Preparation method of ink for automobile tempered glass

Abstract

The application provides a preparation method of ink for automobile tempered glass and belongs to the technical field of ink preparation. The 3,6-dimercapto pyridazine respectively and 2-(tributylstannyl)-2-methyl acrylate, bisphenol A epoxy vinyl resin are subjected to double bond and mercapto click reaction; the bisphenol A epoxy resin containing pyridazine group and stannyl group is obtained; the ink for automobile tempered glass prepared by the application is gradually fused and flowed after high-temperature sintering, the crystal of tin oxide fills the gap between the resin molecules, so that the surface layer of the glaze layer is the most dense and has no cavity and the like; the structure can improve the adhesion resistance of the ink, so that the ink is more suitable for the surface coating of automobile tempered glass; the gloss of the glaze layer is gradually improved, the acid and alkali resistance is enhanced, meanwhile, the surface crystallization is increased, and the adhesion resistance of the glaze layer is improved.

Description

Technical Field

[0001] This invention relates to the field of ink preparation technology, and more specifically, to a method for preparing ink for automotive tempered glass. Background Technology

[0002] Automotive tempered glass ink is a glass-ceramic ink used on the edges of automotive tempered glass. It is primarily composed of ink oil, low-melting-point glass powder, high-temperature ceramic pigments, and additives, all ground together. The ink is screen-printed onto a glass substrate, dried at 150°C, and then transferred to a high-temperature tempering furnace for hot bending and sintering. Finally, it is cooled and molded to obtain tempered glass covered with an ink enamel layer. The ink effectively reduces ultraviolet transmittance, prevents chemical changes in the adhesive bonding the glass and the vehicle body, and simultaneously masks conductive silver paste, contributing to the aesthetic appeal of the automotive appearance.

[0003] Chinese Patent CN111333335B relates to the field of ink technology. To improve the acid resistance of glass inks, this invention employs a two-step melting method to produce acid-resistant glass powder. First, a precursor microcrystalline powder is pre-melted. Then, appropriate types and proportions of oxides and elements are added through suitable batching materials. After secondary melting, the resulting glass powder is sintered in the ink, resulting in a significant accumulation of silica on the ink surface. This silica enrichment improves the density of the network structure on the ink surface, greatly enhancing the ink's acid resistance. The beneficial effects of this invention are: after sintering at 560-720℃ for 2.5-10 minutes, this glass ink exhibits excellent acid resistance while also maintaining good opacity, adhesion, coefficient of thermal expansion, and anti-sticking properties.

[0004] Chinese Patent CN110655822A relates to a method for preparing a high-acid-resistant and anti-sticking automotive tempered glass ink, belonging to the field of automotive materials technology. This invention uses cyclohexane, dicyclopentadiene hydrogenated resin, glycerol, and paraffin oil as raw materials to prepare an ink base, and adds erucamide to prepare a high-acid-resistant and anti-sticking automotive tempered glass ink. The dicyclopentadiene hydrogenated resin has advantages such as light color, low odor, strong heat resistance, and high stability. After hydrogenation modification, the resin exhibits good antioxidant and acid / alkali resistance. The addition of glycerol and paraffin oil effectively improves the stability of the ink base. Erucamide, a derivative of erucic acid, has a high melting point and good thermal stability. In the high-acid-resistant and anti-sticking automotive tempered glass ink, it plays a role in smoothing, anti-adhesion, and anti-fouling, delaying pigment and filler sedimentation and agglomeration, aiding redispersibility, increasing the abrasion resistance, scratch resistance, and surface smoothness of the ink, and particularly improving its smoothness and anti-sticking properties.

