CN111302647A

CN111302647A - Zinc and boron-free glass pigment flux and preparation method and application thereof

Info

Publication number: CN111302647A
Application number: CN202010236741.5A
Authority: CN
Inventors: 任明祥; 刘守江
Original assignee: Shandong Province Zibo City Boshan Changhong Ceramics Decoration Materials Factory
Current assignee: Shandong Province Zibo City Boshan Changhong Ceramics Decoration Materials Factory
Priority date: 2020-03-30
Filing date: 2020-03-30
Publication date: 2020-06-19

Abstract

The invention belongs to the technical field of glass pigment flux, and particularly relates to a zinc-boron-free glass pigment flux, a preparation method and an application thereof, wherein the zinc-boron-free glass pigment flux comprises the following ingredients in percentage by weight: SiO 2₂5‑40％；Bi₂O₃15 to 40 percent; 1-10% of BaO; 1-10% of fluorite; 1-10% of talc; na (Na)₂O 1‑5％K₂O 1‑5％；Li₂O 1‑5％；Al₂O₃0‑4％；ZrO₂0‑3％；SnO₂0‑3％；TiO₂1 to 10 percent. The raw materials adopted by the invention are directly added with fluorite and talcum, compared with the formula containing zinc and boron in the prior art, the invention can greatly reduce the production cost, is beneficial to large-scale production and can increase the economic benefit of enterprises. The formula of the invention does not contain heavy goldAnd the harm to human bodies and the environment can be reduced.

Description

Zinc and boron-free glass pigment flux and preparation method and application thereof

Technical Field

The invention belongs to the technical field of glass pigment flux, and particularly relates to a zinc-boron-free glass pigment flux and a preparation method and application thereof.

Background

The toughened glass is mostly applied to automobile glass, building glass, inner clapboards of refrigerators, glass screens of microwave ovens, toughened glass utensils and the like. The toughened glass pigment is a pigment printed on the surface of glass in the toughening process of the glass and consists of a fusing agent and a coloring agent. The melting point of the toughened glass pigment is similar to that of glass, the pigment with the same melting point can be printed and sprayed on the glass while the glass is toughened, the color mainly comprises black and white, and the other colors comprise red, yellow, blue, green and the like, the required color agents with various colors and glass fusing agents can be mixed according to a proper proportion and then are prepared into ink by ink rolling, the pigment after the ink rolling is printed or sprayed on the surface of the glass to form patterns or patterns, and then the toughening furnace is subjected to toughening treatment at the temperature of 680-720 ℃. The toughened glass pigment is fused on the glass, so that the glass can be subjected to color and pattern decoration, and the effects of shielding, protecting and decorating are achieved. Therefore, there is a need to research and discuss the formulation composition of the toughened glass pigment and the work of reducing energy consumption and protecting environment.

Currently, zinc and boron are the main raw materials in existing glass pigment fluxes. CN101244888 is a glass pigment, the weight percentage of the flux is 80-85%, wherein the weight percentage of the boron oxide is 24-28%, and the weight percentage of the zinc oxide is 5.8-6.2%. CN109748514A an environmental protection impact-resistant glass pigment, which comprises a flux and a pigment, wherein the weight part of boron oxide in the flux is 20-30 parts, and the weight part of zinc oxide is 4-6 parts.

Under the condition of free oxygen, boron oxygen triangle [ BO₃]Convertible into boron-oxygen tetrahedron (BO)₄]The structure of boron is changed from a layer shape to a frame shape and is B₂O₃With SiO₂Forming uniform and consistent glass creating conditions; b is₂O₃With [ BO ]₃]Or [ BO ]₄]Into glass structures, especially when treated with [ BO ]₄]And [ SiO ]₂]When a structural network is formed together, the integrity and the compactness of the network are increased, and after zinc is added, zinc borosilicate microcrystal can be formed, so that the zinc borosilicate microcrystal has good thermal stability, chemical stability, mechanical property, process property, optical property and the like, and the proportion of the zinc element and the boron element in a formula is about 25-35 percent (otherwise, a glass body cannot be formed). If the proportion of the two elements is 30 percent, the production cost of the two elements is about 500 yuan/ton according to the current raw material price, which is not beneficial to the large-scale production of enterprises. How to reduce the production cost is a problem which needs to be solved urgently.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, the zinc-boron-free glass pigment flux is provided, fluorite and talc are used for replacing zinc and boron, the production cost can be greatly reduced, the prepared glass pigment has good chromaticity, and the corrosion resistance and the expansion coefficient can meet the use requirements of toughened glass.

