CN116535103A - Preparation process of impact-resistant photovoltaic toughened glass and double-glass assembly - Google Patents

Abstract

The invention belongs to the technical field of photovoltaic tempered glass, and in particular relates to a preparation process of impact-resistant photovoltaic tempered glass and a double-glass component, comprising the following steps: step S1, preparing tempered glass; step S2, printing low-temperature glaze on the tempered glass with screen printing material grid; Step S3, bake in a baking oven at 110-240°C for 1-5 minutes, and wait until the low-temperature glaze is fully cured and cross-linked to obtain a pre-prepared tempered glass; Step S4, corona-treating the pre-prepared tempered glass to obtain Impact photovoltaic tempered glass; the preparation process of impact-resistant photovoltaic tempered glass of the present invention, the double-glass component uses low-temperature baking and low-temperature glaze to make the coating itself flexible, and because the process does not involve the process of glass high-temperature tempering and molding , will not form a large concentrated stress on the glass surface, effectively improving the impact resistance of tempered glass, so there will be no fragments during the lamination, transportation or component use of the finished glass.

Description

Preparation process of impact-resistant photovoltaic toughened glass, double glass module

technical field

The invention belongs to the technical field of photovoltaic tempered glass, and in particular relates to a preparation process of impact-resistant photovoltaic tempered glass and a double-glass module.

Background technique

At present, the coating used for the mainstream grid glass in the market is glaze coating. The main components of the coating are low-melting glass powder, pigments and fillers, dispersants, solvents and a small amount of resin. The coating curing process is 100-150℃*1-2min Solvent volatilization and 600-700℃*2-3min glass powder melting to form glaze, pigments and fillers will be wrapped by glass glaze, other organic components will be thermally decomposed and volatilize and disappear. The curing process of this coating is also the process of simultaneous tempering of the glass, which requires rapid heating and cooling. Because the expansion coefficients of the cured glaze layer and the tempered glass are inconsistent, a large concentrated stress will be generated between the glaze layer and the glass after the glass is cooled, and the glass needs to be stacked for transportation, so this grid glass exists High fragmentation rate. Nowadays, the size of the battery sheet is getting bigger and bigger, and the size of the glass has also increased by 20-40% on the original basis, which leads to a higher fragmentation rate of the glass after printing the glazing paint. The fragmentation rate of the existing grid glass is 0.3-0.8%, and the glass manufacturers are miserable.

Therefore, there is an urgent need for a grid tempered glass with low fragmentation rate and high impact resistance.

Contents of the invention

The invention provides a preparation process of impact-resistant photovoltaic toughened glass and a double-glass module, so as to solve the problem that the toughened glass prepared in the existing process is not impact-resistant and easily fragmented.

In order to solve the above-mentioned technical problems, the present invention provides a preparation process of impact-resistant photovoltaic tempered glass, comprising the following steps: step S1, preparing tempered glass; step S2, printing low-temperature glaze grid on tempered glass with screen; step S3, bake in a baking oven at 110-240° C. for 1-5 minutes, and wait until the low-temperature glaze is fully cured and cross-linked to obtain pre-prepared tempered glass; Step S4, corona-treating the pre-prepared tempered glass to obtain impact-resistant photovoltaic tempered glass.

In another aspect, the present invention also provides a double-glass module, including the impact-resistant photovoltaic tempered glass prepared by the above-mentioned preparation process.

The beneficial effect of the present invention is that the preparation process of the impact-resistant photovoltaic toughened glass and the double-glass component of the present invention make the coating itself flexible by using low-temperature baking and low-temperature glaze, and at the same time, because the process does not involve high-temperature tempering of glass The process will not form a large concentrated stress on the glass surface, which effectively improves the impact resistance of the tempered glass, so there will be no fragments during the lamination, transportation or component use of the finished glass.

Additional features and advantages of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the invention.

In order to make the above-mentioned objects, features and advantages of the present invention more comprehensible, preferred embodiments will be described in detail below together with the accompanying drawings.

Description of drawings

In order to more clearly illustrate the specific implementation of the present invention or the technical solutions in the prior art, the following will briefly introduce the accompanying drawings that need to be used in the specific implementation or description of the prior art. Obviously, the accompanying drawings in the following description The drawings show some implementations of the present invention, and those skilled in the art can obtain other drawings based on these drawings without any creative effort.