[0005] Chinese Patent CN110028831A relates to a lead-free glass ink for automotive tempered glass and its preparation method. The glass ink is composed of lead-free low-melting-point glass powder, inorganic pigments, ink oil, and additives. The lead-free low-melting-point glass powder is composed of the following molar percentage components: SiO2 32.0%-32.6%, B2O3 15.1%-15.7%, Bi2O3 12.2%-12.8%, ZnO2 2.8%-23.4%, TiO2 4.0%-4.6%, Al2O3 2.6%-3.2%, Li2O 2.2%-2.8%, Na2O 2.2%-2.4%, CaO 2.0%-2.6%, ZrO2 1.8%-2.0%, and Y2O3 0.45%-0.50%. This lead-free glass ink has good storage properties, printability, anti-sticking properties, acid and alkali resistance, and opacity, making it suitable for use in automotive tempered glass.

[0006] The inks prepared by the above patents and existing technologies have poor anti-sticking properties: the sintered ink glaze layer and the molding die covered with glass fiber mold cloth will stick together, resulting in damage to the glaze surface; and the ink has poor acid and alkali resistance. Summary of the Invention

[0007] To address the above problems, this invention provides a method for preparing ink for automotive tempered glass, comprising the following steps:

[0008] S1: Weigh 15-25 parts of ink thinner, 40-50 parts of low melting point glass powder, 20-30 parts of high temperature ceramic pigment, 1-3 parts of dispersant, 1-3 parts of leveling agent, and 1-3 parts of thixotropic agent according to the weight ratio. Stir at 1000-2000 r / min for 20-40 min, and then ultrasonically disperse for 20-40 min.

[0009] S2: Continue grinding until the fineness is below 10μm;

[0010] S3: Then add a thinner to obtain ink for automotive tempered glass.

[0011] Furthermore, in another embodiment of the present invention, the ink oil is composed of 10-20 parts of ink binder and 60-80 parts of solvent.

[0012] Furthermore, in another embodiment of the present invention, the ink binder consists of 3-7 parts of tin-doped modified epoxy resin, 40-50 parts of bisphenol A type epoxy resin NPEL128, and 10-18 parts of bisphenol A type epoxy resin E20, which are physically mixed uniformly.

[0013] Furthermore, in another embodiment of the present invention, the method for preparing the tin-doped modified epoxy resin is as follows:

[0014] Add 25-50 parts by mass of 3,6-dimercaptopyridazine, 0.5-2 parts by mass of methyl 2-(tributyltinalkyl)-2-acrylate, 200-230 parts by mass of bisphenol A epoxy vinyl resin, and 0.3-0.9 parts by mass of photoinitiator to a stirred tank, and stir at 50-60°C for 30-70 minutes; under argon protection, irradiate with ultraviolet light with a wavelength of 320nm-360nm for 20-40 minutes to initiate a click reaction to obtain tin-doped modified epoxy resin.

[0015] Furthermore, in another embodiment of the present invention, the photoinitiator is one of benzoin dimethyl ether or 2-hydroxy-2-methyl-1-phenyl-1-propanone.

[0016] Furthermore, in another embodiment of the present invention, the solvent is one or more of glycerol, paraffin oil, cyclohexane, turpentine, terpineol, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol, diethylene glycol butyl ether acetate, and hydrogenated castor oil.

[0017] Furthermore, in another embodiment of the present invention, the dispersant is sodium oleate, carboxylate, sulfate ester, or sulfonate.

[0018] Furthermore, in another embodiment of the present invention, the leveling agent is an acrylate leveling agent.

[0019] Furthermore, in another embodiment of the present invention, the thixotropic agent is an organic thixotropic agent RC-HST.

[0020] Furthermore, in another embodiment of the present invention, the bisphenol A epoxy vinyl resin is a commercially available product, such as TM-V201 or Fuchem854.

[0021] Reaction mechanism:

[0022] The preparation mechanism of the tin-doped modified epoxy resin is as follows:

[0023] 3,6-Dimercaptopyridazine reacted with methyl 2-(tributyltinalkyl)-2-acrylate and bisphenol A epoxy vinyl resin respectively via double bond and mercapto click reactions to obtain bisphenol A epoxy resin containing pyridazine and tinalkyl groups.

