Multicolored ceramic article and method of making

Abstract

The application provides a multicolor ceramic product and a preparation method thereof. The preparation method of the multicolor ceramic product comprises the following steps: obtaining a porous first ceramic body; infiltrating a first photocuring glue on the first ceramic body to obtain a second ceramic body, wherein the first photocuring glue comprises first color powder; performing partial light shielding on the second ceramic body by using a first light shielding piece, and then performing photocuring treatment on the second ceramic body; cleaning the second ceramic body after photocuring treatment by using a solvent to remove the un-solidified first photocuring glue, and obtaining a third ceramic body; and performing sintering treatment on the third ceramic body to obtain a multicolor ceramic product. The preparation method of the multicolor ceramic product provided by the application solves the problem that deformation is prone to occurring in the secondary injection molding process of the existing multicolor ceramic product.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic injection molding, in particular to a multi-color ceramic product and a preparation method thereof. BACKGROUND

[0002] Ceramics are widely used in the fields of electronics, construction, medical treatment and the like due to excellent mechanical properties and chemical stability. More and more ceramic products are improved in appearance by multi-color injection molding to meet application requirements and improve user experience. However, the multi-color injection molding process of plastic materials is relatively mature, and the multi-color injection molding process of ceramic materials is still immature and in the exploratory stage, and there are still many problems to be solved, for example, in the process of double-color injection molding, the high temperature generated in the second injection molding will cause the structure of the ceramic product formed by the first injection molding to deform, and thus the expected double-color ceramic product cannot be obtained. SUMMARY

[0003] In view of the problem of deformation in the process of secondary injection molding of the existing multi-color ceramic product, the present application provides a multi-color ceramic product and a preparation method thereof.

[0004] The technical solution adopted by the present application to solve the above technical problems is as follows:

[0005] The present application provides a preparation method of a multi-color ceramic product, comprising the following steps:

[0006] Obtaining a porous first ceramic body;

[0007] Infiltrating a first photocuring glue on the first ceramic body to obtain a second ceramic body, wherein the first photocuring glue comprises a first color powder;

[0008] After partially shielding the second ceramic body by using a first light shielding member, performing photocuring treatment on the second ceramic body;

[0009] Cleaning the second ceramic body after photocuring treatment by using a solvent to remove the uncured first photocuring glue, to obtain a third ceramic body;

[0010] Performing sintering treatment on the third ceramic body to obtain a multi-color ceramic product.

[0011] Optionally, before the sintering treatment of the third ceramic body, infiltrating a second photocuring glue on the third ceramic body, wherein the second photocuring glue comprises a second color powder;

[0012] After partially shielding the third ceramic body by using a second light shielding member, performing photocuring treatment on the third ceramic body.

[0013] Optionally, the porosity of the first ceramic body is 35%-50%; and the pore size of the pores in the first ceramic body ranges from 170nm to 250nm.

[0014] Optionally, the first photocuring glue comprises the following weight components: 15-30 parts of vinyl chloride-maleic acid diethyl ester copolymer resin, 140-150 parts of trimethylolpropane triacrylate, 4-10 parts of initiator, and 1-74 parts of first toner.

[0015] The second photocuring glue comprises the following weight components: 15-30 parts of vinyl chloride-maleic acid diethyl ester copolymer resin, 140-150 parts of trimethylolpropane triacrylate, 4-10 parts of initiator, and 1-74 parts of second toner.

[0016] Optionally, the first toner and the second toner are different in color, the particle size of the first toner ranges from 0.5nm to 50nm; and the particle size of the second toner ranges from 0.5nm to 50nm.

[0017] Optionally, the viscosity of the first photocuring glue ranges from 0.05Pa*S to 0.2Pa*S; and the viscosity of the second photocuring glue ranges from 0.05Pa*S to 0.2Pa*S.

[0018] Optionally, the step of obtaining the porous first ceramic body comprises the following steps: injection molding of injection material to obtain an injection body, and performing a debinding treatment and a pre-burning treatment on the injection body to obtain the porous first ceramic body.

[0019] Optionally, the injection material comprises the following weight components: 80-85 parts of ceramic powder and 15-20 parts of organic binder.

