A high-gloss blue glaze composition

Abstract

This application relates to the field of glaze technology, specifically providing a high-gloss blue glaze composition. The raw material components, calculated by weight, include: 20-30 parts potassium feldspar, 30-50 parts quartz powder, 1-5 parts kaolin, 1-4 parts calcined kaolin, 3-7 parts alumina powder, 4-9 parts calcite, 3-10 parts dolomite, 10-20 parts wollastonite, 0.5-2 parts zinc oxide, 2-5 parts strontium carbonate, 5-10 parts zirconium silicate, and 1-6 parts of coated cobalt blue; the coated cobalt blue is silica-coated cobalt blue. The use of silica-coated cobalt blue in this application can improve the glaze's color stability and the cobalt blue's heat resistance.

Description

Technical Field

[0001] The present application relates to the technical field of glazes, and in particular to a high-gloss blue glaze composition. Background Art

[0002] Bathroom products are usually white in color. Although white has many different specific colors, it is difficult to meet the personalized needs of consumers. It is of certain significance to develop bathroom products with blue glaze (blue glaze). Blue glaze is usually added with cobalt blue as a pigment, but there are also the following problems: (1) Cobalt blue has a strong color rendering ability, but it is easy to migrate and flow, making it difficult to locate during decoration, and it will cause uneven color distribution, affecting the decorative effect; (2) Cobalt blue has a temperature resistance of 1200℃, and glaze sintering generally exceeds 1200℃, such as 1220~1250℃, which will affect the color of the glaze. Summary of the Invention

[0003] In order to solve the above problems, the present application provides a high-gloss blue glaze composition, in which the cobalt blue raw material is wrapped with silica. It is found that by replacing cobalt blue with wrapped cobalt blue, the color uniformity of the glaze layer is better, and no color deviation will occur after sintering at high temperature.

[0004] This application adopts the following technical solutions:

[0005] A high-gloss blue glaze composition, comprising, by weight, 20-30 parts of potassium feldspar, 30-50 parts of quartz powder, 1-5 parts of kaolin, 1-4 parts of calcined kaolin, 3-7 parts of alumina powder, 4-9 parts of calcite, 3-10 parts of dolomite, 10-20 parts of wollastonite, 0.5-2 parts of zinc oxide, 2-5 parts of strontium carbonate, 5-10 parts of zirconium silicate, and 1-6 parts of coated cobalt blue.

[0006] The encapsulated cobalt blue is silica-encapsulated cobalt blue.

[0007] Preferably, the average particle size of the encapsulated cobalt blue is 50 to 500 nm.

[0008] Preferably, the preparation method of the encapsulated cobalt blue is: co-hydrolyzing trialkoxysilane and alkyl orthosilicate to obtain a hydrolyzate; adding cobalt blue to the hydrolyzate, ultrasonically dispersing for 1 to 10 minutes, stirring for 5 to 120 minutes, filtering, washing, and drying to obtain the product.

[0009] More preferably, the general formula of the trialkoxysilane is R 1 Si(OR 2 )3, where R 1 Selected from C1-C4 alkyl, amino-substituted C3-C8 alkyl, epoxy-substituted C3-C10 alkyl, epoxy-substituted C6-C10 cycloalkyl or polyether structure, R2 Selected from C1-C4 alkyl or C2-C4 acyl.

[0010] More preferably, the alkyl orthosilicate is selected from methyl orthosilicate and / or ethyl orthosilicate.

[0011] More preferably, the weight ratio of the trialkoxysilane to the alkyl orthosilicate is 0.01 to 0.1:1.

[0012] More preferably, the average particle size of the cobalt blue is 30 to 400 nm.

[0013] More preferably, the weight ratio of the cobalt blue to the hydrolyzed solution is 0.05 to 1:1.

[0014] Preferably, the raw material components further comprise: 1 to 3 parts of coated cobalt black, wherein the cobalt black is silica coated cobalt black.

[0015] More preferably, the average particle size of the coated cobalt black is 50 to 500 nm.

