Photocurable silver line ink for automotive rear window, preparation and use

Abstract

The application provides a light-curing automobile rear windshield shielding silver line ink, which comprises the following raw materials in percentage by mass: glass powder 40-80%, light-curing ink oil 10-25%, inorganic pigment 5-30%, inorganic additive 1-8% and organic additive 0-5%; wherein the inorganic additive comprises one or more of boron powder, zinc powder, iron powder, bismuth powder, sulfur powder, aluminum powder and silicon powder. The application also provides a preparation method of the light-curing automobile rear windshield shielding silver line ink, and the finished ink has good shielding effect on silver paste, strong anti-sticking property, great advantages in environmental protection and energy consumption efficiency, and is worth promoting.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of ink, and particularly relates to a light-curing automobile rear windshield shielding silver line ink and a preparation method and application thereof. BACKGROUND

[0002] The automobile windshield ink is coated on the surface of the automobile windshield and can effectively reduce the ultraviolet transmittance after high-temperature tempering treatment at 600-700 DEG C, prevent the chemical change of the glue used for bonding the glass and the vehicle body, shield the conductive silver paste, and thus play a role in decorating the appearance of the vehicle body.

[0003] With the rapid development of the automobile industry and the increasing demand of people for the environmental living standard, the demand for the automobile windshield ink is increased, and the performance requirements for the ink are improved, mainly including the adhesion resistance, acid and alkali resistance of the glass ink, and the shielding performance of the silver paste.

[0004] However, the automobile windshield ink prepared by the related art has color difference between the automobile windshield and the automobile glass, poor shielding effect of the silver paste, and product performance to be improved.

[0005] The product performance mainly includes the adhesion resistance, weather resistance, shielding performance of the silver paste, and softening point of the glass ink.

[0006] In the existing glass ink manufacturing technology, the ink oil components are mixed by using traditional resins, solvents, and related additives, and other components in the ink are mixed and rolled. The product needs to be dried before sintering on the automobile glass, which increases energy consumption, VOCs (organic waste gas) emission, and processing time.

[0007] To solve the above technical problems of the automobile windshield ink, such as color difference between the automobile windshield and the automobile glass, poor shielding effect of the silver paste, product performance to be improved, high energy consumption of glass sintering, and much waste emission, the present application provides a light-curing automobile rear windshield shielding silver line ink SUMMARY

[0008] To solve the above technical problems of the automobile windshield ink, such as color difference between the automobile windshield and the automobile glass, poor shielding effect of the silver paste, product performance to be improved, high energy consumption of glass sintering, and much waste emission, the present application provides a light-curing automobile rear windshield shielding silver line ink, which comprises the following raw materials in mass percentage: glass powder 40-80%, light-curing ink oil 10-25%, inorganic pigment 5-30%, inorganic additive 1-8%, and organic additive 0-5%.

[0009] The inorganic additive includes one or more of boron powder, zinc powder, iron powder, bismuth powder, sulfur powder, aluminum powder, and silicon powder.

[0010] Further, the inorganic auxiliary agent includes silicon powder and inorganic powder, the inorganic powder includes one or more of boron powder, zinc powder, iron powder, bismuth powder, sulfur powder, and aluminum powder.

[0011] Further, the glass raw material includes the following components in mass percentage: 20-45% of silicon dioxide, 1-15% of titanium dioxide, 1-8% of zirconium dioxide, 0-60% of bismuth trioxide, 4-25% of boron oxide, 0-6% of aluminum oxide, 1-3% of potassium oxide, 0-10% of lithium oxide, 0-8% of phosphorus pentoxide, and 0-15% of magnesium oxide.

[0012] Further, the inorganic pigment is one or more of copper-chromium black, iron-chromium-manganese black, and cobalt black.

[0013] Further, the photocuring ink oil includes the following components in mass percentage: 60%-90% of photosensitive prepolymer, 10-20% of active diluent, 1-5% of photoinitiator, and 0.1%-0.01% of polymerization inhibitor, wherein:

[0014] The photosensitive prepolymer includes one or more of acrylated epoxy resin, unsaturated polyester, polyurethane, and polythiol / polyene photocuring resin;

[0015] The active diluent includes one or more of diol-based diacrylate;

[0016] The photoinitiator includes one or more of benzoin and its derivatives, acetophenone derivatives, and triarylthiolum salts, the mass percentage of the photoinitiator in the photocuring ink oil is 1-5%;

[0017] The polymerization inhibitor includes one or more of p-hydroxyanisole, hydroquinone, and 2,6-di-tert-butyl-p-cresol.