The glass pigment flux without zinc and boron comprises the following ingredients in percentage by weight:

preferably, the ingredients comprise the following components in percentage by weight:

the formula of the invention adopts alkaline earth metal to replace zinc and boron, and simultaneously adopts SiO with higher content₂And Bi₂O₃The stability and the color development effect are ensured by adjusting the proportion combination of the formula, the foundation is laid for preparing the toughened glass pigment with pure color and good chemical stability, the acid resistance of the pigment is greatly improved by virtue of the mixed alkali effect, and SnO₂And ZrO₂The high molecular weight stabilizer makes the glass structure more compact, makes up the increase of expansion coefficient caused by the addition of alkali metal and alkaline earth metal due to the low expansibility, and makes the expansion coefficient suitable due to the mutual complementation and mutual synergy of the components in the flux.

The preparation method of the zinc-boron-free glass pigment flux is that the ingredients are mixed uniformly according to the proportion, and after passing through a 60-100 mesh sieve, the ingredients are melted at the high temperature of 1200-1300 ℃, quenched with water and dried to obtain the zinc-boron-free glass pigment flux.

The application of the glass pigment flux without zinc and boron is to mix the flux with a colorant and ball mill the mixture until the particle size of the particles is less than 0.5 mu m, and the finished product of the glass pigment is obtained after the mixture is ground, dried and crushed.

Wherein, the weight ratio of the fusing agent to the coloring agent is generally as follows: in the black pigment, 60-70% of flux and 30-40% of black agent are added.

The glass pigment containing no zinc and boron is used in the same way as common pigment products, and the decoration is completed along with the toughening treatment at 680-720 ℃.

Compared with the prior art, the invention has the following beneficial effects:

1. the invention adopts the raw materials which are directly added with the talcum and the fluorite to replace zinc and boron, thereby greatly reducing the production cost of the raw materials, and compared with the formula containing zinc and boron in the prior art, the cost is reduced by more than 80 percent, thereby being beneficial to large-scale production and increasing the enterprise benefit.

2. Tests show that the black glass pigment product prepared by the invention has good blackness, corrosion resistance and expansion coefficient which can meet the use requirements of toughened glass, and has the following physical and chemical performance indexes:

coefficient of thermal expansion: 75.0-90.0 x 10^-7℃^-1(measured using a type 402E electron dilatometer from west de);

chemical stability: after being soaked in 4 percent acetic acid solution for 24 hours, the color tone and the color are not obviously changed; in 0.5% Na₂CO₃After the solution is soaked for 40 hours, the color tone and the color have no obvious change.

3. The formula of the invention does not contain heavy metal, so that the harm to human bodies and the environment can be reduced.

Detailed Description

The present invention will be further described with reference to the following examples.

All the starting materials used in the examples are commercially available, except where otherwise indicated.

In the preparation method of the glass pigment containing no zinc and boron in the embodiment, the materials are prepared according to the formula composition, the flux is prepared firstly, and then the pigment is prepared, and the preparation method comprises the following steps:

(1) preparation of a fusing agent: uniformly mixing the raw materials required by the purchased fusing agent according to a proportion, sieving by a 60-100 mesh sieve, melting at the high temperature of 1250 +/-30 ℃, water quenching and drying for later use;

(2) ball milling: and mixing the glass pigment flux and a pigment, ball-milling until the particle size of the particles is less than 0.5 mu m, and drying after milling to obtain the finished glass pigment.

The compositions of the zinc and boron-free glass pigments and their fluxes in weight percent according to the examples of the present invention are shown in table 1.

TABLE 1 EXAMPLES 1-5 ZINC-BORON-FREE GLASS PIGMENTS AND ITS SOLUTION COMPOUNDS in weight percent

The glass pigments prepared in examples 1 to 5, which do not contain zinc and boron, were subjected to the performance test, and the test results are shown in Table 2.

Table 2 examples 1-5 performance test results for zinc and boron free glass pigment products

The thermal expansion coefficient was measured by a model 402E electron dilatometer manufactured by West Germany.

Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.

Claims

1. A zinc boron-free glass pigment flux characterized by: the weight percentage of the ingredients is as follows:

2. a zinc boron-free glass pigment flux according to claim 1, characterized in that: the weight percentage of the ingredients is as follows:

3. a method of preparing a zinc boron-free glass pigment flux according to any one of claims 1-2, characterized by: the ingredients are uniformly mixed according to a proportion, and are subjected to high-temperature melting at 1200-1300 ℃, water quenching and drying after being sieved by a 60-100-mesh sieve.

4. Use of a zinc boron-free glass pigment flux according to any one of claims 1-2, characterized in that: and mixing the flux and the colorant, ball-milling until the particle size of the particles is less than 0.5 mu m, drying after grinding, and crushing to obtain a finished glass pigment product.