Fig. 1 is a diagram of the preparation process of the impact-resistant photovoltaic toughened glass of the present invention.

Detailed ways

In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present invention, not all of them. the embodiment. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

The reason for glass fragments is mainly that low-melting point glass powder is melted into glaze at 600-700°C, and 600-700°C is also the process of glass tempering and molding. The expansion coefficient of glass is inconsistent with that of low-melting point glass glaze, resulting in glass and Large concentrated stresses are formed between the glass glazes, so glass shards can be a problem during lamination of the finished glass, transportation or assembly use.

As shown in Figure 1, the present invention provides a kind of preparation technology of impact-resistant photovoltaic toughened glass, comprises the following steps: step S1, prepare toughened glass; Step S2, use screen printing low-temperature glaze grid on toughened glass; S3, bake in a baking oven at 110-240° C. for 1-5 minutes, and wait until the low-temperature glaze is fully cured and cross-linked to obtain pre-prepared tempered glass; Step S4, corona-treating the pre-prepared tempered glass to obtain impact-resistant photovoltaic tempered glass.

In this embodiment, specifically, the components of the low-temperature glaze include the following raw materials in parts by mass: fluororesin: 60-100 parts; pigments and fillers: 50-75 parts; dispersant: 1-4 parts; Non-toxic polymer: 5-26 parts; Leveling agent: 0.5-1.0 parts; Antioxidant: 0.2-0.6 parts; Blocked cyanate ester curing agent: 6-18 parts; Catalyst: 0.1-0.4 parts; Solvent: 35 parts -60 parts; wherein the modified polymer is based on hydroxyl-terminated polybutadiene, glycerin and maleic anhydride as the main chain, and the two ends of the molecular chain are terminated with N, N-(aminopropyl triethoxy) silane .

In this embodiment, specifically, the modified polymer includes the following components in parts by mass: hydroxyl-terminated polybutadiene: 20.0-180.0 parts; glycerin: 0.5-3.0 parts; maleic anhydride: 4.0- 8.0 parts; N,N-(aminopropyltriethoxy)silane: 7.0-9.0 parts; Propylene glycol methyl ether acetate: 21.0-50.0 parts; The molecular weight Mn of the hydroxyl-terminated polybutadiene is 1000-4500; The maleic anhydride needs to be dissolved in propylene glycol methyl ether acetate and then added dropwise for use.

In this embodiment, specifically, the fluororesin is tetrafluoroethylene-vinyl ether resin, tetrafluoroethylene-vinyl ester resin, chlorotrifluoroethylene-vinyl ether, chlorotrifluoroethylene- One or more of vinyl ester resins; the hydroxyl value of the fluororesin is 50-80mgKOH/g; specifically, such as Dongfluor Chemical ZHM-2 or HLR-6 fluororesin, Changxing 41011 fluororesin, Daikin GK -570 fluororesin, etc.; fluororesin is added to improve the weather resistance and dirt resistance of the coating, and is one of the main film-forming substances of the coating.

In this embodiment, specifically, the low-temperature cured polyurethane coating itself has flexibility, does not involve the process of glass tempering and molding at high temperature, and does not form a large stress concentration on the glass surface, so there is no problem of fragmentation.

In this embodiment, specifically, the blocked polyisocyanate curing agent is one or more of blocked HDI trimers, blocked H6XDI adducts, and blocked XDI adducts; Chuang’s 3175 blocked isocyanate curing agent; each molecule of blocked polyisocyanate curing agent has more than two blocked -NCO groups, the blocked curing agent is not active at room temperature, and the blocking agent is released at high temperature , so that the -NCO group is released, and the -NCO group can react with the -OH in the coating component to form a network crosslinking structure, so that the physical and chemical properties of the coating can be maintained stably for a long time.

In this embodiment, specifically, the pigments and fillers are titanium dioxide, precipitated barium sulfate, lithopone, zinc oxide, calcium carbonate, copper chrome black, iron chrome black, carbon black, aniline black, iron red, cadmium red , Lithor red, scarlet, cadmium yellow, lead chrome yellow, ultramarine blue, phthalocyanine blue, peacock blue, chrome green, zinc green, cobalt violet, ultramarine violet, silica, kaolin, bentonite, glass powder, hollow glass micro One or more of beads, alumina powder, PTFE micropowder, PVDF micropowder, PE wax powder, PP wax powder; the addition of pigments and fillers is mainly to impart color and improve hiding power; , chemical resistance, heat resistance, mechanical properties and feel of the coating film have certain influences, and the addition of pigments and fillers can also reduce the cost of coatings; some pigments and fillers also have an impact on the flame retardancy and electrical conductivity of the coating.

