Soft-light skin-feeling glaze, soft-light skin-feeling ceramic rock plate with digital three-dimensional effect and preparation method of soft-light skin-feeling glaze and soft-light skin-feeling ceramic rock plate

Abstract

The invention relates to the technical field of ceramic rock plate production, in particular to soft light skin feeling glaze, a soft light skin feeling ceramic rock plate with a digital three-dimensional effect and a preparation method thereof.According to the soft light skin feeling ceramic rock plate with the digital three-dimensional effect, the formula of a blank, the formula of soft light ground glaze and the formula of soft light cover glaze all belong to clay minerals and are good in plasticity, and meanwhile a toughening composition is added into the blank; the strength and toughness of the ceramic rock plate blank can be greatly enhanced, the toughening composition has certain cohesiveness, a bridge effect can be formed among ceramic particles, and the binding force among the particles is enhanced. In the green body drying process, the bonding effect is beneficial to keeping the relative position of particles and reducing the movement and agglomeration of the particles, so that a more uniform and compact microstructure is formed, the toughness of the ceramic rock plate is improved, the stress in the sintering process is effectively eliminated, the sintering qualification rate is improved, cracking is reduced, and the quality of the ceramic rock plate is improved. Wide application prospects are realized.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic rock slab production, and in particular to a soft-light skin-feeling glaze, a soft-light skin-feeling ceramic rock slab with a digital three-dimensional effect, and a preparation method thereof. Background Art

[0002] As a new type of ceramic product, ceramic rock slabs can carry richer texture elements than traditional ceramic tiles with their super large specifications. Combined with advanced technology, they can achieve high flexural and high strength green quality. Ceramic rock slabs have the advantages of simple and elegant decorative effects, few seams, avoiding dirt and grime, and high construction and paving efficiency. The Mohs hardness of ceramic rock slabs can reach above level 6, and they are scratch-resistant and wear-resistant, and are not easily scratched by sharp objects. They are suitable for easily worn areas such as kitchen countertops. They are fired at a high temperature of more than 1200℃ and meet the A1 fire protection standard. They do not change color, smoke, or release harmful substances when burned by open flames, and can be used in high temperature environments such as near stoves. The surface porosity is almost zero, the water absorption rate is low, stains are difficult to penetrate, and they are easy to clean. The stain resistance level reaches the 5th level of health standards.

[0003] Soft light skin-feel glaze is a glaze used on the surface of ceramic rock slabs, which can make the rock slabs present a soft luster and delicate touch, similar to the texture of skin. Its glossiness is usually around 15-30 degrees, which can reduce the reflectivity, reduce visual pollution, and give people a sense of visual comfort; the soft light skin-feel ceramic rock slab with digital three-dimensional effect is based on ceramic rock slabs, combining soft light skin-feel glaze and digital three-dimensional technology. It not only has the advantages of soft light skin-feel glaze, but also uses digital technology to accurately control the texture and pattern to form a unique three-dimensional effect, making the texture on the surface of the rock slab more layered and realistic.

[0004] Although the ceramic rock slab has high hardness, it is brittle and is prone to cracking and breaking when subjected to large external impact, especially thinner rock slabs, which have limited load-bearing capacity. For example, patent technical document CN110627532A discloses a large-scale ceramic rock slab and its production process. The raw materials used for the rock slab blank are composed of: 40%-55% medium-temperature sand, 15%-25% low-temperature sand, 16%-25% ball clay, 5%-10% burned talc, 2%-5% calcined kaolin and 1%-3% zirconium silicate. It has the characteristics of realistic simulated 3D texture, delicate texture and hardness, but the blank formula basically follows the traditional formula, with less clay mineral raw materials, poor plasticity, low blank strength, high brittleness of the product, and easy cracking during secondary processing;

[0005] Patent technology document CN115536372B discloses a ceramic rock plate, a dry-process powdered ceramic rock plate blank and a preparation method thereof, comprising the following components in parts by weight: 0.1-0.5 parts of sodium hexametaphosphate, 0.1-0.5 parts of gas-phase nano-alumina, 0.2-0.8 parts of precipitated nano-silicon dioxide; and also comprising the following components in parts by weight: 4-8 parts of calcined coal gangue, 4-10 parts of bauxite, 8-16 parts of potassium-sodium water abrasive, 2-6 parts of pyrophyllite, 13-23 parts of potassium sand, and 0.2-0.8 parts of potassium-sodium slag. 10-30 parts of mixed sand, 10-20 parts of silica sand, 5-17 parts of bentonite, and 2-6 parts of diopside are selected and compounded to ensure that both the dry pulverizing process goes smoothly and that the green body has sufficient strength. However, the powder particles obtained by dry pulverizing have a rough and irregular surface, a narrow particle size distribution range, and coarse particles, which makes it difficult for the powder to be densely packed during the pressing process. The internal porosity of the green body is high, and the structure is not dense enough, thereby reducing the strength and toughness of the green body and making it prone to cracking.

[0006] Therefore, according to the relevant technologies mentioned above, there is an urgent need to develop a soft skin-feeling glaze, a soft skin-feeling ceramic rock plate with a digital three-dimensional effect, and a preparation method thereof. Summary of the invention

[0007] In view of this, the purpose of the present invention is to propose a soft skin-feel glaze, a soft skin-feel ceramic rock plate with a digital three-dimensional effect and a preparation method thereof, so as to solve the problems of low toughness, brittle texture and easy cracking of ceramic rock plates in the prior art.

[0008] Based on the above objectives, the present invention provides a soft-light skin-feeling glaze, a soft-light skin-feeling ceramic rock plate with a digital three-dimensional effect, and a preparation method thereof.

