A sunken fine carving ceramic ink with obvious line effect and no bottom color and application thereof

Abstract

The application belongs to the field of ceramic ink, and discloses a concave engraving ceramic ink with obvious line effect and no background color and application thereof. The first part of the ink contains bismuth vanadate, and the second part contains hydrated magnesium silicate and / or fumed silica. The inventor finds that the finer the particle size of the bismuth vanadate, the lighter the background color after firing, and the specific surface area of the hydrated magnesium silicate and / or fumed silica is relatively large, which can be well combined with the bismuth vanadate to form a glass phase to dissolve the background color formed by vanadium elements in a high-temperature molten state. After the hydrated magnesium silicate and / or fumed silica is ground, the ceramic ink with a more hydrophobic enamel stripping effect can be formed. The first part makes the glaze surface form a concave effect, and the second part has a hydrophobic and enamel-repellent effect, and the two mechanisms jointly act to achieve the effect of obvious line effect and no background color. The concave engraving ceramic ink has excellent printing performance, and the concave line effect of the ceramic tile is obvious and has no background color.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of ceramic ink, and particularly relates to a sinking fine carving ceramic ink with obvious line effect and no background color and application thereof. BACKGROUND

[0002] With the continuous development and progress of inkjet printing technology, the decoration effect of ceramic tiles is also continuously upgraded. The emergence of sinking ceramic ink gives full-finished glaze marble ceramic tiles a real 3D stereoscopic effect, making the decoration effect more realistic and closer to natural stone. However, since the sinking ink used at present is mostly prepared by a solid-phase sintering method, the biggest defect of the bismuth yellow plus some strong fluxing effect oxides of low-temperature materials is that it is easy to leave a light yellow background color and the line effect is not coherent. To solve these problems, it is necessary to start from the sinking raw material production process and find a breakthrough in the principle of forming sinking line effect, so as to better solve the above problems.

[0003] In Chinese patent CN102491786A, a sinking printing glaze and a preparation method thereof are introduced. The patent uses low-temperature solvents and vanadium pentoxide to make the ceramic tiles produce a sinking effect. In Chinese patent CN10628078A, a sinking negative ion ceramic ink for ceramic inkjet and a preparation method thereof are introduced.

[0004] In Chinese patent CN106366765A, a sinking photochromic ceramic ink for ceramic inkjet and a preparation method thereof are introduced. In Chinese patent CN106634204A, a sinking antibacterial ceramic ink for ceramic inkjet and a preparation method thereof are introduced. The above three patents use low-temperature solvents, vanadium pentoxide, bismuth oxide and bismuth yellow to make the ceramic tiles produce a sinking effect, and then compound silver ion antibacterial powder, deodorant and negative ion compound to achieve some special auxiliary functions. In Chinese patent CN105176196A, a marble crack line effect ceramic inkjet ink and a preparation method thereof are introduced. In Chinese patent CN104194495A, a sinking separated ceramic inkjet ink and a preparation and use method thereof and ceramic tiles are introduced. In Chinese patent CN103965687A, a ceramic ink with sinking effect and a preparation method thereof are introduced. The above patents generally use K2O, Na2O, PbO, Bi2O and other strong fluxing effect oxides of low-temperature materials and V2O5 to make the glaze surface form a smooth local sinking effect. Since the above patents all use solid-phase raw materials, the sinking effect cannot achieve the best, and a yellowish background color is easy to produce, which cannot well meet the requirements of the current ceramic enterprise production. SUMMARY

[0005] The present application aims to overcome at least one deficiency of the prior art, and provide a line effect obvious and colorless sunken engraving ceramic ink and application thereof.

[0006] The technical scheme adopted by the present application is:

[0007] In a first aspect, the present application provides:

[0008] A line effect obvious and colorless sunken engraving ceramic ink is composed of two parts, the mass composition of the first part is: bismuth vanadate 25-50%, super dispersant 2-10%, defoaming agent 0-2%, solvent 40-60%; the mass composition of the second part is: inorganic powder 1-50%, super dispersant 2-30%, defoaming agent 0-2%, solvent 40-60%, the inorganic powder is composed of hydrated magnesium silicate and / or fumed silica.