[0020] Optionally, the organic binder comprises the following weight components: 50-70 parts of polymethyl methacrylate, 10-20 parts of polyethylene wax, 10-15 parts of paraffin wax, 10-15 parts of dibutyl phthalate, and 1-3 parts of stearic acid, based on the organic binder.

[0021] Optionally, the debinding treatment is performed by the following method: increasing the temperature of the injection body to 130-170℃ at a temperature increasing rate of 0.2-0.5℃ / min, and maintaining the temperature for 1-3h; then increasing the temperature to 250℃ at a temperature increasing rate of 0.05-0.08℃ / min, and maintaining the temperature for 1-3h; finally increasing the temperature to 430-470℃ at a temperature increasing rate of 0.1-0.4℃ / min, and maintaining the temperature for 1-3h.

[0022] Optionally, the pre-burning treatment is performed by the following method: increasing the temperature of the injection body after the debinding treatment to 800-1100℃ at a temperature increasing rate of 1.3-2℃ / min, and pre-burning for 1-3h.

[0023] Optionally, the solvent includes one or both of N,N-dimethylformamide and xylene.

[0024] In another aspect, the present application also provides a multi-color ceramic product prepared by the method for preparing a multi-color ceramic product.

[0025] According to the method for preparing a multi-color ceramic product provided by the present application, the first light-cured glue is used to fill the first ceramic body, and then the light-cured treatment is performed to form the multi-color ceramic product with the expected combination, so that the deformation of the injection molding body caused by the high temperature generated during the secondary injection molding is avoided. The first light-shielding member is used to perform the partial light shielding on the surface of the second ceramic body, and the part that needs to be colored is exposed, so that the color boundary of the multi-color ceramic product is clear, the pattern profile is good, the accuracy is high, the pattern can be designed, the appearance is diversified, and the pattern color with complex structure is realized. DETAILED DESCRIPTION

[0026] In order to make the technical problems, technical solutions and beneficial effects solved by the present application clearer, the present application will be further described in detail below in combination with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application, and are not used to limit the present application.

[0027] The present application provides a method for preparing a multi-color ceramic product, which comprises the following steps:

[0028] S1, obtaining a porous first ceramic body.

[0029] Preferably, the porosity of the first ceramic body is 35-50%, and the pore size is 170-250 nm. By setting the appropriate pore size range and porosity, the structural strength of the first ceramic body is ensured.

[0030] S2, infiltrating a first light-cured glue into the first ceramic body to obtain a second ceramic body, wherein the first light-cured glue comprises a first color powder.

[0031] Specifically, the first light-cured glue is naturally infiltrated into the first ceramic body under vacuum or is pressurized to infiltrate into the first ceramic body. Specifically, the vacuum degree under vacuum is-0.08-0.1 MPa. The pressurized infiltration is to apply a pressure of 1 MPa to the first light-cured glue on the surface of the first ceramic body after vacuumizing.

[0032] In some embodiments, the first color powder is an inorganic color powder. The inorganic color powder includes one or more of yellow iron oxide, red iron oxide, black iron oxide, cobalt oxide, nickel oxide, manganese oxide, chromium oxide and titanium white.

[0033] S3, performing the light-cured treatment on the second ceramic body after the first light-shielding member is used to perform the partial light shielding on the second ceramic body.

[0034] The second ceramic body surface is partially shielded by the first light shielding member, so that the part of the second ceramic body that needs to be colored is exposed to the outside to facilitate the curing of the first photocuring glue under light. Specifically, the first photocuring glue is a UV curing glue, the photocuring treatment is UV irradiation, and the irradiation time is 60-120S.

[0035] S4, cleaning the second ceramic body after photocuring treatment with a solvent to remove uncured first photocuring glue, to obtain a third ceramic body.

[0036] The uncured first photocuring glue is dissolved by the solvent.

[0037] S5, sintering the third ceramic body to obtain a multi-color ceramic product.

[0038] In this embodiment, the first photocuring glue is used to fill the first ceramic body, and then the multi-color ceramic product of the desired combination is formed by photocuring treatment, avoiding deformation of the injection molding body caused by high temperature during secondary injection molding. The surface of the second ceramic body is partially shielded by the first light shielding member, and the part that needs to be colored is exposed to the outside, so that the color boundary of the multi-color ceramic product is clear, the pattern profile is good, the accuracy is high, and the pattern can be designed, the appearance is diversified, and the pattern color of complex structure is realized.

