CN113478855B

CN113478855B - Shell, manufacturing method thereof and electronic equipment

Info

Publication number: CN113478855B
Application number: CN202110743108.XA
Authority: CN
Inventors: 胡梦; 陈奕君; 李聪
Original assignee: Guangdong Oppo Mobile Telecommunications Corp Ltd
Current assignee: Guangdong Oppo Mobile Telecommunications Corp Ltd
Priority date: 2021-06-30
Filing date: 2021-06-30
Publication date: 2023-06-27
Anticipated expiration: 2041-06-30
Also published as: CN113478855A

Abstract

The application provides a preparation method of a shell, which comprises the following steps: modifying a polymer to obtain a modified polymer, wherein the modified polymer comprises the polymer and an aromatic group connected to a chain structure of the polymer, and/or the modified polymer comprises the polymer and a reactive group connected to a chain structure tail end of the polymer; and (3) blending the ceramic powder with the modified polymer, carrying out banburying granulation and injection molding to obtain a polymer ceramic sheet, and pressing the polymer ceramic sheet to obtain a polymer ceramic layer to obtain the shell. The preparation method is simple and easy to operate, can prepare the shell with excellent performance, and is beneficial to the application of the shell. The application also provides a preparation method of the shell, the shell and electronic equipment.

Description

Shell, manufacturing method thereof and electronic equipment

Technical Field

The application belongs to the technical field of electronic products, and particularly relates to a shell, a preparation method thereof and electronic equipment.

Background

With the increase of the consumption level, consumers are not only pursuing diversification of functions, but also increasingly demanding the appearance, texture, etc. of electronic products. In recent years, ceramic materials have been a hot spot in research into electronic device housings because of their moist texture. However, at present, the ceramic-like composite material with the glossiness higher than that of plastics and lower than that of ceramics is mainly realized by blending resin and ceramic powder. The composite material mainly utilizes the selective regulation and control of the content, the type, the morphology and the particle size of ceramic powder to realize the expected characteristics, but has the advantages of limited solid content, weak interface combination and poor compactness, and compared with the real ceramic, the composite material has larger gap in terms of hardness, luster and texture, and is difficult to meet the high pursuit of consumers on the appearance and the texture of the product. At present, a ceramic shell and a preparation method thereof still need to be improved.

Disclosure of Invention

In view of the above, the present application provides a housing, a method of manufacturing the same, and an electronic apparatus.

In a first aspect, the present application provides a method for preparing a shell, comprising:

modifying a polymer to obtain a modified polymer, wherein the modified polymer comprises the polymer and an aromatic group connected to a chain structure of the polymer, and/or the modified polymer comprises the polymer and a reactive group connected to a chain structure tail end of the polymer;

and (3) blending the ceramic powder with the modified polymer, carrying out banburying granulation and injection molding to obtain a polymer ceramic sheet, and pressing the polymer ceramic sheet to obtain a polymer ceramic layer to obtain the shell.

In a second aspect, the present application provides a method for manufacturing a housing, comprising:

blending ceramic powder, a prepolymer and a material containing a modified group, carrying out banburying granulation and injection molding to obtain a polymer ceramic piece, and pressing the polymer ceramic piece to obtain a polymer ceramic layer to obtain a shell, wherein the material containing the modified group is provided with an aromatic group and/or a reactive group, the prepolymer and the material containing the modified group react to generate a modified polymer, the modified polymer comprises a polymer composed of the prepolymer and the aromatic group connected to a chain structure of the polymer, and/or the modified polymer comprises the polymer and the reactive group connected to a chain structure end of the polymer.

In a third aspect, the present application provides a housing comprising a polymeric ceramic layer comprising a ceramic powder and a modified polymer comprising a polymer and an aromatic group attached to the chain structure of the polymer, and/or comprising the polymer and a reactive group attached to the chain structure end of the polymer.

In a fourth aspect, the present application provides an electronic device, including a housing manufactured by the manufacturing method described in the first aspect or the second aspect, or a housing described in the third aspect.

The application provides a shell and a preparation method of the shell, wherein the mechanical property of the shell is improved by adopting a modified polymer, the service life of the shell is prolonged, and the application of the shell is facilitated; the preparation method of the shell is simple, easy to operate and capable of realizing industrial production; the electronic equipment with the shell has excellent mechanical property and strong product competitiveness, and can meet the requirements of users.

Drawings

In order to more clearly describe the technical solutions in the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be described below.

Fig. 1 is a flowchart of a method for manufacturing a housing according to an embodiment of the present application.

Fig. 2 is a flowchart of a method for manufacturing a housing according to another embodiment of the present disclosure.

Fig. 3 is a flowchart of a method for manufacturing a housing according to another embodiment of the present disclosure.

Fig. 4 is a flowchart of a method for manufacturing a housing according to another embodiment of the present disclosure.

Fig. 5 is a schematic structural diagram of a housing according to an embodiment of the present application.

Fig. 6 is a schematic structural diagram of a housing according to another embodiment of the present application.

Fig. 7 is a schematic structural diagram of an electronic device according to an embodiment of the present application.

Fig. 8 is a schematic structural diagram of an electronic device according to an embodiment of the present application.

Detailed Description

The following are preferred embodiments of the present application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present application and are intended to be within the scope of the present application.

The following disclosure provides many different embodiments or examples for implementing different structures of the present application. In order to simplify the disclosure of the present application, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present application. Furthermore, the present application may repeat reference numerals and/or letters in the various examples, which are for the purpose of brevity and clarity, and which do not in themselves indicate the relationship between the various embodiments and/or arrangements discussed. In addition, the present application provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize the application of other processes and/or the use of other materials.

Referring to fig. 1, a flowchart of a method for manufacturing a shell according to an embodiment of the present application includes:

s101: modifying the polymer to obtain a modified polymer, wherein the modified polymer comprises a polymer and an aromatic group connected to the chain structure of the polymer, and/or the modified polymer comprises a polymer and a reactive group connected to the tail end of the chain structure of the polymer.

S102: and (3) blending the ceramic powder with the modified polymer, carrying out banburying granulation and injection molding to obtain a polymer ceramic sheet, and pressing the polymer ceramic sheet to obtain a polymer ceramic layer to obtain the shell.

In the application, the mechanical property of the shell 100 is improved by adopting the modified polymer, so that the service life of the shell 100 is prolonged, and the application of the shell 100 is facilitated; the manufacturing method of the housing 100 is simple and is easy for mass production.

