A red pigment for ceramic inkjet printing ink, and a preparation method and application thereof

Abstract

The present application provides a kind of red pigment for ceramic inkjet printing ink, which is composed of frit powder, aluminum hydroxide and iron red; the D50 of the frit powder is 0.2-0.3 μm; the particle size of the aluminum hydroxide is 8000-10000 mesh; the iron red is red iron oxide, and the D90 of the iron red is less than 3 μm. The present application uses ultra-fine high-temperature transparent frit powder, ultra-fine aluminum hydroxide and ultra-fine iron red to form high-temperature coated pigment. The ceramic ink made of the pigment can produce bright red at high temperature of 1200℃, solving the problem that conventional silicon iron red and zirconium iron red pigments cannot produce color at high temperature after being prepared into ink. The ink can be applied in ceramic ink to replace coated red pigment ink or red-brown ink. Compared with the current cadmium sulfide / selenium coated red technology, it has the advantages of green environmental protection and the absence of cadmium, a highly toxic substance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of ceramic ink, and particularly relates to a novel ceramic inkjet printing red ink and a preparation method and application thereof. BACKGROUND

[0002] With the continuous improvement of living standards, people have higher pursuit of modern design decoration diversification and healthy green building materials. The development of ink for decorating on wall and floor tiles has extremely high commercial value and application prospect. With the attention of people to the lead and cadmium leaching problem of building ceramics, the development of lead-free and cadmium-free building ceramics is becoming more and more intense, and it has very important significance for the development of future ceramic unmanned factory printing technology, and has become a research hotspot in the field of building ceramics.

[0003] The conventional silicon iron red and zirconium iron red pigments on the market have the problem of not developing color at high temperature after being prepared into ink, and the cadmium sulfide and selenide (cadmium red) used in the encapsulated red pigment technology contains cadmium, a highly toxic element, so it is urgent to find a green and environmentally friendly red ink for ceramics that can develop color at high temperature. SUMMARY

[0004] The present application aims to at least solve one of the technical problems existing in the prior art. To this end, the present application proposes a novel ceramic inkjet printing red ink and a preparation method and application thereof. The ceramic inkjet printing red ink can produce bright red color at a high temperature of 1150-1200 DEG C, can replace the encapsulated red pigment ink or red-brown ink on the market, and has obvious color development advantage over traditional red-brown ordinary ink in the color development of full-digital glaze.

[0005] According to a first aspect of the present application, a red pigment for ceramic inkjet printing ink is provided, which is composed of frit powder, aluminum hydroxide and iron red;

[0006] The D50 of the frit powder is 0.2-0.3 microns;

[0007] The particle size of the aluminum hydroxide is 8000-10000 mesh;

[0008] The iron red is iron oxide red, and the D90 of the iron red is less than 3 microns.

[0009] Preferably, the particle size D90 of the aluminum hydroxide is about 1.5 microns.

[0010] Preferably, the composition of the frit powder comprises: Al2O3 5-8%, SiO2 60-65%, CaO 13-18%, MgO 1-1.5%, K2O 2.8-4.8%, Na2O 0.3-1% and ZnO 8-12%. The frit powder has suitable refractoriness, which is conducive to improving the encapsulation effect and stability of the encapsulation structure.

[0011] More preferably, the composition of the frit powder further comprises: B2O30-3%. The addition of boron oxide is conducive to reducing the expansion coefficient of the frit.

[0012] Preferably, the frit powder is prepared by the following steps: ingredients are proportioned according to the ratio, and after being heated and melted, the frit semi-finished product is obtained by water quenching; the frit semi-finished product is sequentially subjected to wet ball milling and wet sand milling to obtain a D50 of 0.2-0.3 μm, and then dried to obtain the frit powder.

[0013] More preferably, the frit semi-finished product is subjected to wet ball milling, and then the slurry is sieved through a 325 mesh sieve, and then subjected to wet sand milling to obtain a D50 of 0.2-0.3 μm. This grinding method can make the particle size of the frit powder smaller and more uniform, and the coating effect is better.

[0014] More preferably, the temperature of the melting is about 1560°C.