[0039] In some embodiments, before "sintering the third ceramic body", a second photocuring glue is infiltrated on the third ceramic body, and the second photocuring glue includes a second color powder. After the third ceramic body is partially shielded by a second light shielding member, the third ceramic body is subjected to photocuring treatment. In this embodiment, the part of the third ceramic body not filled with the first photocuring glue is filled with the second photocuring glue, so that the multi-color ceramic product is multi-colored.

[0040] Further, in some embodiments, the third ceramic body after photocuring treatment is cleaned with a solvent to remove uncured second photocuring glue.

[0041] In some embodiments, the solvent includes one or both of N,N-dimethylformamide and xylene. The first photocuring glue and / or the second photocuring glue can be well removed.

[0042] In some embodiments, the second color powder includes one or more of yellow iron oxide, red iron oxide, black iron oxide, and titanium white powder.

[0043] In some embodiments, the first photocuring glue comprises the following weight components: 15-30 parts of vinyl chloride-maleic acid diethyl ester copolymer resin, 140-150 parts of trimethylolpropane triacrylate, 4-10 parts of initiator, and 1-74 parts of first color powder. By setting the initiator to make the trimethylolpropane triacrylate polymerize itself, the vinyl chloride-maleic acid diethyl ester copolymer resin and the trimethylolpropane triacrylate are cross-linked and cured under the action of the initiator, thereby increasing the strength of the third ceramic body. By selecting appropriate weight parts of the vinyl chloride-maleic acid diethyl ester copolymer resin and the trimethylolpropane triacrylate, the viscosity of the first photocuring glue is controlled, and the penetration efficiency of the first photocuring glue is improved.

[0044] In some embodiments, the second photocuring glue comprises the following weight components: 15-30 parts of vinyl chloride-maleic acid diethyl ester copolymer resin, 140-150 parts of trimethylolpropane triacrylate, 4-10 parts of initiator, and 1-74 parts of second color powder.

[0045] In some embodiments, the first color powder and the second color powder are different in color, and the particle size of the first color powder ranges from 0.5 nm to 50 nm. The particle size of the second color powder ranges from 0.5 nm to 50 nm. By selecting appropriate particle sizes of the first color powder and the second color powder, the first color powder is facilitated to penetrate into the pores of the first ceramic body, and the second color powder is facilitated to penetrate into the pores of the third ceramic body.

[0046] In some embodiments, there are at least two colors on the multi-color ceramic product, and the multi-color ceramic product is prepared by selecting photocuring glue containing color powder of different colors according to the steps of S3 and S4.

[0047] In some embodiments, the initiator is selected from one or more of benzophenone, dibenzyl ketone, 4,4'-bisbenzophenone, dibenzoyl phenyl phosphine oxide, hydroxybenzophenone, acrylated benzophenone, 4,4'-dichlorobenzophenone, benzoyl diphenyl phosphine oxide, and 3,3'-dimethyl-2-methoxybenzophenone.

[0048] In some embodiments, the viscosity of the first photocuring glue ranges from 0.05 Pa*S to 0.2 Pa*S, and the viscosity of the second photocuring glue ranges from 0.05 Pa*S to 0.2 Pa*S. By controlling the appropriate viscosity range, the penetration efficiency is improved.

[0049] In some embodiments, the step of obtaining the first porous ceramic body is: injection molding of the injection material to obtain an injection body, and performing a debinding treatment and a pre-burning treatment on the injection body to obtain the first porous ceramic body. Specifically, the particle size of the injection material is smaller than the pore size of the first ceramic body, so as to meet the strength requirement of the ceramic body.

[0050] In some embodiments, the injection material comprises the following weight components: 80-85 parts of ceramic powder and 15-20 parts of organic binder. By controlling the components of the organic binder, the porosity of the first ceramic green body is controlled.