In S101, the performance of the case 100 is improved by modifying the polymer; the modified polymer includes a polymer and an aromatic group attached to the chain structure of the polymer, and/or the modified polymer includes a polymer and a reactive group attached to the chain structure end of the polymer.

In one embodiment of the present application, the modified polymer includes a polymer and an aromatic group attached to the chain structure of the polymer. The attached aromatic groups are advantageous in improving the hardness and refractive index of the modified polymer, thereby being advantageous in improving the hardness and gloss of the case 100, and further, enabling the case 100 to have excellent wear resistance and ceramic texture.

It will be appreciated that the smallest unit of identical chemical composition in a polymer is referred to as a repeat unit and the number of repetitions of the repeat unit in the polymer molecular chain is referred to as the degree of polymerization of the polymer. In this application, the polymer includes a first repeat unit. In one embodiment, the polymer is formed from a plurality of first repeat units joined together. In another embodiment, the polymer comprises a first repeat unit and a second repeat unit, the first repeat unit and the second repeat unit being of different structural formulas; for example, the polymer is a block copolymer or the like. In one embodiment of the present application, the polymer includes a first repeat unit and the modified polymer includes the first repeat unit and an aromatic group attached to the first repeat unit. That is, each repeating unit of the modified polymer is grafted with an aromatic group, so that the content of the aromatic group in the modified polymer is greatly improved, the hardness and refractive index of the modified polymer are greatly improved, the hardness and glossiness of the shell 100 are improved, and the shell 100 has excellent wear resistance and ceramic texture. It will be appreciated that when the polymer has a plurality of structurally different repeat units, at least one of the repeat units in the modified polymer may have an aromatic group attached thereto; the aromatic group connected to the first repeating unit is grafted onto the molecular chain of the first repeating unit. In the present application, when the polymer includes a plurality of repeating units having different structures, and an aromatic group is attached to each of the plurality of repeating units, the aromatic groups may be the same or different among the different repeating units, which is not limited. In one embodiment, when the polymer comprises a first repeat unit and a second repeat unit, the modified polymer comprises the first repeat unit, the second repeat unit, and an aromatic group attached to the first repeat unit; or when the polymer comprises a first repeating unit and a second repeating unit, the modified polymer comprises the first repeating unit, the second repeating unit, and an aromatic group attached to the second repeating unit; or when the polymer comprises a first repeating unit and a second repeating unit, the modified polymer comprises the first repeating unit, the second repeating unit, an aromatic group attached to the first repeating unit and an aromatic group attached to the second repeating unit, wherein the aromatic group attached to the first repeating unit and the aromatic group attached to the second repeating unit may have the same or different structures. In the application, the modified polymer comprises a first repeating unit and an aromatic group connected to the first repeating unit, the modified polymer is the modified resin, and the main chain or the branched chain of the repeating unit in the modified polymer is grafted with the aromatic group.

In one embodiment of the present application, the aromatic group includes at least one of phenyl, biphenyl, and acenyl. The aromatic group has high refractive index, and is beneficial to improving the glossiness of the modified polymer. Specifically, biphenyl is an aromatic group formed by connecting a plurality of benzene rings by single bonds, and biphenyl can include at least one of biphenyl, terphenyl, tetrabiphenyl, pentabiphenyl, hexabiphenyl, heptabiphenyl and octabiphenyl according to the number of benzene rings; the acenyl group has a plurality of benzene rings, and adjacent benzene rings share two carbon atoms, and the acenyl group may include, but is not limited to, at least one of naphthyl group, anthryl group, phenanthryl group, and pyrenyl group. In another embodiment of the present application, the aromatic group has 6 to 48 carbon atoms, which is advantageous for improving the hardness and gloss of the modified polymer, and for reducing the preparation cost, with low preparation difficulty. Further, the number of carbon atoms of the aromatic group is 6 to 36. Further, the number of carbon atoms of the aromatic group is 6 to 24. In yet another embodiment of the present application, when the modified polymer includes a polymer and an aromatic group attached to the chain structure of the polymer, the refractive index of the modified polymer is greater than 1.7. By linking the aromatic group having a high refractive index, the refractive index of the modified polymer is further improved, thereby being advantageous to improve the glossiness and ceramic texture of the housing 100. Further, when the modified polymer includes a first repeating unit and an aromatic group attached to the first repeating unit, the modified polymer has a refractive index greater than 1.76. Further, when the modified polymer includes a first repeating unit and an aromatic group attached to the first repeating unit, the refractive index of the modified polymer is greater than 1.8. In the present application, the aromatic group may be attached to the main chain of the first repeating unit or may be attached to a branched chain of the first repeating unit; one or more aromatic groups may be grafted onto the first repeat unit, selected as desired. In one embodiment, when the first repeating unit has a benzene ring and the aromatic group is attached to the benzene ring, adjacent positions on the benzene ring in the first repeating unit are not grafted simultaneously, so that steric hindrance is reduced and modification difficulty is reduced.

In another embodiment of the present application, the modified polymer includes a polymer and a reactive group attached to the end of the chain structure of the polymer. By adopting the modified polymer with the reactive group, the interfacial bonding capability between the modified polymer and the ceramic powder is improved in the preparation process of the shell 100, which is beneficial to improving the compactness and strength of the shell 100, and/or the modified polymer is subjected to chain extension reaction, so that the strength and toughness of the shell 100 are improved, and the mechanical property of the shell 100 is further improved.

In one embodiment of the present application, the polymer includes a first repeating unit, and the modified polymer has a reactive group at least one end of the polymer. It will be appreciated that the difference between the modified polymer and the polymer is that the modified polymer has a reactive group attached to at least one end of the backbone structure containing the first repeat unit, which may also be referred to as a reactive end group; the polymer main chain structure has both ends as the ends of the polymer, so that during the modification process, the reactive end group can be connected to at least one end of the polymer, thereby obtaining the modified polymer. In this application, the modified polymer has a reactive group at least one end of the polymer. It will be appreciated that the functional groups attached to one of the ends of the modified polymer may have reactive groups; to facilitate grafting of the reactive groups, the reactive groups may be grafted to the ends of the polymer along with other groups.

