A high-hardness glass paste and a preparation process thereof

Abstract

The application discloses a kind of high-hardness glass paste and its preparation process, belong to glass paste technical field, by solid phase powder and ink adjusting oil composition, and the ink adjusting oil weight accounts for solid phase powder weight ratio is 15~35%;The solid phase powder is by main phase glass powder, strengthening powder, black pigment is composed, and by weight percentage: main phase glass powder 50~68%, strengthening powder 2~5%, pigment 30~45%.High-hardness glass paste prepared by the application, after tempering, with black bright gloss high and good shielding ability, high hardness and other properties, suitable for household appliance glass product and the surface coating of automobile, building glass.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of high hardness glass paste and its preparation process, belong to glass paste technical field. BACKGROUND

[0002] With the rapid progress of science and technology and the improvement of life quality, the household appliance and automobile industry are in the development climax. Intelligent household appliances and various functional household appliances, such as microwave ovens, electric ovens, range hoods, etc., have deeply integrated into daily life, and the automobile industry has emerged intelligent technology to improve the driving experience. In order to meet the demand for beautiful and durable household appliances, the performance of glass products is continuously improved, and the automobile industry also has high requirements for the scratch resistance and shielding ability of glass.

[0003] Nowadays, household appliances and automobiles have high requirements for the shielding ability and scratch resistance of glass ink. Although the existing glass ink products on the market can basically meet the application, there are still performance defects in high shielding and high hardness scratch resistance. SUMMARY

[0004] At least for one problem of the prior art, the present application provides a kind of high hardness glass paste and its preparation process. After the glass paste is tempered, it has high black and bright gloss and good shielding ability, high hardness and other performances.

[0005] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows: a kind of high hardness glass paste is composed of solid phase powder and ink adjusting oil, and the weight of the ink adjusting oil accounts for 15-35% of the weight of the solid phase powder; the solid phase powder is composed of main phase glass powder, strengthening powder and black pigment, and the weight percentage is: main phase glass powder 50-68%, strengthening powder 2-5%, pigment 30-45%.

[0006] Preferably, the main phase glass powder comprises the following raw materials and their weight percentages: bismuth oxide 15-55%, silicon dioxide 6-35%, boric acid 8-25%, sodium oxide 3-10%, potassium oxide 1-6%, sodium fluoride 1-5%, titanium dioxide 1-8%, sodium fluorosilicate 0-5%, barium carbonate 0-6%, zinc oxide 0-5%, and iron oxide 0-4%; and the weight of silicon dioxide accounts for less than 53% of the sum of the weights of bismuth oxide, silicon dioxide and boric acid, and sodium fluorosilicate, barium carbonate, zinc oxide and iron oxide contain at least one kind.

[0007] Preferably, the weight of the silicon dioxide accounts for 10-45% of the sum of the weights of bismuth oxide and silicon dioxide and boric acid.

[0008] Preferably, the main phase glass powder contains at least one of barium carbonate or zinc oxide.

[0009] Preferably, the weight of the barium carbonate accounts for 0-3% of the total weight of the main phase glass powder.

[0010] Preferably, the reinforcing powder comprises at least two of zirconium silicate, silicon nitride, silicon carbide or aluminum oxide.

[0011] Preferably, each of the zirconium silicate, silicon nitride, silicon carbide or aluminum oxide accounts for 0-3% of the total weight of the solid-phase powder.

[0012] Preferably, the particle size D90 of the main-phase glass powder is 1-6 μm.

[0013] Preferably, the particle size D90 of the reinforcing powder is 1-7 μm.

[0014] Preferably, the particle size D90 of the black pigment is 1-5 μm.

[0015] Preferably, the black pigment comprises at least one of copper-chromium black pigment or manganese-iron black pigment.

[0016] Preferably, the ink adjusting oil is water-based ink adjusting oil.