[0018] Further, the organic auxiliary agent system includes defoaming agent, leveling agent, and dispersant, wherein the mass ratio of the defoaming agent, the leveling agent, and the dispersant is 0-0.5:0-1:0-2.

[0019] Further, the defoaming agent includes one or more of BYK-060N, BYK-066N, BYK-052, and BYK-053; the leveling agent includes one or more of BYK-350, BYK-352, and BYK-354; and the dispersant includes one or more of DISPERBYK-115, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-164, and DISPERBYK-165.

[0020] The application further provides a preparation method of the light-cured automobile rear windshield shielding silver line ink, comprising the following steps:

[0021] S1. melting the glass raw material in a reducing atmosphere at a temperature of 1250-1350 DEG C for 20-30 min, and then cooling to obtain a crude glass; and ball-milling the crude glass to obtain a glass powder;

[0022] The particle size of the glass powder is 1-10 microns.

[0023] S2. mixing the glass powder, light-cured ink oil, inorganic pigment, inorganic additive and organic additive according to a mass fraction of 40-80%, 10-25%, 5-30%, 1-8% and 0-5%, and then grinding to obtain the automobile rear windshield shielding silver line ink, wherein the inorganic additive comprises one or more of boron powder, zinc powder, iron powder, bismuth powder, sulfur powder, aluminum powder and silicon powder.

[0024] The application further provides an application of the light-cured automobile rear windshield shielding silver line ink according to any one of the above in the automobile rear windshield.

[0025] Further, the method comprises the following steps:

[0026] S10. coating the automobile rear windshield shielding silver line ink on the surface of the automobile rear windshield and then light-curing, wherein the energy density of the light-curing is 800-900 mJ / cm 2 ;

[0027] S20. sintering the automobile rear windshield treated by the step S10, wherein the sintering temperature is 700-850 DEG C.

[0028] Compared with the prior art, the application has at least the following advantages:

[0029] 1. The inorganic additive in the application is a combination of elemental powders, which effectively prevents the dispersion of silver ions at high temperatures, avoids the color difference between the glass ink and the glass contact surface, and improves the silver paste shielding performance of the glass ink.

[0030] 2. In the application, the glass powder is melted in a reducing state, so that a small amount of bismuth metal is reduced (0.1-1%) and uniformly distributed in the glass body; the diffusion of silver ions is blocked, and the corrosion resistance and anti-sticking performance of the glass are improved.

[0031] The silica of the glass phase basic structure is a stable tetrahedral structure itself, the Si-O bond can exist independently in a crystal state and form a large network structure, and the reduced bismuth element uniformly filled in the glass phase network structure under a reducing atmosphere enhances the structural toughness, and the reduction is more stable, which is beneficial to the improvement of the barrier ability of silver ion diffusion, corrosion resistance and the enhancement of the glass ink adhesion. BRIEF DESCRIPTION OF DRAWINGS

[0032] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and any person skilled in the art can obtain other drawings according to the structures shown in the drawings without creative labor.

[0033] Figure 1 The figure is the automobile rear windshield glass prepared in the embodiment of the present application.

[0034] Figure 2 The figure is the automobile rear windshield glass prepared in the embodiment 1 of the present application. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the present application will be described clearly and completely. Obviously, the described embodiments are only some of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, any person skilled in the art can obtain all other embodiments without creative labor, which are within the protection scope of the present application.

[0036] In addition, the technical solutions of each embodiment of the present application can be combined with each other, but it must be based on the fact that a person skilled in the art can realize it. When the combination of technical solutions appears contradictory or unachievable, it should be considered that the combination of technical solutions does not exist and is not within the protection scope of the present application.

[0037] When the embodiments give numerical ranges, it should be understood that, unless otherwise stated by the present application, each numerical range and any number between the two endpoints of the numerical range can be selected. Unless otherwise defined, all technical and scientific terms used in the present application are mastered by the person skilled in the art of the prior art and the description of the present application, and any method, equipment and material of the prior art similar or equivalent to the method, equipment and material of the embodiments of the present application can be used to realize the present application.