[0051] In some embodiments, the organic binder comprises the following weight components: 50-70 parts of polymethyl methacrylate, 10-20 parts of polyethylene wax, 10-15 parts of paraffin wax, 10-15 parts of dibutyl phthalate and 1-3 parts of stearic acid, based on the organic binder. By adding dibutyl phthalate, the flexibility of the injection molded green body is enhanced, and the breaking tensile rate of the multi-color ceramic product is enhanced.

[0052] In some embodiments, the method for the debinding treatment is as follows: the injection molded green body is raised to 130-170℃ at a temperature raising rate of 0.2-0.5℃ / min, and is kept for 1-3h. Then it is raised to 250℃ at a temperature raising rate of 0.05-0.08℃ / min, and is kept for 1-3h. Finally, it is raised to 430-470℃ at a temperature raising rate of 0.1-0.4℃ / min, and is kept for 1-3h. By debinding in stages, the binder and other components can be removed more gently, and the structural strength is avoided from being damaged.

[0053] In some embodiments, the method for the pre-sintering treatment is as follows: the injection molded green body after the debinding treatment is raised to 800-1100℃ at a temperature raising rate of 1.3-2℃ / min, and is pre-sintered for 1-3h.

[0054] In some embodiments, the method for the sintering treatment is as follows: the third ceramic green body is sintered at 1400-1450℃ for 1-3h.

[0055] In some embodiments, the injection material is injection molded at 200-210℃.

[0056] In another aspect, an embodiment of the present application also provides a multi-color ceramic product, which is prepared by the method for preparing a multi-color ceramic product according to any one of the above embodiments.

[0057] The present application is further illustrated by the following examples. PMMA is polymethyl methacrylate, and DBP is dibutyl phthalate.

[0058] Example 1

[0059] In this embodiment, the injection material comprises the following weight components: 83 parts of white ceramic powder, 10.5 parts of PMMA, 2 parts of PE wax, 2 parts of paraffin wax, 2 parts of DBP and 0.5 parts of stearic acid.

[0060] The first photocuring glue: vinyl chloride-maleic acid diethyl ester copolymer resin 20 parts, trimethylolpropane triacrylate 146 parts, initiator benzophenone 5 parts, black color powder 50 parts. The viscosity of the first photocuring glue is 0.15 Pa*S.

[0061] Injection molding: injection material is injection molded at 200-210°C.

[0062] Degreasing: the injection molded body is subjected to a degreasing treatment, and the treatment conditions are as follows: the temperature is raised to 150°C at a rate of 0.3°C / min, and the temperature is maintained for 3h. Then the temperature is raised to 250°C at a rate of 0.07°C / min, and the temperature is maintained for 3h. Finally, the temperature is raised to 450°C at a rate of 0.2°C / min, and the temperature is maintained for 3h.

[0063] Pre-burning: the injection molded body after the degreasing treatment is pre-burned at a rate of 1.6°C / min to 1000°C for 2h to obtain a first ceramic body.

[0064] Glue impregnation and curing: the first ceramic body is vacuum impregnated with the first photocuring glue to obtain a second ceramic body. According to the required pattern, the surface of the second ceramic body is partially shielded by a shielding piece, and then the second ceramic body after shielding is subjected to UV irradiation. The photocuring time is 60S.

[0065] Cleaning: the uncured first photocuring glue is cleaned with N,N-dimethylformamide to obtain a third ceramic body.

[0066] Sintering: 1400°C for 2h to obtain a black and white dual-color ceramic.

[0067] Example 2

[0068] In this example, the second photocuring glue is added, which is different from example 1. The second photocuring glue: vinyl chloride-maleic acid diethyl ester copolymer resin 20 parts, trimethylolpropane triacrylate 146 parts, initiator benzophenone 5 parts, blue color powder 50 parts.

[0069] After cleaning, the third ceramic body is vacuum impregnated with the second photocuring glue. According to the required pattern, the surface of the third ceramic body is partially shielded by a shielding piece, and then the third ceramic body after shielding is subjected to UV irradiation. The photocuring time is 60S. Then sintering is carried out to obtain a black and blue dual-color ceramic.

[0070] Example 3

[0071] In this example, the ceramic powder is black ceramic powder, and the color powder in the first photocuring glue is blue color powder, which is different from example 1. The obtained is a black and blue dual-color ceramic.