[0009] A soft light skin-feeling glaze, comprising a soft light base glaze and a soft light surface glaze;

[0010] The soft gloss base glaze is obtained by mixing the following raw materials in parts by weight: 45-50 parts of potassium feldspar, 8-12 parts of kaolin, 4-6 parts of sodium feldspar, 2-4 parts of calcined alumina, 2-3 parts of calcined talc, 2-4 parts of dolomite, 3-5 parts of calcined kaolin, 10-15 parts of iodine, 30-35 parts of ethylene glycol butyl ether acetate, 2-5 parts of sodium lauryl sulfate and 1-2 parts of triethanolamine;

[0011] The soft gloss glaze is obtained by mixing the following raw materials in parts by weight: 40-45 parts of potassium feldspar, 5-15 parts of sodium feldspar, 8-12 parts of kaolin, 10-15 parts of quartz, 10-15 parts of calcined alumina, 2-4 parts of wollastonite and 4-6 parts of calcined talc, 30-35 parts of ethylene glycol butyl ether acetate, 2-5 parts of sodium lauryl sulfate and 1-2 parts of triethanolamine.

[0012] A soft light skin-feeling ceramic rock plate with digital three-dimensional effect, comprising a blank and a soft light skin-feeling glaze;

[0013] The blank is obtained by mixing the following raw materials in parts by weight: 40-50 parts of potassium feldspar, 4-8 parts of talc, 20-30 parts of kaolin, 5-10 parts of raw ore mud, 4-6 parts of wollastonite and 5-10 parts of toughening composition;

[0014] The toughening composition is obtained by mixing a reinforcing agent, lignin, hydroxypropyl methylcellulose and sodium polyacrylate in a mass ratio of 10-15:5-8:3-5:5-8;

[0015] The reinforcing agent is prepared from octamethylcyclotetrasiloxane, gamma-methacryloxypropyltrimethoxysilane, butyl acrylate and hydroxyethyl acrylate.

[0016] Preferably, the preparation method of the enhancer is as follows:

[0017] Step A1. Disperse dodecylbenzene sulfonic acid and octylphenol polyoxyethylene ether in deionized water, add octamethylcyclotetrasiloxane and γ-methacryloxypropyltrimethoxysilane, stir at 60-65°C for 6-8h, and then cool to room temperature to obtain a pretreatment solution;

[0018] Step A2. Use sodium hydroxide solution to adjust the pH value of the pretreatment liquid to 8-10, heat to 70-80°C, add butyl acrylate and hydroxyethyl acrylate, and then add potassium persulfate aqueous solution, react at 70-80°C for 3-6 hours, cool to room temperature, add calcium chloride aqueous solution, filter, wash, and dry to obtain an enhancer.

[0019] Preferably, the mass ratio of dodecylbenzenesulfonic acid, octylphenol polyoxyethylene ether, deionized water, octamethylcyclotetrasiloxane and γ-methacryloxypropyltrimethoxysilane in step A1 is 0.05-0.1:0.05-0.1:100-120:41-45:3-5.

[0020] Preferably, the mass ratio of the pretreatment liquid, butyl acrylate, hydroxyethyl acrylate, potassium persulfate aqueous solution and calcium chloride aqueous solution in step A2 is 55-60:31-35:13-18:1-3:25-30;

[0021] The mass fraction of the potassium persulfate aqueous solution in step A2 is 10%-15%;

[0022] The mass fraction of the calcium chloride aqueous solution in step A2 is 10%-15%.

[0023] A method for preparing a soft light skin-feeling ceramic rock plate with a digital three-dimensional effect comprises the following steps:

[0024] Step B1. Potash feldspar, talc, kaolin, raw ore mud, wollastonite and toughening composition are added, processed by ball milling equipment, and placed in a slurry tank for aging for 24-32 hours to obtain a slurry;

[0025] Step B2. spray-drying the slurry to obtain slurry particles;

[0026] Step B3. After the slurry particles are dry-pressed and formed, they are dried by heating, cast, blown, and sprayed with water to obtain a green body;

[0027] Step B4. After applying soft light base glaze on the surface of the blank, inkjet printing is performed on the surface with the soft light base glaze, and then soft light top glaze is applied on the surface, and firing treatment is performed under a nitrogen atmosphere to obtain soft light skin-feel glaze and soft light skin-feel ceramic rock plate with digital three-dimensional effect.

[0028] Preferably, the particle size after ball milling in step B1 is 200-300 mesh.

[0029] Preferably, the air inlet temperature in the spray drying powder making in step B2 is 350-400°C, and the air outlet temperature is 70-75°C.

[0030] Preferably, the pressing pressure in the dry pressing molding in step B3 is 370-400 kg / cm 2 ;

[0031] The soft gloss base glaze in step B4 is applied by pouring glaze, and the amount of soft gloss base glaze applied is 240-260g / m 2 ;

[0032] The soft gloss glaze in step B4 is applied by pouring glaze, and the amount of soft gloss glaze applied is 650-700g / m 2 .

[0033] Preferably, the temperature in the sintering treatment in step B4 is:

[0034] From room temperature to 500°C, the heating rate is 30-40°C / min;

[0035] From 500℃ to 850℃, the heating rate is 20-40℃ / min;

[0036] From 850℃ to 1100℃, the heating rate is 10-20℃ / min, and the temperature is kept at 1100℃ for 8-12min.