[0016] In summary, this application has the following beneficial effects:

[0017] 1. The present application adopts a coating structure to wrap cobalt blue, which neither affects the color-rendering ability of cobalt blue nor the problem of its easy migration and flow. The obtained glaze has a high color uniformity. Moreover, due to the insulating effect of silica in the coating layer, the cobalt blue has better temperature resistance, and the cobalt blue will not affect its color when the glaze is sintered.

[0018] 2. When the cobalt blue of this application is coated, the treatment liquid used contains organic groups, which can improve the dispersion stability in the slurry and further promote the uniformity of the glaze color after sintering. Moreover, a small amount of organic groups can be removed during the sintering process without affecting the glaze performance or color. DETAILED DESCRIPTION

[0019] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be described in detail below.

[0020] Throughout this specification, unless otherwise specified, the terms used herein should be understood as having the same meaning as commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event of any conflict, the present specification shall take precedence.

[0021] The present application provides a high-gloss blue glaze composition, which comprises, by weight, 20-30 parts of potassium feldspar, 30-50 parts of quartz powder, 1-5 parts of kaolin, 1-4 parts of calcined kaolin, 3-7 parts of aluminum oxide powder, 4-9 parts of calcite, 3-10 parts of dolomite, 10-20 parts of wollastonite, 0.5-2 parts of zinc oxide, 2-5 parts of strontium carbonate, 5-10 parts of zirconium silicate, and 1-6 parts of coated cobalt blue.

[0022] Encapsulated cobalt blue is silica-encapsulated cobalt blue.

[0023] Using silica to wrap cobalt blue can improve the heat resistance of cobalt blue, prevent color change when the glaze is sintered at high temperature, and avoid color migration of cobalt blue, thereby improving color stability.

[0024] Among the above raw material components, the particle size of potassium feldspar, quartz powder, kaolin, calcined kaolin, alumina powder, calcite, dolomite, wollastonite, zinc oxide, strontium carbonate, and zirconium silicate is not particularly limited. Specifically, it can be 1-50 μm, or it can be a graded distribution of different particle sizes, for example, 1-10 μm accounts for 70-80%, 10-20 μm accounts for 15-20%, and 20-40 μm accounts for 5-10%.

[0025] In a preferred embodiment of the present application, the average particle size of the encapsulated cobalt blue is 50 to 500 nm. If the particle size of the encapsulated cobalt blue is too small, it will be difficult to disperse in the glaze. If the particle size is too high, the smoothness of the glaze layer after the glaze is sintered will be deteriorated. For example, the average particle size of the encapsulated cobalt blue in the present application can be any value among 50 nm, 80 nm, 100 nm, 120 nm, 150 nm, 170 nm, 200 nm, 220 nm, 250 nm, 280 nm, 300 nm, 330 nm, 350 nm, 370 nm, 400 nm, 420 nm, 450 nm, 480 nm, 500 nm, etc.

[0026] In a preferred embodiment of the present application, the preparation method of the encapsulated cobalt blue is: trialkoxysilane and alkyl orthosilicate are co-hydrolyzed to obtain a hydrolyzate; cobalt blue is added to the hydrolyzate, ultrasonically dispersed for 1 to 10 minutes, stirred for 5 to 120 minutes, filtered, washed, and dried to obtain the product.

[0027] The method of co-hydrolyzing trialkoxysilane and alkyl orthosilicate and then coating cobalt blue is adopted. The surface of the obtained silica coating layer contains organic groups on the trialkoxysilane, which can give the coated cobalt blue more performance characteristics.

[0028] In a more preferred embodiment of the present application, the general formula of trialkoxysilane is R 1 Si(OR 2 )3, where R 1Selected from C1-C4 alkyl, amino-substituted C3-C8 alkyl, epoxy-substituted C3-C10 alkyl, epoxy-substituted C6-C10 cycloalkyl or polyether structure, R 2 is selected from C1-C4 alkyl or C2-C4 acyl. 1 Substituting C3-C8 alkyl with amino, C3-C10 alkyl with epoxy or C6-C10 cycloalkyl with epoxy can give the surface of the cobalt blue some properties (such as hydrophilicity) or higher reactivity. The higher reactivity allows it to react with other organic compounds (such as epoxy polyether or amino polyether, etc.) to further modify and improve the properties of the cobalt blue, such as dispersibility and stability in glaze. 1 When it is a polyether structure, such as -O(CH2CH2O) m (CHCH3CH2O) n H, m=5-50, n=0-30, m≥n, the polyether structure has good hydrophilicity, which can improve the dispersion and stability of the cobalt blue in the glaze, and further improve the color uniformity of the glaze layer.