[0072] Example 4

[0073] In this embodiment, different from the embodiment 1, the injection material contains PMMA 14 parts, PE wax 2.5 parts.

[0074] Embodiment 5

[0075] In this embodiment, different from the embodiment 1, the injection material contains PMMA 10 parts, DBP 2.5 parts.

[0076] Embodiment 6

[0077] In this embodiment, different from the embodiment 1, the injection material contains PMMA 21 parts, PE wax 3 parts, paraffin wax 3 parts, DBP 3 parts, stearic acid 0.5 parts.

[0078] Embodiment 7

[0079] In this embodiment, different from the embodiment 1, the injection material contains PMMA 7 parts, PE wax 1 part, paraffin wax 1 part, DBP 1 part, stearic acid 0.1 part.

[0080] Embodiment 8

[0081] In this embodiment, different from the embodiment 1, the injection material contains chloroethylene-maleic acid diethyl ester copolymer resin 15 parts, trimethylolpropane triacrylate 140 parts. The viscosity of the first photocuring adhesive is 0.05 Pa*S.

[0082] Embodiment 9

[0083] In this embodiment, different from the embodiment 1, the injection material contains chloroethylene-maleic acid diethyl ester copolymer resin 30 parts.

[0084] The viscosity of the first photocuring adhesive is 0.2 Pa*S.

[0085] Embodiment 10

[0086] In this embodiment, different from the embodiment 1, the injection material contains chloroethylene-maleic acid diethyl ester copolymer resin 50 parts.

[0087] The viscosity of the first photocuring adhesive is 0.5 Pa*S.

[0088] Embodiment 11

[0089] In this embodiment, different from the embodiment 1, the injection material contains chloroethylene-maleic acid diethyl ester copolymer resin 5 parts, trimethylolpropane triacrylate 100 parts. The viscosity of the first photocuring adhesive is 0.01 Pa*S.

[0090] Comparative Example 1

[0091] In this comparative example, different from the embodiment 1, the injection material with different color ceramic powder in molten state is injected into the first ceramic body after pre-burning to obtain a double-color ceramic.

[0092] The strength and pattern profile of the multi-color ceramic of examples 1-11 and comparative example 1 were tested, and the test results are shown in Table 1.

[0093] DuPont impact strength test, test equipment: DuPont impact tester XM-865-II. Test method: the sample is processed into 0.5-0.55mm thickness, both sides are polished. The middle of the sample is aligned with the falling hammer during testing, and then a 60g weight is dropped from a height of 5cm to hit the hammer head and strike the sample. If the sample is not broken, continue to test by increasing the height by 5cm each time. Record the height at which the last sample is destroyed as the falling hammer impact strength.

[0094] Profile test: draw the sample pattern through the image measuring instrument, and compare with the design pattern. Define the part outside the design pattern as positive tolerance, and the part inside the design pattern as negative tolerance.

[0095] Table 1

[0096] Group Profile 0.5mm DuPont Impact Example 1 ±0.03 25 cm Example 2 ±0.05 20 cm Example 3 ±0.03 25 cm Example 4 ±0.05 20 cm Example 5 ±0.05 25 cm Example 6 ±0.07 15 cm Example 7 ±0.05 20 cm Example 8 ±0.03 25 cm Example 9 ±0.10 25 cm Example 10 ±0.2 25 cm Example 11 ±0.15 25 cm Comparative Example 1 ±0.15 15 cm

[0097] As can be seen from examples 1-3 and comparative example 1, increasing or changing the color type of the toner, the profile accuracy of the pattern on the multi-color ceramic product in the present embodiment is much higher than that of the comparative example. The multi-color ceramic prepared by the preparation method of the multi-color ceramic product provided by the present application realizes multi-color patterns through the light-curable glue which can be selectively cured, and the pattern boundary is clear and the accuracy is high. As can be seen from the test results of examples 1, 4-7, the strength of the multi-color ceramic product is related to the weight parts of the organic binder by increasing the weight parts of the organic binder, and by selecting the appropriate weight parts of the organic binder, the porosity of the first ceramic body is controlled, and the strength of the multi-color ceramic product is improved.