[0037] Beneficial effects of the present invention:

[0038] The formulas of the blank, soft-gloss base glaze and soft-gloss top glaze in the present invention all belong to clay minerals with good plasticity. At the same time, adding a toughening composition to the blank can greatly enhance the strength and toughness of the ceramic rock slab blank. The toughening composition has a certain adhesiveness and can form a bridge between ceramic particles to enhance the bonding force between particles. It has good thickening properties and can increase the viscosity of the ceramic slurry, so that the ceramic particles in the slurry are evenly dispersed and effective bonding is formed between the particles. During the drying process of the blank, this bonding effect helps to maintain the relative position of the particles, reduce the movement and agglomeration of the particles, thereby forming a more uniform and dense microstructure and improving the toughness of the ceramic rock slab. The present invention also effectively eliminates stress during the firing process through step-by-step temperature rise firing, improves the firing pass rate, and reduces cracking, and has broad application prospects. DETAILED DESCRIPTION

[0039] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0040] The sources and properties of some of the raw materials used in the present invention are as follows:

[0041] Octamethylcyclotetrasiloxane was purchased from Jiangxi Lanxing Xinghuo Silicone Co., Ltd.; γ-methacryloxypropyltrimethoxysilane was purchased from Chengdu Kelon Chemical Reagent Factory; butyl acrylate was purchased from Shandong Langcheng Chemical Co., Ltd.; and hydroxyethyl acrylate was purchased from Liaoning Kelon Fine Chemical Co., Ltd.

[0042] Embodiment 1: A soft light skin-feeling glaze, comprising the following preparation steps:

[0043] S1. Mix 45 g of potassium feldspar, 8 g of kaolin, 4 g of sodium feldspar, 2 g of calcined alumina, 2 g of calcined talc, 2 g of dolomite, 3 g of calcined kaolin, 10 g of iodine, 30 g of ethylene glycol butyl ether acetate, 2 g of sodium lauryl sulfate and 1 g of triethanolamine to obtain a soft base glaze;

[0044] S2. 40 g of potassium feldspar, 5 g of sodium feldspar, 8 g of kaolin, 10 g of quartz, 10 g of calcined alumina, 2 g of wollastonite and 4 g of calcined talc, 30 g of ethylene glycol butyl ether acetate, 2 g of sodium lauryl sulfate and 1 g of triethanolamine were mixed to obtain a soft glaze;

[0045] S3. Soft light skin-feel glaze consists of soft light base glaze and soft light top glaze.

[0046] Embodiment 2: A soft light skin-feeling glaze, comprising the following preparation steps:

[0047] S1. 47 g of potassium feldspar, 10 g of kaolin, 5 g of sodium feldspar, 3 g of calcined alumina, 2.5 g of calcined talc, 3 g of dolomite, 4 g of calcined kaolin, 12 g of iodine, 32 g of ethylene glycol butyl ether acetate, 3 g of sodium lauryl sulfate and 1.5 g of triethanolamine were mixed to obtain a soft base glaze;

[0048] S2. 42 g of potassium feldspar, 10 g of sodium feldspar, 10 g of kaolin, 12 g of quartz, 12 g of calcined alumina, 3 g of wollastonite and 5 g of calcined talc, 32 g of ethylene glycol butyl ether acetate, 3 g of sodium lauryl sulfate and 1.5 g of triethanolamine were mixed to obtain a soft glaze;

[0049] S3. Soft light skin-feel glaze consists of soft light base glaze and soft light top glaze.

[0050] Embodiment 3: A soft light skin-feeling glaze, comprising the following preparation steps:

[0051] S1. 48 g of potassium feldspar, 11 g of kaolin, 5.5 g of sodium feldspar, 3.5 g of calcined alumina, 2.8 g of calcined talc, 3.5 g of dolomite, 4.5 g of calcined kaolin, 13 g of iodine, 33 g of ethylene glycol butyl ether acetate, 4 g of sodium lauryl sulfate and 1.8 g of triethanolamine were mixed to obtain a soft base glaze;

[0052] S2. 43 g of potassium feldspar, 12 g of sodium feldspar, 11 g of kaolin, 13 g of quartz, 13 g of calcined alumina, 3.5 g of wollastonite and 5.5 g of calcined talc, 33 g of ethylene glycol butyl ether acetate, 4 g of sodium lauryl sulfate and 1.8 g of triethanolamine were mixed to obtain a soft glaze;

[0053] S3. Soft light skin-feel glaze consists of soft light base glaze and soft light top glaze.

[0054] Embodiment 4: A soft light skin-feeling glaze, comprising the following preparation steps:

[0055] S1. 50 g of potassium feldspar, 12 g of kaolin, 6 g of sodium feldspar, 4 g of calcined alumina, 3 g of calcined talc, 4 g of dolomite, 5 g of calcined kaolin, 15 g of iodine, 35 g of ethylene glycol butyl ether acetate, 5 g of sodium lauryl sulfate and 2 g of triethanolamine were mixed to obtain a soft base glaze;

[0056] S2. 45 g of potassium feldspar, 15 g of sodium feldspar, 12 g of kaolin, 15 g of quartz, 15 g of calcined alumina, 4 g of wollastonite and 6 g of calcined talc, 35 g of ethylene glycol butyl ether acetate, 5 g of sodium lauryl sulfate and 2 g of triethanolamine were mixed to obtain a soft glaze;

[0057] S3. Soft light skin-feel glaze consists of soft light base glaze and soft light top glaze.