In this embodiment, specifically, the dispersant is anionic wetting and dispersing agent, cationic wetting and dispersing agent, nonionic wetting and dispersing agent, amphoteric wetting and dispersing agent, polymer hyperdispersant, One or more of the controlled free radical hyperdispersants; specifically, Efka PU 4010; the dispersant is a surfactant with two opposite properties of lipophilicity and hydrophilicity in the molecule, which can reduce the complete The time and energy required for the dispersion process modify the surface properties of the particles and adjust the mobility of the pigment particles, thereby improving the stability of the powder and avoiding flocculation and sedimentation.

In this embodiment, specifically, the leveling agent is one or more of acrylic leveling agent, silicone leveling agent, fluorosilicon leveling agent and high boiling point solvent; the boiling point of the high boiling point solvent Above 150°C; specifically, BYK-300; the leveling agent migrates to the surface of the wet film through limited compatibility, affecting the surface tension of the paint film, prompting the paint to form a smooth and uniform coating during the drying process, and improving the paint on the surface. The permeability of the substrate reduces appearance defects such as spots and traces produced during painting.

In this embodiment, specifically, the antioxidant is one or more of hindered amines, hindered phenols, phosphites, thiodipropionates, and mercaptans; specifically, such as 1010, 1076 , 164, 168 and other antioxidants; antioxidants are a class of substances that delay or inhibit the thermal oxidative decomposition of polymers, which can delay the aging of polymers and prolong their service life.

In this embodiment, specifically, the catalyst is one or more of organic tin, organic zinc, organic bismuth, and amines; specifically, dibutyltin dilaurate; the addition of the catalyst is to reduce The unblocking temperature of the closed catalyst, the active groups such as -OH, -COOH, amino, epoxy, etc. in the catalytic coating accelerate the reaction with -NCO groups, improve production efficiency, and avoid incomplete reactions of the components in the coating Problems with tacky coatings and poor performance occur.

In this embodiment, specifically, the solvent is 783 slow-drying water, diethylene glycol butyl ether, divalent ester, butyl acetate, toluene, xylene, ethyl acetate, propylene glycol methyl ether acetate, n- One or more of butanol, acetone, methyl ethyl ketone, and No. 200 mineral spirits; the solvent can dissolve the organic reactants to form a homogeneous system, so that the components in the coating can fully and evenly react and crosslink. Solvents with different boiling points are selected according to the baking temperature to ensure that the coating is not sticky and has sufficient cross-linking curing time. The use of some high boiling point solvents can also meet the requirements of slow drying and low odor of screen printing.

In this embodiment, specifically, low-melting-point glass powder is used in the enamel coating on the traditional grid glass. In order to lower the melting point of the low-melting point glass powder, it is necessary to add sodium-potassium alkali metal components when the glass is mixed at high temperature. This sodium-potassium alkali metal component will dissociate when the crystalline silicon module is used for a long time after encapsulation, resulting in PID failure, that is, potential-induced decay, which affects the service life of the photovoltaic module. In addition, the peeling strength of the traditional glazing coating with the adhesive film decays significantly after short-term damp heat aging of PCT and long-term damp heat aging of double 85, and water vapor easily penetrates into the component, resulting in leakage failure of the component; while the thermosetting coating used in the present invention The layer has no alkali metal components, which has excellent anti-PID effect, and the peel strength of the coating and film has little attenuation after damp heat aging.

In this embodiment, specifically, the mesh of the screen printing is 80-200 mesh.

In this embodiment, specifically, the thickness of the screen-printed low-temperature glaze grid is 5-25 μm.

In this embodiment, specifically, the corona intensity of the corona treatment is 3-5 kW.

Example 1:

According to the formula ratio shown in Table 1, paint preparation, stirring and silk screen printing were carried out. Oven baking temperature 110-220 ℃, baking time 2min; corona intensity 4.5kW.

