CN110272207A - A kind of unglazed porcelain matter polished bricks penetration glaze and preparation method thereof - Google Patents

Abstract

The invention provides an infiltrating glaze for an unglazed porcelain polished tile and a preparation method thereof, belonging to the technical field of porcelain polished tiles. An infiltrating glaze for an unglazed porcelain polished tile is obtained by neutralizing an aqueous solution of fluozirconic acid and alcohol amine. The unglazed porcelain polished tile provided by the invention has stable glaze penetration performance, is convenient and quick to use, does not need to be regrinded, and can be used not only for screen printing, but also for printing on rubber roller printing machines. For the brick surface of porcelain polished tiles, the infiltrating glaze does not need to go through the dissolution process, and it infiltrates in the form of the original form of the product. The data in the examples show that the infiltrated glaze of the unglazed porcelain polished tiles provided by the present invention is a light yellow clear solution with no risk of precipitation. It can be used for rubber roller printing to obtain more vivid and delicate patterns, and it can be used for screen printing to obtain more vivid and delicate patterns. Fine pattern, less dosage and can make the tiles appear white.

Description

A kind of infiltration glaze of unglazed porcelain polished tile and preparation method thereof

technical field

The invention relates to the technical field of porcelain polished tiles, in particular to a glaze-free porcelain polished tile penetration glaze and a preparation method thereof.

Background technique

Porcelain polished tiles have the advantages of high hardness, elegant appearance, and easy cleaning, and are widely used in floor paving. The pattern decoration of porcelain polished tiles is produced by using an aqueous solution of metal ions to penetrate into the billet and then burnt and polished. The specific pattern printing methods include screen printing and rubber roller printing.

The rubber roller printing process can realize automatic production. The screen printing process requires more labor assistance. With the increase of labor costs, it is also the general trend for rubber roller printing to replace screen printing.

In the prior art, ammonium fluorozirconate is currently used to print white patterns on the surface of porcelain polished tiles. Because ammonium fluorozirconate has low water solubility, it can only be used by adding water and grinding it into a slurry. This slurry is ammonium fluorozirconate particles. The dispersion mixed with water is printed on the brick surface and sprayed with a large amount of water, then dissolves into the inside of the brick and turns white after firing. Because ammonium fluorozirconate has certain water solubility, the particles of this slurry are easy to grow up during storage, so it can only be used for screen printing, and the slurry needs to be ground again after being stored for a long time to meet the requirements of screen printing. Therefore, printing methods with better quality, such as rubber roller printing, cannot use the slurry obtained by grinding ammonium fluorozirconate, which will cause clogging of the pores on the surface of the rubber roller.

Contents of the invention

In view of this, the object of the present invention is to provide a non-glazed porcelain polished tile penetration glaze and a preparation method thereof. The unglazed porcelain polished tile provided by the invention has stable glaze penetration and can be used for rubber roller printing.

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

The invention provides an infiltrating glaze for an unglazed porcelain polished tile, which is obtained by neutralizing an aqueous solution of fluozirconic acid and alcohol amine.

Preferably, the molar ratio of the fluozirconic acid to the alcohol amine in the fluozirconic acid aqueous solution is 1:1-3.

Preferably, the molar ratio of the fluozirconic acid to the alcohol amine in the fluozirconic acid aqueous solution is 1:1.5-2.5.

Preferably, the alcohol amines include monoethanolamine, diethanolamine, triethanolamine, n-propanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N,N-dimethylethanolamine, N , one or more of N-diethylethanolamine and diglycolamine.

Preferably, the mass concentration of the fluozirconic acid aqueous solution is 40-50%, and the mass concentration of the alcoholamine is 98-99.9%.

The present invention also provides a preparation method of the glaze-free porcelain polished tile permeable glaze described in the above technical solution, comprising the following steps:

The aqueous solution of fluorozirconic acid and alcohol amine are neutralized to obtain the permeable glaze of the glaze-free porcelain polished tile.

Preferably, after the neutralization reaction, the obtained neutralization reaction product is concentrated by heating distillation at normal pressure or concentrated by distillation under reduced pressure.