[0058] Embodiment 5: A method for preparing a soft light skin-feeling ceramic rock plate with digital three-dimensional effect, comprising the following steps:

[0059] S1. 0.05 g of dodecylbenzene sulfonic acid and 0.05 g of octylphenol polyoxyethylene ether were dispersed in 100 g of deionized water, and then 41 g of octamethylcyclotetrasiloxane and 3 g of γ-methacryloxypropyltrimethoxysilane were added, stirred at 60 ° C for 6 h and then cooled to room temperature to obtain a pre-treated solution;

[0060] S2. The pretreatment solution was adjusted to pH 8 with 55 g of sodium hydroxide solution, heated to 70 ° C, 31 g of butyl acrylate and 13 g of hydroxyethyl acrylate were added, and then 1 g of 10% potassium persulfate aqueous solution was added, and the reaction was allowed to react at 70 ° C for 3 h, and then cooled to room temperature, 25 g of 10% calcium chloride aqueous solution was added, filtered, washed and dried to obtain an enhancer;

[0061] S3. 10 g of a reinforcing agent, 5 g of lignin, 3 g of hydroxypropyl methylcellulose and 5 g of sodium polyacrylate were mixed to obtain a toughening composition;

[0062] S4. The potassium feldspar 40g, talc 4g, kaolin 20g, raw ore mud 5g, wollastonite 4g and toughening composition 5g were mixed to obtain a blank;

[0063] S5. Potassium feldspar, talc, kaolin, raw ore mud, wollastonite and toughening composition were fed, processed by ball milling equipment, and placed in a slurry tank for aging for 24 hours to obtain a slurry, wherein the particle size after ball milling was 200 mesh;

[0064] S6. The slurry is spray dried to obtain slurry particles, wherein the inlet air temperature in the spray drying is 350°C and the outlet air temperature is 70°C;

[0065] S7. After the slurry particles are dry-pressed, they are dried, thrown, blown, and sprayed with water to obtain a green body, wherein the pressing pressure of the dry pressing is 370kg / cm 2 ;

[0066] S8. After applying the soft light base glaze prepared in Example 1 on the surface of the body, inkjet printing is performed on the surface on which the soft light base glaze is applied, and then the soft light top glaze prepared in Example 1 is applied on the surface, and the sintering treatment is performed to obtain a soft light skin-feeling glaze and a soft light skin-feeling ceramic rock plate with a digital three-dimensional effect, wherein the soft light base glaze is applied by pouring glaze, and the applied amount is 240g / m 2 ; The soft gloss glaze is applied by pouring glaze, and the application amount is 650g / m 2The temperature during the sintering treatment is: from room temperature to 500°C, the heating rate is 30°C / min; from 500°C to 850°C, the heating rate is 20°C / min; from 850°C to 1100°C, the heating rate is 10°C / min, and the temperature is kept at 1100°C for 8 minutes.

[0067] Embodiment 6: A method for preparing a soft light skin-feeling ceramic rock plate with a digital three-dimensional effect, comprising the following steps:

[0068] S1. 0.07 g of dodecylbenzene sulfonic acid and 0.07 g of octylphenol polyoxyethylene ether were dispersed in 110 g of deionized water, and then 43 g of octamethylcyclotetrasiloxane and 4 g of γ-methacryloxypropyltrimethoxysilane were added, stirred at 62 ° C for 7 h and then cooled to room temperature to obtain a pre-treated solution;

[0069] S2. The pretreatment solution was adjusted to pH 9 with 57 g of sodium hydroxide solution, heated to 75 ° C, 33 g of butyl acrylate and 15 g of hydroxyethyl acrylate were added, and then 2 g of 12% potassium persulfate aqueous solution was added, and the reaction was allowed to react at 75 ° C for 4 h, and then cooled to room temperature, 27 g of 12% calcium chloride aqueous solution was added, filtered, washed and dried to obtain an enhancer;

[0070] S3. 12g of a reinforcing agent, 6g of lignin, 4g of hydroxypropyl methylcellulose and 6g of sodium polyacrylate were mixed to obtain a toughening composition;

[0071] S4. The potassium feldspar 45g, talc 6g, kaolin 25g, raw ore mud 7g, wollastonite 5g and toughening composition 7g were mixed to obtain a blank;

[0072] S5. Potassium feldspar, talc, kaolin, raw ore mud, wollastonite and toughening composition were fed, processed by ball milling equipment, and placed in a slurry tank for aging for 28h to obtain a slurry, wherein the particle size after ball milling was 250 mesh;

[0073] S6. The slurry is spray dried to obtain slurry particles, wherein the inlet air temperature in the spray drying is 370°C and the outlet air temperature is 72°C;

[0074] S7. The slurry particles are dry pressed by a belt-type frameless press, and then heated and dried, thrown, blown, and sprayed with water to obtain a green body, wherein the pressing pressure of the dry pressing is 380kg / cm 2 ;

[0075] S8. After applying the soft light base glaze prepared in Example 2 on the surface of the body, inkjet printing is performed on the surface on which the soft light base glaze is applied, and then the soft light top glaze prepared in Example 2 is applied on the surface, and the sintering treatment is performed to obtain a soft light skin-feeling glaze and a soft light skin-feeling ceramic rock plate with a digital three-dimensional effect, wherein the soft light base glaze is applied by pouring glaze, and the application amount is 250g / m 2 ; The soft gloss glaze is applied by pouring glaze, and the application amount is 670g / m 2 The temperature during the sintering treatment is: from room temperature to 500°C, the heating rate is 34°C / min; from 500°C to 850°C, the heating rate is 30°C / min; from 850°C to 1100°C, the heating rate is 14°C / min, and the temperature is kept at 1100°C for 10 minutes.