In one embodiment of the present application, the reactive group includes at least one of an alkylene group, an alkyne group, an epoxy group, an amino group, a hydroxyl group, and a carboxyl group. In one embodiment, the reactive group includes at least one of an alkylene group, an alkyne group, and an epoxide group. The modified polymer with the reactive group can be heated in the process after injection molding to generate a chain extension reaction, so that the chain length of the polymer is increased, the strength and toughness of the modified polymer are improved, and the strength and toughness of the shell 100 are improved. In another embodiment, the reactive group includes at least one of an epoxy group, an amino group, a hydroxyl group, and a carboxyl group. The modified polymer having the above reactive group is easily chemically reacted with the group on the surface of the ceramic powder to generate bonding, thereby improving the interfacial bonding strength between the modified polymer and the ceramic powder, and being beneficial to improving the compactness and strength of the housing 100. In one embodiment, the ceramic powder has hydroxyl groups on the surface, so that hydrogen bond or chemical bond action can be generated between the ceramic powder and the modified polymer with the reactive groups, the bonding performance between the ceramic powder and the modified polymer is improved, and the strength of the shell 100 is improved. It is understood that the reactive groups may also include other groups capable of hydrogen bonding or chemical bonding with the surface of the ceramic powder.

In yet another embodiment of the present application, the modified polymer includes a polymer, an aromatic group attached to the chain structure of the polymer, and a reactive group attached to the end of the chain structure of the polymer. In an embodiment of the present application, the modified polymer includes a first repeating unit and an aromatic group connected to the first repeating unit, and the modified polymer has a reactive group at least one end of the polymer, thereby facilitating improvement of mechanical properties and ceramic texture of the housing 100 and improving product competitiveness.

In an embodiment of the present application, the polymer includes at least one of polyphenylene sulfide (PPS), polycarbonate (PC), polyamide (PA), polymethyl methacrylate (PMMA), and polybutylene terephthalate (PBT). That is, the modified polymer includes at least one of modified polyphenylene sulfide, modified polycarbonate, modified polyamide, modified polymethyl methacrylate, and modified polybutylene terephthalate. The modified polymer can obviously improve the comprehensive performance of the shell 100, and meanwhile, the physicochemical performance of the modified polymer can be matched with the preparation process of the shell 100, so that the modified polymer cannot be decomposed in the preparation process, the difficulty of the preparation process cannot be increased, and the production cost can be reduced. In the embodiment of the application, the polymerization degree of the polymer is 500-10000, so that the polymer has higher mechanical properties. Further, the polymerization degree of the polymer is 2000 to 9000. Further, the degree of polymerization of the polymer is 4000 to 8000. Referring to table 1, the first repeating unit and the corresponding structural formula of the exemplary polymer are shown in table 1, wherein PA includes PA6, PA10, PA12, PA66, PA1010, PA10T, and the like, and the structural formula of the exemplary PA is shown in table 1, wherein R may be other groups except H.

TABLE 1 structural formulas corresponding to polymers and first repeating units

In one embodiment of the present application, the repeating units of the polymer are grafted with benzene rings, and the structural formula of the modified polymer is shown in table 2.

TABLE 2 structural formula of modified Polymer

In another embodiment of the present application, the terminal grafted olefin groups of the polymer are exemplified, and the structural formula of the modified polymer is shown in Table 3.

TABLE 3 structural formula of modified Polymer

In yet another embodiment of the present application, the terminal grafted amino groups of the polymer are exemplified, and the structural formula of the modified polymer is shown in Table 4.

TABLE 4 structural formula of modified Polymer

In embodiments of the present application, the modified polymer is obtained by mixing the polymer with a material having aromatic groups and/or reactive groups, such as a reactive monomer having aromatic groups and/or reactive groups, and adding a catalyst to react. Specifically, the catalyst may be, but is not limited to, at least one of peroxides such as ammonium persulfate, potassium persulfate, benzoyl peroxide, and the like; the mixed solvent may include, but is not limited to, at least one of acetone, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, chloroform, and the like. Optionally, the mass of the catalyst accounts for 1-3% of the mass of the polymer, and the mass of the active monomer accounts for 5-30% of the mass of the polymer. Further, the mass of the catalyst accounts for 1.5-2.5% of the mass of the polymer, and the mass of the active monomer accounts for 10-20% of the mass of the polymer. Specifically, the reaction temperature is 30-100 ℃ and the reaction time is 30-360 min when the aromatic group is connected to the monomer; the reaction temperature is 100-320 ℃ and the reaction time is 30-300 min when the epoxy group, the amino group, the hydroxyl group and the carboxyl end group are connected, so that strong bonding is generated between the modified polymer and the ceramic powder; the reaction temperature is 30-100 ℃ and the reaction time is 30-360 min when the end groups of the alkylene, alkyne and epoxy groups are connected, so that the modified polymer is subjected to chain extension. It will be appreciated that when the modified polymer has epoxy groups, bonding with the ceramic powder may occur or chain extension of the modified polymer may occur.

In a specific embodiment, taking the modification of PA as an example to carry out the description of the modification process, wherein PA is dissolved in N, N-Dimethylformamide (DMF) solvent to prepare a solution with the solid content of 40%, then ammonium persulfate with the mass of 1-3% relative to the mass of the polymer and phenolic naphthalene monomer with the mass of 10-30% relative to the mass of the polymer are added, stirring is carried out at 75 ℃ for 180min, and then the modified polymer is obtained after air flow drying at 70 ℃, wherein naphthyl groups are connected to the monomers of the modified polymer; ball milling and blending the polymer, ammonium persulfate accounting for 1-3% of the polymer mass and aminosilane powder accounting for 5-8% of the polymer mass for 30min, and banburying for 60min at 260 ℃ after the mixture is uniform, so that aminosilane is grafted to the tail end of the polymer to obtain a modified polymer; dissolving PA in DMF solvent to prepare solution with solid content of 40%, adding ammonium persulfate 1-3% of the polymer mass and propylene oxide monomer 8-15% of the polymer mass, stirring at 75 ℃ for reaction for 180min, and then air-drying at 70 ℃ to obtain the modified polymer. In another embodiment, the modified polymer with an amino terminus is formed by reacting aniline as the reactive monomer with the polymer; the p-phenol ethylene is used as an active monomer to react with a polymer to generate a modified polymer with an olefin group terminal, so that chain extension can occur in a subsequent heating process, and the structural strength is improved.