[0017] Preferably, the preparation process of the main-phase glass powder is as follows:

[0018] (1) 15-55% bismuth oxide, 6-35% silicon dioxide, 8-25% boric acid, 3-10% sodium oxide, 1-6% potassium oxide, 1-5% sodium fluoride, 1-8% titanium dioxide, 0-5% sodium fluorosilicate, 0-6% barium carbonate, 0-5% zinc oxide, and 0-4% iron oxide are weighed according to the weight percentage of raw materials to obtain a base material;

[0019] (2) The base material of step (1) is placed in a crucible and heat-treated at 1100-1250°C for 0.5-2 h to form a molten glass liquid, and the molten glass liquid is then water-quenched to obtain a glass frit;

[0020] (3) The glass frit of step (2) is added with water and ball-milled to form a suspension with a particle size of 3-10 μm, dried and crushed to a particle size D90 of 1-6 μm to obtain a main-phase glass powder.

[0021] Preferably, the ball-milling conditions in step (3) are as follows: agate balls or high-aluminum balls with a diameter of 10-15 mm.

[0022] The present application provides a preparation process of a high-hardness glass paste, comprising the following steps:

[0023] S1, the main-phase glass powder with a particle size D90 of 1-6 μm, the reinforcing powder with a particle size D90 of 1-7 μm, and the black pigment with a particle size D90 of 1-5 μm are mixed and pretreated according to the above components and weight percentages to obtain a solid-phase powder;

[0024] S2, according to the weight ratio, the solid phase powder and ink oil are mixed, and after mixing, grinding is carried out to obtain a glass paste.

[0025] Preferably, the pretreatment in step S1 is ball milling with water to form a mixed powder suspension with a particle size of less than 5 μm, and then drying and crushing.

[0026] Preferably, the ball milling condition for the pretreatment in step S1 is a diameter of 10 mm to 15 mm of agate ball or high-aluminum ball.

[0027] Preferably, the grinding in step S2 is carried out using a three-roll machine.

[0028] Preferably, the high-hardness glass paste prepared by the present application has a scratch resistance greater than 18 N and an OD value greater than 4.2 after tempering at 580 ℃ to 720 ℃.

[0029] The beneficial effects of the present application are:

[0030] 1. The high-hardness glass paste prepared by the present application has a high hardness and wear resistance by reasonably controlling the metal oxide and alkaline earth metal components of the main phase glass powder and the appropriate proportion of the strengthening powder phase, and effectively improves the chemical stability of the glass paste, so that it has a higher hardness level and shielding ability.

[0031] 2. The high-hardness glass paste prepared by the present application has a tight network structure formed by adjusting Bi2O3, H3BO3 and SiO2 in the main phase glass powder.

[0032] 3. The high-hardness glass paste prepared by the present application has high hardness, scratch resistance, high black luster and high shielding property after tempering at 580 ℃ to 720 ℃.

[0033] 4. The high-hardness glass paste prepared by the present application has easy-to-obtain raw materials and simple process, and is particularly suitable for surface coating of household appliance glass products, automobile and building glass. DETAILED DESCRIPTION

[0034] The following is a clear and complete description of the technical solutions in the implementation of the present application. The described embodiments are only a part of the embodiments of the present application, not all embodiments. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application. The specific conditions are not specified in the embodiments, and are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments, components used are not specified by the manufacturer, and are conventional products that can be purchased on the market.

[0035] The high-hardness glass paste of the application is composed of solid-phase powder and ink oil, and the weight percentage of the ink oil in the solid-phase powder is 15-35%; the solid-phase powder is composed of main-phase glass powder, reinforcing powder and black pigment, and the weight percentage of the main-phase glass powder, reinforcing powder and black pigment is 50-68%, 2-5% and 30-45% respectively; and the ink oil is water-based ink oil.