[0076] Embodiment 7: A method for preparing a soft light skin-feeling ceramic rock plate with digital three-dimensional effect, comprising the following steps:

[0077] S1. 0.08 g of dodecylbenzene sulfonic acid and 0.08 g of octylphenol polyoxyethylene ether were dispersed in 115 g of deionized water, and then 44 g of octamethylcyclotetrasiloxane and 4.5 g of γ-methacryloxypropyltrimethoxysilane were added, stirred at 63 ° C for 7.5 h and then cooled to room temperature to obtain a pre-treated solution;

[0078] S2. The pretreatment solution was adjusted to pH 9 with 58 g of sodium hydroxide solution, heated to 78 ° C, 34 g of butyl acrylate and 16 g of hydroxyethyl acrylate were added, and then 2.5 g of 13% potassium persulfate aqueous solution was added, and the reaction was carried out at 78 ° C for 5 h, and then cooled to room temperature, 28 g of 13% calcium chloride aqueous solution was added, filtered, washed and dried to obtain an enhancer;

[0079] S3. 13g of a reinforcing agent, 7g of lignin, 4.5g of hydroxypropyl methylcellulose and 7g of sodium polyacrylate were mixed to obtain a toughening composition;

[0080] S4. The potassium feldspar 48g, talc 7g, kaolin 28g, raw ore mud 8g, wollastonite 5.5g and toughening composition 8g were mixed to obtain a blank;

[0081] S5. Potassium feldspar, talc, kaolin, raw ore mud, wollastonite and toughening composition were fed, processed by ball milling equipment, and placed in a slurry tank for aging for 30h to obtain a slurry, wherein the particle size after ball milling was 280 mesh;

[0082] S6. The slurry is spray dried to obtain slurry particles, wherein the inlet air temperature in the spray drying is 380°C and the outlet air temperature is 73°C;

[0083] S7. After the slurry particles are dry-pressed, they are dried, thrown, blown, and sprayed with water to obtain a green body, wherein the pressing pressure of the dry pressing is 390kg / cm 2 ;

[0084] S8. After applying the soft light base glaze prepared in Example 3 on the surface of the body, inkjet printing is performed on the surface on which the soft light base glaze is applied, and then the soft light top glaze prepared in Example 3 is applied on the surface, and the sintering treatment is performed to obtain a soft light skin-feeling glaze and a soft light skin-feeling ceramic rock plate with a digital three-dimensional effect, wherein the soft light base glaze is applied by pouring glaze, and the application amount is 255g / m 2 ; The soft gloss glaze is applied by pouring glaze, and the application amount is 680g / m 2 The temperature during the sintering treatment is: from room temperature to 500°C, the heating rate is 36°C / min; from 500°C to 850°C, the heating rate is 35°C / min; from 850°C to 1100°C, the heating rate is 16°C / min, and the temperature is kept at 1100°C for 11 minutes.

[0085] Embodiment 8: A method for preparing a soft light skin-feeling ceramic rock plate with digital three-dimensional effect, comprising the following steps:

[0086] S1. 0.1 g of dodecylbenzene sulfonic acid and 0.1 g of octylphenol polyoxyethylene ether were dispersed in 120 g of deionized water, and then 45 g of octamethylcyclotetrasiloxane and 5 g of γ-methacryloxypropyltrimethoxysilane were added, stirred at 65 ° C for 8 h and then cooled to room temperature to obtain a pre-treated solution;

[0087] S2. The pretreatment solution was adjusted to pH 10 with 60 g of sodium hydroxide solution, heated to 80 ° C, 35 g of butyl acrylate and 18 g of hydroxyethyl acrylate were added, and then 3 g of 15% potassium persulfate aqueous solution was added, reacted at 80 ° C for 6 h, cooled to room temperature, and 30 g of 15% calcium chloride aqueous solution was added, filtered, washed and dried to obtain an enhancer;

[0088] S3. 15g of a reinforcing agent, 8g of lignin, 5g of hydroxypropyl methylcellulose and 8g of sodium polyacrylate were mixed to obtain a toughening composition;

[0089] S4. The potassium feldspar 50g, talc 8g, kaolin 30g, raw ore mud 10g, wollastonite 6g and toughening composition 10g were mixed to obtain a blank;

[0090] S5. Potassium feldspar, talc, kaolin, raw ore mud, wollastonite and toughening composition were fed, processed by ball milling equipment, and placed in a slurry tank for aging for 32h to obtain a slurry, wherein the particle size after ball milling was 300 mesh;

[0091] S6. spray drying the slurry to obtain slurry particles, wherein the inlet air temperature in the spray drying is 400°C and the outlet air temperature is 75°C;

[0092] S7. After the slurry particles are dry-pressed, they are dried at elevated temperatures, thrown into the blank, blown with soot, and sprayed with water to obtain a blank, wherein the pressing pressure of the dry-pressing molding is 400 kg / cm 2 ;

[0093] S8. After applying the soft light base glaze prepared in Example 4 on the surface of the body, inkjet printing is performed on the surface on which the soft light base glaze is applied, and then the soft light top glaze prepared in Example 4 is applied on the surface, and the sintering treatment is performed to obtain a soft light skin-feeling glaze and a soft light skin-feeling ceramic rock plate with a digital three-dimensional effect, wherein the soft light base glaze is applied by pouring glaze, and the applied amount is 260g / m 2 ; The soft gloss glaze is applied by pouring glaze, and the application amount is 700g / m 2 The temperature during the sintering treatment is: from room temperature to 500°C, the heating rate is 40°C / min; from 500°C to 850°C, the heating rate is 40°C / min; from 850°C to 1100°C, the heating rate is 20°C / min, and the temperature is kept at 1100°C for 12 minutes.

[0094] Comparative Example 1:

[0095] Compared with Example 1, this comparative example does not add an enhancer during the preparation process of the soft light skin-feel ceramic rock plate, and the remaining steps and parameters are the same. This comparative example will not be repeated, and finally a soft light skin-feel ceramic rock plate is obtained.

[0096] Comparative Example 2:

[0097] Compared with Example 1, this comparative example did not add a toughening composition during the preparation process of the soft-light skin-feel ceramic rock plate, and the remaining steps and parameters were the same, which will not be repeated in this comparative example. Finally, a soft-light skin-feel ceramic rock plate was obtained.

