WO2020042355A1

WO2020042355A1 - Dry granules, dry granular glaze, and dry granular glazed tile

Info

Publication number: WO2020042355A1
Application number: PCT/CN2018/114130
Authority: WO
Inventors: 程贵生; 范新晖; 廖花妹; 吴志坚; 吴柏惠
Original assignee: 佛山石湾鹰牌陶瓷有限公司
Priority date: 2018-08-27
Filing date: 2018-11-06
Publication date: 2020-03-05
Also published as: CN109052958B; CN109052958A

Abstract

The present application provides dry granules, a dry granular glaze, and a dry granular glazed tile. Dry granules comprise, in mass percentage: Al₂O₃ 5-15%, SiO₂ 40-55%, CaO 10-18%, K₂O 5-10%, MgO 5-12%, BaO 4-10%, ZnO 2-5%, and RuO₂ 0.1-0.5%. A dry granular glaze comprises 40-50 parts of the dry granules, and further comprises: 10-20 parts of a protective glaze, 1-3 parts of a kaolin slurry, 0.5-1.5 parts of a calcined talc slurry, 90-110 parts of a suspending agent, and 0.05-0.1 parts of an inkjet glaze surfactant. A dry granular glazed tile comprises adobe, a base glaze, and the dry granular glaze.

Description

Dry grain, dry grain glaze and dry grain glazed tile Ranch

Technical field

The present application relates to the field of ceramics, and in particular, to a dry grain, a dry grain glaze, and a dry grain glazed tile.

Background technique

In recent years, the market share of modern antique bricks is getting higher and higher, and the cultural elements such as the sense of history, nostalgia, naturalness, return, and personalization, as well as both fashion and fashion, have gradually gained more and more. Attention and recognition. The matte soft dry grain glazed tile is an upgraded product of modern antique tiles. It not only inherits the unique cultural elements of antique tiles and the super hardness of polished tiles, but also gives it a more realistic stone texture, and at the same time has a warm touch. Jade without the cold feeling of stone. The matte soft dry grain glazed tile is a floor tile with stronger texture, softer touch, stronger hardness and better anti-fouling and anti-slip effect. This kind of floor tile is different from other floor tiles when you step on it to give you the feeling of cold, stiff, sticky feet, matte soft dry grain glaze tile will make people feel very comfortable, step on it has a sense of solidity, warmth, and relaxation, it is very suitable for advocating People returning to nature.

The prior art has the following shortcomings: the product surface has jamming and dirt absorption problems. At present, there are many such products on the market, but they are simply mixed with a certain proportion of dry particles and suspending agent, and then sprayed uniformly on the surface of the product with a spray glaze cabinet. This process is mostly used on antique brick products to play a role in decorating the surface of the product. However, due to the unevenness of the product surface, the gap between the dry particles is large or small, and the surface is prone to jamming and staining after being affixed inside the product.

In view of this, this application is hereby filed.

Application content

The first object of the present application is to provide a dry grain, and the second object is to provide a dry grain glaze. The dry grain glaze prepared by using the dry grain can obtain a surface with good antifouling performance and good antique ornamental performance. Dry grain glazed tiles.

A third object of the present application is to provide the dry-grain glazed tile.

In order to achieve the above purpose of this application, the following technical solutions are adopted:

A dry pellet, in mass percent, including:

Al ₂ O ₃ 5-15%, SiO ₂ 40-55%, CaO10-18%, K ₂ O5-10%, MgO5-12%, BaO4-10%, ZnO2-5%, RuO ₂ 0.1-0.5%.

RuO ₂ is very stable during firing and will decompose above 1400 ° C. At 1170-1185 ° C, it forms a stable distribution center on the surface of the brick, and the other components are in a molten or semi-molten state, which together form a relatively uniform size of semi-spherical particles to cover the surface of the product, which plays a role in preventing soiling and suction. At the same time, it makes the glaze feel warm and comfortable.

Optionally, the dry particles are further included in a percentage by mass, and further include: V ₂ O ₅ 0.1-0.5% and Bi ₂ O ₃ 0.1-0.5%.