[0038] The application provides a light-curing type automobile rear windshield shielding silver line ink, which comprises the following raw materials in percentage by mass: glass powder 40-80%, light-curing ink oil 10-25%, inorganic pigment 5-30%, inorganic additive 1-8% and organic additive 0-5%.

[0039] The inorganic additive comprises one or more of boron powder, zinc powder, iron powder, bismuth powder, sulfur powder, aluminum powder and silicon powder.

[0040] The application further provides a preparation method of the light-curing type automobile rear windshield shielding silver line ink, which comprises the following steps:

[0041] S1. glass raw materials are fused under a reducing atmosphere at a temperature of 1250-1350 DEG C for 20-30 min and then cooled to obtain coarse glass; the coarse glass is ball milled to obtain glass powder;

[0042] The particle size of the glass powder is 1-10 microns.

[0043] In some embodiments, the glass raw materials comprise the following components in percentage by mass: silicon dioxide 20-45%, titanium dioxide 1-15%, zirconium dioxide 1-8%, bismuth trioxide 0-60%, boron oxide 4-25%, aluminum oxide 0-6%, potassium oxide 1-3%, lithium oxide 0-10%, phosphorus pentoxide 0-8% and magnesium oxide 0-15%.

[0044] It can be seen that the glass powder selected in the application does not contain sodium elements, avoiding the situation that, in the related art, due to the close atomic cloud radius of sodium ions and silver ions, ion exchange occurs between silver ions and sodium ions at high temperature, and then silver ions penetrate the ink layer to form brown or brown yellow marks on the glass surface. The glass ink prepared by the application has uniform and stable color on the glass surface, effectively improving the aesthetic degree and performance of the glass ink.

[0045] Through multiple tests and finished product verification, the application adopts reasonable collocation of various oxides, so that the glass powder forms bismuth titanate, bismuth silicate and zirconium silicate in the molten state, and forms part of the crystal in the glass system in proportion, so that the glass structure is more dense, and the diffusion of silver ions is blocked, and the anti-sticking performance of the glass is improved.

[0046] Compared with ordinary glass, the crystalline glass can adjust the heat treatment temperature and time to change the performance of the glass, so as to better match the printed automobile glass substrate; and the crystalline glass also has a certain passivation effect on the expansion of the ink layer microcracks in the sintering process, so as to enhance the adhesion of the ink and effectively improve the problems such as easy discoloration of the ink. In addition, the crystalline glass also increases the chemical stability of the glass ink to a certain extent.

[0047] It is known that in the related art, the activity of silver ions is improved under high temperature conditions and is easy to diffuse, causing differences in color between the glass ink and the glass contact surface, affecting the shielding performance of the glass ink silver paste and affecting the performance of the glass.

[0048] The glass raw material is melted under a reducing atmosphere in the present application, so that the bismuth element present in the reducing glass is converted into elemental bismuth and uniformly distributed in the glass powder, effectively blocking the dispersion of silver ions while effectively improving the performance of the glass ink, including the anti-sticking property, weather resistance, shielding performance of the silver paste, and softening point of the glass ink.

[0049] The requirement of the glass ink for the anti-sticking property mainly reflects that in the preparation process of the automobile windshield, if the curvature of the glass is large, a mold coated with a glass fiber mold cloth is used to roll press the automobile glass original piece printed with the automobile glass ink, which requires the glass ink to have good anti-sticking property to avoid the adhesion of the ink to the glass fiber mold cloth, causing damage to the surface of the ink layer.

[0050] The requirement of the glass ink for weather resistance mainly reflects the acid and alkali resistance: the acid and alkali resistance of the automobile glass ink largely determines its service life. After the ink is just printed and sintered, there is little difference in appearance, shielding property, etc. between products with different acid and alkali resistance, however, after a period of use, exposure to sunlight and rain or long-term contact with acidic and alkaline substances in the surrounding environment, the ink products with insufficient acid and alkali resistance will show discoloration or ink layer peeling and falling off, etc., thereby affecting the service life of the glass.