[0009] In some examples of the sunken engraving ceramic ink, the mass mixing ratio of the first part and the second part is (5:5)-(6:4).

[0010] In some examples of the sunken engraving ceramic ink, the particle size of the bismuth vanadate is not greater than 200 nm.

[0011] In some examples of the sunken engraving ceramic ink, the preparation method of the bismuth vanadate comprises:

[0012] S1) Bi(NO3)3 is added to nitric acid to dissolve, to obtain a Bi(NO3)3 solution;

[0013] S2) NH4VO3 is added to a strong alkali solution to dissolve, to obtain an NH4VO3 solution;

[0014] S3) the Bi(NO3)3 solution and the NH4VO3 solution are simultaneously added dropwise and mixed, and a precipitate is reacted;

[0015] S4) the precipitate is separated, washed, dried, crushed, and calcined to obtain bismuth vanadate powder.

[0016] In some examples of the sunken engraving ceramic ink, the molar ratio of Bi and V is 1:1, and the nitric acid and the strong alkali are neutralized after the dropping is completed.

[0017] In some examples of the sunken engraving ceramic ink, the super dispersant is selected from at least one of a polyester type super dispersant, a polyamide type super dispersant, a polyacrylate type super dispersant, and a polyurethane type dispersant.

[0018] In some examples of the sunken engraving ceramic ink, the defoaming agent is selected from at least one of a silicone type defoaming agent and a polyether type defoaming agent.

[0019] In some examples of the sunken engraving ceramic ink, the solvent is selected from at least one of isooctyl cocoate, isopropyl laurate, isooctyl palmitate, myristate, methyl oleate, butyl oleate, methyl laurate, and a low-polarity alkane solvent, the low-polarity alkane being a normal alkane or an isomeric alkane with a carbon number of C13-C30.

[0020] In a second aspect of the present application, there is provided:

[0021] A ceramic tile with sunken engraving effect, the glaze surface of which is applied with the sunken engraving ceramic ink according to the first aspect of the present application.

[0022] In a third aspect of the present application, there is provided:

[0023] Use of the sunken engraving ceramic ink according to the first aspect of the present application in the manufacture of a ceramic tile with sunken engraving effect.

[0024] The present application has the following beneficial effects:

[0025] The sunken engraving ceramic ink according to some examples of the present application overcomes the inherent light yellow undertone of traditional bismuth vanadate, and achieves a printing effect without undertone. The sunken engraving effect ceramic prepared using the sunken engraving ceramic ink has obvious and coherent line effects.

[0026] The sunken engraving ceramic ink according to some examples of the present application is composed of two parts: the effect powder of the first part is bismuth vanadate with a particle size of no more than 200 nm. The present inventors have found that the thinner the particle size of bismuth vanadate, the lighter the undertone after firing. The effect powder of the second part is hydrated magnesium silicate and / or fumed silica, which can form a glass phase to dissolve the undertone formed by vanadium elements in a high-temperature molten state. At the same time, due to the relatively large specific surface area of the hydrated magnesium silicate and / or fumed silica, the two parts of the effect ink are combined using a sand mill. The first part of the ink forms a sunken effect on the glaze surface, and the second part has a hydrophobic and glaze-repellent effect. The two mechanisms work together to achieve an obvious line effect without undertone. The sunken engraving ceramic ink prepared according to the present application can be used to prepare a sunken engraving ceramic ink with excellent printing performance, obvious line effect, and no undertone. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 are photos of the squeegees of sunken engraving ceramic inks of different examples. DETAILED DESCRIPTION

[0028] A line effect obvious and no color of subsidence engraving ceramic ink, two parts mixed composition, the first part of the mass composition: bismuth vanadate 25-50%, super dispersant 2-10%, defoaming agent 0-2%, solvent 40-60%; the second part of the mass composition: inorganic powder 1-50%, super dispersant 2-30%, defoaming agent 0-2%, solvent 40-60%, the inorganic powder is composed of hydrated magnesium silicate and / or fumed silica.

[0029] In some examples of subsidence engraving ceramic ink, the inorganic powder in the second part accounts for 17-22%. In this way, the subsidence engraving ceramic ink with lighter background color can be obtained.