[0029] For example, taking the trialkoxysilane as epoxy trialkoxysilane, such as KH-560, the following steps can be performed to coat cobalt blue: disperse the coated cobalt blue in a solvent, add amino-terminated polyether, stir at room temperature for 0.5 to 2 hours, heat to 50 to 70°C and stir for 0.5 to 1 hour, filter, wash, and dry. The solvent can be water or an organic solvent, such as anhydrous ethanol, acetone, butyl acetate, ethyl acetate, etc. The weight ratio of the coated cobalt blue to the solvent can be 1:10 to 100; the structure of the amino-terminated polyether can be NH2CH2CH2(OCH2CH2) x (OCH2CHCH3) y R 3 , where x = 5 to 50, y = 0 to 30, x ≥ y, R 3 It can be amino, hydroxyl, C1-C4 alkoxy, etc. The weight ratio of amino-terminated polyether to wrapped cobalt blue can be 0.03-0.2:1. Of course, trialkoxysilane can also be aminotrialkoxysilane, such as 3-aminopropyltrimethoxysilane, and the corresponding polyether is epoxy-terminated polyether with the structure of (CH2CHO)CH2(OCH2CH2) p (OCH2CHCH3) q R 4 , where p = 5 to 50, q = 0 to 30, p ≥ q, R 4 It may be a hydroxyl group, a C1-C4 alkoxy group, or the like.

[0030] In a more preferred embodiment of the present application, the alkyl orthosilicate is selected from methyl orthosilicate and / or ethyl orthosilicate. Methyl orthosilicate and ethyl orthosilicate have high reactivity and can fully undergo hydrolysis and condensation, resulting in a better structure of the silica coating.

[0031] In a more preferred embodiment of the present application, the weight ratio of trialkoxysilane to alkyl orthosilicate is 0.01 to 0.1:1. The weight ratio of trialkoxysilane to alkyl orthosilicate can be adjusted to adjust the distribution density of organic groups on the surface of the coating layer that encapsulates cobalt blue. The higher the weight ratio, the greater the distribution density of organic groups on the surface of the coating layer. For example, the weight ratio of trialkoxysilane to alkyl orthosilicate can be any value of 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, etc.

[0032] In a more preferred embodiment of the present application, the average particle size of the cobalt blue is 30 to 400 nm. The average particle size of the cobalt blue will affect the average particle size of the encapsulated cobalt blue. In order to obtain an encapsulated cobalt blue with an appropriate particle size, the particle size of the cobalt blue must also be appropriate. For example, the average particle size of the cobalt blue can be any value among 30 nm, 50 nm, 80 nm, 100 nm, 120 nm, 150 nm, 170 nm, 200 nm, 230 nm, 250 nm, 270 nm, 290 nm, 300 nm, 320 nm, 350 nm, 370 nm, 400 nm, etc.

[0033] In a more preferred embodiment of the present application, the weight ratio of cobalt blue to the hydrolyzed solution is 0.05 to 1:1. Using the above technical solution, the weight ratio of cobalt blue to the hydrolyzed solution is in an appropriate range to obtain better encapsulated cobalt blue. Furthermore, the weight ratio of cobalt blue to the hydrolyzed solution can be 0.1 to 0.6:1. For example, the weight ratio can be any value of 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1, 0.6:1, etc.

[0034] In a preferred embodiment of the present application, the raw material components further comprise: 1 to 3 parts of coated cobalt black, wherein the cobalt black is silicon dioxide coated cobalt black. The method for coating the cobalt black can be the same as the preparation method of coated cobalt blue.