In S102, the ceramic powder and the modified polymer are blended, and the shell 100 is manufactured after banburying granulation, injection molding and lamination. In an embodiment of the present application, the ceramic powder includes Al ₂ O ₃ 、ZrO ₂ 、Si ₃ N ₄ 、SiO ₂ 、TiO ₂ At least one of AlN, siC and Si. The ceramic powder has high temperature resistance, corrosion resistance, high hardness and good strength, and is beneficial to the improvement and use of the performance of the shell 100. In the embodiment of the present application, the refractive index of the ceramic powder is greater than 2. By providing the ceramic powder having a high refractive index, the surface gloss and ceramic texture of the case 100 are improved, so that the appearance of the case 100 is more similar to that of a ceramic case. In the embodiment of the present application, the particle diameter D50 of the ceramic powder is 200nm to 5. Mu.m. By adopting the ceramic powder with the particle size, the strength and the hardness of the shell 100 can be improved, and meanwhile, the brittleness of the shell 100 can not be excessively increased. Further, the particle diameter D50 of the ceramic powder is 500nm-4 μm. Further, the particle diameter D50 of the ceramic powder is 1 μm to 2.5. Mu.m.

It is understood that the mixing ratio of the ceramic powder and the modifying polymer may be selected according to the content of the ceramic powder and the modifying polymer in the polymer ceramic layer 10, which is not limited. In one embodiment, the modified polymer is mixed according to the mass ratio of 10-50% and the ceramic powder is mixed according to the mass ratio of 50-90%. Further, an auxiliary agent is added during blending, and the auxiliary agent comprises at least one of a leveling agent, a cosolvent and an antioxidant. Specifically, the mass ratio of the blended auxiliary agent is 0.1% -1%. In another embodiment, blending includes milling by dry or wet methods. Further, the efficiency is improved by dry blending.

In the present application, the blend is obtained after blending, and the blend may be, but is not limited to, placed in a banburying granulation integrated machine for banburying granulation, which is beneficial to the injection molding process. In embodiments of the present application, the temperature of the banburying granulation is above the melting point of the modified polymer and below the decomposition temperature of the modified polymer. In one embodiment, the temperature of the banburying granulation may be, but not limited to, 150-350 ℃, and the time of the banburying granulation may be, but not limited to, 1-12 h. Further, the banburying is performed under a negative pressure, the air pressure is less than 0.01MPa or the banburying is performed under a nitrogen atmosphere, so that the polymer can be effectively prevented from being oxidized, and the removal of gas generated by side reaction can be effectively promoted. In another embodiment, the injection molding feed has a diameter of 2mm to 3mm and a length of 3mm to 4mm, thereby facilitating the injection molding process.

In this application, the process parameters of injection molding may be selected according to the nature of the modified polymer selected. In one embodiment, the injection molding temperature is 150-350 ℃, the injection molding speed is 50-98%, and the injection pressure is 80-160 MPa. In a specific embodiment, the injection molding temperature may be 290 ℃ to 330 ℃ when the modified polymer is selected from modified polyphenylene sulfide. The shape of the polymer ceramic plate obtained by injection molding can be selected, and the thickness of the polymer ceramic plate can be selected according to the needs, and meanwhile, the thickness in the follow-up pressing and processing processes can be reduced, so that the thickness can be increased during injection molding. It will be appreciated that other shaping means such as cast shaping may also be used to prepare the polymeric ceramic sheet. In the application, the injection molding method is simpler to operate, and compared with casting molding, the preparation cost is low without considering the problem of compatibility between the solvent and the modified polymer.

In an embodiment of the present application, laminating the polymeric ceramic sheet comprises: the polymer ceramic sheet is subjected to warm isostatic pressing. And reducing air holes in the polymer ceramic sheet through temperature isostatic pressing, and enhancing the compactness between the ceramic powder and the modified polymer to obtain a lamination structure. The isostatic pressing technique is a technique of molding a product in a sealed high-pressure container under an ultrahigh pressure state with equal directions. Isostatic pressing technology is divided into three different types of cold isostatic pressing, warm isostatic pressing and hot isostatic pressing according to the temperature during forming and consolidation. In the application, the temperature of the temperature isostatic pressing is larger than the glass transition temperature of the modified polymer, so that the modified polymer in the polymer ceramic sheet can be softened, and meanwhile, the compactness is better under the action of pressure, the air holes in the polymer ceramic sheet are eliminated, and the binding force between the ceramic powder and the modified polymer is improved. In one embodiment, the pressure of the warm isostatic pressing is 50MPa-500MPa, and the temperature is 80-300 ℃, so that the polymer ceramic sheet is fully compacted; the process has low requirements on equipment and good safety, is more beneficial to actual operation and application, and is also beneficial to improving the strength of the whole structure. Further, the temperature isostatic pressing pressure is 100MPa-400MPa, and the temperature is 100-280 ℃. In this application, the time of warm isostatic pressing may be selected according to the thickness of the polymer ceramic sheet. In one embodiment, the temperature of the warm isostatic pressing is 80-300 ℃, the time is 0.5-2 h, and the pressure is 50-500 MPa, so that the porosity of the polymer ceramic sheet can be further reduced, and the internal binding force is improved. In one embodiment, the polymer ceramic sheet may be vacuum sealed and then subjected to warm isostatic pressing.

In embodiments of the present application, the ceramic powder may further include sanding the ceramic powder prior to blending with the modifying polymer. The surface hydroxyl content of the ceramic powder can be increased by the sanding treatment, so that the compatibility and the bonding performance between the ceramic powder and the modified polymer are improved, and the mechanical performance of the shell 100 is further improved. In one embodiment, the sanding speed is 300r/min-2500r/min, the particle size of the sanding beads is 0.5mm-10mm, the sanding cycle times are 20-100 times, and the sanding time is 10-30 min, so that the particle size of the ceramic powder can be improved, and the hydroxyl content on the surface of the ceramic powder can be improved.

Referring to fig. 2, a flowchart of a method for manufacturing a shell according to another embodiment of the present application includes:

s201: modifying the polymer to obtain a modified polymer, wherein the modified polymer comprises a polymer and an aromatic group connected to the chain structure of the polymer, and/or the modified polymer comprises a polymer and a reactive group connected to the tail end of the chain structure of the polymer.

S202: and (3) performing sanding treatment on the ceramic powder, wherein the sanding rotating speed is 300-2500 r/min, the particle size of the sand beads is 0.5-10 mm, the sanding cycle times are 20-100 times, and the sanding time is 10-30 min.