[0051] The requirement of the glass ink for the silver paste shielding performance mainly reflects that the conductive heating silver wire busbar is printed on the surface layer of the black glass ink and is sintered synchronously to form a stable film layer with a multi-layer structure. However, during high-temperature sintering, silver ions are easy to migrate due to their activity, penetrating through the base glass ink layer to the bottom glass substrate, causing Ag + diffusion on the surface of the float glass substrate (silver diffusion path: 2Ag + + Sn 2+ > 2Ag + Sn 4+ ), at this time, the dense and stable glass ink layer with reducing property can effectively hinder the migration of Ag + ions in the conductive silver paste and effectively shield the silver paste.

[0052] It is known to those skilled in the art that the softening point as an important performance indicator of the glass ink, the melting point of the glass powder is lower than the softening temperature of the vehicle glass. The general vehicle glass will be heat-bent and tempered at 600-750℃. In order to ensure that the vehicle glass ink can be well sintered to the vehicle glass within this temperature range, it is necessary to meet the low melting point of the glass powder, that is, the vehicle glass starts to soften when the glass powder is completely molten, so that the low melting point glass powder can penetrate into the surface layer of the vehicle glass, and the mutual diffusion between the two makes the ink and the vehicle glass tightly bonded. Therefore, the softening point of the glass powder is generally between 450-600℃.

[0053] And the reducing agent element produced by melting in a reducing atmosphere can quickly fill the Si-O structure of the glass phase, quickly form a stable melting state, and reduce the softening point of the glass raw material melting, so that the softening point of the glass powder is controlled at 450-600℃, thereby ensuring the tight connection between the glass ink and the vehicle glass, and preventing the glass ink from falling off during subsequent sintering.

[0054] It is worth mentioning that the effect of the bismuth element obtained by melting in a reducing state on optimizing the performance of the glass ink is better than that of the added bismuth powder, and the reduced bismuth element accounts for about 0.1-1% of the mass percentage of metals in the glass ink.

[0055] In addition, the glass powder is melted in a reducing state, which effectively avoids the case that the color-developing ions (copper, chromium, cobalt) in the glass powder or inorganic pigments are reduced by the inorganic additives with reducing property during high-temperature sintering, thereby the color development occurs.

[0056] In some embodiments, the reducing atmosphere for the melting of the glass raw material can be provided by introducing nitrogen or helium into the reaction container.

[0057] In other embodiments, the rapid cooling can accelerate the formation of the crude glass.

[0058] S2. The glass powder, photocuring ink oil, inorganic pigment, inorganic additive and organic additive are mixed according to the mass fraction of 40-80%, 10-25%, 5-30%, 1-8%, 0-5%, and then ground to obtain the automobile rear windshield shading silver line ink, wherein the inorganic additive includes one or more of boron powder, zinc powder, iron powder, bismuth powder, sulfur powder, aluminum powder and silicon powder.

[0059] In some embodiments, the photocuring ink oil contains a photosensitive prepolymer, an active diluent, a photoinitiator and a polymerization inhibitor.

[0060] The photosensitive prepolymer comprises one or more resins of acrylated epoxy resin, unsaturated polyester, polyurethane and polysulfide / polyene photocuring resin, and the mass fraction of the photosensitive prepolymer in the photocuring ink vehicle is 60%-90%;

[0061] The active diluent comprises one or more of ethylene glycol diacrylate, propylene glycol diacrylate and other glycol diacrylates, and the mass fraction of the active diluent in the photocuring ink vehicle is 10-20%;

[0062] The photoinitiator comprises one or more of benzoin and its derivatives, acetophenone derivatives and triaryl sulfonium salts, and the mass fraction of the photoinitiator in the photocuring ink vehicle is 1-5%;

[0063] The polymerization inhibitor comprises one or more of p-hydroxyanisole, hydroquinone and 2,6-di-tert-butyl-p-cresol, and the mass fraction of the polymerization inhibitor in the photocuring ink vehicle is 0.1%-0.01%;

[0064] The selection of the photocuring resin follows the following characteristics: stable performance in the process of ink preparation, easy curing and easy decomposition of the photocuring resin, and no carbon residue after burning of the photocuring resin, which does not affect the performance of the ink.

[0065] Exemplarily, the inorganic pigment is one or more of copper-chromium black, iron-chromium-manganese black and cobalt black.

[0066] In other embodiments, the inorganic auxiliary agent comprises silicon powder and inorganic powder, and the inorganic powder comprises one or more of boron powder, zinc powder, iron powder, bismuth powder, sulfur powder and aluminum powder.