Vanadium pentoxide will decompose into oxygen and vanadium tetroxide at about 700-1125 ° C. This change will improve the microstructure of the glaze and effectively improve the antifouling performance during the firing process. There are three different crystalline forms of bismuth trioxide. The combination of these different crystalline forms can change the composition of the dry particles after being added to the dry particles, so that the best molten state can be obtained during the preparation process, and then better Surface structure for excellent antifouling performance.

More optionally, the particle size of the dry particles is 120-200 mesh.

The control of the particle size can make the surface morphology more optimized and the antifouling performance better.

The present application also provides a dry grain glaze, which includes 40-50 parts of the dry grains in terms of parts by weight, and further includes:

10-20 parts of protective glaze, 1-3 parts of kaolin pulp, 0.5-1.5 parts of calcined talc pulp, 90-110 parts of suspending agent and 0.05-0.1 parts of ink discharging agent.

The role of the protective glaze is to form an effective filling effect between the dry particles, so that the glaze can obtain semi-circular protrusions of the appropriate size, improve the surface structure, and improve the antifouling effect; the kaolin slurry is kaolin and water, which acts as a dispersion At the same time, the firing temperature of dry grain glaze can be increased; the calcined talc slurry is calcined talc and water, which mainly plays a role in reducing the firing temperature of dry grain glaze. It cooperates with kaolin slurry to obtain a suitable firing temperature, which is beneficial Control the state of the dry particles and protective glaze components during firing to obtain a better molten or semi-melted form, thereby ensuring the microstructure of the glaze and ensuring antifouling performance. The use of the suspending agent is to ensure that the components can be better dispersed in the system, to prevent quality defects caused by local unevenness during the firing process; the use of the ink discharge agent is to avoid the following situations: The dissolution causes oil-water separation between the inkjet printing part and the joint of the water-based glaze, which causes defects such as glaze, pits and bubbles on the surface of the tile after firing, which seriously affects the product quality. In addition to the above defects, the ink discharge agent can greatly improve the glaze slurry leveling and cohesiveness, thereby improving the glaze surface level and cohesiveness.

Optionally, the dry grain glaze has a specific gravity of 1.23-1.27 g / ml and a fineness of 0.4% -0.6% by weight of the dry material after passing through a 200 mesh sieve.

The specific gravity and sieve residue are controlled to obtain better product performance.

Further optionally, the protective glaze includes 55-65% of transparent glaze powder, sodium carboxymethyl cellulose in a mass percentage. 0.2-0.5%, sodium tripolyphosphate 0.2-0.4%, aluminum chloride 1-2%, aluminum sulfate 1-2%, potassium potassium sulfate dodecahydrate 1-2%, water 30-36%, and printing paste 1- 5%.

The optimization of the protective glaze can better match with the dry particles, obtain the best surface microstructure, and then obtain the best antifouling performance.

More optionally, the suspending agent is sodium carboxymethyl cellulose, and the ink discharging agent is polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt, and polyethylene. One of the diols.

There are many kinds of suspending agents and ink discharge agents, and the above-mentioned preferred results can make the overall performance reach the best.

The present application also provides a dry-grain glazed tile, including a brick blank, a base glaze, and the dry-grain glaze.

Optionally, the base glaze includes SiO ₂ 40-55%, Al ₂ O ₃ 10-15%, CaO8-10%, MgO5-8%, ZnO10-15%, and K ₂ O4-6% by mass percentage. , Na ₂ O1-3%, BaO1-3%.

The choice of the base glaze can make the brick, base glaze and dry grain glaze match better, and the strength and antique performance are better.

More optionally, the firing temperature is 1170-1185 ° C.

The control of the firing temperature is to control each component in the dry grain glaze to obtain the best micro-morphology during firing, to achieve the best mutual coordination and coating form, and to obtain the best antifouling performance.