S203: and (3) blending the ceramic powder subjected to sand milling treatment with the modified polymer, carrying out banburying granulation and injection molding to obtain a polymer ceramic sheet, and pressing the polymer ceramic sheet to obtain a polymer ceramic layer, thereby obtaining the shell.

It can be understood that, for the detailed description of S201 and S203, please refer to the description of the corresponding parts of S101 and S102 in the above embodiment, and the detailed description is omitted here.

In S202, the ceramic powder is subjected to a sanding process. The surface hydroxyl content of the ceramic powder can be increased by the sanding treatment, so that the compatibility and the bonding performance between the ceramic powder and the modified polymer are improved, and the mechanical performance of the shell 100 is further improved. It will be appreciated that the ceramic powder may be further surface modified to increase the surface active group content.

Referring to fig. 3, a flowchart of a method for manufacturing a housing according to another embodiment of the present application includes:

s301: modifying the polymer to obtain a modified polymer, wherein the modified polymer comprises a polymer and an aromatic group connected to the chain structure of the polymer, and/or the modified polymer comprises a polymer and a reactive group connected to the tail end of the chain structure of the polymer.

S302: and (3) blending the ceramic powder with the modified polymer, carrying out banburying granulation and injection molding to obtain a polymer ceramic sheet, pressing the polymer ceramic sheet, and then carrying out heat treatment to obtain a polymer ceramic layer, thus obtaining the shell.

It can be understood that, please refer to the description of the corresponding portion of S101 in the above embodiment for the detailed description of S301, and the detailed description is omitted herein.

In S302, heat treatment is further included after the lamination. Bonding between the modified polymer and the ceramic powder can be promoted by heat treatment, and compatibility and binding force are improved, so that the strength of the shell 100 is improved; for example, the resin modified by the end groups such as amino, carboxyl, epoxy groups and the like reacts with the surface of the filler at high temperature to generate strong linkage, so that the compatibility and the connection force of the filler and the resin are greatly improved, and the toughness of the composite material is improved. The heat treatment can promote the chain extension reaction of the modified polymer, improve the chain length of the polymer, improve the flexibility, be favorable for forming a more compact network structure and improve the strength and the toughness of the shell 100; for example, chain extension reaction can be carried out between the end group modified resins such as hydrocarbon groups, epoxy groups and the like at high temperature under the action of a catalyst, so that the polymer molecular chain is longer, the flexibility is better, and a more compact network structure is formed by winding, thereby further improving the toughness of the composite material. In the present application, the heat treatment temperature is determined according to the properties of the modified polymer; for example, the heat treatment temperature is greater than the melting temperature of the polymer and less than the decomposition temperature of the polymer. In one embodiment, the temperature of the heat treatment is between 100 ℃ and 350 ℃ and the time of the heat treatment is between 5 hours and 48 hours. Further, the temperature of the heat treatment is 150-310 ℃, and the time of the heat treatment is 6-36 h. In one embodiment, when the polymer is polyphenylene sulfide, the heat treatment may be performed at a temperature of 100 ℃ to 350 ℃ for a time of 5 hours to 48 hours; specifically, it may be, but is not limited to, treatment at 310℃for 24 hours.

In embodiments of the present application, the method of manufacturing the housing 100 may further include performing computer numerically controlled precision machining (CNC machining). The final desired assembled fit size of the housing 100 is obtained by CNC machining. For example, by CNC machining, making the housing 100 more flat, etc. In another embodiment of the present application, the method for manufacturing the housing 100 further includes polishing the housing 100. The surface of the housing 100 is polished and ground, so that the roughness of the surface of the housing 100 is reduced, and the ceramic texture of the surface of the housing 100 is improved. In one embodiment, the surface roughness of the housing 100 is less than 0.1 μm. By providing the housing 100 with small surface roughness, the surface glossiness and ceramic texture of the housing are enhanced, and the visual effect is improved. Further, the surface roughness of the case 100 is 0.02 μm to 0.08 μm. In the embodiment of the present application, the protective layer 20 may be formed by spraying or vapor-depositing a protective material on the surface of the case 100. In an embodiment, an anti-fingerprint layer is formed by evaporating an anti-fingerprint material on the surface of the housing 100, so as to improve the anti-fingerprint effect of the housing 100.

The present application also provides a second preparation method of the housing 100, as shown in fig. 4, including:

S401: and (3) mixing ceramic powder, a prepolymer and a material containing a modified group, and carrying out banburying granulation and injection molding to obtain the polymer ceramic piece.

S402: and pressing the polymer ceramic piece to obtain a polymer ceramic layer, and obtaining the shell.

Wherein the modified group-containing material has an aromatic group and/or a reactive group, the prepolymer and the modified group-containing material react to form a modified polymer, the modified polymer comprises a polymer composed of the prepolymer and the aromatic group attached to the chain structure of the polymer, and/or the modified polymer comprises a polymer and the reactive group attached to the chain structure end of the polymer. The second preparation method is different from the above method in that the prepolymer and the material containing the modifying group are mixed with the ceramic powder, and the modified polymer is generated by heating and reacting in the preparation process, so that the modification of the polymer and the molding of the shell 100 are simultaneously carried out, the preparation process period is reduced, and the comprehensive performance of the shell 100 is improved.

In the application, the prepolymer refers to a substance formed by preliminary polymerization of monomers, and the prepolymer has the same structure as the corresponding repeating units in the polymer, such as a first repeating unit, and the like, and is different in polymerization degree; the corresponding prepolymer can be selected according to the required polymer, and the material containing the modified group can be selected according to the group to be grafted; furthermore, a chain extender can be added to increase the chain extension speed.

In the present application, the mixing ratio of the ceramic powder and the prepolymer may be determined according to the desired mass ratio of the ceramic powder to the modified polymer in the housing 100; the mixing ratio of the prepolymer and the modifying group-containing material may be determined according to the amount of the modifying polymer required, and is not limited thereto; the processes of banburying granulation, injection molding and lamination are detailed in the above embodiments, and will not be described again. In the present application, modified polymers, prepolymers and materials containing modified groups may be present in the "polymer ceramic part", while modified polymers are present in the "polymer ceramic sheet", and there is a certain difference in the composition of the two materials.