[0024] Technical effects:

[0025] The present invention provides a method for preparing ink for automotive tempered glass, which, compared with the prior art, has the following significant advantages:

[0026] The automotive tempered glass ink prepared by this invention, after high-temperature sintering, allows the low-melting-point glass powder in the ink to gradually melt and flow. The crystallization of tin oxide fills the gaps between resin molecules, making the glaze surface the densest and free of voids. This structure improves the ink's anti-stick properties, making it more suitable for use as a surface coating for automotive tempered glass. The gloss of the glaze gradually increases, its acid and alkali resistance is enhanced, and the increased surface crystallization further improves the glaze's anti-stick properties. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0028] The method for testing anti-sticking properties is as follows: the ink is screen-printed onto a glass slide, then dried in a 150℃ oven for 4 minutes, removed and placed in a muffle furnace, sintered at 660℃ for 6 minutes, the glass slide is removed, a glass fiber mold cloth is immediately placed on it and a 2kg weight is placed on the mold cloth, held for 5 seconds, the weight and mold cloth are removed, and the ink glaze surface is observed to see if there are any traces of the mold cloth. If there are no traces, it means that the anti-sticking property meets the standard.

[0029] The acid resistance test method is as follows: ink is screen-printed onto a glass slide, then dried in a 150℃ oven for 4 minutes, removed and placed in a muffle furnace, sintered at 660℃ for 6 minutes, the glass slide is removed, cooled to room temperature, and then immersed in a 0.1mol / L sulfuric acid solution at 80℃ for 300 hours, and its mass loss rate is tested.

[0030] The method for testing alkali resistance is as follows: ink is screen-printed onto a glass slide, then dried in a 150°C oven for 4 minutes, removed and placed in a muffle furnace for sintering at 660°C for 6 minutes. After removing the glass slide and cooling it to room temperature, it is immersed in a 0.5% NaOH solution at room temperature for 300 hours, and its mass loss rate is tested.

[0031] Example 1

[0032] A method for preparing ink for automotive tempered glass, comprising the following steps:

[0033] S1: Weigh 15g of ink thinner, 40g of low melting point glass powder, 20g of high temperature ceramic pigment, 1g of dispersant, 1g of leveling agent, and 1g of thixotropic agent. Stir at 1000r / min for 20min and then ultrasonically disperse for 20min.

[0034] S2: Continue grinding until the fineness is below 10μm;

[0035] S3: Then add a thinner to obtain ink for automotive tempered glass.

[0036] The ink oil is formulated from 10g of ink binder and 60g of solvent.

[0037] The ink binder consists of 3g of tin-doped modified epoxy resin, 40g of bisphenol A type epoxy resin NPEL128, and 10g of bisphenol A type epoxy resin E20, which are physically mixed evenly.

[0038] The preparation method of the tin-doped modified epoxy resin is as follows:

[0039] 25g of 3,6-dimercaptopyridazine, 0.5g of methyl 2-(tributyltinalkyl)-2-acrylate, 200g of bisphenol A epoxy vinyl resin, and 0.3g of photoinitiator were added to a stirred tank and stirred at 50°C for 30 minutes. Under argon protection, the mixture was irradiated with ultraviolet light at a wavelength of 320nm for 20 minutes to initiate a click reaction, thus obtaining tin-doped modified epoxy resin.

[0040] The photoinitiator is benzoin dimethyl ether.

[0041] The solvent is glycerol.

[0042] The dispersant is sodium oleate.

[0043] The leveling agent is an acrylate leveling agent.

[0044] The thixotropic agent is an organic thixotropic agent RC-HST.

[0045] The bisphenol A epoxy vinyl resin mentioned is the commercially available product TM-V201.

[0046] Example 2

[0047] A method for preparing ink for automotive tempered glass, comprising the following steps:

[0048] S1: Weigh 18g of ink thinner, 43g of low melting point glass powder, 24g of high temperature ceramic pigment, 2g of dispersant, 2g of leveling agent, and 2g of thixotropic agent. Stir at 1400r / min for 25min and then ultrasonically disperse for 25min.

[0049] S2: Continue grinding until the fineness is below 10μm;

[0050] S3: Then add a thinner to obtain ink for automotive tempered glass.