[0035] In a more preferred embodiment of the present application, the average particle size of the coated cobalt black is 50 to 500 nm. For example, the average particle size of the coated cobalt black in the present application can be any value of 50 nm, 80 nm, 100 nm, 120 nm, 150 nm, 170 nm, 200 nm, 220 nm, 250 nm, 280 nm, 300 nm, 330 nm, 350 nm, 370 nm, 400 nm, 420 nm, 450 nm, 480 nm, 500 nm, etc.

[0036] The technical solution of the present application is described in detail below with reference to preparation examples, embodiments and comparative examples.

[0037] Preparation Example 1-4 Preparation of Coated Cobalt Blue

[0038] Preparation Example 1

[0039] 1.02 parts of ethyl orthosilicate were added to 50 parts of an alcohol-water solution composed of anhydrous ethanol and water in a volume ratio of 8:2, and stirred for 0.5 hours for co-hydrolysis to obtain a hydrolyzate; 0.2 parts of cobalt blue with an average particle size of 280 nm were added to 1 part of the above hydrolyzate, ultrasonically dispersed for 6 minutes, stirred for 60 minutes, filtered, washed with deionized water twice, dried at 60°C for 1 hour, and then dried at 120°C for 2 hours to obtain encapsulated cobalt blue.

[0040] Preparation Example 2

[0041] The difference between Preparation Example 2 and Preparation Example 1 is that 1.02 parts of ethyl orthosilicate in Preparation Example 1 is replaced by a combination of 0.02 parts of 3-aminopropyltrimethoxysilane and 1 part of ethyl orthosilicate.

[0042] Preparation Example 3

[0043] 1 part of the cobalt blue prepared in Preparation Example 2 was added to 50 parts of anhydrous ethanol and ultrasonically dispersed for 5 minutes. 0.12 parts of epoxy polyether (CH2CHO)CH2(OCH2CH2) was added. 8.3 OCH3, stirred at room temperature for 0.5 hours, heated to 55 ° C and stirred for 1 hour, filtered, washed with deionized water twice, dried at 60 ° C for 1 hour, and then dried at 120 ° C for 2 hours to obtain encapsulated cobalt blue.

[0044] Preparation Example 4

[0045] 0.08 parts of 3-aminopropyltrimethoxysilane and 1 part of ethyl orthosilicate were added to 50 parts of an alcohol-water solution composed of anhydrous ethanol and water in a volume ratio of 8:2, and stirred for 0.5 hours for co-hydrolysis to obtain a hydrolyzate; 0.5 parts of cobalt blue with an average particle size of 200 nm were added to 1 part of the above hydrolyzate, ultrasonically dispersed for 9 minutes, stirred for 90 minutes, filtered, washed with deionized water twice, dried at 60°C for 1 hour, and then dried at 120°C for 2 hours to obtain a crude product of coated cobalt blue.

[0046] 1 part of the above cobalt blue crude product was added to 50 parts of anhydrous ethanol, ultrasonically dispersed for 5 minutes, and 0.15 parts of epoxy polyether (CH2CHO)CH2(OCH2CH2) was added. 10.5 (OCH2CHCH3) 5.1 OCH3, stirred at room temperature for 0.5 hours, heated to 60 ° C and stirred for 1 hour, filtered, washed with deionized water twice, dried at 60 ° C for 1 hour, and then dried at 120 ° C for 2 hours to obtain encapsulated cobalt blue.

[0047] Example 1

[0048] The blue glaze composition comprises raw materials including: 25 parts of potassium feldspar, 38 parts of quartz powder, 2.3 parts of kaolin, 1.7 parts of calcined kaolin, 5.1 parts of aluminum oxide powder, 5.7 parts of calcite, 6.2 parts of dolomite, 14.3 parts of wollastonite, 1.1 parts of zinc oxide, 3.4 parts of strontium carbonate, 8.2 parts of zirconium silicate and 3 parts of the cobalt blue packaged in Preparation Example 1.

[0049] The above raw material components were mixed, and an appropriate amount of water was added, stirred at 600 rpm for 5 min, and transferred to a ball mill and ball-milled until the residue on a 325-mesh sieve was less than 0.1% and the 10 μm content was 71%. After iron removal through sieving, the specific gravity was adjusted to 1.751, and the flow rate was 135 seconds to obtain a glaze slurry.