[0067] By adding the inorganic auxiliary agent, the change of elemental silver to ionic state is prevented, the activity of elemental silver at high temperature is reduced, the diffusion of silver ions is effectively prevented, the silver paste shielding performance of the glass ink is improved, and the influence of silver ion diffusion on the performance of the glass ink is avoided.

[0068] The combination of silicon powder and other powders is preferred, so that the SI-O structure of the glass phase is more dense, and superior acid and alkali resistance is achieved; and the metal element in the inorganic powder has a greater reducing property than silver ions, effectively reducing the activity of silver ions, avoiding the migration of silver ions under subsequent high temperature conditions, causing color difference between the glass ink and the glass contact surface, and affecting the appearance of the glass.

[0069] The particle size of the inorganic auxiliary agent can be D50 of 2-5 μm, so that the metal ion powder is uniformly dispersed in the glass ink, so that the blocking ability of the inorganic auxiliary agent to silver ion diffusion and the optimization degree of the performance of the glass ink are maximized.

[0070] The organic auxiliary agent includes the following mass percentage of components: defoaming agent 10-50%, leveling agent 10-70%, dispersing agent 20-40%.

[0071] The defoaming agent includes one or more of BYK-060N, BYK-066N, BYK-052 and BYK-053, which eliminates bubbles by changing the internal tension of the glass ink.

[0072] Among them, BYK-060N, BYK-066N, BYK-052 and BYK-053 are defoaming agents commonly used in the field of automotive glass ink produced by BYK company.

[0073] The leveling agent includes one or more of BYK-350, BYK-352, BYK-354, which adjusts the flowability by changing the surface tension of the glass ink.

[0074] Among them, BYK-350, BYK-352, BYK-354 are leveling agents commonly used in the field of automotive glass ink produced by BYK company.

[0075] The dispersing agent is one or more of DISPERBYK-115, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-164, DISPERBYK-165, which further adjusts the emulsification and dispersibility of the glass ink.

[0076] Among them, the dispersing agent DISPERBYK-115, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-164, DISPERBYK-165 are commonly used dispersing agents in the field of automotive ink produced by BYK company.

[0077] The glass powder, photocuring ink oil, inorganic pigment, inorganic auxiliary agent and organic auxiliary agent obtained in step S1 can be uniformly dispersed by high-speed stirring, and the hydraulic three-roller machine is tightly rolled and ground for more than three times to obtain a homogeneous slurry with fine particles, that is, a glass ink.

[0078] Step S2 further includes vacuum filtration of the glass ink, and dispensing after removing false large particles and impurities.

[0079] The application also provides a photocuring method for a silver line ink for shielding the rear windshield of an automobile.

[0080] The application of the photocuring method for a silver line ink for shielding the rear windshield of an automobile as above can include the following steps:

[0081] S10. The silver line ink for shielding the rear windshield of the automobile is coated on the surface of the rear windshield of the automobile and then photocured, wherein the energy density of the photocuring is 800-900 mJ / cm 2 .

[0082] In some embodiments, the photocuring can be lamp irradiation of the rear windshield of the automobile coated with the silver line ink for shielding the rear windshield of the automobile by using an ultraviolet lamp, and the surface can be changed after 2-3 s, wherein the energy density of the ultraviolet lamp is 800-900 mJ / cm 2 Compared with the drying and curing of the glass ink in the traditional technology, the photocuring has better energy-saving and emission-reducing effects.

[0083] In the common manufacturing technology of the glass ink, for the ink mixing oil component, the traditional resin, solvent, related additives and other components in the ink are mixed and then rolled. The product needs to go through a drying process before being sintered and formed on the automobile glass, which causes the increase of energy consumption, VOCs (organic waste gas) emission and processing time.

[0084] The present application belongs to the field of ink, and is a photocuring method for automobile windshield glass ink. The photocuring ink is coated on the automobile glass, and the traditional drying process is replaced by the photocuring method.

[0085] The photocuring method used in the present application mainly has the following advantages:

[0086] 1. Fast curing, which can be completed within a few seconds, greatly shortening the processing time and improving the production efficiency;

[0087] 2. Curing by ultraviolet lamp device irradiation without the need for oven heating and drying, which reduces the energy consumption cost, simplifies the deployment of related equipment, and reduces carbon emissions;

[0088] 3. Almost no VOCs (organic waste gas) emission during the curing process, and the photocuring resin is completely burned in the furnace during the subsequent high-temperature sintering process, without solid waste generation, which is environmentally friendly, efficient, and reduces the environmental emission pressure of enterprises;

[0089] 4. Automation operation and curing can be realized, which improves the automation degree of production and thus improves the production efficiency and economic benefits.