Preferably, the temperature of the atmospheric pressure heating distillation concentration is 100-120° C., and the time is 2-3 hours.

Preferably, the atmospheric pressure heating distillation concentration temperature is 105-115°C.

Preferably, the pressure of the vacuum distillation and concentration is -0.01-0.03 MPa, the temperature is 60-110° C., and the time is 2-3 hours.

The invention provides an infiltrating glaze for an unglazed porcelain polished tile, which is obtained by neutralizing an aqueous solution of fluozirconic acid and alcohol amine. The unglazed porcelain polished tile provided by the present invention does not have particles in the permeable glaze, and there is no risk of particle growth during use and storage. Alcoholamine has a larger molecular weight and a more complex molecular structure than monovalent metal alkalis, making it compatible with fluorine The product obtained by zirconic acid reaction is difficult to crystallize; at the same time, alcohol amine contains a large number of hydroxyl groups, has a strong affinity with water molecules, and has a sufficient solubility in water. , stable performance, easy and quick to use, no need to regrind, and not only can be used for screen printing, but also can be used for printing with rubber roller printing machines. It needs to go through the dissolution process and infiltrate directly in the form of the product's original form solution. The data in the examples show that the infiltrated glaze of the unglazed porcelain polished tiles provided by the present invention is a light yellow clear solution with no risk of precipitation. It can be used for rubber roller printing to obtain more vivid and delicate patterns, and it can be used for screen printing to obtain more vivid and delicate patterns. Fine pattern, less dosage and can make the tiles appear white.

Detailed ways

The invention provides an infiltrating glaze for an unglazed porcelain polished tile, which is obtained by neutralizing an aqueous solution of fluozirconic acid and alcohol amine.

In the present invention, the molar ratio of fluozirconic acid to alcohol amine in the fluozirconic acid aqueous solution is preferably 1:1-3, more preferably 1:1.5-2.5.

In the present invention, the alcohol amine preferably includes monoethanolamine, diethanolamine, triethanolamine, n-propanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N,N-dimethyl One or more of ethanolamine, N,N-diethylethanolamine and diglycolamine. When the alcoholamine is preferably a mixture, the present invention has no special limitation on the mass ratio of each substance in the mixture, and any mixture with any mass ratio can be used.

In the present invention, the mass concentration of the fluozirconic acid aqueous solution is preferably 40-50%, and the mass concentration of the alcoholamine is preferably 98-99.9%.

The present invention also provides a preparation method of the glaze-free porcelain polished tile permeable glaze described in the above technical solution, comprising the following steps:

The aqueous solution of fluorozirconic acid and alcohol amine are neutralized to obtain the permeable glaze of the glaze-free porcelain polished tile.

In the present invention, the temperature of the neutralization reaction is preferably room temperature. In the present invention, there is no special limitation on the time of the neutralization reaction, as long as the neutralization reaction can be completely carried out.

In the present invention, after the neutralization reaction, the obtained neutralization reaction product is preferably concentrated by distillation under normal pressure or under reduced pressure.

In the present invention, the temperature of the atmospheric pressure heating distillation concentration is preferably 100-120° C., more preferably 105-115° C., and the time is preferably 2-3 hours.

In the present invention, the temperature of the atmospheric pressure heating distillation concentration In the present invention, the pressure of the vacuum distillation concentration is preferably -0.01 to -0.03MPa, more preferably the pressure is -0.01 to -0.02MPa, and the temperature is preferably 60-110°C, more preferably 70-100°C, and the time is preferably 2-3 hours.

In the present invention, the product after the atmospheric pressure heating distillation concentration or vacuum distillation concentration is preferably adjusted to the flow rate of the Tu-4 viscosity cup and the outflow time is normal temperature (20-30° C.) for 12-30 seconds before running on the drum. More preferably, it is 16 to 25 seconds, and 30 seconds or more can be used on a screen.

In the present invention, during the neutralization reaction, the pH value of the reaction system is preferably 7-9.

In the present invention, the alcohol amine is preferably added to the aqueous solution of fluorozirconic acid.

In the present invention, the inner contact surface of the neutralization reaction container is preferably non-metallic and heat-resistant (130° C. or above).