[0050] Example 2

[0051] The difference between Example 2 and Example 1 is that in Example 1, the coated cobalt blue of Preparation Example 1 is replaced by an equal weight of the coated cobalt blue obtained in Preparation Example 2. The remaining steps remain unchanged.

[0052] Example 3

[0053] The difference between Example 3 and Example 1 is that in Example 1, the coated cobalt blue of Preparation Example 1 is replaced by an equal weight of the coated cobalt blue obtained in Preparation Example 3. The remaining steps remain unchanged.

[0054] Example 4

[0055] The difference between Example 4 and Example 1 is that in Example 1, the coated cobalt blue of Preparation Example 1 is replaced by an equal weight of the coated cobalt blue obtained in Preparation Example 4. The remaining steps remain unchanged.

[0056] Example 5

[0057] The difference between Example 5 and Example 3 is that in Example 3, the amount of encapsulated cobalt blue in Preparation Example 3 was adjusted from 3 parts to 1 part. The remaining steps remained unchanged.

[0058] Example 6

[0059] The difference between Example 6 and Example 3 is that in Example 3, the amount of encapsulated cobalt blue in Preparation Example 3 was adjusted from 3 parts to 6 parts. The remaining steps remained unchanged.

[0060] Comparative Example 1

[0061] The difference between Comparative Example 1 and Example 1 is that in Example 1, the coated cobalt blue of Preparation Example 1 is replaced by an equal weight of the cobalt blue of Preparation Example 1 (the cobalt blue is not coated). The remaining steps remain unchanged.

[0062] Comparative Example 2

[0063] The difference between Comparative Example 2 and Comparative Example 1 is that in Comparative Example 1, the amount of cobalt blue was adjusted from 3 parts to 1 part, and the remaining steps remained unchanged.

[0064] Comparative Example 3

[0065] The difference between Comparative Example 3 and Comparative Example 1 is that in Comparative Example 1, the amount of cobalt blue was adjusted from 3 parts to 6 parts, and the remaining steps remained unchanged.

[0066] Example 7

[0067] The blue glaze composition comprises raw materials including: 22 parts of potassium feldspar, 45 parts of quartz powder, 3.1 parts of kaolin, 3.5 parts of calcined kaolin, 4.5 parts of aluminum oxide powder, 7.3 parts of calcite, 8.1 parts of dolomite, 17.1 parts of wollastonite, 1.7 parts of zinc oxide, 4.2 parts of strontium carbonate, 5.8 parts of zirconium silicate and 2.5 parts of the cobalt blue prepared in Preparation Example 3.

[0068] The above raw material components were mixed, and an appropriate amount of water was added, stirred at 600 rpm for 5 min, and transferred to a ball mill and ball-milled until the residue on a 325-mesh sieve was less than 0.1% and the 10 μm content was 68%. After iron removal through sieving, the specific gravity was adjusted to 1.747, and the flow rate was 128 seconds to obtain a glaze slurry.

[0069] Example 8

[0070] The difference between Example 8 and Example 7 is that cobalt black with an average particle size of 360 nm is added to the raw material components of Example 7. The other steps remain unchanged.

[0071] Example 9

[0072] The difference between Example 9 and Example 7 is that coated cobalt black with an average particle size of 410 nm is added to the raw material components of Example 7. The other steps remain unchanged.

[0073] Encapsulated cobalt black was prepared according to the following method: 0.05 parts of 3-aminopropyltrimethoxysilane and 1 part of ethyl orthosilicate were added to 50 parts of an alcohol-water solution composed of anhydrous ethanol and water in a volume ratio of 8:2, and the mixture was stirred for 0.5 hours for co-hydrolysis to obtain a hydrolyzate; 0.5 parts of cobalt blue with an average particle size of 360 nm were added to 1 part of the above hydrolyzate, ultrasonically dispersed for 9 minutes, stirred for 90 minutes, filtered, washed with deionized water twice, dried at 60°C for 1 hour, and then dried at 120°C for 2 hours to obtain encapsulated cobalt black.