[0051] The ink oil is formulated from 13g of ink binder and 65g of solvent.

[0052] The ink binder consists of 4g of tin-doped modified epoxy resin, 43g of bisphenol A type epoxy resin NPEL128, and 12g of bisphenol A type epoxy resin E20, which are physically mixed evenly.

[0053] The preparation method of the tin-doped modified epoxy resin is as follows:

[0054] 30g of 3,6-dimercaptopyridazine, 1g of methyl 2-(tributyltinalkyl)-2-acrylate, 210g of bisphenol A epoxy vinyl resin, and 0.5g of photoinitiator were added to a stirred tank and stirred at 55°C for 40 minutes. Under argon protection, the mixture was irradiated with ultraviolet light at a wavelength of 330nm for 25 minutes to initiate a click reaction, thus obtaining tin-doped modified epoxy resin.

[0055] The photoinitiator is benzoin dimethyl ether.

[0056] The solvent is paraffin oil.

[0057] The dispersant is a carboxylate.

[0058] The leveling agent is an acrylate leveling agent.

[0059] The thixotropic agent is an organic thixotropic agent RC-HST.

[0060] The bisphenol A epoxy vinyl resin mentioned is the commercially available product TM-V201.

[0061] Example 3

[0062] A method for preparing ink for automotive tempered glass, comprising the following steps:

[0063] S1: Weigh 23g of ink oil, 48g of low melting point glass powder, 28g of high temperature ceramic pigment, 2g of dispersant, 2g of leveling agent, and 2g of thixotropic agent. Stir at 1800r / min for 35min and then ultrasonically disperse for 35min.

[0064] S2: Continue grinding until the fineness is below 10μm;

[0065] S3: Then add a thinner to obtain ink for automotive tempered glass.

[0066] The ink oil is formulated from 18g of ink binder and 75g of solvent.

[0067] The ink binder consists of 6g of tin-doped modified epoxy resin, 48g of bisphenol A type epoxy resin NPEL128, and 16g of bisphenol A type epoxy resin E20, which are physically mixed evenly.

[0068] The preparation method of the tin-doped modified epoxy resin is as follows:

[0069] 45g of 3,6-dimercaptopyridazine, 1.5g of methyl 2-(tributyltinalkyl)-2-acrylate, 220g of bisphenol A epoxy vinyl resin, and 0.8g of photoinitiator were added to a stirred tank and stirred at 55°C for 60 minutes. Under argon protection, the mixture was irradiated with ultraviolet light at a wavelength of 350nm for 35 minutes to initiate a click reaction, thus obtaining tin-doped modified epoxy resin.

[0070] The photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone.

[0071] The solvent is turpentine.

[0072] The dispersant is a sulfate ester salt.

[0073] The leveling agent is an acrylate leveling agent.

[0074] The thixotropic agent is an organic thixotropic agent RC-HST.

[0075] The bisphenol A epoxy vinyl resin mentioned is the commercially available product Fuchem854.

[0076] Example 4

[0077] A method for preparing ink for automotive tempered glass, comprising the following steps:

[0078] S1: Weigh 25g of ink oil, 50g of low melting point glass powder, 30g of high temperature ceramic pigment, 3g of dispersant, 3g of leveling agent, and 3g of thixotropic agent. Stir at 2000r / min for 40min and then ultrasonically disperse for 40min.

[0079] S2: Continue grinding until the fineness is below 10μm;

[0080] S3: Then add a thinner to obtain ink for automotive tempered glass.

[0081] The ink oil is formulated from 0g of ink binder and 80g of solvent.

[0082] The ink binder consists of 7g of tin-doped modified epoxy resin, 50g of bisphenol A type epoxy resin NPEL128, and 18g of bisphenol A type epoxy resin E20, which are physically mixed evenly.

[0083] The preparation method of the tin-doped modified epoxy resin is as follows:

[0084] 50g of 3,6-dimercaptopyridazine, 2g of methyl 2-(tributyltinalkyl)-2-acrylate, 230g of bisphenol A epoxy vinyl resin, and 0.9g of photoinitiator were added to a stirred tank and stirred at 60°C for 70 minutes. Under argon protection, the mixture was irradiated with ultraviolet light at a wavelength of 360nm for 40 minutes to initiate a click reaction, thus obtaining tin-doped modified epoxy resin.