A kind of unglazed porcelain polished tile permeable glaze provided by the present invention and its preparation method are described in detail below in conjunction with the examples, but they should not be interpreted as limiting the protection scope of the present invention.

Example 1.

Slowly add 1000g of 50% aqueous solution of fluozirconic acid into the reaction vessel, slowly add 872g of triethanolamine under the condition of stirring, continue to stir and react for 2 hours after the addition, and obtain about 1750g of clear light yellow viscous solution, use the Tu-4 viscosity cup to measure the flow rate , the time is 25s, and the pH value is 8.

Example 2.

Slowly add 1000g of 50% aqueous solution of fluozirconic acid into the reaction vessel, slowly add 507.4g of diethanolamine under the condition of stirring, continue to stir after the addition is completed, continue to heat after the completion of the reaction, keep the temperature at 105°C for 2h, and obtain a clear light yellow color The viscous solution is about 1050g, the flow rate is measured with a Tu-4 viscosity cup, the time is 20s, and the pH value is 8.3.

Example 3.

Slowly add 1000g of 50% aqueous solution of fluozirconic acid into the reaction vessel, slowly add 254g of monoethanolamine under stirring conditions, continue to stir after the addition is completed, and continue to heat after the reaction is completed, keeping the temperature at 110°C for 2 hours, adding pressure -0.01MPa , Obtain about 980 g of a clear light yellow viscous solution, use the Tu-4 viscosity cup to measure the flow rate, the time is 18 s, and the pH value is 8.0.

Example 4.

Slowly add 1000g of 50% aqueous solution of fluozirconic acid into the reaction vessel, slowly add 612g of diglycolamine under stirring condition, continue to stir after the addition is completed, continue to heat after the reaction is completed, keep the temperature at 100°C, 2h, add pressure- 0.02MPa, about 1263g of a clear light yellow viscous solution was obtained, the flow rate was measured with a Tu-4 viscosity cup, the time was 23s, and the pH value was 8.7.

Example 5.

Slowly add 1000g of 50% aqueous solution of fluozirconic acid into the reaction vessel, slowly add 254g of monoethanolamine and 1238g of triethanolamine under the condition of stirring, continue to stir after the addition is completed, continue heating after the completion of the reaction, keep the temperature at 105°C for 2 hours, add Pressure -0.03MPa, about 1520g of a clear light yellow viscous solution was obtained, the flow rate was measured with a Tu-4 viscosity cup, the time was 38s, and the pH value was 8.9.

Example 6.

Slowly add 1700g of 50% aqueous solution of fluozirconic acid into the reaction vessel, slowly add 933g of isopropanolamine under stirring condition, continue to stir and react for 1 hour after the addition, and obtain about 2500g of clear light yellow viscous solution, use Tu-4 viscosity cup Measure the flow rate, the time is 21s, and the pH value is 8.7.

Example 7.

Slowly add 1,600 g of 50% aqueous solution of fluozirconic acid into the reaction vessel, slowly add 293 g of isopropanolamine and 1,038 g of diisopropanolamine under stirring conditions, and continue to stir and react for 1 hour after the addition, to obtain about 2,500 g of a clear light yellow viscous solution , use the Tu-4 viscosity cup to measure the flow rate, the time is 23s, and the pH value is 8.8.

Example 8.

Slowly add 1600 g of 50% fluorozirconic acid aqueous solution into the reaction vessel, slowly add 238 g of monoethanolamine, 410 g of diethanolamine and 581.6 g of triethanolamine under stirring conditions, continue to stir after the addition is completed, and continue heating after the completion of the reaction to keep the temperature at React at 60°C for 2 hours, add pressure -0.02MPa, and obtain about 2000g of a clear light yellow viscous solution, use a Tu-4 viscosity cup to measure the flow rate, the time is 35s, and the pH value is 8.8.

Example 9.

Slowly add 1600 g of 50% fluorozirconic acid aqueous solution into the reaction vessel, slowly add 238 g of monoethanolamine, 410 g of diethanolamine and 581.6 g of triethanolamine under stirring conditions, continue to stir after the addition is completed, and continue heating after the completion of the reaction to keep the temperature at React at 70°C for 3 hours, add pressure -0.03MPa, and obtain about 2000g of a clear light yellow viscous solution, use a Tu-4 viscosity cup to measure the flow rate, the time is 33s, and the pH value is 8.4.

