CN105761777B - A kind of vehicle glass fine rule silver paste and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of vehicle glass fine rule silver paste and preparation method thereof, raw material uses following components and weight percent content：Silver powder 60 80%；Glass dust 3 7%；Macromolecule resin 1 8%；Organic additive 1 3%；Organic solvent 10 25%, vehicle glass fine rule silver paste is prepared by steps such as stock, the preparation of carrier, the preparation of silver paste, the productions of silver paste.Compared with prior art, the product that is prepared of the present invention solves the problems such as printing fineness of silver paste, electric conductivity, compactness.

Description

A kind of fine line silver paste for automobile glass and preparation method thereof

technical field

The invention relates to a silver paste for automobile glass and a preparation method thereof, in particular to a fine wire silver paste for automobile glass and a preparation method thereof.

Background technique

With the continuous development of my country's economy, the automobile industry has also developed rapidly and vigorously, and the output of automobiles has also increased year by year. At the same time, the demand for silver paste and black glaze for automotive glass is also increasing, and the quality requirements are getting higher and higher.

In order to quickly eliminate fog and frost, the rear glass of the car is generally equipped with defogging and frost heating wires. The heating wire generally prints the silver paste on the surface of the automobile glass and black glaze by screen printing technology, and tempers it in a tempering furnace for 3-5 minutes, so that the silver paste adheres to the surface of the automobile glass and black glaze to form a silver layer. The resistance of the heating wire after sintering is generally 0.5-1.2Ω. Weld the power line on the silver surface on both sides of the car glass. After the voltage of 12-13V is applied, the entire heating wire starts to generate heat, thereby achieving the effect of defogging. Since the heating wire may be exposed to hot and humid environments along with the car, high technical requirements are put forward for the acid resistance, wear resistance, adhesion, and oxidation resistance of the silver paste for automotive glass. At the same time, since the silver paste is actually printed on the black glaze, the compatibility between the silver paste and the black glaze also puts forward high technical requirements.

At present, most of the silver pastes used in domestic auto glass factories are domestic silver pastes, and a small part of them are foreign products such as DuPont, Fluor and Johnson Matthey. The main problems are as follows: the line width of silver paste screen printing is generally 0.6- 0.9mm, not suitable for thin wire products with a line width of about 0.3mm, and the frequency of wire breakage is high.

Chinese patent CN101613186A discloses lead-free silver paste for high-temperature sintered automotive glass heating wire and its preparation method. The lead-free silver paste includes the following components and content (weight): 50% to 85% of silver powder; 3% of lead-free silver glass powder ~7%; polymer binder 3% ~ 12%; organic solvent 7% ~ 23%; ultrafine metal compound 1% ~ 5%; additive 0.5% ~ 3%, the components are mixed, dissolved, ground, filtered Obtain lead-free silver paste for high-temperature sintered automotive glass heating wire. The difference between this application and this patent lies in the control of particle size by glass powder and silver powder, and silver paste with large particle size is not suitable for thin wire products of about 0.3mm.

Contents of the invention

The purpose of the present invention is exactly to solve the printing fineness, electric conductivity, compactness problem of silver paste and provide the fine line silver paste for automobile glass and its preparation method.

The purpose of the present invention can be achieved through the following technical solutions:

A fine wire silver paste for automobile glass, the raw material adopts the following components and weight percentage content: 60-80% of metal silver powder; 3-7% of glass powder; 1-8% of polymer resin; 1-3% of organic additive; Solvent 10-25%.

The metallic silver powder is a compound composed of spherical silver powder and flake silver powder, the particle size of the spherical silver powder is 0.3-3.0 μm, and the tap density is 2.0-4.0 g/ml; the particle size of the flake silver powder is 1-7 μm, The tap density is 1.0-3.0g/ml.

As a preferred embodiment, the particle size of the spherical silver powder is preferably 1.0-3.0 μm, and the particle size of the flake silver powder is 5-6 μm.