[0030] In some examples of subsidence engraving ceramic ink, the mass mixing ratio of the first part and the second part is (5:5)-(6:4).

[0031] In some examples of subsidence engraving ceramic ink, the particle size of the bismuth vanadate is not more than 200 nm. In this way, it is beneficial to further reduce the background color of bismuth vanadate.

[0032] The particles of bismuth vanadate prepared by liquid phase method can be ground to 200 nm, even below 100 nm. In some examples of subsidence engraving ceramic ink, the preparation method of the bismuth vanadate comprises:

[0033] S1) Bi(NO3)3 is added to nitric acid to dissolve, to obtain a Bi(NO3)3 solution;

[0034] S2) NH4VO3 is added to a strong alkali solution to dissolve, to obtain an NH4VO3 solution;

[0035] S3) the Bi(NO3)3 solution and the NH4VO3 solution are simultaneously added and mixed, and the reaction precipitate is obtained;

[0036] S4) the precipitate is separated, washed, dried, crushed, and calcined to obtain bismuth vanadate powder.

[0037] In some examples of subsidence engraving ceramic ink, the molar ratio of Bi and V is 1:1, and the nitric acid and the strong alkali are neutralized after the dripping is completed. In this way, bismuth vanadate can be obtained, and unnecessary waste is reduced.

[0038] The type of hyperdispersant is not limited, and any hyperdispersant acceptable in the ceramic industry can be used. In some examples of the undercut engraving ceramic ink, the hyperdispersant is selected from at least one of a polyester hyperdispersant, a polyamide hyperdispersant, a polyacrylate hyperdispersant, and a polyurethane dispersant. For example, Lubrizol-13940, Lubrizol-J980, Lubrizol-J1280, Disuper S35, 1028, CH-6, Dow polyester dispersant DS13000, Dow polyester dispersant DS20000, and the like.

[0039] The type of defoaming agent is not limited, and any defoaming agent acceptable in the ceramic industry can be used. In some examples of the undercut engraving ceramic ink, the defoaming agent is selected from at least one of a silicone defoaming agent and a polyether defoaming agent. For example, BYK-066N, BYK-019, BYK-1719, BYK-1770, BYK-067, 3017, 3206, IC-20, and the like.

[0040] The type of solvent is not limited, and any solvent acceptable in the ceramic industry can be used. In some examples of the undercut engraving ceramic ink, the solvent is selected from at least one of isooctyl cocoate, isopropyl laurate, isooctyl palmitate, myristate, methyl oleate, butyl oleate, methyl laurate, and a low-polarity alkane solvent, wherein the low-polarity alkane is a normal alkane or an isomeric alkane having a carbon number of 13-30. For example, one or more of TOTAL 25-28H, 30-35H, 30-36H, 30-38H, 35-40H.

[0041] The undercut engraving ceramic ink of the present application can be prepared by a conventional method or by the following method:

[0042] S1) mixing the solvent, the hyperdispersant, and the defoaming agent to prepare a dispersion liquid;

[0043] S2) adding a first part of the inorganic powder bismuth vanadate to the dispersion liquid, grinding with a sand mill, and grinding until the ink reaches a certain particle size and viscosity, preferably grinding until the ink has a particle size D50 of less than 200 nm;

[0044] S3) adding a second part of the inorganic powder hydrated magnesium silicate and fumed silica to the dispersion liquid, grinding with a sand mill, and grinding until the ink reaches a certain particle size and viscosity, preferably grinding until the ink has a particle size D50 of less than 150 nm;

[0045] S4) mixing the first part and the second part of the ink according to a certain proportion and grinding to make the two parts uniform;

[0046] S5) the ground ink is filtered, i.e. the line effect obvious and colorless sunken fine carving ceramic ink is prepared.

[0047] The technical solutions of the present application are further illustrated below in combination with examples.