[0015] Preferably, the red pigment is composed of the following ingredients by mass percentage: frit powder 40%-60%, aluminum hydroxide 7%-15%, and iron red 30%-45%.

[0016] Preferably, the D50 of the red pigment for ceramic inkjet printing ink is 0.2-0.23 μm.

[0017] According to a second aspect of the present application, a preparation method of the red pigment for ceramic inkjet printing ink as described in the first aspect of the present application is provided, comprising the following steps:

[0018] S1: aluminum hydroxide and frit powder are slurried respectively, iron red is subjected to first water milling, aluminum hydroxide slurry is added for second water milling, and frit slurry is added for third water milling, and then dried and powdered;

[0019] S2: the powder obtained in step S1 is calcined, and then subjected to fourth water milling, and then dried and powdered to obtain the red pigment for ceramic inkjet printing ink.

[0020] Preferably, in step S1, the process of the first water milling is: gradually adding water to about 40% solid content during sand milling.

[0021] Preferably, in step S1, the solid content of the aluminum hydroxide slurry is about 40%; and / or, the solid content of the frit slurry is about 40%.

[0022] Preferably, in step S1, the flow rate of the slurry after the first water milling is greater than 30 seconds; the flow rate of the slurry after the second water milling is greater than 30 seconds; and the flow rate of the slurry after the third water milling is greater than 40 seconds. The test method of the above flow rate is: measuring the time of 100 mL slurry passing through a flowmeter.

[0023] Preferably, in step S1, the temperature of the drying is 200-250°C; and the water content of the powder after drying is less than 0.3%.

[0024] Preferably, in step S2, the temperature of the calcination is 990-1010°C, and the holding time of the calcination is 2-4h.

[0025] More preferably, the process of the calcination is as follows: heating from room temperature to 650°C for 1.5h, then heating to 1000°C for 1.5h, and then holding at 1000°C for 2h.

[0026] Preferably, in step S2, after the fourth water milling, the particle size D50 of the powder is 0.2-0.23μm.

[0027] More preferably, the process of the fourth water milling is as follows: sequentially performing wet ball milling and wet sand milling until the particle size D50 of the powder is 0.2-0.23μm.

[0028] Preferably, in step S2, after the drying treatment, the water content of the powder is less than 0.3%.

[0029] According to a third aspect of the present application, a ceramic inkjet printing red ink is provided, comprising the red pigment for ceramic inkjet printing ink as described in the first aspect of the present application.

[0030] Preferably, the ceramic inkjet printing red ink comprises the following raw materials in mass percentage: the red pigment for ceramic inkjet printing ink 40%-45%, organic solvent 50%-55%, and dispersant 5%-10%.

[0031] Preferably, the organic solvent is composed of ester solvent and white oil solvent.

[0032] More preferably, the ceramic inkjet printing red ink is prepared from the following raw materials in mass percentage: the red pigment for ceramic inkjet printing ink 40%-45%, ester solvent 28%-31%, white oil solvent 22%-25%, and dispersant 5%-10%.

[0033] Preferably, the dispersant is a polyester dispersant.

[0034] Preferably, the solid content of the ceramic inkjet printing red ink is 40%-45%.

[0035] Preferably, the ceramic inkjet printing red ink is prepared by the following steps: sanding the ceramic inkjet printing ink mixed with red pigment, organic solvent and dispersant, and then removing iron, and then solid-liquid separation to obtain the ceramic inkjet printing red ink. The process of removing iron is to remove free iron such as rust by using an iron removal machine; the purpose of solid-liquid separation is to remove impurities such as large particles and iron hydroxide colloid in the ink.

[0036] Preferably, the D50 of the ceramic inkjet printing red ink is 0.2-0.3 μm.

[0037] According to a fourth aspect of the present application, a ceramic pattern layer is provided, which is prepared by inkjet printing and firing the ceramic inkjet printing red ink according to the third aspect of the present application.

[0038] The firing temperature is 900-1220℃; and / or, the holding time of the firing is about 20 min.

[0039] Preferably, the total firing time of the firing is about 60 min.