The present application also provides a housing 100, referring to fig. 5, which is a schematic structural diagram of a housing according to an embodiment of the present application, wherein the housing 100 includes a polymer ceramic layer 10, the polymer ceramic layer 10 includes ceramic powder and a modified polymer, the modified polymer includes a polymer and an aromatic group connected to a chain structure of the polymer, and/or the modified polymer includes a polymer and a reactive group connected to a chain structure end of the polymer. The adoption of the modified polymer with aromatic groups is beneficial to improving the hardness and glossiness of the shell 100; the use of a modified polymer having reactive groups is advantageous in improving the strength of the housing 100.

In the present embodiment, the case 100 may be manufactured by the manufacturing method of the case 100 described in any of the above embodiments.

In the embodiment of the present application, the mass ratio of the ceramic powder in the polymer ceramic layer 10 is 50% -90%. The high content of ceramic powder in the polymer ceramic layer 10 can improve the surface hardness and the ceramic texture. In one embodiment, the ceramic powder content of the polymer ceramic layer 10 is 60% -85%. In another embodiment, the ceramic powder content in the polymer ceramic layer 10 is 65% -80%. Specifically, the content of the ceramic powder in the polymer ceramic layer 10 may be, but is not limited to, 55%, 60%, 65%, 70%, 72%, 75%, 80%, 85%, or the like.

In an embodiment of the present application, the ceramic powder includes Al ₂ O ₃ 、ZrO ₂ 、Si ₃ N ₄ 、SiO ₂ 、TiO ₂ At least one of AlN, siC and Si. The ceramic described aboveThe powder has high temperature resistance, corrosion resistance, high hardness and good strength, and is beneficial to the improvement and use of the performance of the shell 100. In the embodiment of the present application, the refractive index of the ceramic powder is greater than 2. By providing the ceramic powder having a high refractive index, the surface gloss and ceramic texture of the case 100 are improved, so that the appearance of the case 100 is more similar to that of a ceramic case.

In the present application, the modified polymer in the polymer ceramic layer 10 is crosslinked into a three-dimensional network structure in which the ceramic powder is dispersed. In the embodiment of the present application, the mass ratio of the modified polymer in the polymer ceramic layer 10 is not greater than the mass ratio of the ceramic powder, so that the ceramic texture of the housing 100 is advantageously improved. Further, the mass ratio of the modified polymer in the polymer ceramic layer 10 is 10% -50%. Further, the mass ratio of the modified polymer in the polymer ceramic layer 10 is 15% -40%. Specifically, the mass ratio of the modified polymer in the polymer ceramic layer 10 may be, but is not limited to, 10%, 20%, 25%, 30%, 37%, 40%, 45%, 50%, or the like. The ceramic texture of the housing 100 is further enhanced by using the modified polymer in the above content.

In the present application, the modified polymer includes a polymer and an aromatic group attached to the chain structure of the polymer, and/or the modified polymer includes a polymer and a reactive group attached to the chain structure end of the polymer. That is, grafting an aromatic group on the chain structure of the polymer results in a modified polymer, and/or grafting a reactive group on the chain structure end of the polymer results in a modified polymer. In one embodiment of the present application, the aromatic group includes at least one of phenyl, biphenyl, and acenyl. The aromatic group has a high refractive index, and can improve the glossiness of the modified polymer, which is beneficial to improving the hardness and ceramic texture of the shell 100. In one embodiment of the present application, the reactive group includes at least one of an alkylene group, an alkyne group, an epoxy group, an amino group, a hydroxyl group, and a carboxyl group. In one embodiment of the present application, the reactive group includes at least one of an epoxy group, an amino group, a hydroxyl group, and a carboxyl group. The modified polymer with the reactive group is easy to chemically react with the group on the surface of the ceramic powder to generate bonding, so that the interface bonding strength between the modified polymer and the ceramic powder is improved, and the compactness and strength of the shell 100 are improved.

In an embodiment of the present application, the polymer comprises at least one of polyphenylene sulfide, polycarbonate, polyamide, polymethyl methacrylate, and polybutylene terephthalate; accordingly, the modified polymer includes at least one of modified polyphenylene sulfide, modified polycarbonate, modified polyamide, modified polymethyl methacrylate and modified polybutylene terephthalate. The modified polymer can obviously improve the comprehensive performance of the shell 100, and meanwhile, the physicochemical performance of the modified polymer can be matched with the preparation process of the shell 100, so that the modified polymer cannot be decomposed in the preparation process, the difficulty of the preparation process cannot be increased, and the production cost can be reduced.

The preparation method of the shell and the performance of the prepared shell are further described below through specific examples and comparative examples.

Example 1

In the preparation process of the shell, zirconia and modified polyphenylene sulfide (PPS) are blended, and the shell is prepared after banburying granulation, injection molding and pressing. Wherein, the weight ratio of zirconia in the shell is 75 percent, the weight ratio of modified PPS is 25 percent, and the modified PPS is PPS with a side chain grafted with naphthalene groups, and the structural formula is shown as follows:

Example 2

The procedure is substantially as in example 1, except that the modified PPS is a PPS having amino end groups grafted to the ends of the main chain, and the structural formula is as follows:

example 3

The procedure is substantially as in example 1, except that the modified PPS is a PPS having an olefin terminal group grafted to the terminal of the main chain, and the structural formula is as follows:

comparative example 1

Substantially the same as in example 1, except that pure PPS was used without any modification treatment.

Comparative example 2

The zirconia ceramic shell is formed by sintering pure zirconia ceramic powder.

Performance detection

The pencil hardness of the surfaces of the casings provided in the above examples and comparative examples was examined using GB/T6739-1996; the glossiness of the surfaces of the shells provided by the examples and the comparative examples is detected, and the glossiness meter angles are 20 degrees, 60 degrees and 80 degrees; the shells in the above examples and comparative examples were provided with the same size, 150mm in length, 73mm in width and 0.8mm in thickness, and were supported on a jig (3 mm supports on each of four sides and suspended in the middle), and were freely dropped from a certain height to the surface to be measured using a stainless steel ball of 32g, five points were set at four corners and the center of the shell, each point was measured 5 times until broken, and the drop height at this time was recorded, and the detection results are shown in table 5.