The permeable glaze of the unglazed porcelain polished tiles prepared in Examples 1 to 9 of the present invention is a light yellow clear solution without risk of precipitation.

Comparative example 1.

Take 100mL of the unglazed porcelain polished tile infiltration glaze and 100mL of the traditional white infiltration glaze (ammonium fluorozirconate dispersion slurry) obtained in Example 1, and let it stand for observation. The appearance of the infiltration glaze in Example 1 is a light yellow clear solution, while the traditional white infiltration glaze The appearance of the penetrating glaze is a dispersion of white particles, which can pass through the 80-mesh sieve respectively. After one week of storage at room temperature (20-30°C), the light yellow infiltrated glaze of Example 1 has no change in appearance, and the traditional white infiltrated glaze is layered. The yellow penetrating glaze passes through normally, but the traditional white penetrating glaze has a large number of particles that cannot pass through.

Comparative example 2.

Get the non-glazed porcelain polished tile penetration glaze 50L and 50L traditional white penetration glaze (ammonium fluorozirconate dispersion slurry) that Example 1 makes, put up the roller test respectively, the light yellow penetration glaze cloth glaze of Example 1 is normal, the brick The pattern of the roller can be clearly printed on the brick when passing through. In the test of the traditional white penetrating glaze roller, the printed pattern is incomplete, and the complete pattern cannot be printed by adjusting the roller speed and the pressing depth, and there is a phenomenon of roller sealing (the roller pores are blocked by foreign matter) after long-term operation. The penetrating glaze of the present invention can be printed with rubber rollers to obtain more vivid and delicate patterns, while the ammonium fluorozirconate dispersion cannot be printed with rubber rollers at all.

Comparative example 3.

Get 10 pieces of the unglazed porcelain polished tiles obtained in Example 1 with 50 L of permeable glaze on the upper roller, and screen-print 10 pieces of newly made 50 L of traditional white permeable glaze (ammonium fluorozirconate dispersion slurry). Both the roll pattern and the screen pattern are the same. After firing and polishing, the thickness of the line is measured. In Example 1, the thickness of the line at the thinnest part of the light yellow infiltrated glaze pattern is 1-1.2 mm, and the thickness of the line at the thinnest part of the traditional white infiltrated pattern is 1.5-2 mm, indicating that the infiltrated glaze of the present invention It can be used for printing with finer silk to obtain finer patterns.

Comparative example 4.

Get 10 pieces of the unglazed porcelain polished tiles obtained in Example 1 with 50 L of permeable glaze on the upper roller, and screen-print 10 pieces of newly made 50 L of traditional white permeable glaze (ammonium fluorozirconate dispersion slurry). Both the roll pattern and the screen pattern are the same. After firing, the section is cut, and the light yellow infiltrating glaze pattern penetration depth of embodiment 1 is 2.5～3mm, and the traditional white infiltration pattern penetration depth is 2～2.8mm, illustrating that the penetration performance of the permeable glaze of the present invention is stronger than the traditional permeable glaze. The penetration is better during use. When the ammonium fluorozirconate dispersion is used on the surface of the brick, it must be dissolved by sprayed water before infiltration, while the infiltration glaze of the present invention infiltrates directly without a dissolution process, so the infiltration effect is better.

Comparative example 5.

Take 100 mL of the infiltrated glaze of the unglazed porcelain polished tiles prepared in Example 1, prepare 100 mL of ammonium fluorozirconate saturated solution, and use the same screen printing to test the tiles respectively. After firing the test bricks, the light yellow penetrating glaze pattern of Example 1 is milky white, while the saturated ammonium fluorozirconate solution pattern has only very slight pattern traces. After the test brick was polished, the light yellow penetrating glaze pattern of Example 1 appeared white and bright, while the saturated ammonium fluorozirconate solution pattern disappeared. It shows that if ammonium fluozirconate is made into a transparent solution similar to this patent and used as a penetrating glaze, since the solubility of ammonium fluozirconate is very low, the content of zirconium in the transparent solution obtained is very low, which cannot make the tiles appear white. Effect.