Compared with the prior art, the technical effects of this application are:

1. By selecting the ingredients of the dry granules, especially adding ruthenium dioxide, after firing at high temperature, hemispherical granules of relatively uniform size are formed to cover the surface of the product, making the glaze feel warm and comfortable;

2. Add protective glaze to the dry grain glaze, which can solve the problem that the gap between the particles and the particles does not get stuck and suck;

3. Optimizing the composition and firing temperature, the molten state formed during the firing process, the best surface microstructure is obtained after cooling, and the antifouling performance is improved.

detailed description

The following describes the implementation of the present application in detail with reference to the examples, but those skilled in the art will understand that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. If the specific conditions are not indicated in the examples, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

Example 1

Follow the steps below to prepare dry-grain glazed tiles:

1. The bricks laid by the press are dried to remove the free water inside, so that the moisture of the bricks is less than 0.5%; after the bricks are out of the drying kiln, water is sprayed on the surface to form a water film on the surface;

2. Then glaze the base body with a glaze of 87g (340 * 670 tray); the base glaze includes SiO ₂ 40%, Al ₂ O ₃ 15%, CaO10%, MgO8%, ZnO15% , K ₂ O6%, Na ₂ O3%, BaO3%;

3. The inkjet machine prints the pattern and is dried by the second drying kiln to shorten the drying time of the ink;

4. Spray dry grain glaze; dry grain glaze flow rate is 26s, specific gravity is 1.27g / ml, glaze volume is 67g (340 * 670 tray), the fineness is 0.4% by weight after 200 mesh sieve; the dry grain glaze is based on parts by weight, including 40 parts of dry grain, 20 parts of protective glaze, 1 part of kaolin slurry, and burned talc 1.5 parts of pulp, 90 parts of suspending agent and 0.1 parts of ink-discharging agent;

The dry particles include Al ₂ O ₃ 5%, SiO ₂ 55%, CaO10%, K ₂ O10%, MgO5%, BaO10%, ZnO4.5%, RuO ₂ 0.5%; the particle size of the dry particles is 120 mesh. ;

Protective glaze includes transparent glaze powder 60%, sodium carboxymethyl cellulose 0.3%, sodium tripolyphosphate 0.2%, aluminum chloride 1%, aluminum sulfate 1.5%, aluminum potassium sulfate dodecahydrate 2%, water 30% and printing paste 5%; transparent glaze powder includes Al ₂ O ₃ 15%, SiO ₂ 55%, CaO10%, K ₂ O5%, MgO5%, BaO4.5%, ZnO5%, Lu ₂ O ₃ 0.5%;

The suspending agent is sodium carboxymethyl cellulose, and the ink discharging agent is polyacrylamide;

5. The bricks sprayed with dry grain glaze are dried in the drying kiln for the third time and then entered into the kiln. 1170 ° C (based on the temperature measured by the temperature measurement ring), fired at high temperature for 70min to obtain a semi-finished product;

6. Semi-finished products are packaged as finished products after edging and 800-mesh fiber polishing module combination.

Example 2

Follow the steps below to prepare dry-grain glazed tiles:

1. The bricks laid by the press are dried to remove the free water inside, so that the moisture of the bricks is less than 0.5%; after the bricks are out of the drying kiln, water is sprayed on the surface to form a layer of water film on the surface;

2. Then glaze the base body with a glaze of 93g (340 * 670 tray); the base glaze includes SiO ₂ 55%, Al ₂ O ₃ 13%, CaO8%, MgO5%, ZnO10% by mass percentage. , K ₂ O5%, Na ₂ O2%, BaO2%;

4. Spray dry grain glaze; dry grain glaze flow rate is 31s, specific gravity is 1.23g / ml, glaze volume is 73g (340 * 670 tray), the fineness is 0.6% by weight after 200 mesh sieve; dry grain glaze is based on weight parts, including 50 parts of dry grain, 10 parts of protective glaze, 3 parts of kaolin slurry, and burned talc 0.5 parts of pulp, 110 parts of suspending agent and 0.05 parts of ink discharge agent;