[0036] In a further aspect of the application, the preparation process of the main-phase glass powder is as follows:

[0037] (1) 15-55% bismuth oxide, 6-35% silicon dioxide, 8-25% boric acid, 3-10% sodium oxide, 1-6% potassium oxide, 1-5% sodium fluoride, 1-8% titanium dioxide, 0-5% sodium fluorosilicate, 0-6% barium carbonate, 0-5% zinc oxide and 0-4% iron oxide are weighed according to the weight percentage of raw materials to obtain a base material;

[0038] (2) The base material of step (1) is placed in a crucible and heat-treated and sintered at 1100-1250°C for 0.5-2h to form a molten glass liquid, and the molten glass liquid is then water-quenched to obtain a glass frit;

[0039] (3) The glass frit of step (2) is added with water and ball-milled under the following ball-milling conditions: agate balls or high-aluminum balls with a diameter of 10-15mm to form a suspension with a particle size of 3-10μm, and the suspension is dried and crushed to a particle size D90 of 1-6μm to obtain the main-phase glass powder.

[0040] In a further aspect of the application, the main-phase glass powder contains at least one of barium carbonate or zinc oxide, and the weight percentage of barium carbonate in the total weight of the main-phase glass powder is 0-3%.

[0041] In a further aspect of the application, the reinforcing powder includes at least two of zirconium silicate, silicon nitride, silicon carbide or aluminum oxide, and the black pigment includes at least one of copper-chromium black pigment or manganese-iron black pigment.

[0042] In a further aspect of the application, the weight percentage of each of zirconium silicate, silicon nitride, silicon carbide or aluminum oxide in the total weight of the solid-phase powder is 0-3%.

[0043] The application provides a preparation process of high-hardness glass paste, which comprises the following steps:

[0044] S1, the main-phase glass powder with a particle size D90 of 1-6μm, the reinforcing powder with a particle size D90 of 1-7μm and the black pigment with a particle size D90 of 1-5μm are mixed and pretreated according to the above components and weight percentages: water is added and ball-milling is performed to form a mixed powder suspension with a particle size of less than 5μm, and then the mixed powder suspension is dried and crushed to obtain the solid-phase powder;

[0045] S2, the solid phase powder and the aqueous ink oil are mixed, wherein the ink oil accounts for 15-35% of the weight of the solid phase powder, and after mixing, grinding and mixing are performed by a three-roller machine to obtain a glass slurry.

[0046] The high-hardness glass slurry prepared by the method has a scratch resistance greater than 18N and an OD value greater than 4.2 after tempering at 580-720 DEG C.

[0047] I. Preparation of solid phase powder

[0048] Specific process: step 1, preparation of main phase glass powder: 1) according to the weight percentage of the raw materials in Table 1, bismuth oxide, silicon dioxide, boric acid, sodium oxide, potassium oxide, sodium fluoride, titanium dioxide, sodium fluorosilicate, barium carbonate, zinc oxide, iron oxide are weighed to obtain a base material;

[0049] 2) the base material in step 1) is placed in a crucible and heat treated at 1100-1250 DEG C for 0.5-2h to form a molten glass liquid, and then the molten glass liquid is quenched by water to obtain a glass melt;

[0050] 3) the glass melt in step 2) is added with water and ball milled to form a suspension with a particle size of 3-10 microns, dried and crushed to a particle size D90 of 1-6 microns to obtain a main phase glass powder;

[0051] Step 2, according to Table 2, zirconium silicate, silicon nitride, silicon carbide and aluminum oxide are mixed and crushed to a particle size D90 of 1-7 microns to obtain a strengthening powder;

[0052] Step 3, copper-chromium black pigment or manganese-iron black pigment is weighed and crushed to a particle size D90 of 1-5 microns to obtain a black pigment;

[0053] Step 4, according to Table 2, the main phase glass powder of step 1, the strengthening powder of step 2 and the black pigment of step 3 are mixed and pretreated: water is added and ball milled to form a mixed powder suspension with a particle size of less than 5 microns, and then dried and crushed to obtain a solid phase powder.

[0054] Table 1: content of each raw material of the main phase glass powder of the example

[0055]

[0056] In Table 1, the sum of the mass of bismuth oxide, silicon dioxide and boric acid is T.