Table 1

Example 2:

According to the formula ratio shown in Table 2, paint preparation, stirring, and silk screen printing were carried out. Oven baking temperature 110-240 ℃, baking time 2min; corona intensity 4.5kW.

Table 2

type Specific composition/ratio Dosage/parts by weight Fluorine resin HLR-6 fluororesin 86 Pigments Titanium dioxide: precipitated barium sulfate: bentonite = 6:2:1 72 Dispersant BYK-111 2.9 modified polymer modified polymer 12 leveling agent BYK-306 0.8 antioxidant 1076 0.5 Sealed curing agent Mitsui G282 closed curing agent 11 catalyst Organotin catalyst 0.2 solvent Butyl acetate 38

Example 3:

According to the formula ratio shown in Table 3, paint preparation, stirring, and silk screen printing were carried out. Oven baking temperature 110-220 ℃, baking time 2min; corona intensity 4.5kW.

table 3

Example 4:

Paint preparation, stirring, and silk screen printing were carried out according to the formula ratio shown in Table 4. Oven baking temperature 110-230 ℃, baking time 2min; corona intensity 4.5kW.

Table 4

type Specific composition/ratio Dosage/parts by weight Fluorine resin HLR-6 fluororesin 86 Pigments Copper chrome black: silica = 15:1 52 Dispersant EFKA 4310 2.5 modified polymer modified polymer 25 leveling agent BYK-331 0.5 antioxidant 1076:168=6:1 0.5 Sealed curing agent Covestro 3175 closed curing agent 9 catalyst Organotin catalyst 0.2 solvent Xylene: Butyl acetate = 1:1 42

Example 5:

Paint preparation, stirring, and silk screen printing were carried out according to the formula ratio shown in Table 5. Oven baking temperature 110-230 ℃, baking time 2min; corona intensity 4.5kW.

table 5

Example test results:

Table 6 Initial performance

Table 7 Aging performance

Attachment: PID test refers to IEC TS 62804-2:2022; falling ball test refers to GB/T 15763.2-2005 impact resistance test.

It can be seen from the above test results that:

(1) 1, 2, 3, 4, and 5 groups of embodiments are all low-temperature thermosetting grid glass coatings, compared with glaze-plated grid glass coatings, and 5 groups of thermosetting coatings are comparable to those of plating in terms of initial performance. The glaze coating is basically the same, with no obvious difference;

(2) In terms of humidity and heat aging of PCT and double 85, the peel strength of the glaze-plated coating attenuates significantly, which is not as good as that of the low-temperature thermosetting coating;

(3) In terms of PID test, the glaze layer in the glazed grid glass has the risk of electrical breakdown, and the battery will fail, while the low-temperature thermosetting coating is normal;

(4) In the falling ball test, the glazed grid glass has a certain probability of fragmentation, while the low temperature thermosetting coated grid glass will not be fragmented.

It can be seen that although the present invention needs to increase the coating baking and corona process, it also reduces the fragmentation rate of the glass, reduces the customer complaints and claims received by the glass factory, and is positive in the long run; and the photovoltaic module The bigger and bigger the glass, the greater the probability of its fragmentation. Under the trend of large glass size, the impact-resistant photovoltaic tempered glass prepared by the present invention has higher income.

At the same time, the components produced by the impact-resistant photovoltaic tempered glass of the present invention have no risk of PID failure, and the coating performance has no obvious attenuation under long-term humidity and heat aging conditions, which can effectively prolong the service life of the components.

In another aspect, the present invention also provides a double-glass module, including the impact-resistant photovoltaic tempered glass prepared by the above-mentioned preparation process.

To sum up, the preparation process of impact-resistant photovoltaic toughened glass and the double-glass module of the present invention make the coating itself flexible by using low-temperature baking and low-temperature glaze, and because the process does not involve the process of high-temperature tempering and forming of glass , will not form a large concentrated stress on the glass surface, effectively improving the impact resistance of tempered glass, so there will be no fragments during the lamination, transportation or component use of the finished glass.

Inspired by the above-mentioned ideal embodiment according to the present invention, through the above-mentioned description content, relevant workers can make various changes and modifications within the scope of not departing from the technical idea of the present invention. The technical scope of the present invention is not limited to the content in the specification, but must be determined according to the scope of the claims.

