cure it.

10. The clear glazed panel of claim 8, wherein, The wet curing is: under the condition of relative humidity 100%, temperature 90-180 DEG C and pressure 0.8-3 atmospheres, water boiling for 5-180 min.

11. The clear glazed panel of claim 8, wherein, The wet curing is: under the condition of relative humidity 100%, temperature 90-180 DEG C and pressure 0.8-3 atmospheres, water vapor steaming for 1-120 min.

12. The clear glazed panel of claim 9, wherein, The photo-curing includes: irradiating the wet-cured glaze layer with ultraviolet light of 250-450 nm, and the irradiation energy is 250-5000 mj / cm 2 .

13. The transparent enameled panel according to claim 9 or 12, characterized in that, In the light curing, the relative humidity is 20-95% and the temperature is less than or equal to 100 DEG C.

14. The clear-glazed panel according to claim 6, characterized in that, The auxiliary agent is a transparent particulate filler.

15. The clear glazed panel of claim 14, wherein, The auxiliary agent is at least one of silicon dioxide powder, silicon micro powder and glass powder.

16. The transparent enameled panel according to claim 14 or 15, characterized in that, The particle size of the auxiliary agent is 10 nm-10 microns.

17. The clear-glazed panel according to claim 1, characterized in that, The thickness of each layer of the transparent color coating and the transparent enamel layer is independently 1-150 microns.

18. The clear glazed panel according to claim 1 or 17, wherein The transparent color coating is a high-temperature tempered color glaze layer or a low-temperature cured color coating.

19. The clear-glazed panel according to claim 1, characterized in that, The heat resistance temperature of the transparent enamel layer is 400 DEG C.

20. A colored photovoltaic module, characterized by The transparent color glaze panel, the transparent adhesive layer A, the battery layer, the adhesive layer B and the back plate are sequentially laminated and packaged. The transparent color glaze panel is the transparent color glaze panel according to any one of claims 1-19.

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