[0090] In summary, the photocuring method of the automobile glass ink has great advantages over the existing ink.

[0091] S20. The automobile rear windshield treated in step S10 is sintered, wherein the sintering temperature is 700-850 DEG C. During the sintering of the automobile rear windshield treated in step S10, the organic material therein is carbonized, and the resin and monomer are burned in the furnace, which has the effects of energy saving and VOCs (organic waste gas) emission reduction, and is more friendly to the environment.

[0092] In the commonly used glass ink making technology, the ink adjusting oil component is usually mixed with traditional resin, solvent, related additives, etc., and then added into other components of the ink for mixing and rolling. The product needs to be dried before sintering and forming of the automobile glass, which causes increase of energy consumption, VOCs (organic waste gas) emission, and lengthening of processing time, etc.

[0093] The present application belongs to the field of light-cured automobile windshield glass ink, which is coated on the automobile glass and replaces the traditional drying process by light-curing.

[0094] In summary, the light-cured automobile glass ink has great advantages compared with the existing ink.

[0095] In order to facilitate further understanding of the present application by those skilled in the art, examples are given as follows:

[0096] Example 1

[0097] S1. Preparation of glass powder: melt the glass raw materials: silica 20%, titanium dioxide 15%, zirconium dioxide 5%, bismuth oxide 20%, boron oxide 20%, aluminum oxide 5%, potassium oxide 3%, lithium oxide 10%, and phosphorus pentoxide 2% under the conditions of reducing atmosphere and temperature of 1250-1350℃ for 20-30min, and then cool down to obtain coarse glass; ball mill the coarse glass to obtain glass powder;

[0098] The particle size of the glass powder is 1-10μm;

[0099] S2. Mix the above glass powder, light-cured ink adjusting oil, inorganic pigment, inorganic additive, and organic additive according to the mass fraction of 40%, 25%, 25%, 8%, and 2%, and then grind to obtain glass ink;

[0100] The light-cured ink adjusting oil is a photosensitive prepolymer, active diluent, photoinitiator, and polymerization inhibitor with a mass ratio of 82:14:4:0.01. The photosensitive prepolymer is a resin with a mass ratio of bisphenol A epoxy acrylate to 1,6-hexanediol diacrylate of 1:1; the active diluent is a mixture of tripropylene glycol diacrylate and 1,6-hexanediol diacrylate; the photoinitiator is a mixture of 2-hydroxy-2-methyl-1-phenyl-1-propanone and o-benzoylbenzoic acid methyl ester; and the polymerization inhibitor is 2,6-di-tert-butyl-p-cresol.

[0101] The inorganic auxiliary agent is silicon powder, boron powder and iron powder with a mass ratio of 3:3:2. The organic auxiliary agent components are defoaming agent, leveling agent and dispersing agent with a mass ratio of 5:1:4. The defoaming agent is BYK-060N and BYK-066N with a mass ratio of 2:3. The leveling agent is BYK-350 and BYK-352 with a mass ratio of 1:2. The dispersing agent is DISPERBYK-115 and DISPERBYK-160 with a mass ratio of 2:1.

[0102] The automobile rear windshield shielding silver line ink prepared in Example 1 is applied to the surface of the automobile rear windshield and photocured, wherein the energy density of the photocuring is 800 mJ / cm 2 ;

[0103] The automobile rear windshield subjected to the step treatment is sintered again, wherein the sintering temperature is 700-850℃, and the automobile rear windshield prepared is shown in the actual figure Figure 1 、 Figure 2 .