[0048] In the following examples, the composition percentage of the ink is mass percentage, for the convenience of comparison,

[0049] The bismuth vanadate is preferably prepared by a liquid phase method, specifically comprising the following steps:

[0050] S1) Bi(NO3)3 is added into dilute HNO3 for dissolution, and NH4VO3 is added into dilute NaOH solution for dissolution, the molar ratio of Bi and V is 1:1, and the molar ratio of HNO3 and NaOH is 1:1;

[0051] S2) the Bi(NO3)3 solution and the NH4VO3 solution are simultaneously dropped into the bottom liquid, and the reaction precipitate is separated out;

[0052] S3) after the precipitate is separated out, the powder is obtained through pressure filtration;

[0053] S4) the powder obtained after pressure filtration is washed with water to remove excess ions;

[0054] S5) the powder after water washing is dried;

[0055] S6) the dried powder is crushed, and the 325 mesh screen is required to be fully passed;

[0056] S7) the crushed powder is fired at 500℃ for 4 hours;

[0057] S8) the fired powder is crushed, and the 600 mesh screen is required to be fully passed, so that the finished bismuth vanadate powder is obtained.

[0058] The preparation method of the slip is specifically as follows:

[0059] S1) the first part: the dispersant, the defoaming agent and the solvent are mixed and stirred uniformly, and are added into a grinding device for circulation grinding until the solid particle size D50 is less than 200 nm through sampling detection;

[0060] S2) the second part: the dispersant CH-6 22%, the defoaming agent BYK06 70.1% and the solvent methyl laurate 57.9% are mixed and stirred uniformly, and are added into a grinding device for circulation grinding until the solid particle size D50 is less than 150 nm through sampling detection;

[0061] S3) the ink prepared in the first part and the second part is mixed according to the proportion, and is then ground in a sand mill for 4 cycles;

[0062] S4) After the ink particle size is ground to pass the qualification, an appropriate amount of solvent is added to control the performance parameters of the ink, the solid content of the ink is controlled between 20-40wt%, the 40℃ viscosity is controlled between 10-18cp, the surface tension is controlled between 25-40mN / m, and the density is 1.0-1.7;

[0063] S5) The prepared ink is filtered through a multi-stage 1μm filter element, and the ceramic ink finished product is packaged after filtration.

[0064] Example 1

[0065] The undercut fine carving ceramic ink is composed of two parts:

[0066] The first part: bismuth vanadate 50%, DS13000 7%, BYK067 0.1%, butyl oleate 35.9%, and methyl laurate 7%.

[0067] The second part: hydrated magnesium silicate 20%, CH-6 22%, BYK067 0.1%, and methyl laurate 57.9%. The mass mixing ratio of the first part and the second part is 6:4.

[0068] Example 2

[0069] The undercut fine carving ceramic ink is composed of two parts:

[0070] The first part: bismuth vanadate 50%, CH-6 7%, BYK067 0.1%, 25-28H 35.9%, and 30-35H 7%.

[0071] The second part: fumed silica 15%, CH-6 18%, BYK067 0.1%, and methyl oleate 66.9%. The mass mixing ratio of the first part and the second part is 5.5:4.5.

[0072] Example 3

[0073] The undercut fine carving ceramic ink is composed of two parts:

[0074] The first part: bismuth vanadate 50%, J980 7%, BYK067 0.1%, and 25-28H 42.9%.

[0075] The second part: hydrated magnesium silicate 10%, fumed silica 12%, CH-6 16%, BYK067 0.1%, and 25-28H 61.9%.

[0076] The mass mixing ratio of the first part and the second part is 5:5.

[0077] Example 4

[0078] The sunken engraving ceramic ink is composed of two parts:

[0079] First part: bismuth vanadate 50%, J980 7%, BYK067 0.1%, 25-28H 42.9%

[0080] Second part: hydrated magnesium silicate 5%, fumed silica 12%, CH-6 16%, BYK067 0.1%, 25-28H 66.9%.

[0081] The mass mixing ratio of the first part and the second part is 5:5.

[0082] Comparative Example 1

[0083] The sunken engraving ceramic ink is composed of two parts:

[0084] First part: common bismuth vanadate 50%, J980 7%, BYK067 0.1%, 25-28H 42.9%

[0085] Second part: magnesium silicate 10%, silica 12%, CH-6 16%, BYK067 0.1%, 25-28H 61.9%.

[0086] The mass mixing ratio of the first part and the second part is 5:5.