[0040] Preferably, the process of inkjet printing uses an eight-channel inkjet testing machine.

[0041] According to a fifth aspect of the present application, a ceramic is provided, which comprises a ceramic substrate and a face glaze layer, a pattern layer and a protective glaze layer attached to the surface of the ceramic substrate in sequence, wherein the pattern layer is prepared by the ceramic pattern layer according to the fourth aspect of the present application.

[0042] Preferably, the face glaze layer is composed of the following raw materials in mass percentage: 30-33% of sodium feldspar, 12-15% of potassium feldspar, 0.5-1.5% of calcined zinc oxide, 38-42% of quartz, 10-14% of kaolin and 3-5% of frit.

[0043] According to an embodiment of the present application, at least the following beneficial effects are achieved:

[0044] When conventional silicon iron red or zirconium iron red pigment is used in ceramic ink, the encapsulation structure will be destroyed at high temperature, resulting in no color development. The present application uses ultra-fine frit powder, 10000 mesh aluminum hydroxide and ultra-fine iron red as the basic material to prepare a red pigment, which has good encapsulation effect and stable structure; the ceramic inkjet printing red ink prepared by using the red pigment can develop color at high temperature. The contact area between the three kinds of ultra-fine materials is larger, and compared with the traditional 325 mesh material, the encapsulation rate is significantly improved, and the color development and temperature resistance of the pigment are also significantly improved.

[0045] And the existing package red technology (sulfur selenium cadmium package) although the package structure is stable, the color is good, but the particle size is coarse, D50 is about 0.7 mu m, and toxic cadmium raw materials are used. And the present application adopts the raw material without cadmium to prepare a new type of red pigment for ceramic inkjet printing ink, which is environment-friendly and non-toxic, and the particle size is smaller, which is more suitable for application in ceramic inkjet printing ink. DETAILED DESCRIPTION

[0046] The concept and technical effects of the present application will be described below in conjunction with examples, so as to fully understand the purpose, features and effects of the present application. The raw materials used in the following examples and comparative examples are conventional products that can be obtained by market purchase, unless otherwise specified.

[0047] Example 1

[0048] The present embodiment provides a red pigment for ceramic inkjet printing ink, and the particle size D50 is 0.4 mu m. The formula is: 130 iron oxide red with D50 of 0.2-0.3 mu m 50%, high temperature transparent frit powder with D50 of 0.2 mu m 41% and 10000 mesh aluminum hydroxide 9%;

[0049] Among them, the formula of the high temperature transparent frit powder is: Al2O3 6.5%, SiO2 62%, CaO 15.7%, MgO 1.4%, K2O 2.7%, Na2O 0.4% and ZnO 10.8%, and the balance is loss on ignition;

[0050] Among them, the preparation method of the high temperature transparent frit powder is as follows: first, the raw materials are proportioned according to the above formula, then melted at 1560 DEG C high temperature, and then quenched into frit semi-finished product by water, then the frit semi-finished product is ground twice, the first time is ground by water ball mill to 325 mesh, the second time is ground by water sand mill to D50 between 0.2-0.3, then dried and ground to be ready for use.

[0051] The present embodiment also provides a preparation method of the above-mentioned red pigment for ceramic inkjet printing ink, which comprises the following steps:

[0052] 1. Sand mill 130 iron oxide red, slowly add water to solid content of 40% during the process, grind to thickening (flow rate greater than 30 seconds), then add aluminum hydroxide slurry (10000 mesh aluminum hydroxide is made into slurry with solid content of 40%) for second sand mill to flow rate greater than 30 seconds, continue to grind for 0.5h, then add ultra-fine frit slurry (high temperature transparent frit powder is made into slurry with solid content of 40%) for third sand mill to flow rate greater than 40 seconds, then discharge, then dry and grind;

[0053] 2. The powder obtained in step 1 is calcined by using a shuttle kiln firing schedule, i.e. the temperature is raised from room temperature to 650℃ for 1.5h, then raised to 1000℃ for 1.5h, and then kept at 1000℃ for 2h. The calcined material is then ground to 325 mesh by using a water ball mill, and then ground to the desired particle size by using a water sand mill. After drying and powdering, the ceramic inkjet printing red pigment for ink is obtained.