[0104] Example 2

[0105] S1. Preparation of glass powder: Glass raw materials: silicon dioxide 45%, titanium dioxide 1%, zirconium dioxide 4%, bismuth trioxide 0%, boron oxide 25%, aluminum oxide 0%, potassium oxide 1%, lithium oxide 5%, phosphorus pentoxide 8%, magnesium oxide 11% are melted under a reducing atmosphere at a temperature of 1250-1350℃ for 20-30 min, and then cooled to obtain coarse glass. The coarse glass is ball milled to obtain glass powder;

[0106] The particle size of the glass powder is 1-10 μm;

[0107] S2. The above glass powder, photocuring ink oil, inorganic pigment, inorganic auxiliary agent and organic auxiliary agent are mixed in a mass fraction of 80%, 5%, 10%, 5% and 0% respectively, and then ground to obtain a glass ink;

[0108] The photocuring ink oil is photosensitive prepolymer, active diluent, photoinitiator and polymerization inhibitor with a mass ratio of 93:18:6:0.015. The photosensitive prepolymer is a mixture of bisphenol A epoxy acrylate resin and 1,6-hexanediol diacrylate with a mass ratio of 1.2:1. The active diluent is a mixture of tripropylene glycol diacrylate and 1,6-hexanediol diacrylate. The photoinitiator is a mixture of 2-hydroxy-2-methyl-1-phenyl-1-propanone and methyl o-benzoylbenzoate. The polymerization inhibitor is 2,6-di-tert-butyl-p-cresol. The inorganic pigment is iron chromium manganese black. The inorganic auxiliary agent is bismuth powder, iron powder and silicon powder with a mass ratio of 4:3:1;

[0109] The inorganic auxiliary agent is silicon powder, boron powder and iron powder with a mass ratio of 3:3:2. The organic auxiliary agent components and mass ratio are defoaming agent, leveling agent and dispersing agent with a mass ratio of 5:1:4. The defoaming agent is BYK-052 and BYK-053 with a mass ratio of 1:2; the leveling agent is BYK-352 and BYK-354 with a mass ratio of 1:1; and the dispersing agent is DISPERBYK-161 and DISPERBYK-162 with a mass ratio of 2:1.

[0110] The automobile rear windshield shielding silver line ink prepared in Example 2 is light-cured on the surface of the automobile rear windshield, wherein the energy density of light-curing is 800 mJ / cm 2 ;

[0111] The automobile rear windshield shielding silver line ink prepared in Example 2 is light-cured on the surface of the automobile rear windshield, wherein the energy density of light-curing is 800 mJ / cm Figure 1 、 Figure 2 The automobile rear windshield shielding silver line ink prepared in Example 2 is light-cured on the surface of the automobile rear windshield, wherein the energy density of light-curing is 800 mJ / cm

[0112] Comparative Example 1

[0113] S1. Preparation of glass powder: melt the glass raw materials: silicon dioxide 45%, titanium dioxide 10%, zirconium dioxide 1%, bismuth trioxide 30%, boron oxide 4%, aluminum oxide 0%, potassium oxide 3%, lithium oxide 7%, phosphorus pentoxide 2% under the conditions of a reducing atmosphere and a temperature of 1250-1350°C for 20-30 min, and then cool down to obtain crude glass; and ball mill the crude glass to obtain glass powder;

[0114] The particle size of the glass powder is 1-10 μm;

[0115] S2. Mix the above glass powder, light-curing ink oil, inorganic pigment, inorganic auxiliary agent and organic auxiliary agent according to a mass fraction of 60%, 20%, 10%, 8% and 2%, and then grind to obtain glass ink;

[0116] The organic auxiliary agent components and mass ratio are defoaming agent, leveling agent and dispersing agent with a mass ratio of 5:1:4. The defoaming agent is BYK-052 and BYK-053 with a mass ratio of 1:2; the leveling agent is BYK-350 and BYK-352 with a mass ratio of 2:5; and the dispersing agent is DISPERBYK-164 and DISPERBYK-165 with a mass ratio of 1:4.

[0117] The automobile rear windshield shielding silver line ink prepared in Comparative Example 1 is baked in a 130°C oven for 5 min, and then the automobile rear windshield after the step is sintered, wherein the sintering temperature is 700-850°C;

[0118] Comparative Example 2

[0119] The other operations of Comparative Example 2 are the same as those of Example 1, only the step of adding inorganic additives is removed.

[0120] Comparative Example 3

[0121] The other steps of Comparative Example 3 are the same as those of Example 1, only the condition of melting under a reducing atmosphere is removed.