[0098] As can be seen from examples 8-11, by changing the content of each component of the first light-curable glue, the viscosity of the first light-curable glue also changes, and according to the test data of examples 8-11, the first light-curable glue with low or high viscosity affects the profile of the multi-color ceramic product, therefore, the viscosity range of the first light-curable glue is controlled, thereby improving the profile of the pattern of the multi-color ceramic product.

[0099] The above only describes the preferred embodiments of the present application, and is not intended to limit the present application. Any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for producing a multi-colored ceramic article, characterized by, The method comprises the following steps: obtaining a porous first ceramic body, injecting a material to obtain an injection body, and performing a debinding treatment and a pre-burning treatment on the injection body to obtain a porous first ceramic body; the material comprises the following components by weight: 80-85 parts of ceramic powder and 15-20 parts of organic binder; a first photocuring glue is infiltrated on the first ceramic body to obtain a second ceramic body, the first photocuring glue comprises the following components by weight: 15-30 parts of a vinyl chloride-maleic acid diethyl ester copolymer resin, 140-150 parts of trimethylolpropane triacrylate, 4-10 parts of an initiator and 1-74 parts of a first color powder; the viscosity of the first photocuring glue ranges from 0.05 Pa*S to 0.2 Pa*S; a first shading member is used to partially shield the second ceramic body, and then the second ceramic body is subjected to a photocuring treatment; a solvent is used to clean the second ceramic body after the photocuring treatment to remove the uncured first photocuring glue, thereby obtaining a third ceramic body; the third ceramic body is subjected to a sintering treatment to obtain a multi-color ceramic product.

2. The method for producing a multi-colored ceramic article according to claim 1, characterized by, Before the sintering treatment, a second photocuring glue is infiltrated on the third ceramic body, and the second photocuring glue comprises a second color powder; a second shading member is used to partially shield the third ceramic body, and then the third ceramic body is subjected to a photocuring treatment.

3. Process for the preparation of polychrome ceramic articles according to claim 2, characterized in that, The porosity of the first ceramic body ranges from 35% to 50%, and the pore size of the pores in the first ceramic body ranges from 170 nm to 250 nm.

4. The method for producing a multi-colored ceramic article according to claim 2, characterized by, The second photocuring glue comprises the following components by weight: 15-30 parts of a vinyl chloride-maleic acid diethyl ester copolymer resin, 140-150 parts of trimethylolpropane triacrylate, 4-10 parts of an initiator and 1-74 parts of a second color powder.

5. Process for the preparation of polychrome ceramic articles according to claim 4, characterized in that, The first color powder and the second color powder are different in color, the particle size of the first color powder ranges from 0.5 nm to 50 nm, and the particle size of the second color powder ranges from 0.5 nm to 50 nm.

6. The method for producing a multi-colored ceramic article according to claim 2, characterized by, The viscosity of the second photocuring glue ranges from 0.05 Pa*S to 0.2 Pa*S.

7. The method of making a multi-colored ceramic article according to claim 1, wherein, The organic binder comprises the following components by weight based on the organic binder: 50-70 parts of polymethyl methacrylate, 10-20 parts of polyethylene wax, 10-15 parts of paraffin wax, 10-15 parts of dibutyl phthalate and 1-3 parts of stearic acid.

8. The method of making a multi-colored ceramic article according to claim 1, wherein, The debinding treatment is performed by raising the temperature of the injection body to 130-170°C at a temperature raising rate of 0.2-0.5°C / min, maintaining the temperature for 1-3 h, then raising the temperature to 250°C at a temperature raising rate of 0.05-0.08°C / min, maintaining the temperature for 1-3 h, and finally raising the temperature to 430-470°C at a temperature raising rate of 0.1-0.4°C / min, maintaining the temperature for 1-3 h.

9. The method of making a multi-colored ceramic article according to claim 1, wherein, The pre-burning treatment is performed by raising the temperature of the injection body after the debinding treatment to 800-1100°C at a temperature raising rate of 1.3-2°C / min, and pre-burning for 1-3 h.

10. The method of making a multi-colored ceramic article according to claim 1, wherein, The solvent comprises one or both of N,N-dimethylformamide and xylene.

11. A multi-colored ceramic article, characterized in that, The multi-color ceramic product is prepared by the method of any one of claims 1-10.