Described glass powder is the mixture that glass powder-L and glass powder-H form,

The glass powder-L is lead-free glass powder with a particle size of 0.5-2 μm and a sintering temperature of 550-650°C, including the following components and weight percentages: Bi ₂ O ₃ 55-75, B ₂ O ₃ 10 -30, ZnO 5-15, SiO ₂ 3-10, Al ₂ O ₃ 0-3, Na ₂ O 0-3, Fe ₂ O ₃ 0-1, ZrO ₂ 0-1,

The glass powder-H is lead-free glass powder with a particle size of 0.5-2 μm and a sintering temperature of 650-750°C, including the following components and weight percentages: Bi ₂ O ₃ 50-70, B ₂ O ₃ 10 -30, ZnO 5-15, SiO ₂ 3-10, Sb ₂ O ₃ 3-10, Al ₂ O ₃ 0-3, Na ₂ O 0-3, Cr ₂ O ₃ 0-2, Fe ₂ O ₃ 0- 1. ZrO ₂ 0-1, NiO 0-1, Ag ₂ O 0-1.

The polymer resin is one or more of ethyl cellulose, nitrocellulose, ethyl hydroxyethyl cellulose, and wood rosin, preferably ethyl cellulose. Described organic additive comprises plasticizer, leveling agent, coupling agent,

The plasticizer is one or more of dibutyl phthalate, tributyl citrate, dioctyl phthalate, and trioctyl citrate;

The leveling agent is one or more of silicone resin, hydrogenated castor oil, polyvinyl butyral, polyacrylate;

The coupling agent is one or more of silane coupling agents KH550, KH560, and KH570.

Described organic solvent is the one in terpineol, turpentine, diethylene glycol butyl ether, diethylene glycol dibutyl ether, butyl carbitol acetate, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether or a mixture of several.

The preparation method of fine line silver paste for automobile glass adopts the following steps:

(1) Prepare materials according to the following components and weight percentages:

(2) Preparation of the carrier: Weigh the polymer resin and organic solvent, then heat it up to 80°C and keep the temperature constant. After the polymer resin is completely dissolved, filter and remove impurities on a mesh cloth of 400-500 mesh to obtain the carrier ;

(3) Preparation of silver paste: After weighing metal silver powder, glass powder, and organic additives, fully mix them with the carrier in a mixer, and then use a high-speed dispersant for high-speed dispersion to obtain a uniform slurry;

(4) Production of silver paste: Grind the above paste in a three-roll rolling mill, and control the fineness of the silver paste below 8 μm by fine-tuning the rollers, and the viscosity is 20-30 Pa·S, that is, the fine powder for automobile glass is obtained. Silver paste.

Compared with the existing technology, since the particle size of the glass powder and silver powder in the silver paste plays a decisive role in the screen printing of automotive glass fine wire products, when the particle size is too large, the silver wire often breaks after sintering The present invention solves the printing fineness, conductivity and compactness of the silver paste through the selection and matching of ultra-fine ball powder and flake powder; through the selection and matching of glass powder, the adhesion between the silver paste and the glass is solved. , and the color depth of the glass tin surface; through the selection of organic additives, to solve the process performance of silver paste printing.

detailed description

The present invention will be described in detail below in conjunction with specific embodiments.

Example 1

(1) Prepare 1000g of raw materials, according to the following components and quality:

The particle size of the spherical silver powder used is 1.0 μm, and the tap density is 2.2 g/ml; the particle size of the flake silver powder is 6.2 μm, and the tap density is 2.5 g/ml;

Among the glass powders used, the glass powder-L is 10g, the particle size is 1.35μm, and its components and percentages are: Bi ₂ O ₃ 65, B ₂ O ₃ 18, ZnO 9, SiO ₂ 4, Al ₂ O ₃ 2. Na ₂ O 1, Fe ₂ O ₃ 0.5, ZrO ₂ 0.5; glass powder-H is 20g, particle size is 1.50μm, its components and percentages are: Bi ₂ O ₃ 60, B ₂ O ₃ 19. ZnO 8, SiO ₂ 5, Sb ₂ O ₃ 4, Al ₂ O ₃ 1, Na ₂ O 1, Cr ₂ O ₃ 0.5, Fe ₂ O ₃ 0.4, ZrO ₂ 0.4, NiO 0.3, Ag ₂ O 0.5;

The organic additives used are 5g of dibutyl phthalate, 2.5g of silicone resin and 2.5g of silane coupling agent KH550.