[0122] The performance of the glass inks prepared in Examples 1-2 and Comparative Examples 1-3 is shown in Table 1:

[0123]

[0124] It can be seen that the silver line ink for shielding the rear windshield of a car by light curing in Examples 1 and 2 is superior to the traditional drying method in Comparative Example 1 in terms of silver paste shielding performance and acid resistance, and it can be seen that the light curing method is excellent for the performance of the finished glass ink.

[0125] And the silver paste shielding performance and acid resistance of Comparative Example 2 without adding inorganic additives and Comparative Example 3 without melting under a reducing atmosphere are not as good as those of the examples, and it can be seen that the addition of inorganic additives and the reducing atmosphere are excellent for the performance optimization of the finished glass ink.

[0126] In the above technical scheme of the present application, the above is only the preferred embodiment of the present application, and does not limit the patent scope of the present application, and any equivalent structural transformation made under the technical concept of the present application, or direct / indirect application in other related technical fields is included in the patent protection scope of the present application.

Claims

1. A method for preparing a light-curing silver line ink for shielding automobile rear windshields, characterized in that: The following steps are involved: S1. Melting the glass raw materials in a reducing atmosphere at a temperature of 1250-1350°C for 20-30 minutes and then cooling to obtain a coarse glass; ball-milling the coarse glass to obtain a glass powder; Wherein, the particle size of the glass powder is 1-10 μm; S2. The glass powder, light-curable varnish, inorganic pigment, inorganic additive, and organic additive are mixed in mass fractions of 40-80%, 10-25%, 5-30%, 1-8%, and 0-5%, respectively, and then ground to obtain the automotive rear windshield shielding silver line ink, wherein the inorganic additive comprises silicon powder and inorganic powder, the inorganic powder comprises one or more of boron powder, zinc powder, iron powder, bismuth powder, sulfur powder, and aluminum powder, and the glass powder does not contain sodium. The glass raw materials include the following components in mass percentage: 20-45% silicon dioxide, 1-15% titanium dioxide, 1-8% zirconium dioxide, 20-60% bismuth trioxide, 4-25% boron oxide, 0-6% aluminum oxide, 1-3% potassium oxide, 0-10% lithium oxide, 0-8% phosphorus pentoxide, and 0-15% magnesium oxide.

2. The method for preparing a light-curing silver line ink for automobile rear windshield according to claim 1, characterized in that: The inorganic pigment is one or more of copper chrome black, iron chrome manganese black and cobalt black.

3. The method for preparing a light-curing silver line ink for automobile rear windshield according to claim 1, characterized in that: The photocurable varnish comprises the following components in percentage by mass: 60%-90% of a photosensitive prepolymer, 10%-20% of a reactive diluent, 1%-5% of a photoinitiator, and 0.01%-0.1% of a polymerization inhibitor, and the sum of the percentages by mass of the components is 100%, wherein; The photosensitive prepolymer includes one or more of acrylated epoxy resin, unsaturated polyester, polyurethane and polythiol / polyene photocurable resin; The reactive diluent includes glycol diacrylate; The photoinitiator comprises one or more of benzoin and its derivatives, and acetophenone derivatives, and the mass fraction of the photoinitiator in the photocurable varnish is 1-5%; The polymerization inhibitor comprises one or more of p-hydroxyanisole, hydroquinone and 2,6-di-tert-butyl-p-cresol.

4. The method for preparing a light-curing silver line ink for automobile rear windshield according to claim 1, characterized in that: The organic additives include a defoamer, a leveling agent and a dispersant, wherein the mass ratio of the defoamer, the leveling agent and the dispersant is 0-0.5:0-1:0-2.

5. The method for preparing a light-curing silver line ink for shielding automobile rear windshield according to claim 4, characterized in that: The defoamer includes one or more of BYK-060N, BYK-066N, BYK-052 and BYK-053; the leveling agent includes one or more of BYK-350, BYK-352 and BYK-354; and the dispersant includes one or more of DISPERBYK-115, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-164 and DISPERBYK-165.

6. Use of the light-curing automobile rear windshield shielding silver line ink prepared by the preparation method according to any one of claims 1 to 5 in automobile rear windshields.

7. The use according to claim 6, characterized in that Including steps: S10. Apply the automobile rear windshield shielding silver line ink to the surface of the automobile rear windshield and then light cure it, wherein the energy density of the light curing is 800-900 mJ / cm 2 ; S20. Sintering the automobile rear windshield processed in step S10, wherein the sintering temperature is 700-850°C.

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