[0054] The embodiment also provides a ceramic inkjet printing red ink with a D50 of 0.2μm and a solid content of 41%, which is prepared from the following raw materials in percentage by mass: the ceramic inkjet printing red pigment for ink 41%, isopropyl laurate 30%, white mineral oil 24%, and dispersant (Qingdao Zhuoyi 1310) 5%.

[0055] The ceramic inkjet printing red ink is prepared by the following steps:

[0056] The ceramic inkjet printing red pigment is mixed with the organic solvent and the dispersant, and then sand ground. The iron is removed by using an iron removal machine, and then filtered to obtain the ceramic inkjet printing red ink.

[0057] The embodiment also provides a ceramic pattern layer, which is prepared by inkjet printing the ceramic inkjet printing red ink and then firing. The inkjet printing is performed by using an eight-channel inkjet test machine of Xingtai, and the nozzle is 1024MC. The gray scale is 40%, and the firing temperature is 1000℃.

[0058] The embodiment also provides a ceramic, which comprises a ceramic base material, a face glaze layer, a pattern layer and a protective glaze layer attached to the surface of the ceramic base material in sequence. The pattern layer is made of the ceramic pattern layer.

[0059] The formula of the ceramic face glaze is as follows: sodium feldspar 31%, potassium feldspar 14%, calcined zinc oxide 1%, quartz 39%, kaolin 12%, and high-temperature transparent clinker 3%.

[0060] The ceramic inkjet printing red ink prepared in the embodiment has good printing effect and the best color development. However, the ceramic inkjet printing red pigment has a relatively large particle size, and the filtering performance is slightly poor.

[0061] Example 2

[0062] The difference from Example 1 is that the formula of the red pigment is as follows: 130 iron red 50%, low-temperature transparent clinker with a D50 of 0.2μm 41%, and 10000-mesh aluminum hydroxide 9%.

[0063] The low-temperature transparent frit has the following formulation: Al203 5.7%, SiO2 62%, CaO 13.9%, MgO 1%, K2O 4.8%, Na2O 0.67%, B2O3 2.2%, and ZnO 8.9%, with the balance being a loss on ignition.

[0064] The ceramic inkjet printing red ink prepared in this example has good printing effect and slightly poor color development.

[0065] Example 3

[0066] The difference from Example 1 is that the sintering temperature of the ceramic pattern layer is 900°C.

[0067] The ceramic inkjet printing red ink prepared in this example has good printing effect and slightly poor color development.

[0068] Example 4

[0069] The difference from Example 1 is that the red pigment has the following formulation: 130 iron red 45%, high-temperature transparent frit with D50 of 0.2 μm 45%, and 10,000-mesh aluminum hydroxide 10%.

[0070] The ceramic inkjet printing red ink prepared in this example has good printing effect and slightly poor color development.

[0071] Example 5

[0072] The difference from Example 1 is that the sintering temperature of the ceramic pattern layer is 1100°C.

[0073] The ceramic inkjet printing red ink prepared in this example has good printing effect and slightly poor color development.

[0074] Comparative Example 1

[0075] The difference from Example 1 is that in the preparation method of the red pigment for the ceramic inkjet printing ink, the temperature for calcining the powder in Step 2 is 900°C.

[0076] The ceramic inkjet printing red ink prepared in this comparative example has no color after sintering.

[0077] Comparative Example 2

[0078] The difference from Example 1 is that in the preparation method of the red pigment for the ceramic inkjet printing ink, the red pigment for the ceramic inkjet printing ink is replaced with an equal amount of silicon-iron red pigment.

[0079] The ceramic inkjet printing red ink prepared in this comparative example has no color after sintering.

[0080] Comparative Example 3

[0081] The difference from Example 1 is that no frit powder is added in the formulation of the red pigment for the ceramic inkjet printing ink.

[0082] The ceramic inkjet printing red ink prepared in this comparative example is used for printing, and no color is obtained after firing.