[0085] The photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone.

[0086] The solvent is diethylene glycol ethyl ether.

[0087] The dispersant is a sulfonate.

[0088] The leveling agent is an acrylate leveling agent.

[0089] The thixotropic agent is an organic thixotropic agent RC-HST.

[0090] The bisphenol A epoxy vinyl resin mentioned is the commercially available product Fuchem854.

[0091] Comparative Example 1

[0092] A method for preparing ink for automotive tempered glass, comprising the following steps:

[0093] S1: Weigh 15g of ink thinner, 40g of low melting point glass powder, 20g of high temperature ceramic pigment, 1g of dispersant, 1g of leveling agent, and 1g of thixotropic agent. Stir at 1000r / min for 20min and then ultrasonically disperse for 20min.

[0094] S2: Continue grinding until the fineness is below 10μm;

[0095] S3: Then add a thinner to obtain ink for automotive tempered glass.

[0096] The ink oil is formulated from 10g of ink binder and 60g of solvent.

[0097] The ink binder consists of 3g of bisphenol A epoxy vinyl resin, 40g of bisphenol A type epoxy resin NPEL128, and 10g of bisphenol A type epoxy resin E20, which are physically mixed evenly.

[0098] The solvent is glycerol.

[0099] The dispersant is sodium oleate.

[0100] The leveling agent is an acrylate leveling agent.

[0101] The thixotropic agent is an organic thixotropic agent RC-HST.

[0102] The bisphenol A epoxy vinyl resin mentioned is the commercially available product TM-V201.

[0103] Comparative Example 2

[0104] A method for preparing ink for automotive tempered glass, comprising the following steps:

[0105] S1: Weigh 15g of ink thinner, 40g of low melting point glass powder, 20g of high temperature ceramic pigment, 1g of dispersant, 1g of leveling agent, and 1g of thixotropic agent. Stir at 1000r / min for 20min and then ultrasonically disperse for 20min.

[0106] S2: Continue grinding until the fineness is below 10μm;

[0107] S3: Then add a thinner to obtain ink for automotive tempered glass.

[0108] The ink oil is formulated from 10g of ink binder and 60g of solvent.

[0109] The ink binder consists of 3g of tin-doped modified epoxy resin, 40g of bisphenol A type epoxy resin NPEL128, and 10g of bisphenol A type epoxy resin E20, which are physically mixed evenly.

[0110] The preparation method of the tin-doped modified epoxy resin is as follows:

[0111] 0.5g of methyl 2-(tributyltinalkyl)-2-acrylate, 200g of bisphenol A epoxy vinyl resin, and 0.3g of photoinitiator were added to a stirred tank and stirred at 50°C for 30 minutes. Under argon protection, the mixture was irradiated with ultraviolet light at a wavelength of 320nm for 20 minutes to initiate a click reaction, thus obtaining tin-doped modified epoxy resin.

[0112] The photoinitiator is benzoin dimethyl ether.

[0113] The solvent is glycerol.

[0114] The dispersant is sodium oleate.

[0115] The leveling agent is an acrylate leveling agent.

[0116] The thixotropic agent is an organic thixotropic agent RC-HST.

[0117] The bisphenol A epoxy vinyl resin mentioned is the commercially available product TM-V201.

[0118] Comparative Example 3

[0119] A method for preparing ink for automotive tempered glass, comprising the following steps:

[0120] S1: Weigh 15g of ink thinner, 40g of low melting point glass powder, 20g of high temperature ceramic pigment, 1g of dispersant, 1g of leveling agent, and 1g of thixotropic agent. Stir at 1000r / min for 20min and then ultrasonically disperse for 20min.

[0121] S2: Continue grinding until the fineness is below 10μm;

[0122] S3: Then add a thinner to obtain ink for automotive tempered glass.