Claims (10)

1. A preparation process for impact-resistant photovoltaic toughened glass, characterized in that, comprising the steps: Step S1, preparing tempered glass; Step S2, printing a low-temperature glaze grid on the tempered glass by screen printing; Step S3, baking in a baking oven at 110-240° C. for 1-5 minutes, until the low-temperature glaze is fully cured and cross-linked to obtain pre-prepared tempered glass; Step S4, corona-treating the pre-prepared toughened glass to obtain impact-resistant photovoltaic toughened glass. 2. preparation technology as claimed in claim 1, is characterized in that, The components of the low-temperature glaze include the following raw materials in parts by mass: Fluorine resin: 60-100 parts; Pigment and filler: 50-75 parts; Dispersant: 1-4 parts; Modified polymer: 5-26 parts; Leveling agent: 0.5-1.0 parts; Antioxidant: 0.2-0.6 parts; Blocked cyanate curing agent: 6-18 parts; Catalyst: 0.1-0.4 parts; Solvent: 35-60 parts; The modified polymer is mainly composed of hydroxyl-terminated polybutadiene, glycerin and maleic anhydride, and the two ends of the molecular chain are terminated with N, N-(aminopropyl triethoxy) silane. 3. preparation technology as claimed in claim 2 is characterized in that, The modified polymer comprises the following components in parts by mass: Hydroxyl-terminated polybutadiene: 20.0-180.0 parts; Glycerin: 0.5-3.0 parts; Maleic anhydride: 4.0-8.0 parts; N,N-(aminopropyltriethoxy)silane: 7.0-9.0 parts; Propylene glycol methyl ether acetate: 21.0-50.0 parts; The molecular weight Mn of the hydroxyl-terminated polybutadiene is 1000-4500; The maleic anhydride needs to be dissolved in propylene glycol methyl ether acetate and then added dropwise for use. 4. preparation technology as claimed in claim 2 is characterized in that, The fluororesin is one of tetrafluoroethylene-vinyl ether resin, tetrafluoroethylene-vinyl ester resin, chlorotrifluoroethylene-vinyl ether and chlorotrifluoroethylene-vinyl ester resin in FEVE resin or more; The hydroxyl value of the fluororesin is 50-80 mgKOH/g. 5. preparation technology as claimed in claim 2 is characterized in that, The blocked polyisocyanate curing agent is one or more of blocked HDI trimers, blocked H6XDI adducts, and blocked XDI adducts. 6. preparation technology as claimed in claim 2 is characterized in that, The pigments and fillers are titanium dioxide, precipitated barium sulfate, lithopone, zinc oxide, calcium carbonate, copper chrome black, iron chrome black, carbon black, aniline black, iron red, cadmium red, Lisol red, scarlet, cadmium Yellow, lead chrome yellow, ultramarine blue, phthalocyanine blue, peacock blue, chrome green, zinc green, cobalt violet, ultramarine violet, silica, kaolin, bentonite, glass powder, hollow glass microspheres, alumina powder, PTFE powder, One or more of PVDF micropowder, PE wax powder, PP wax powder; The dispersant is an anionic wetting and dispersing agent, a cationic wetting and dispersing agent, a nonionic wetting and dispersing agent, an amphoteric wetting and dispersing agent, a polymer hyperdispersant, and a controlled free radical hyperdispersant. one or more of The leveling agent is one or more of acrylic leveling agent, silicone leveling agent, fluorosilicon leveling agent and high boiling point solvent; The antioxidant is one or more of hindered amines, hindered phenols, phosphites, thiodipropionates, and mercaptans; The catalyst is one or more of organotin, organozinc, organobismuth and amine; Described solvent is 783 slow drying water, diethylene glycol butyl ether, divalent acid ester, butyl acetate, toluene, xylene, ethyl acetate, propylene glycol methyl ether acetate, n-butanol, acetone, methyl ethyl ketone, 200 One or more of No. solvent oils. 7. preparation technology as claimed in claim 1, is characterized in that, The mesh number of the screen printing is 80-200 mesh. 8. preparation technology as claimed in claim 1, is characterized in that, The thickness of the screen-printed low-temperature glaze grid is 5-25 μm. 9. preparation technology as claimed in claim 1, is characterized in that, The corona intensity of the corona treatment is 3-5kW. 10. A double-glass component, characterized in that, Including impact-resistant photovoltaic tempered glass prepared by adopting the preparation process described in any one of claims 1-9.