[0057] Table 2: content of each component of the solid phase powder of the example

[0058]

[0059] II. Examples Glass paste preparation

[0060] Specific process: mix the solid phase powder and the water-based ink oil, wherein the weight percentage of the ink oil in the solid phase powder is 15-35%, and after mixing, grind and mix by a three-roll machine to obtain a glass paste. Among them:

[0061] Examples 1-18 Glass paste

[0062] The solid phase powder of examples 1-18 is mixed with water-based ink oil, and the weight percentage of the ink oil in the solid phase powder is 20%, forming the glass paste of examples 1-18.

[0063] Example 19 Glass paste

[0064] The solid phase powder of example 18 is mixed with water-based ink oil, and the weight percentage of the ink oil in the solid phase powder is 15%, forming the glass paste of example 19.

[0065] Example 20 Glass paste

[0066] The solid phase powder of example 18 is mixed with water-based ink oil, and the weight percentage of the ink oil in the solid phase powder is 35%, forming the glass paste of example 20.

[0067] III. Comparative example Solid phase powder preparation

[0068] Specific process: step 1, main phase glass powder preparation: 1) weigh the bismuth oxide, silicon dioxide, boric acid, sodium oxide, potassium oxide, sodium fluoride, titanium dioxide, sodium fluorosilicate, barium carbonate, zinc oxide, iron oxide according to the weight percentage of the raw materials in the following table 3 to obtain the base material;

[0069] 2) Put the base material of step 1) into a crucible and heat at 1100-1250℃ for 0.5-2h to form a molten glass liquid, then quench the molten glass liquid by water to obtain a glass melt;

[0070] 3) Add water to the glass melt of step 2) and ball mill, the ball milling conditions are: diameter of 10-15mm agate ball or high alumina ball, form a suspension with particle size of 3-10μm, dry and crush to particle size D90 of 1-6μm, to obtain the main phase glass powder;

[0071] Step 2, mix zirconium silicate, silicon nitride, silicon carbide, and aluminum oxide according to the following table 4, and crush to a particle size D90 of 1-7μm to obtain a strengthening powder;

[0072] Step 3, weigh the copper-chromium black pigment or manganese-iron black pigment, and crush to a particle size D90 of 1-5μm to obtain a black pigment;

[0073] Step 4, the main phase glass powder of step 1, the strengthening powder of step 2 and the black pigment of step 3 are weighed according to the following table 4, pretreated by adding water and ball milling, ball milling conditions: agate ball or high alumina ball with a diameter of 10mm-15mm, forming a mixed powder suspension with a particle size of less than 5um, then drying and crushing to obtain a solid phase powder.

[0074] Table 3, the main phase glass powder of the comparative example contains each raw material

[0075]

[0076] Table 4, the main phase glass powder of the comparative example contains each raw material

[0077]

[0078] Four, comparative example glass paste preparation

[0079] Specific process: mix the solid phase powder and water-based ink oil, wherein the weight of the ink oil accounts for 15-35% of the weight of the solid phase powder, mix uniformly, then grind and mix by three-roller machine to obtain glass paste. Among them:

[0080] Comparative examples 1-12 glass paste

[0081] The solid phase powder of comparative examples 1-12 is mixed with water-based ink oil, and the weight of the ink oil accounts for 20% of the weight of the solid phase powder to form the glass paste of comparative examples 1-12.

[0082] After the glass paste of the above examples 1-20 and comparative examples 1-12 is tempered at 580-720℃, performance test is carried out, and the results are shown in the following table 5. Standard requirement: the larger the N value, the better the scratch resistance, greater than 18N; the larger the OD value, the better the hiding property, ranging from 4.2 to 6.