[0123] The ink oil is formulated from 10g of ink binder and 60g of solvent.

[0124] The ink binder consists of 3g of tin-doped modified epoxy resin, 40g of bisphenol A type epoxy resin NPEL128, and 10g of bisphenol A type epoxy resin E20, which are physically mixed evenly.

[0125] The preparation method of the tin-doped modified epoxy resin is as follows:

[0126] 25g of 3,6-dimercaptopyridazine, 200g of bisphenol A epoxy vinyl resin, and 0.3g of photoinitiator were added to a stirred tank and stirred at 50°C for 30 minutes. Under argon protection, the mixture was irradiated with ultraviolet light at a wavelength of 320nm for 20 minutes to initiate a click reaction, thus obtaining tin-doped modified epoxy resin.

[0127] The photoinitiator is benzoin dimethyl ether.

[0128] The solvent is glycerol.

[0129] The dispersant is sodium oleate.

[0130] The leveling agent is an acrylate leveling agent.

[0131] The thixotropic agent is an organic thixotropic agent RC-HST.

[0132] The bisphenol A epoxy vinyl resin mentioned is the commercially available product TM-V201.

[0133] Test results:

[0134]

[0135]

[0136] Based on the data analysis of the above embodiments and comparative examples, the automotive tempered glass ink prepared by the present invention has good anti-sticking properties and excellent acid and alkali resistance.

[0137] The embodiments described above are some, but not all, embodiments of the present invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

Claims

1. A method for preparing ink for automotive tempered glass, comprising the following steps: S1: Weigh 15-25 parts of ink thinner, 40-50 parts of low melting point glass powder, 20-30 parts of high temperature ceramic pigment, 1-3 parts of dispersant, 1-3 parts of leveling agent, and 1-3 parts of thixotropic agent according to the weight ratio. Stir at 1000-2000 r / min for 20-40 min, and then ultrasonically disperse for 20-40 min. S2: Continue grinding until the fineness is below 10μm; S3: Then add a thinner to obtain ink for automotive tempered glass; The ink oil is formulated from 10-20 parts of ink binder and 60-80 parts of solvent; The ink binder consists of 3-7 parts tin-doped modified epoxy resin, 40-50 parts bisphenol A type epoxy resin NPEL128, and 10-18 parts bisphenol A type epoxy resin E20, which are physically mixed evenly. The preparation method of the tin-doped modified epoxy resin is as follows: Add 25-50 parts by weight of 3,6-dimercaptopyridazine, 0.5-2 parts by weight of methyl 2-(tributyltinalkyl)-2-acrylate, 200-230 parts by weight of bisphenol A epoxy vinyl resin, and 0.3-0.9 parts by weight of photoinitiator to a stirred tank, and stir at 50-60°C for 30-70 minutes; under argon protection, irradiate with ultraviolet light with a wavelength of 320nm-360nm for 20-40 minutes to initiate a click reaction to obtain tin-doped modified epoxy resin.

2. The method for preparing an ink for automotive tempered glass according to claim 1, characterized in that: The photoinitiator is one of benzoin dimethyl ether or 2-hydroxy-2-methyl-1-phenyl-1-propanone.

3. The method for preparing an ink for automotive tempered glass according to claim 1, characterized in that: The solvent is one or more of the following: glycerol, paraffin oil, cyclohexane, turpentine, terpineol, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol, diethylene glycol butyl ether acetate, and hydrogenated castor oil.

4. The method for preparing an ink for automotive tempered glass according to claim 1, characterized in that: The dispersant is a carboxylate, sulfate, or sulfonate.

5. The method for preparing an ink for automotive tempered glass according to claim 1, characterized in that: The leveling agent is an acrylate leveling agent.

6. The method for preparing an ink for automotive tempered glass according to claim 1, characterized in that: The thixotropic agent is an organic thixotropic agent RC-HST.

7. The method for preparing an ink for automotive tempered glass according to claim 1, characterized in that: The bisphenol A epoxy vinyl resin is TM-V201 or Fuchem854.

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