[0098] Comparative Example 3:

[0099] Compared with Example 1, this comparative example only replaces "41g octamethylcyclotetrasiloxane and 3g γ-methacryloxypropyltrimethoxysilane" with "41g octamethylcyclotetrasiloxane and 20g γ-methacryloxypropyltrimethoxysilane", and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a soft light skin-feel ceramic rock plate is obtained.

[0100] Comparative Example 4:

[0101] Compared with Example 1, this comparative example only replaces "100 g of ethylene glycol butyl ether acetate" with "100 g of water", and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a soft light skin-feel ceramic rock plate is obtained.

[0102] Comparative Example 5:

[0103] Compared with Example 1, this comparative example only replaces "the temperature in the firing treatment is: from room temperature to 500°C, the heating rate is 30°C / min; from 500°C to 850°C, the heating rate is 20°C / min; from 850°C to 1100°C, the heating rate is 10°C / min, and keeping warm at 1100°C for 8 min" with "the temperature in the firing treatment is: from room temperature to 1100°C, the heating rate is 30°C / min, and keeping warm at 1100°C for 8 min". The remaining steps and parameters are the same and will not be repeated in this comparative example. Finally, a soft skin-feel ceramic rock plate is obtained.

[0104] Performance Test:

[0105] Bending strength determination:

[0106] With reference to the test standard GB / T4741-1999 "Test method for flexural strength of ceramic materials", the ceramic rock slabs prepared in Example 4-Example 8 and Comparative Example 1-Comparative Example 5 were cut into specimens with a length of 30 mm, a width of 5 mm, and a thickness of 3 mm. The surface of the specimens was polished smooth and placed on the supporting device of a three-point bending tester. The loading pressure head was located at the midpoint directly above the specimen. Pressure was applied to the specimen at a constant rate, and the maximum fracture load borne by the specimen when it broke was recorded. The flexural strength of the ceramic rock slabs was calculated by the formula. The measured results are shown in Table 1.

[0107] Calculation formula for flexural strength:

[0108] Wherein, σ is the bending strength, in MPa; F is the maximum breaking load, in N; L is the support point spacing, in mm; b is the specimen width, in mm; h is the specimen thickness, in mm.

[0109] Processing fracture rate determination:

[0110] Cutting processing breakage rate: Take 50 ceramic rock slabs prepared in Example 4 to Example 8 and Comparative Example 1 to Comparative Example 5 respectively, and use an electric saw cutting machine to cut through the edges (within 1 / 3 of the side length) and the center (center line) of the ceramic rock slabs.

[0111] If after cutting, cracks or fracture lines other than cutting lines are produced, it is counted as a fracture. If after cutting, no visible cracks are produced, the fracture modulus of the ceramic rock slab after cutting is measured. If the fracture modulus changes to less than 90% of the original fracture modulus, it is calculated as a fracture; otherwise, it is counted as no fracture. The measured results are shown in Table 1.

[0112] Engraving cracking rate: Take 50 ceramic rock slabs prepared in Example 4 to Example 8 and Comparative Example 1 to Comparative Example 5 respectively, and use a CNC water jet to engrave the central area of ​​the ceramic rock slab to engrave an annular hole with a depth of 5 mm, an inner diameter of 495 mm, and an outer diameter of 500 mm.

[0113] If the ceramic rock slab breaks during or after engraving, it is recorded as broken; if the ceramic rock slab does not produce visible cracks after engraving, the fracture modulus of the ceramic rock slab after engraving is measured, and if the fracture modulus changes to less than 80% of the original fracture modulus, it is recorded as broken. Otherwise, it is recorded as not broken. The measured results are shown in Table 1.

[0114] Qualification rate determination:

[0115] Drying qualified rate:

[0116] Take 500 pieces of the green bodies prepared in Examples 4 to 8 and Comparative Examples 1 to 5 and dry them. After drying, if the green bodies are broken or have small cracks on the edges and corners, they are considered unqualified, otherwise they are considered qualified;

[0117] In addition, after drying, 20 qualified green bodies were selected, and the edge curvature and center curvature of the green bodies were measured with reference to the test standard GB3810.2-2016 "Ceramic Tile Test Method Part 2". The results are shown in Table 2.

[0118] Firing qualification rate:

[0119] The qualified green body after drying is fired.

[0120] After firing, if there is a break or crack on the corners, or obvious warping is visible to the naked eye, it is considered unqualified; otherwise, it is considered qualified;

[0121] After firing, 20 qualified ceramic slabs were selected and the edge curvature and center curvature were measured according to the test standard GB3810.2-2016 "Ceramic Tile Test Method Part 2". The results are shown in Table 2.

[0122] Table 1 Statistics of bending strength, cutting cracking rate and engraving cracking rate

[0123] project Bending strength / MPa Cutting process fracture rate / % Engraving cracking rate / % Example 5 43.8 1 4 Example 6 47.1 2 4 Example 7 41.5 1 4 Example 8 42.3 1 6 Comparative Example 1 31.8 5 34 Comparative Example 2 36.4 10 32 Comparative Example 3 29.6 16 27 Comparative Example 4 40.7 24 38 Comparative Example 5 40.2 25 40

[0124] Table 2 Statistics of drying and sintering pass rates

[0125]

[0126]

[0127] Data Analysis:

[0128] It can be seen from Table 1 that the soft light skin-feeling glaze and the soft light skin-feeling ceramic rock plate with digital three-dimensional effect prepared by the present invention have higher toughness, higher bending strength, and are not easy to break;