(2) Preparation of carrier: Weigh 10g of ethyl cellulose and 150g of terpineol, then heat them up to 80°C and keep the temperature constant. Miscellaneous, that is, get the carrier;

(3) Preparation of silver paste: After weighing 700g spherical silver powder, 100g flake silver powder, 30g glass powder, and 10g organic additives, fully mix with organic carrier in a mixer, and then use high-speed dispersant for high-speed dispersion, that is Obtain a homogeneous slurry;

(4) Production of silver paste: Grind the above paste 6 times in a three-roll rolling mill, control the fineness of the silver paste below 8 μm and the viscosity of 20-30 Pa·S through fine-tuning of the rollers, and then obtain automobile glass The fine line silver paste used.

Example 2

(1) Prepare 1000g of raw materials, according to the following components and quality:

The particle size of the spherical silver powder used is 1.0 μm, and the tap density is 2.2 g/ml; the particle size of the flake silver powder is 7.6 μm, and the tap density is 2.1 g/ml;

Among the glass powders used, the glass powder-L is 15g, the particle size is 1.65μm, and its components and percentages are: Bi ₂ O ₃ 70, B ₂ O ₃ 16, ZnO 8, SiO ₂ 3.5, Al ₂ O ₃ 1.5, Na ₂ O 1.0, Fe ₂ O ₃ 0, ZrO ₂ 0; glass powder-H is 25g, the particle size is 1.50μm, and its components and percentages are: Bi ₂ O ₃ 60, B ₂ O ₃ 19. ZnO 8, SiO ₂ 5, Sb ₂ O ₃ 4, Al ₂ O ₃ 1, Na ₂ O 1, Cr ₂ O ₃ 0.5, Fe ₂ O ₃ 0.4, ZrO ₂ 0.4, NiO 0.3, Ag ₂ O 0.5;

The organic additives used are 6g of dioctyl phthalate, 2g of silicone resin and 2g of silane coupling agent KH560.

(2) Preparation of the carrier: Weigh 30g of nitrocellulose and 170g of diethylene glycol butyl ether, then heat it up to 80°C and keep the temperature constant. Impurities are removed by upper filtration to obtain the carrier;

(3) Preparation of silver paste: After weighing 650g spherical silver powder, 100g flake silver powder, 40g glass powder, and 10g organic additives, fully mix with organic carrier in a mixer, and then use high-speed dispersant for high-speed dispersion, that is Obtain a homogeneous slurry;

(4) Production of silver paste: Grind the above paste 7 times in a three-roll rolling mill, control the fineness of the silver paste below 8 μm and the viscosity of 20-30 Pa·S by fine-tuning the rollers, and then obtain automobile glass The fine line silver paste used.

Example 3

(1) Prepare 1000g of raw materials, according to the following components and quality:

The particle size of the spherical silver powder used is 1.8 μm, and the tap density is 2.6 g/ml; the particle size of the flake silver powder is 8.2 μm, and the tap density is 2.5 g/ml;

Among the glass powders used, the glass powder-L is 20g, the particle size is 1.65μm, and its components and percentages are: Bi ₂ O ₃ 70, B ₂ O ₃ 16, ZnO 8, SiO ₂ 3.5, Al ₂ O ₃ 1.5, Na ₂ O 1.0, Fe ₂ O ₃ 0, ZrO ₂ 0; glass powder-H is 30g, particle size is 1.80μm, its components and percentages are: Bi ₂ O ₃ 62, B ₂ O ₃ 16. ZnO 10, SiO ₂ 4, Sb ₂ O ₃ 5, Al ₂ O ₃ 1, Na ₂ O 1, Cr ₂ O ₃ 0.5, Fe ₂ O ₃ 0, ZrO ₂ 0, NiO0, Ag ₂ O 0.5;

The organic additive used is 10g tributyl citrate, 5g hydrogenated castor oil and 5g silane coupling agent

KH570.

(2) Preparation of carrier: Weigh 50g of ethyl hydroxyethyl cellulose, 90g of terpineol and 90g of butyl carbitol acetate, then heat it up to 80°C and keep the temperature constant until ethyl hydroxyethyl cellulose After completely dissolving, filter and remove impurities on a mesh cloth of 400-500 mesh to obtain the carrier;

(3) Preparation of silver paste: After weighing 600g spherical silver powder, 100g flake silver powder, 50g glass powder, and 20g organic additives, fully mix with organic carrier in a mixer, and then use high-speed dispersant for high-speed dispersion, that is Obtain a homogeneous slurry;

(4) Production of silver paste: Grind the above paste 6 times in a three-roll rolling mill, control the fineness of the silver paste below 8 μm and the viscosity of 20-30 Pa·S through fine-tuning of the rollers, and then obtain automobile glass The fine line silver paste used.