TABLE 5 Performance test results

	Example 1	Example 2	Example 3	Comparative example 1	Comparative example 2
						Pencil hardness/H	5-8	4-7	4-7	3-5	Greater than 9
Gloss (20 degree)	170-240	150-220	150-210	130-190	230-260
						Gloss (60 degree)	140-170	130-160	130-155	120-140	160-180
Glossiness (80 degree)	95-115	90-110	90-110	90-100	100-120
						Ball drop height/cm	70-90	90-100	100-120	50-90	50-70
Elongation at break/%	2-6	8-12	15-25	3-8	Less than 1

The monomer of the modified polymer in the embodiment 1 is connected with an aromatic group (naphthyl), the pencil hardness and the glossiness of the prepared shell are high, and the performance of the shell prepared in the embodiment 1 is obviously superior to that of the shell provided in the comparative example 1, and even is equivalent to that of the pure ceramic shell provided in the comparative example 2; therefore, the shell provided in embodiment 1 of the application has good wear resistance and strong ceramic texture. The modified polymers in the examples 2 and 3 of the application have reactive end groups, and the prepared shells have high ball drop height and elongation at break, and are obviously superior to those of the shells provided in the comparative examples 1 and 2; therefore, the shells provided in examples 2 and 3 of the present application have strong toughness and good impact resistance. In conclusion, compared with the comparative example, the shell provided by the application has excellent comprehensive performance and is beneficial to the application.

It should be noted that, in the present application, when the modified polymer includes a polymer and an aromatic group attached to the chain structure of the polymer, the produced shell 100 has high hardness and high glossiness, thereby providing the shell 100 with excellent wear resistance and ceramic texture. In one embodiment of the present application, when the modified polymer includes a polymer and an aromatic group attached to the chain structure of the polymer, the 20 ° angular glossiness of the polymer ceramic layer 10 is greater than or equal to 140, the 60 ° angular glossiness is greater than or equal to 130, and the 80 ° angular glossiness is greater than or equal to 95. Further, when the modified polymer includes a first repeating unit and an aromatic group attached to the first repeating unit, the polymer ceramic layer 10 has an angular 20 ° gloss of 170 to 260, an angular 60 ° gloss of 140 to 180, and an angular 80 ° gloss of 95 to 120. In another embodiment of the present application, the hardness of the polymeric preceramic layer 10 is greater than 4H. Further, the hardness of the polymer ceramic layer 10 is 5H to 9H. In particular, the hardness of the polymer ceramic layer 10 may be, but is not limited to, 5H, 6H, 7H, 8H, 9H, or the like.

In the present application, when the modified polymer includes a polymer and a reactive group attached to the end of the chain structure of the polymer, the produced shell 100 has good strength and toughness, thereby improving the mechanical properties of the shell 100. In one embodiment of the present application, when the polymer ceramic layer 10 is prepared using a modified polymer having a reactive end group, the elongation at break of the polymer ceramic layer 10 is greater than or equal to 8%. Further, the elongation at break of the polymer ceramic layer 10 is 8% to 30%. Further, the elongation at break of the polymer ceramic layer 10 is 10% to 25%. Specifically, the elongation at break of the polymer ceramic layer 10 may be, but is not limited to, 8%, 10%, 13%, 15%, 16%, 19%, 20%, 22%, 23%, 25%, or the like. When the shell 100 is prepared using a modified polymer having reactive end groups, the ball drop height of the shell 100 is greater than or equal to 90cm. Further, the ball drop height of the housing 100 is 90cm to 120cm.

Referring to fig. 6, in order to provide a schematic structural diagram of a housing according to another embodiment of the present application, the housing 100 may further include a protection layer 20, where the protection layer 20 is disposed on a surface of the polymer ceramic layer 10. The housing 100 has oppositely disposed inner and outer surfaces during use, and the protective layer 20 is located on one side of the outer surface to provide protection during use of the housing 100. Specifically, the protective layer 20 may be, but is not limited to, an anti-fingerprint layer, a hardened layer, and the like. Specifically, the thickness of the protective layer 20 may be, but is not limited to, 5nm to 20nm. In one embodiment, the protective layer 20 includes an anti-fingerprint layer. Optionally, the contact angle of the anti-fingerprint layer is greater than 105 °. The contact angle is an important parameter for measuring the wettability of the liquid on the surface of the material, and the contact angle of the anti-fingerprint layer is larger than 105 degrees, which indicates that the liquid can easily move on the anti-fingerprint layer, so that the pollution to the surface of the anti-fingerprint layer is avoided, and the anti-fingerprint material has excellent anti-fingerprint performance. Optionally, the anti-fingerprint layer comprises a fluorine-containing compound. In particular, the fluorine-containing compound may be, but is not limited to, fluorosilicone resin, perfluoropolyether, fluoroacrylate, and the like. Furthermore, the anti-fingerprint layer further comprises silicon dioxide, and the friction resistance of the anti-fingerprint layer is further improved by adding the silicon dioxide. In another embodiment, the protective layer 20 includes a hardened layer. The surface hardness of the case 100 is further enhanced by providing a hardened layer. Optionally, the material of the hardening layer comprises at least one of polyurethane acrylate, organic silicon resin and perfluoropolyether acrylate.

In the present embodiment, the polymer ceramic layer 10 may further have a colorant so that the case 100 has a different color appearance, improving visual effect. Specifically, the colorant may be, but is not limited to, at least one selected from the group consisting of iron oxide, cobalt oxide, cerium oxide, nickel oxide, bismuth oxide, zinc oxide, manganese oxide, chromium oxide, copper oxide, vanadium oxide, and tin oxide, respectively. In one embodiment, the mass content of the colorant in the polymer ceramic layer 10 is less than or equal to 10%, thereby improving the color of the polymer ceramic layer 10 without affecting the ceramic powder and polymer content. Further, the mass content of the colorant in the polymer ceramic layer 10 is 0.5% to 10%.

In the present application, the thickness of the housing 100 may be selected according to the requirements of the application scenario, which is not limited; in an embodiment, the housing 100 may be used as a housing, a middle frame, a decoration, etc. of an electronic device, such as a housing of a mobile phone, a tablet computer, a notebook computer, a watch, an MP3, an MP4, a GPS navigator, a digital camera, etc. The housing 100 in the embodiment of the present application may be a 2D structure, a 2.5D structure, a 3D structure, or the like, and may be specifically selected as needed. In one embodiment, the thickness of the housing 100 is 0.6mm-1.2mm when the housing 100 is used as a rear cover of a mobile phone. Specifically, the thickness of the housing 100 may be, but is not limited to, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 1.1mm, or 1.2mm. In another embodiment, when the housing 100 is used as a mobile phone rear cover, the housing 100 includes a main body portion and an extension portion disposed at an edge of the main body portion, and the extension portion is bent toward the main body portion; the housing 100 is curved at this time.