[0129] This may be because the formulas of the blank, soft-gloss base glaze and soft-gloss surface glaze in the present invention all belong to clay minerals with good plasticity. At the same time, adding a toughening composition to the blank can greatly enhance the strength and toughness of the ceramic rock slab blank. The toughening composition has a certain adhesiveness and can form a bridge between ceramic particles to enhance the bonding force between particles. It has good thickening properties and can increase the viscosity of the ceramic slurry, so that the ceramic particles in the slurry are evenly dispersed and form an effective bond between the particles. During the drying process of the blank, this bonding effect helps to maintain the relative position of the particles, reduce the movement and agglomeration of the particles, thereby forming a more uniform and dense microstructure and improving the toughness of the ceramic rock slab. The present invention also effectively eliminates stress during the firing process through step-by-step temperature increase, improves the firing pass rate, and reduces cracking;

[0130] The toughening composition in the blank is mainly used to improve the performance of the blank by its role in the blank forming and drying stages; during the drying process, the moisture in the blank gradually evaporates, the blank volume shrinks, and cracks and other defects are easily generated. The toughening composition can form a network structure between the blank particles, play a bridging and supporting role, improve the drying strength of the blank, and reduce cracking during the drying process; although the toughening composition will decompose under high-temperature sintering, before decomposition, they play a role in making the particles tightly combined and evenly distributed in the blank. After decomposition, the blank has formed a relatively stable and tight particle stacking structure, which improves the strength and toughness of the rock plate to a certain extent.

[0131] The organic solvents in the soft base glaze and soft top glaze will gradually and slowly evaporate as the firing temperature gradient increases. Since the ceramic body and glaze have certain pores and channels, these volatile substances can be discharged in an orderly manner along these paths. A large pressure difference will not be formed inside the rock slab, which will not cause obvious holes in the rock slab and will not affect the mechanical properties of the ceramic rock slab.

[0132] In Comparative Example 1, since no reinforcing agent was added during the preparation of the ceramic rock plate, it can be seen from Tables 1 and 2 that the flexural strength of the prepared ceramic rock plate decreased, the toughness was low, and it was easy to crack. This may be because the reinforcing agent not only has the excellent adhesion and film-forming properties of polyacrylate, but also has the heat resistance and weather resistance of silicone. The reinforcing agent is a core-shell structure polymer with silicone polymer as the core and polyacrylate as the shell. It can solve the problem of phase separation in the polymerization process caused by the difference in polarity between silicone monomers and acrylate monomers. The reinforcing agent can improve the toughness of the ceramic rock plate;

[0133] Comparative Example 2: Since no toughening composition was added during the preparation of the ceramic rock board, it can be seen from Tables 1 and 2 that the flexural strength of the prepared ceramic rock board decreased, the toughness was low, and it was easy to crack. This may be because the reinforcing agent, lignin, hydroxypropyl methylcellulose and sodium polyacrylate in the toughening composition are mixed in a specific proportion, which can improve the toughness of the ceramic rock board. The toughening composition has a certain adhesiveness and can form a bridge between ceramic particles to enhance the bonding force between particles; it has good thickening properties and can increase the viscosity of the ceramic slurry, so that the ceramic particles in the slurry are evenly dispersed and form an effective bond between the particles. During the drying and sintering process of the green body, this bonding effect helps to maintain the relative position of the particles, reduce the movement and agglomeration of the particles, thereby forming a more uniform and dense microstructure and improving the toughness of the ceramic rock board;

[0134] Comparative Example 3 replaces "41g octamethylcyclotetrasiloxane and 3g γ-methacryloxypropyltrimethoxysilane" with "41g octamethylcyclotetrasiloxane and 20g γ-methacryloxypropyltrimethoxysilane". It can be seen from Tables 1 and 2 that the flexural strength and toughness of the ceramic rock plate decrease. This may be because the content of γ-methacryloxypropyltrimethoxysilane is too high. On the one hand, γ-methacryloxypropyltrimethoxysilane will undergo hydrolysis and self-polymerization reactions, resulting in the formation of a cross-linked structure, which destroys the copolymerization reaction with octamethylcyclotetrasiloxane and cannot play the role of the flexibility of the silicone polymer chain segment; on the other hand, the increase in the amount of γ-methacryloxypropyltrimethoxysilane reduces the number of silicon-oxygen bonds on the polysiloxane chain, reduces the flexibility of the polysiloxane chain, and thus leads to a decrease in toughness;

[0135] Comparative Example 4 Since "100g of ethylene glycol butyl ether acetate" is replaced by "100g of water", it can be seen from Tables 1 and 2 that the flexural strength of the ceramic rock plate decreases and the toughness decreases. This may be because ethylene glycol butyl ether acetate is an organic solvent, which has good solubility in the film-forming substances in the base glaze and can help form a continuous, uniform and dense film. As a solvent, water has limited solubility in some film-forming substances, which may cause defects in the film-forming process, such as discontinuous film and pinholes, which affects the protective effect of the base glaze on the ceramic rock plate, and makes the rock plate more susceptible to damage such as cracks when subjected to external forces, reducing toughness;

[0136] Comparative Example 5 Since the gradient heating in the firing step is changed to one-step heating, it can be seen from Tables 1 and 2 that the bending strength of the ceramic rock plate decreases and the toughness decreases. This may be because the gradient heating allows the ceramic rock plate blank to gradually adapt to thermal changes at different temperature stages, allowing the internal stress to be slowly released and adjusted. When the temperature is raised in one step, the blank is heated rapidly in a short period of time, and due to the difference in heat conduction in different parts, a large temperature gradient will be generated, which will lead to thermal stress concentration. These concentrated thermal stresses may form defects such as microcracks inside the blank, seriously reducing the toughness of the rock plate, making it easier to break when subjected to external forces.