Example 4

(1) Prepare 1000g of raw materials, according to the following components and quality:

The particle size of the spherical silver powder used is 1.8 μm, and the tap density is 2.6 g/ml; the particle size of the flake silver powder is 8.6 μm, and the tap density is 2.1 g/ml;

Among the glass powders used, the glass powder-L is 25g, the particle size is 1.35μm, and its components and percentages are: Bi ₂ O ₃ 65, B ₂ O ₃ 18, ZnO 9, SiO ₂ 4, Al ₂ O ₃ 2. Na ₂ O 1, Fe ₂ O ₃ 0.5, ZrO ₂ 0.5; glass powder-H is 35g, particle size is 1.80μm, its components and percentages are: Bi ₂ O ₃ 62, B ₂ O ₃ 16. ZnO 10, SiO ₂ 4, Sb ₂ O ₃ 5, Al ₂ O ₃ 1, Na ₂ O 1, Cr ₂ O ₃ 0.5, Fe ₂ O ₃ 0, ZrO ₂ 0, NiO0, Ag ₂ O 0.5;

The organic additives used are 15g trioctyl citrate, 10g polyvinyl butyral and 5g silane coupling agent KH560.

(2) Preparation of carrier: Weigh 35g of ethyl cellulose, 35g of nitrocellulose, 100g of tripropylene glycol monomethyl ether and 100g of turpentine, then heat it up to 80°C and keep the temperature constant until ethyl cellulose and nitrocellulose After the cellulose is completely dissolved, filter and remove impurities on a mesh cloth of 400-500 mesh to obtain the carrier;

(3) Preparation of silver paste: After weighing 550g spherical silver powder, 100g flake silver powder, 60g glass powder, and 20g organic additives, fully mix them with organic carrier in a mixer, and then use high-speed dispersant for high-speed dispersion, that is Obtain a homogeneous slurry;

(4) Production of silver paste: Grind the above paste 7 times in a three-roll rolling mill, control the fineness of the silver paste below 8 μm and the viscosity of 20-30 Pa·S by fine-tuning the rollers, and then obtain automobile glass The fine line silver paste used.

Example 5

(1) Prepare 1000g of raw materials, according to the following components and quality:

The particle size of the spherical silver powder used is 2.3 μm, and the tap density is 3.2 g/ml; the particle size of the flake silver powder is 7.2 μm, and the tap density is 2.5 g/ml;

Among the glass powders used, the glass powder-L is 25g, the particle size is 1.35μm, and its components and percentages are: Bi ₂ O ₃ 65, B ₂ O ₃ 18, ZnO 9, SiO ₂ 4, Al ₂ O ₃ 2. Na ₂ O 1, Fe ₂ O ₃ 0.5, ZrO ₂ 0.5; glass powder-H is 45g, particle size is 1.50μm, its components and percentages are: Bi ₂ O ₃ 60, B ₂ O ₃ 19. ZnO 8, SiO ₂ 5, Sb ₂ O ₃ 4, Al ₂ O ₃ 1, Na ₂ O 1, Cr ₂ O ₃ 0.5, Fe ₂ O ₃ 0.4, ZrO ₂ 0.4, NiO 0.3, Ag ₂ O 0.5;

The organic additives used are 15g of dibutyl phthalate, 7.5g of polyacrylate and 7.5g of silane coupling agent KH560.

(2) Preparation of carrier: Weigh 40g of ethyl cellulose, 40g of wood rosin, 110g of tripropylene glycol monomethyl ether and 110g of diethylene glycol dibutyl ether, then heat it up to 80°C and keep the temperature constant. After the element and wood rosin are completely dissolved, filter and remove impurities on a mesh cloth of 400-500 mesh to obtain the carrier;

(3) Preparation of silver paste: After weighing 500g spherical silver powder, 100g flake silver powder, 70g glass powder, and 30g organic additives, fully mix with organic carrier in a mixer, and then use high-speed dispersant for high-speed dispersion, that is Obtain a homogeneous slurry;

(4) Production of silver paste: Grind the above paste 7 times in a three-roll rolling mill, control the fineness of the silver paste below 8 μm and the viscosity of 20-30 Pa·S by fine-tuning the rollers, and then obtain automobile glass The fine line silver paste used.