Dry particles include Al ₂ O ₃ 15%, SiO ₂ 40%, CaO18%, K ₂ O5.3%, MgO12%, BaO4%, ZnO5%, RuO ₂ 0.1%, V ₂ O ₅ 0.5% and Bi ₂ O ₃ 0.1%; the particle size of the dry particles is 200 mesh;

The protective glaze includes transparent glaze powder 63%, sodium carboxymethyl cellulose 0.2%, sodium tripolyphosphate 0.3%, aluminum chloride 2%, aluminum sulfate 1%, aluminum potassium sulfate dodecahydrate 1%, water 30.5% and printing paste 2%; transparent glaze powder includes Al ₂ O ₃ 15%, SiO ₂ 55%, CaO10%, K ₂ O5%, MgO5%, BaO4.5%, ZnO5%, Lu ₂ O ₃ 0.5%;

The suspending agent is sodium carboxymethyl cellulose, and the ink discharging agent is polyacrylic acid;

5. The bricks sprayed with dry grain glaze are dried in the drying kiln for the third time and then entered into the kiln. 1185 ℃ (based on the temperature measured by the temperature measuring ring), and the semi-finished product is obtained by firing at high temperature for 70min;

Example 3

Follow the steps below to prepare dry-grain glazed tiles:

2. Then glaze the base body with a glaze amount of 90g (340 * 670 tray); the base glaze includes SiO ₂ 54%, Al ₂ O ₃ 10%, CaO9%, MgO7%, ZnO14% , K ₂ O4%, Na ₂ O1%, BaO1%;

4. Spray dry grain glaze; dry grain glaze flow rate is 29s, specific gravity is 1.25g / ml, glaze volume is 70g (340 * 670 tray), fineness is 0.5% by weight after 200 mesh sieve; dry grain glaze is based on weight parts, including 48 parts dry grain, 15 parts protective glaze, 2 parts kaolin slurry, and burnt talc 1 part of pulp, 100 parts of suspending agent and 0.08 part of ink-discharging agent;

The dry particles include Al ₂ O ₃ 9%, SiO ₂ 50%, CaO15%, K ₂ O5%, MgO10%, BaO8%, ZnO2%, RuO ₂ 0.4%, V ₂ O ₅ 0.1% and Bi ₂ O ₃ 0.5%; the particle size of the dry particles is 150 mesh;

Protective glaze includes transparent glaze powder 55%, sodium carboxymethyl cellulose 0.5%, sodium tripolyphosphate 0.4%, aluminum chloride 1%, aluminum sulfate 2%, aluminum potassium sulfate dodecahydrate 1.1%, water 36%, and printing paste 4%;

The suspending agent is sodium carboxymethyl cellulose, and the ink discharging agent is polyvinylpyrrolidone;

5. The bricks sprayed with dry grain glaze are dried in the drying kiln for the third time and then entered into the kiln. 1180 ℃ (based on the temperature measured by the temperature measuring ring), and the semi-finished product is obtained by firing at high temperature for 65min;

Example 4

Follow the steps below to prepare dry-grain glazed tiles:

2. Then glaze the base body with a glaze of 91g (340 * 670 tray); the base glaze includes SiO ₂ 53%, Al ₂ O ₃ 11%, CaO8%, MgO8%, ZnO14% , K ₂ O4%, Na ₂ O1%, BaO1%;

4. Spray dry grain glaze; dry grain glaze flow rate is 30s, specific gravity is 1.26g / ml, glaze volume is 69g (340 * 670 tray), the fineness is 0.45% by weight after 200 mesh sieve; the dry grain glaze is based on weight parts, including 48 parts dry grain, 18 parts protective glaze, 2 parts kaolin slurry, and burnt talc 1 part of pulp, 95 parts of suspending agent and 0.1 part of ink discharging agent;

The dry particles include Al ₂ O ₃ 10%, SiO ₂ 45%, CaO17%, K ₂ O8%, MgO8%, BaO7%, ZnO4%, RuO ₂ 0.2%, V ₂ O ₅ 0.4% and Bi ₂ O ₃ 0.4%; the particle size of the dry particles is 180 mesh;