[0137] The present invention is intended to cover all such substitutions, modifications and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A soft light skin-feeling glaze, characterized in that: Including soft gloss base glaze and soft gloss top glaze; The soft gloss base glaze is obtained by mixing the following raw materials in parts by weight: 45-50 parts of potassium feldspar, 8-12 parts of kaolin, 4-6 parts of sodium feldspar, 2-4 parts of calcined alumina, 2-3 parts of calcined talc, 2-4 parts of dolomite, 3-5 parts of calcined kaolin, 10-15 parts of iodine, 30-35 parts of ethylene glycol butyl ether acetate, 2-5 parts of sodium lauryl sulfate and 1-2 parts of triethanolamine; The soft gloss glaze is obtained by mixing the following raw materials in parts by weight: 40-45 parts of potassium feldspar, 5-15 parts of sodium feldspar, 8-12 parts of kaolin, 10-15 parts of quartz, 10-15 parts of calcined alumina, 2-4 parts of wollastonite and 4-6 parts of calcined talc, 30-35 parts of ethylene glycol butyl ether acetate, 2-5 parts of sodium lauryl sulfate and 1-2 parts of triethanolamine.

2. A soft light skin-feeling ceramic rock plate with digital three-dimensional effect, characterized in that: Including blank and soft skin glaze; The blank is obtained by mixing the following raw materials in parts by weight: 40-50 parts of potassium feldspar, 4-8 parts of talc, 20-30 parts of kaolin, 5-10 parts of raw ore mud, 4-6 parts of wollastonite and 5-10 parts of toughening composition; The toughening composition is obtained by mixing a reinforcing agent, lignin, hydroxypropyl methylcellulose and sodium polyacrylate in a mass ratio of 10-15:5-8:3-5:5-8; The reinforcing agent is prepared from octamethylcyclotetrasiloxane, gamma-methacryloxypropyltrimethoxysilane, butyl acrylate and hydroxyethyl acrylate.

3. The soft light skin-feeling ceramic rock plate with digital three-dimensional effect according to claim 2 is characterized in that: The preparation method of the enhancer is as follows: Step A1. Disperse dodecylbenzene sulfonic acid and octylphenol polyoxyethylene ether in deionized water, add octamethylcyclotetrasiloxane and γ-methacryloxypropyltrimethoxysilane, stir at 60-65°C for 6-8h, and then cool to room temperature to obtain a pretreatment solution; Step A2. Use sodium hydroxide solution to adjust the pH value of the pretreatment liquid to 8-10, heat to 70-80°C, add butyl acrylate and hydroxyethyl acrylate, and then add potassium persulfate aqueous solution, react at 70-80°C for 3-6 hours, cool to room temperature, add calcium chloride aqueous solution, filter, wash, and dry to obtain an enhancer.

4. The soft light skin-feeling ceramic rock plate with digital three-dimensional effect according to claim 3 is characterized in that: The mass ratio of dodecylbenzenesulfonic acid, octylphenol polyoxyethylene ether, deionized water, octamethylcyclotetrasiloxane and γ-methacryloxypropyltrimethoxysilane in step A1 is 0.05-0.1:0.05-0.1:100-120:41-45:3-5.

5. The soft light skin-feeling ceramic rock plate with digital three-dimensional effect according to claim 3 is characterized in that: The mass ratio of the pretreatment liquid, butyl acrylate, hydroxyethyl acrylate, potassium persulfate aqueous solution and calcium chloride aqueous solution in step A2 is 55-60:31-35:13-18:1-3:25-30; The mass fraction of the potassium persulfate aqueous solution in step A2 is 10%-15%; The mass fraction of the calcium chloride aqueous solution in step A2 is 10%-15%.

6. A method for preparing a soft light skin-feeling ceramic rock plate with digital three-dimensional effect according to any one of claims 2-5, characterized in that: The following steps are involved: Step B1. Potash feldspar, talc, kaolin, raw ore mud, wollastonite and toughening composition are added, processed by ball milling equipment, and placed in a slurry tank for aging for 24-32 hours to obtain a slurry; Step B2. spray-drying the slurry to obtain slurry particles; Step B3. After the slurry particles are dry-pressed and formed, they are dried by heating, cast, blown, and sprayed with water to obtain a green body; Step B4. After applying soft light base glaze on the surface of the blank, inkjet printing is performed on the surface with the soft light base glaze, and then soft light top glaze is applied on the surface, and firing treatment is performed under a nitrogen atmosphere to obtain soft light skin-feel glaze and soft light skin-feel ceramic rock plate with digital three-dimensional effect.

7. The method for preparing a soft light skin-feeling ceramic rock plate with digital three-dimensional effect according to claim 6, characterized in that: The particle size after ball milling in step B1 is 200-300 mesh.

8. The method for preparing a soft light skin-feeling ceramic rock plate with digital three-dimensional effect according to claim 6, characterized in that: The inlet air temperature in the spray drying powder making in step B2 is 350-400°C, and the outlet air temperature is 70-75°C.

9. The method for preparing a soft light skin-feeling ceramic rock plate with digital three-dimensional effect according to claim 6, characterized in that: The pressing pressure in the dry pressing molding in step B3 is 370-400kg / cm 2 ; The soft gloss base glaze in step B4 is applied by pouring glaze, and the amount of soft gloss base glaze applied is 240-260g / m 2 ; The soft gloss glaze in step B4 is applied by pouring glaze, and the amount of soft gloss glaze applied is 650-700g / m 2 .

10. The method for preparing a soft light skin-feeling ceramic rock plate with digital three-dimensional effect according to claim 6, characterized in that: The temperature in the sintering process in step B4 is: From room temperature to 500°C, the heating rate is 30-40°C / min; From 500℃ to 850℃, the heating rate is 20-40℃ / min; From 850℃ to 1100℃, the heating rate is 10-20℃ / min, and the temperature is kept at 1100℃ for 8-12min.

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