Example 6

A fine-line silver paste for automotive glass, the formula of the raw materials and the synthesis process are the same as in Example 5, the difference is that the particle size of the spherical silver powder used is 1.0 μm, and the particle size of the flake silver powder is 5 μm. The particle size of the silver powder, through the selection and matching of ultra-fine spherical powder and flake powder, greatly improves the adhesion between the silver paste and the glass, and the prepared silver paste also has good electrical conductivity and compactness, and can be prepared Thin wire products with a line width of about 0.3mm.

Claims (7)

1. A fine-line silver paste for automotive glass, characterized in that, the raw material adopts the following components and weight percentage content: silver metal powder 60-80%; glass powder 3-7%; polymer resin 1-8%; organic additive 1-3%; organic solvent 10-25%; Described glass powder is the mixture that glass powder-L and glass powder-H form, The glass powder-L is lead-free glass powder with a particle size of 0.5-2 μm and a sintering temperature of 550-650°C, including the following components and weight percentages: Bi ₂ O ₃ 55-75, B ₂ O ₃ 10 -30, ZnO 5-15, SiO ₂ 3-10, Al ₂ O ₃ 0-3, Na ₂ O 0-3, Fe ₂ O ₃ 0-1, ZrO ₂ 0-1, The glass powder-H is lead-free glass powder with a particle size of 0.5-2 μm and a sintering temperature of 650-750°C, including the following components and weight percentages: Bi ₂ O ₃ 50-70, B ₂ O ₃ 10 -30, ZnO 5-15, SiO ₂ 3-10, Sb ₂ O ₃ 3-10, Al ₂ O ₃ 0-3, Na ₂ O 0-3, Cr ₂ O ₃ 0-2, Fe ₂ O ₃ 0- 1. ZrO ₂ 0-1, NiO 0-1, Ag ₂ O 0-1. 2. A kind of fine line silver paste for automotive glass according to claim 1, characterized in that, said metallic silver powder is a composite of spherical silver powder and flake silver powder, and the particle size of the spherical silver powder is 0.3-3.0 μm , the tap density is 2.0-4.0g/ml; the particle size of flake silver powder is 1-7μm, and the tap density is 1.0-3.0g/ml. 3. a kind of fine line silver paste for automobile glass according to claim 1, is characterized in that, described polymer resin is ethyl cellulose, nitrocellulose, ethyl hydroxyethyl cellulose, wood rosin one or more of them. 4. A kind of fine line silver paste for automobile glass according to claim 1, characterized in that, the polymer resin is ethyl cellulose. 5. a kind of fine line silver paste for automobile glass according to claim 1, is characterized in that, described organic additive comprises plasticizer, leveling agent, coupling agent, The plasticizer is one or more of dibutyl phthalate, tributyl citrate, dioctyl phthalate, and trioctyl citrate; The leveling agent is one or more of silicone resin, hydrogenated castor oil, polyvinyl butyral, polyacrylate; The coupling agent is one or more of silane coupling agents KH550, KH560, and KH570. 6. a kind of thin line silver paste for automotive glass according to claim 1, is characterized in that, described organic solvent is terpineol, turpentine, diethylene glycol butyl ether, diethylene glycol dibutyl ether, One or a mixture of butyl carbitol acetate, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether. 7. the preparation method of the thin wire silver paste for automotive glass as described in any one of claims 1-6, is characterized in that, adopts the following steps: (1) Prepare materials according to the following components and weight percentages: (2) Preparation of the carrier: Weigh the polymer resin and organic solvent, then heat it up to 80°C and keep the temperature constant. After the polymer resin is completely dissolved, filter and remove impurities on a mesh cloth of 400-500 mesh to obtain the carrier ; (3) Preparation of silver paste: After weighing metal silver powder, glass powder, and organic additives, fully mix them with the carrier in a mixer, and then use a high-speed dispersant for high-speed dispersion to obtain a uniform slurry; (4) Production of silver paste: Grind the above paste in a three-roll rolling mill, and control the fineness of the silver paste below 8 μm by fine-tuning the rollers, and the viscosity is 20-30 Pa·S, that is, the fine powder for automobile glass is obtained. Silver paste.