[0087] Comparative Example 2

[0088] First part: common bismuth vanadate 50%, CH-6 7%, BYK067 0.1%, 25-28H 35.9%, 30-35H 7% Second part: magnesium silicate 10%, silica 5%, CH-6 18%, BYK067 0.1%, methyl oleate 66.9%. The mass mixing ratio of the first part and the second part is 5:5.

[0089] Preparation of ceramic tiles:

[0090] The sunken engraving ink doctor blade of different examples was taken respectively, and the ceramic tiles were prepared according to the following steps, and then the effects of different inks were evaluated.

[0091] Preparation method of ceramic tiles:

[0092] S1) After the body is successfully pressed, it is dried;

[0093] S2) After the body is dried, it is glaze;

[0094] S3) The sunken engraving ink is printed on the glaze by using a screen plate (silk screen plate 200 mesh);

[0095] S4) After the ink is printed, the glaze is poured;

[0096] S5) drying;

[0097] S6) firing.

[0098] Figure 1 are different instances of the sinking engraving ink blade photos, tile photos. In the figure 1, 2, 3, 4 are the ink blade effects corresponding to example 1, example 2, example 3, example 4, 5, 6 are the ink blade effects corresponding to comparative example 1, comparative example 2. From the figure, it can be seen that the sinking line effect of example 1, example 2, example 3, example 4 is good, and the background color is very light; among them, the line effect in example 3 is the best, and the background color is the lightest. The line effect of comparative example 1 and comparative example 2 starts to deteriorate and the background color is significantly darker.

[0099] The above is a further detailed description of the present application, which cannot be considered as a specific implementation of the present application. For ordinary skilled in the art to which the present application belongs, without departing from the simple deduction or replacement of the concept of the present application, it is within the protection scope of the present application.

Claims

1. A line effect clear and colorless sinking engraving ceramic ink, consisting of two parts mixed, characterized in that, The first part has a mass composition of 25-50% bismuth vanadate, 2-10% hyperdispersant, 0-2% defoaming agent, and 40-60% solvent, wherein the bismuth vanadate has a particle size of no more than 200 nm; The second part has a mass composition of 1-50% inorganic powder, 2-30% hyperdispersant, 0-2% defoaming agent, and 40-60% solvent, wherein the inorganic powder is composed of hydrated magnesium silicate and / or fumed silica; The mass mixing ratio of the first part and the second part is (5:5) to (6:4).

2. The sunken engraving ceramic ink according to claim 1, characterized in that, The preparation method of the bismuth vanadate comprises: S1) dissolving Bi(NO3)3 in nitric acid to obtain a Bi(NO3)3 solution; S2) dissolving NH4VO3 in a strong alkali solution to obtain an NH4VO3 solution; S3) simultaneously dropping the Bi(NO3)3 solution and the NH4VO3 solution and precipitating by reaction; S4) separating, washing, drying, crushing, and calcining the precipitate to obtain bismuth vanadate powder.

3. The sunken engraving ceramic ink according to claim 2, characterized in that, The molar ratio of Bi to V is 1:1, and the nitric acid and the strong alkali are neutralized after dropping is completed.

4. The sunken engraving ceramic ink according to claim 1, characterized in that, The hyperdispersant is at least one selected from a polyester hyperdispersant, a polyamide hyperdispersant, a polyacrylate hyperdispersant, and a polyurethane dispersant.

5. The sunken engraving ceramic ink according to claim 1, characterized in that, The defoaming agent is at least one selected from a silicone defoaming agent and a polyether defoaming agent.

6. The sunken engraving ceramic ink according to claim 1, characterized in that, The solvent is at least one selected from isooctyl cocoate, isopropyl laurate, isooctyl palmitate, myristate, methyl oleate, butyl oleate, methyl laurate, and a low-polarity alkane solvent, wherein the low-polarity alkane is a normal alkane or an isomeric alkane with a carbon number of 13-30.

7. A ceramic tile having a sunken engraved effect, characterized in that, The glaze surface of the porcelain tile is applied with the sunken fine carving ceramic ink according to any one of claims 1-6.

8. Use of the sunken fine carving ceramic ink according to any one of claims 1-6 in manufacturing porcelain tiles with a sunken carving effect.

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