Comparative example 6.

Slowly add 1000g of 50% aqueous solution of fluozirconic acid into the reaction vessel, slowly add 200g of triethanolamine under stirring condition, continue to stir after the addition is completed, and continue to stir for 2 hours after the completion of the reaction to obtain about 1158g of clear light yellow viscous solution. 4 The viscosity cup measures the flow rate, the time is 10s, and the pH value is 5.5.

When concentrated by heating under normal pressure, the temperature is less than 100°C, the reaction time is long, and the concentration effect cannot be achieved.

Comparative example 7.

Slowly add 1000g of 50% aqueous solution of fluozirconic acid into the reaction vessel, slowly add 254g of monoethanolamine under stirring condition, continue to stir after the addition is completed, continue to heat after the completion of the reaction, keep the temperature at 90°C for 8h, and obtain a clear light yellow viscous The thick solution is about 1200g, the flow rate is measured with a Tu-4 viscosity cup, the time is 10s, and the pH value is 8.0. The flow rate is too small and cannot be used for drum production.

When heating and concentrating under reduced pressure, the temperature is higher than 110°C, and high temperature is easy to decompose the reactant.

Comparative example 8.

Slowly add 1700g of 50% aqueous solution of fluozirconic acid into the reaction vessel, slowly add 933g of isopropanolamine under the condition of stirring, continue to stir and react for 1h after the addition, the solution gradually becomes turbid during the reaction, and a clear light yellow viscous turbid liquid of about 2500g, the turbid liquid has white precipitation and the bottom after standing still, take the supernatant and compare it with the product of Example 6 for printing and firing, the product of color comparison example 8. The color of the product is lighter.

The above is only a preferred embodiment of the present invention, and it should be pointed out that for those of ordinary skill in the art, some improvements and modifications can be made without departing from the principle of the present invention. It should be regarded as the protection scope of the present invention.

Claims (10)

1. a kind of unglazed porcelain matter polished bricks penetration glaze, which is characterized in that carry out neutralization reaction by fluorine zirconic acid aqueous solution and hydramine and obtain It arrives.

2. unglazed porcelain matter polished bricks penetration glaze according to claim 1, which is characterized in that in the fluorine zirconic acid aqueous solution Fluorine zirconic acid and the molar ratio of hydramine are 1:1~3.

3. unglazed porcelain matter polished bricks penetration glaze according to claim 2, which is characterized in that in the fluorine zirconic acid aqueous solution Fluorine zirconic acid and the molar ratio of hydramine are 1:1.5~2.5.

4. unglazed porcelain matter polished bricks penetration glaze according to claim 1, which is characterized in that the hydramine includes an ethyl alcohol Amine, diethanol amine, triethanolamine, n-propanolamine, monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, N, N- dimethyl ethanol Amine, N, one of N- diethyl ethylene diamine and diglycolamine or a variety of.

5. unglazed porcelain matter polished bricks penetration glaze according to claim 1, which is characterized in that the matter of the fluorine zirconic acid aqueous solution Measuring concentration is 40~50%, and the mass concentration of hydramine is 98~99.9%.

6. the preparation method of the described in any item unglazed porcelain matter polished bricks penetration glazes of Claims 1 to 5, which is characterized in that including Following steps:

Fluorine zirconic acid aqueous solution and hydramine are subjected to neutralization reaction, obtain the unglazed porcelain matter polished bricks penetration glaze.

7. preparation method according to claim 6, which is characterized in that by gained neutralization reaction product after the neutralization reaction Normal heating distillation and concentration or vacuum distillation concentration.

8. preparation method according to claim 7, which is characterized in that the temperature of the normal heating distillation and concentration is 100 ~120 DEG C, the time is 2~3 hours.

9. preparation method according to claim 8, which is characterized in that the temperature of the normal heating distillation and concentration is 105 ~115 DEG C.

10. preparation method according to claim 7, which is characterized in that the pressure of the vacuum distillation be -0.01~- 0.03MPa, temperature are 60~110 DEG C, and the time is 2~3 hours.