In the present embodiment, the surface roughness of the case 100 is less than 0.1 μm. By providing the housing 100 with small surface roughness, the ceramic texture is enhanced, and the visual effect is improved. Further, the surface roughness of the case 100 is 0.02 μm to 0.08 μm.

The present application also provides an electronic device 200 comprising the housing 100 of any of the above embodiments. It is understood that the electronic device 200 may be, but is not limited to, a cell phone, tablet, notebook, watch, MP3, MP4, GPS navigator, digital camera, etc. Referring to fig. 7, a schematic structural diagram of an electronic device according to an embodiment of the present application is provided, where an electronic device 200 includes a housing 100. The case 100 can enhance the performance of the electronic device 200, and the electronic device 200 has a ceramic-textured appearance with excellent product competitiveness. Referring to fig. 8, a schematic structural diagram of an electronic device according to an embodiment of the present application is provided, and the electronic device 200 may include an RF circuit 210, a memory 220, an input unit 230, a display unit 240, a sensor 250, an audio circuit 260, a WiFi module 270, a processor 280, a power supply 290, and the like. The RF circuit 210, the memory 220, the input unit 230, the display unit 240, the sensor 250, the audio circuit 260, and the WiFi module 270 are respectively connected to the processor 280; the power supply 290 is used to provide power to the entire electronic device 200. Specifically, RF circuit 210 is used to send and receive signals; memory 220 is used to store data instruction information; the input unit 230 is used for inputting information, and may specifically include a touch panel and other input devices such as operation keys; the display unit 240 may include a display screen or the like; the sensor 250 includes an infrared sensor, a laser sensor, etc., for detecting a user proximity signal, a distance signal, etc.; the speaker 261 and the microphone 262 are connected with the processor 280 through the audio circuit 260 for receiving and transmitting sound signals; the WiFi module 270 is configured to receive and transmit WiFi signals; the processor 280 is used to process data information of the electronic device 200.

The foregoing has outlined rather broadly the more detailed description of the embodiments of the present application in order that the principles and embodiments of the present application may be explained and illustrated herein, the above description being provided for the purpose of facilitating the understanding of the method and core concepts of the present application; meanwhile, as those skilled in the art will have modifications in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.

Claims

1. A method of manufacturing a housing, comprising:

modifying a polymer to obtain a modified polymer, wherein the modified polymer comprises the polymer and an aromatic group connected to a chain structure of the polymer, and/or the modified polymer comprises the polymer and a reactive group connected to a chain structure tail end of the polymer, and the reactive group comprises at least one of an olefin group, an alkyne group and an epoxy group;

2. The method according to claim 1, wherein the aromatic group has 6 to 48 carbon atoms, and the aromatic group includes at least one of a phenyl group, a biphenyl group, and a acene group.

3. The method of making according to claim 1, wherein said polymer comprises a first repeat unit and said modified polymer comprises said first repeat unit and said aromatic group attached to said first repeat unit.

4. The method of claim 1, wherein the polymer comprises at least one of polyphenylene sulfide, polycarbonate, polyamide, polymethyl methacrylate, and polybutylene terephthalate, and the degree of polymerization of the polymer is 500 to 10000.

5. The method of claim 1, further comprising sanding the ceramic powder at a sanding speed of 300r/min to 2500r/min, with a particle size of 0.5mm to 10mm, with a sanding cycle time of 20 times to 100 times, and a sanding time of 10min to 30min.

6. The method of manufacturing of claim 1, wherein pressing the polymeric ceramic sheet comprises: and carrying out temperature isostatic pressing on the polymer ceramic sheet, wherein the temperature of the temperature isostatic pressing is 80-300 ℃, the temperature of the temperature isostatic pressing is higher than the glass transition temperature of the modified polymer, the pressure of the temperature isostatic pressing is 50-500 MPa, and the time of the temperature isostatic pressing is 0.5-2 h.

7. The method of claim 1, further comprising a heat treatment after the lamination, wherein the heat treatment is performed at a temperature of 100 ℃ to 350 ℃ and a time of 5h to 48h.

8. The method of manufacturing according to claim 1, wherein the ceramic powder comprises Al ₂ O ₃ 、ZrO ₂ 、Si ₃ N ₄ 、SiO ₂ 、TiO ₂ At least one of AlN, siC and Si, wherein the particle size D50 of the ceramic powder is 200nm-5 mu m.

9. A method of manufacturing a housing, comprising:

blending ceramic powder, a prepolymer and a material containing a modified group, carrying out banburying granulation and injection molding to obtain a polymer ceramic piece, pressing the polymer ceramic piece to obtain a polymer ceramic layer, and preparing a shell, wherein the material containing the modified group is provided with an aromatic group and/or a reactive group, the prepolymer and the material containing the modified group react to generate a modified polymer, the modified polymer comprises a polymer composed of the prepolymer and the aromatic group connected to a chain structure of the polymer, and/or the modified polymer comprises the polymer and the reactive group connected to a chain structure end of the polymer, and the reactive group comprises at least one of an olefin group, an alkyne group and an epoxy group.

10. A housing comprising a polymeric ceramic layer, the polymeric ceramic layer comprising a ceramic powder and a modifying polymer, the modifying polymer comprising a polymer and an aromatic group attached to a chain structure of the polymer, and/or the modifying polymer comprising the polymer and a reactive group attached to a chain structure end of the polymer, the reactive group comprising at least one of an alkylene group, an alkyne group, and an epoxy group.

11. The housing of claim 10, wherein the polymeric-ceramic layer has a 20 ° angular gloss of greater than or equal to 140, a 60 ° angular gloss of greater than or equal to 130, and an 80 ° angular gloss of greater than or equal to 95, and a hardness of greater than 4H.

12. The housing of claim 10, wherein the polymeric-ceramic layer has an elongation at break of greater than or equal to 8%.

13. The housing of claim 10, wherein the modified polymer comprises at least one of a modified polyphenylene sulfide, a modified polycarbonate, a modified polyamide, a modified polymethyl methacrylate, and a modified polybutylene terephthalate.

14. The housing of claim 10, wherein the ceramic powder in the polymeric ceramic layer comprises 50% -90% by mass.

15. The housing of claim 10, further comprising a protective layer disposed on a surface of the polymeric-ceramic layer.

16. An electronic device comprising a housing produced by the production method according to any one of claims 1 to 9 or a housing according to any one of claims 10 to 15.