[0074] The glaze slurries of Examples 1-9 and Comparative Examples 1-3 were sprayed onto thin blanks measuring 40 cm × 20 cm × 2 cm, respectively, with a thickness controlled at 0.9 ± 0.2 mm. The sintering procedure was as follows: heating from room temperature to 500°C over 2 hours, from 500°C to 900°C over 2 hours, and from 900°C to 1220°C over 1.5 hours. The sintering was then continued at 1220-1240°C for 2 hours, followed by cooling to obtain a ceramic glaze.

[0075] Performance Testing

[0076] On the surface of the ceramic glaze 40cm×20cm, the NH310+ colorimeter of Sanen was used to test the color difference of 7 positions including the middle, 4 corners and 2 middle positions of the upper and lower halves. The color of the middle position of the ceramic glaze obtained in each embodiment and preparation example was used as the benchmark, and the 4 corners and 2 positions in the middle of the upper and lower parts were compared with the middle position, and the average value and standard deviation were calculated. The color difference ΔE is shown in Table 1 below. The larger the color difference ΔE, the more obvious the color difference. ΔE≤0.1, the color difference is invisible to the naked eye; 0.1<ΔE≤0.25, the color difference is basically invisible to the naked eye; 0.25<ΔE≤0.5, the color difference is very small, but can be identified by the naked eye; 0.5<ΔE≤1, the color difference is relatively obvious; ΔE>1, the color difference is obvious.

[0077] Table 1 Color difference ΔE

[0078]

[0079]

[0080] It can be seen from the data results in Table 1 that the blue glaze of the present application uses wrapped cobalt blue, and the color uniformity obtained is high, and the color difference in different positions is very small.

[0081] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A high gloss blue glaze composition, characterized in that: The raw material components include, by weight: 20-30 parts of potassium feldspar, 30-50 parts of quartz powder, 1-5 parts of kaolin, 1-4 parts of calcined kaolin, 3-7 parts of alumina powder, 4-9 parts of calcite, 3-10 parts of dolomite, 10-20 parts of wollastonite, 0.5-2 parts of zinc oxide, 2-5 parts of strontium carbonate, 5-10 parts of zirconium silicate and 1-6 parts of coated cobalt blue; the coated cobalt blue is silica-coated cobalt blue; The average particle size of the cobalt blue coating is 50-500 nm; The preparation method of the coated cobalt blue comprises: co-hydrolyzing trialkoxysilane and alkyl orthosilicate to obtain a hydrolyzate; adding cobalt blue to the hydrolyzate, ultrasonically dispersing for 1 to 10 minutes, stirring for 5 to 120 minutes, filtering, washing, and drying to obtain the coated cobalt blue.

2. The high-gloss blue glaze composition according to claim 1, characterized in that: The general formula of the trialkoxysilane is R 1 Si(OR 2 )3, where R 1 Selected from C1-C4 alkyl, amino-substituted C3-C8 alkyl, epoxy-substituted C3-C10 alkyl, epoxy-substituted C6-C10 cycloalkyl or polyether structure, R 2 Selected from C1-C4 alkyl or C2-C4 acyl.

3. The high-gloss blue glaze composition according to claim 1, characterized in that: The alkyl orthosilicate is selected from one or a combination of methyl orthosilicate and ethyl orthosilicate.

4. The high-gloss blue glaze composition according to claim 1, characterized in that: The weight ratio of the trialkoxysilane to the alkyl orthosilicate is 0.01-0.1:

1.

5. The high-gloss blue glaze composition according to claim 1, characterized in that: The average particle size of the cobalt blue is 30-400 nm.

6. The high-gloss blue glaze composition according to claim 1, characterized in that: The weight ratio of the cobalt blue to the hydrolyzate is 0.05 to 1:

1.

7. The high-gloss blue glaze composition according to claim 1, characterized in that: The raw material components further include: 1 to 3 parts of coated cobalt black, wherein the cobalt black is silica coated cobalt black.

8. The high-gloss blue glaze composition according to claim 7, characterized in that: The average particle size of the encapsulated cobalt black is 50-500 nm.

Images