[0083] Comparative Example 4

[0084] The difference from Example 1 is that the D50 of the ceramic inkjet printing red ink is 0.5 μm.

[0085] The printing effect of the ceramic inkjet printing red ink prepared in this comparative example is poor, and a stringing phenomenon occurs.

[0086] Comparative Example 5

[0087] The difference from Example 1 is that the fineness of the frit powder in the formulation of the red pigment for the ceramic inkjet printing ink is 325 mesh.

[0088] The ceramic inkjet printing red ink prepared in this comparative example is used for printing, and no color is obtained after firing.

[0089] The above is only a preferred embodiment of the present application, and does not limit the present application in any form. Any simple modification, equivalent change or modification of the above embodiment according to the technical essence of the present application is still within the scope of the technical solution of the present application.

Claims

1. A red pigment for ceramic inkjet printing ink, characterized in that, Composed of raw materials in the following mass percentages: 40-60% of frit powder, 7-15% of aluminum hydroxide and 30-45% of iron red; The D50 of the frit powder is 0.2-0.3 μm; The particle size of the aluminum hydroxide is 8000-10000 mesh; The iron red is red iron oxide, and the D90 of the iron red is less than 3 μm; The frit powder is prepared by the following steps: raw materials are proportioned, heated and melted, and then water-quenched to obtain frit semi-finished product; the frit semi-finished product is sequentially subjected to wet ball milling and wet sand milling to obtain a D50 of 0.2-0.3 μm, and then dried to obtain the frit powder; The preparation method of the red pigment for ceramic ink-jet printing ink comprises the following steps: S1: aluminum hydroxide and frit powder are slurried respectively, iron red is subjected to first water milling, aluminum hydroxide slurry is added for second water milling, and frit slurry is added for third water milling, and then dried and powdered; S2: the powder obtained in step S1 is calcined, and then subjected to fourth water milling, and then dried and powdered to obtain the red pigment for ceramic ink-jet printing ink; In step S2, the calcination temperature is 990-1010 ℃, and the holding time of the calcination is 2-4 h; The D50 of the ceramic ink-jet printing red ink containing the red pigment for ceramic ink-jet printing ink is 0.2-0.3 μm.

2. The red pigment for a ceramic ink-jet printing ink according to claim 1, characterized in that, The composition of the frit powder comprises: Al2O3 5-8%, SiO2 60-65%, CaO 13-18%, MgO 1-1.5%, K2O 2.8-4.8%, Na2O 0.3-1% and ZnO 8-12%.

3. A method for producing a red pigment for a ceramic ink-jet printing ink as claimed in any one of claims 1 to 2, characterized in that, The method comprises the following steps: S1: aluminum hydroxide and frit powder are slurried respectively, iron red is subjected to first water milling, aluminum hydroxide slurry is added for second water milling, and frit slurry is added for third water milling, and then dried and powdered; S2: the powder obtained in step S1 is calcined, and then subjected to fourth water milling, and then dried and powdered to obtain the red pigment for ceramic ink-jet printing ink; In step S2, the calcination temperature is 990-1010 ℃, and the holding time of the calcination is 2-4 h.

4. A ceramic ink-jet printing red ink, characterized by, The ceramic ink-jet printing red ink containing the red pigment for ceramic ink-jet printing ink.

5. The ceramic inkjet printing red ink according to claim 4, characterized in that, Composed of raw materials in the following mass percentages: 40-45% of the red pigment for ceramic ink-jet printing ink, 50-55% of organic solvent and 5-10% of dispersant.

6. A ceramic pattern layer, characterized by, The ceramic pattern layer is prepared by ink-jet printing the ceramic ink-jet printing red ink according to claim 4 and then firing; The firing temperature is 900-1220 ℃, and / or the holding time of the firing is 20 min.

7. A ceramic, characterized by, The ceramic substrate comprises a ceramic base material and a face glaze layer, a pattern layer and a protective glaze layer attached to the surface of the ceramic base material in sequence, and the pattern layer is prepared by using the ceramic pattern layer according to claim 6.