Protective glaze includes transparent glaze powder 65%, sodium carboxymethyl cellulose 0.2%, sodium tripolyphosphate 0.2%, aluminum chloride 1.6%, aluminum sulfate 1%, aluminum potassium sulfate dodecahydrate 1%, water 30% and printing paste 1%;

The suspending agent is sodium carboxymethyl cellulose, and the ink discharging agent is polyvinyl alcohol. In other preferred embodiments, the ink discharging agent may also be selected from polymaleic anhydride, polyquaternary ammonium salt, or polyethylene glycol.

5. The bricks sprayed with dry grain glaze are dried in the drying kiln for the third time and then entered into the kiln. 1175 ℃ (based on the temperature measured by the temperature measuring ring), and the semi-finished product is obtained by firing at high temperature for 68min;

Comparative Example 1

Compared with Example 1, the difference is that the dry particles do not contain RuO2;

Comparative Example 2

Compared with Example 2, the difference is that the dry glaze does not contain a protective glaze;

Comparative Example 3

Compared with Example 3, the difference is that it does not contain a suspending agent and an ink discharge agent;

Comparative Example 4

The difference from Example 1 is that the firing temperature is 1200 ° C.

The parameters of the products obtained in Examples 1-4 and Comparative Examples 1-4 were tested, and the results are shown in Table 1 below:

Table 1 Test results

检测项目Test items	光泽度 Gloss	抗折强度MPaFlexural strength MPa	防污性Antifouling
实施例1Example 1	3030	4242	三级Third grade
实施例2Example 2	2525	4545	三级Third grade
实施例3Example 3	2828	4545	三级Third grade
实施例4Example 4	2626	4545	三级Third grade
比较例1Comparative Example 1	6464	4444	二级Secondary
比较例2Comparative Example 2	7272	3939	二级Secondary
比较例3Comparative Example 3	5555	3535	二级Secondary
比较例4Comparative Example 4	101101	4141	二级Secondary

As can be seen from Table 1 above, the addition of RuO ₂ , V ₂ O5 and Bi ₂ O ₃ can effectively improve the gloss of the finished product, make it obtain a matte effect, and change the discomfort caused by the strong light generated by direct reflection to the user. It can also improve the anti-fouling performance. Protecting the use of glaze, suspending agent and ink-discharging agent will help to improve the surface decoration performance and the strength of the product. Control of the firing temperature will help optimize the surface structure. , Improve antifouling performance and antique effect.

Using the dry grain and dry grain glaze provided in this application, the dry grain glazed tile obtained is a matte and soft dry grain glazed tile. In addition to good antifouling performance and good decorative effect, the comprehensive effect can give a very comfortable , Solid, warm, relaxed feeling.

For those skilled in the art, this application may have various modifications and changes. Any modification, equivalent replacement, or improvement made within the spirit and principle of this application shall be included in the protection scope of this application. Although this application has been illustrated and described with specific embodiments, it should be appreciated that many other changes and modifications can be made without departing from the spirit and scope of this application. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this application.

Claims

A dry granule, wherein, in mass percentage, includes:

Al 2 O 3 5-15%, SiO 2 40-55%, CaO10-18%, K 2 O5-10%, MgO5-12%, BaO4-10%, ZnO2-5%, RuO 2 0.1-0.5%.
The dry granule according to claim 1, wherein the dry granule comprises, by mass percentage, SiO 2 40%, Al 2 O 3 15%, CaO10%, MgO8%, ZnO15%, K 2 O6%, Na 2 O3%, BaO3%.
The dry granule according to claim 1, further comprising: V 2 O 5 0.1-0.5% and Bi 2 O 3 0.1-0.5% in terms of mass percentage.
The dry granule according to claim 3, wherein the dry granule comprises, by mass percentage, V 2 O 5 0.1% and Bi 2 O 3 0.1%.
The dry granule according to claim 1, wherein the particle size of the dry granule is 120-200 mesh.
The dry granule according to claim 5, wherein the particle size of the dry granule is 120 mesh.
A dry grain glaze, which comprises 40-50 parts of a dry grain in terms of parts by weight, and the dry grain in mass percentage includes: Al 2 O 3 5-15%, SiO 2 40-55%, CaO10-18%, K 2 O5-10%, MgO5-12%, BaO4-10%, ZnO2-5%, RuO 2 0.1-0.5%; the dry grain glaze also includes:

10-20 parts of protective glaze, 1-3 parts of kaolin pulp, 0.5-1.5 parts of calcined talc pulp, 90-110 parts of suspending agent and 0.05-0.1 parts of ink discharging agent.
The dry grain glaze according to claim 7, wherein the dry grain glaze comprises: 10 parts of protective glaze, 1 part of kaolin pulp, 0.5 part of calcined talc pulp, 90 parts of suspending agent, and 0.05 part of ink discharging agent.
The dry grain glaze according to claim 7, wherein the dry grain glaze has a specific gravity of 1.23-1.27 g / ml and a fineness of 0.4% -0.6% by weight of the dry material after passing through a 200 mesh sieve.
The dry grain glaze according to claim 9, wherein the dry grain glaze comprises: the dry grain glaze has a specific gravity of 1.27 g / ml, and a fineness of 0.4% by weight after drying through a 200-mesh sieve.
The dry grain glaze according to claim 7, wherein the protective glaze comprises a transparent glaze powder of 55-65%, sodium carboxymethyl cellulose in a mass percentage. 0.2-0.5%, sodium tripolyphosphate 0.2-0.4%, aluminum chloride 1-2%, aluminum sulfate 1-2%, potassium potassium sulfate dodecahydrate 1-2%, water 30-36%, and printing paste 1-5%.
The dry-grain glaze according to claim 11, wherein the protective glaze comprises 60% of transparent glaze powder, 0.3% of sodium carboxymethyl cellulose, and sodium tripolyphosphate in terms of mass percentage. 0.2%, aluminum chloride 1%, aluminum sulfate 1.5%, aluminum potassium sulfate dodecahydrate 2%, water 30% and printing paste 5%.
The dry grain glaze according to claim 12, wherein the transparent glaze powder comprises Al 2 O 3 15%, SiO 2 55%, CaO10%, K 2 O5%, MgO5%, BaO4.5% in mass percentage. , ZnO5%, Lu 2 O 3 0.5%.
The dry particle glaze according to claim 7, wherein the suspending agent is sodium carboxymethyl cellulose, and the ink discharging agent is polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride , Polyquaternary amine salt and polyethylene glycol.
A dry grain glazed tile, which includes a brick blank, a base glaze, and a dry grain glaze. The dry grain glaze, based on weight fraction, includes: 10-20 parts of protective glaze, 1-3 parts of kaolin slurry, and 0.5- 1.5 parts, 90-110 parts of suspending agent, 0.05-0.1 parts of ink-removing agent, and 40-50 parts of a dry particle, the dry particle is based on mass percentage, including: Al 2 O 3 5-15%, SiO 2 40-55%, CaO10-18%, K 2 O5-10%, MgO5-12%, BaO4-10%, ZnO2-5%, RuO 2 0.1-0.5%.
The dry-grain glazed tile according to claim 15, wherein the base glaze comprises SiO 2 40-55%, Al 2 O 3 10-15%, CaO8-10%, MgO5-8%, ZnO10 in terms of mass percentage. -15%, K 2 O4-6%, Na 2 O1-3%, BaO1-3%.
The dry-grain glazed tile according to claim 16, wherein the base glaze comprises SiO 2 55%, Al 2 O 3 13%, CaO8%, MgO5%, ZnO10%, K 2 O5%, Na 2 O2%, BaO2%.
The dry-grain glazed tile according to claim 15, wherein the firing temperature is 1170-1185 ° C.
The dry-grain glazed tile according to claim 18, wherein the firing temperature is 1170 ° C.