[0083] Table 5, glass paste performance

[0084]

[0085] As can be seen from table 5, the glass paste of examples 1-20 of the present application has a solid phase powder, which is a combination of a proper amount of main phase glass powder, strengthening powder and black pigment, and an appropriate ratio system, after being tempered at 580-720℃, the OD value range is appropriate, the hiding property is better, the black luster is high, the N value increases, the scratch resistance is good, the hardness and wear resistance of the reinforcing material are enhanced, so that the glass paste has excellent hiding capacity and high hardness.

[0086] Compared with Examples 1-20, the content of the strengthening powder in the solid-phase powder of the glass paste of Comparative Examples 1-6, Comparative Example 10 and Comparative Example 12 is too much or too little, which affects the surface gloss and scratch resistance after tempering. The sintering temperature of the strengthening powder with too much content is high, the surface gloss after tempering is too low, the glaze is matt, and the scratch resistance is reduced. The strengthening powder with too little content has weak structure enhancement ability after tempering, which reduces the scratch resistance. In addition, Comparative Example 1, Comparative Example 2 and Comparative Example 3 have too much or too little silicon dioxide, boric acid and bismuth oxide, Comparative Example 4 has too much zinc oxide, Comparative Example 5 and Comparative Example 6 have too much alkali metal, Comparative Example 7 has too much alkaline earth metal, and Comparative Example 8 has too much titanium dioxide. In such a system, too much or too little content of silicon dioxide, boric acid and bismuth oxide will destroy the balance of the network structure, thereby reducing the structure strength after tempering and affecting the scratch resistance and surface gloss. Comparative Example 9 does not contain any of sodium fluorosilicate, barium carbonate, zinc oxide and iron oxide, which reduces the hiding power and scratch resistance of the surface after tempering. Comparative Example 11 and Comparative Example 12 have too much or too little main phase glass powder, strengthening powder and black pigment, which has an important influence on the hiding power and scratch resistance of the surface after tempering. The solid-phase powder in Examples 1-20 has the main phase glass powder containing an appropriate amount of metal oxides and alkaline earth metal, and the appropriate amount of strengthening powder, which synergistically helps the glass paste to have high hiding power and high hardness.

[0087] In addition, the hiding power and scratch resistance of the surface after tempering are improved by containing any one of barium carbonate or zinc oxide in Examples 12, 16 and 17. The hiding power and scratch resistance of the surface after tempering are further improved by at least one of barium carbonate or zinc oxide in combination with at least one of sodium fluorosilicate or barium carbonate in Examples 1-9. The hiding power and scratch resistance of the surface after tempering are reduced by the content of barium carbonate being 6% in Example 11 and 14, the weight of silicon dioxide accounting for 7.8% of the sum of the weights of bismuth oxide, silicon dioxide and boric acid in Example 10, which is less than 10%, and the weight of silicon dioxide accounting for 52.2% of the sum of the weights of bismuth oxide, silicon dioxide and boric acid in Example 11, which is greater than 45%. The OD value is still in the range of 4.2-6 and the N value is still greater than 18. It is found that the hiding power and scratch resistance of the surface after tempering are improved by containing at least two of zirconium silicate, silicon nitride, silicon carbide or aluminum oxide in the strengthening powder in Examples 1-9, 13, 15 and 18. The glass paste of Examples 1-9 and Example 13 has more excellent hiding power and hardness performance in the present application.

[0088] In summary, the high-hardness glass paste prepared by the application, through reasonable regulation and control of metal oxide, alkaline earth metal and other components of the main phase glass powder and appropriate proportion of the strengthening powder phase, further enhances the hardness and wear resistance of the paste, effectively improves the chemical stability of the glass paste, and makes it have higher hardness level and shielding capacity; the raw materials are easy to obtain, and the process is simple, especially suitable for surface coating of household appliance glass products, automobile and building glass.

[0089] It is apparent for those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, but can be implemented in other concrete forms without departing from the spirit and essential characteristics of the present application. Therefore, the embodiments should be considered in all aspects as illustrative and not restrictive, and the scope of the present application is defined by the appended claims rather than the above description, and all changes falling within the meaning and range of the equivalent elements of the claims are intended to be embraced in the present application.

[0090] In addition, it should be understood that although the present specification is described in terms of embodiments, not every embodiment contains only one independent technical solution, and the description of the specification is only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can be combined appropriately to form other embodiments that those skilled in the art can understand.

Claims

1. A high-hardness glass paste, characterized in that, It is composed of solid powder and ink oil, wherein the weight of the ink oil accounts for 15-35% of the weight of the solid powder; the solid powder is composed of main phase glass powder, reinforcing powder, and black pigment, and by weight percentage: main phase glass powder 50-68%, reinforcing powder 2-5%, and pigment 30-45%; The main phase glass powder comprises the following raw materials and their weight percentages: bismuth oxide 15-55%, silicon dioxide 6-35%, boric acid 8-25%, sodium oxide 3-10%, potassium oxide 1-6%, sodium fluoride 1-5%, titanium dioxide 1-8%, sodium fluorosilicate 0-5%, barium carbonate 0-6%, zinc oxide 0-5%, and iron oxide 0-4%; and the weight percentage of silicon dioxide is less than 53% of the sum of the weights of bismuth oxide, silicon dioxide, and boric acid, and at least one of sodium fluorosilicate, barium carbonate, zinc oxide, and iron oxide is contained; The reinforcing powder includes at least two of zirconium silicate, silicon nitride, silicon carbide, or alumina; the weight percentage of each of zirconium silicate, silicon nitride, silicon carbide, or alumina in the total weight of the solid powder is between 0 and 3%.

2. The high-hardness glass slurry according to claim 1, characterized in that, The weight percentage of silicon dioxide is 10-45% of the sum of the weights of bismuth oxide, silicon dioxide, and boric acid.

3. The high-hardness glass slurry according to claim 1, characterized in that, The main phase glass powder contains at least one of barium carbonate or zinc oxide.

4. The high-hardness glass slurry according to claim 1, characterized in that, The weight of barium carbonate accounts for 0-3% of the total weight of the main phase glass powder.

5. The high-hardness glass slurry according to claim 1, characterized in that, The black pigment includes at least one of copper-chromium melanin or manganese-iron melanin.

6. The high-hardness glass slurry according to claim 1, characterized in that, The preparation process of the main phase glass powder is as follows: (1) Weigh out 15-55% bismuth oxide, 6-35% silicon dioxide, 8-25% boric acid, 3-10% sodium oxide, 1-6% potassium oxide, 1-5% sodium fluoride, 1-8% titanium dioxide, 0-5% sodium fluorosilicate, 0-6% barium carbonate, 0-5% zinc oxide, and 0-4% iron oxide according to the weight percentage of the raw materials to obtain the base material; (2) Place the base material from step (1) into a crucible and heat it at 1100~1250℃ for 0.5~2h to form molten glass. Then quench the molten glass with water to obtain glass frit. (3) Add water to the glass molten block from step (2) and ball mill it to form a suspension with a particle size of 3~10μm. After drying, pulverize it to a particle size D90 of 1~6μm to obtain the main phase glass powder.

7. The high-hardness glass slurry according to claim 1, characterized in that, The particle size D90 of the main phase glass powder is 1~6μm; the particle size D90 of the reinforcing powder is 1~7μm; and the particle size D90 of the black pigment is 1~5μm.

8. A process for preparing a high-hardness glass slurry according to any one of claims 1 to 7, characterized in that, The steps include the following: S1. According to the above components and their weight percentages, the main phase glass powder with a particle size D90 of 1~6μm, the strengthening powder with a particle size D90 of 1~7μm, and the black pigment with a particle size D90 of 1~5μm are mixed and pretreated to obtain solid phase powder. S2. According to the above weight ratio, the solid powder and ink oil are mixed, and after mixing, they are ground to obtain glass paste; The pretreatment in step S1 involves adding water and ball milling to form a mixed powder suspension with a particle size of less than 5 μm, followed by drying and pulverization.

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