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WO2020215975A1 - 外壳及其制作方法、改性环氧树脂、环氧树脂板和电子设备 - Google Patents

外壳及其制作方法、改性环氧树脂、环氧树脂板和电子设备 Download PDF

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Publication number
WO2020215975A1
WO2020215975A1 PCT/CN2020/081315 CN2020081315W WO2020215975A1 WO 2020215975 A1 WO2020215975 A1 WO 2020215975A1 CN 2020081315 W CN2020081315 W CN 2020081315W WO 2020215975 A1 WO2020215975 A1 WO 2020215975A1
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WO
WIPO (PCT)
Prior art keywords
epoxy resin
layer
resin board
modified
adhesive layer
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PCT/CN2020/081315
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English (en)
French (fr)
Inventor
杨光明
Original Assignee
Oppo广东移动通信有限公司
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Publication date
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Publication of WO2020215975A1 publication Critical patent/WO2020215975A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers

Definitions

  • the invention relates to the technical field of electronic equipment, in particular to a housing and a manufacturing method thereof, a modified epoxy resin, an epoxy resin board and electronic equipment.
  • the shell materials of electronic devices are usually made of composite sheets made of PC (polycarbonate) and PMMA (polymethyl methacrylate), pure PC sheets, etc.
  • PC polycarbonate
  • PMMA polymethyl methacrylate
  • the tensile properties of composite sheets Inferior. If bending is used, it is easy to crack when stretched during the bending process.
  • pure PC sheet has good tensile properties, it can solve the cracking problem in the forming and stretching process of composite sheet to a certain extent, but The low hardness of PC board leads to poor wear resistance and scratch resistance, which affects consumer experience.
  • PET (polyethylene terephthalate) sheet has good wear resistance and scratch resistance, some terminal companies are also trying to use PET sheet to make electronic equipment shells, but PET sheet is in the process of bending and forming. It is easy to warp, which limits its application on the back cover.
  • a modified epoxy resin the modified epoxy resin has an epoxy value of 0.25-0.45
  • the modified epoxy resin is an epoxy resin modified by a modified product
  • the modified product is selected from organic At least one of silicon, polyurethane prepolymer and polyimide, and the mass ratio of the modified product to the epoxy resin is 1:5-1:10.
  • An epoxy resin board the material of the epoxy resin board is modified epoxy resin, the epoxy value of the modified epoxy resin is 0.25-0.45, and the modified epoxy resin is a modified product.
  • the modified product is selected from at least one of silicone, polyurethane prepolymer and polyimide, and the mass ratio of the modified product to the epoxy resin is 1:5 -1:10.
  • a manufacturing method of a shell includes the following steps:
  • the material of the epoxy resin board is modified epoxy resin
  • the epoxy value of the modified epoxy resin is 0.25-0.45
  • the modified epoxy resin is modified by the modified product
  • the epoxy resin, the modified substance is selected from at least one of silicone, polyurethane prepolymer and polyimide, and the mass ratio of the modified substance to the epoxy resin is 1:5- 1:10;
  • the epoxy resin board is bent and formed to obtain a shell.
  • An electronic device includes the above-mentioned casing or the casing produced by the above-mentioned casing manufacturing method.
  • Fig. 1 is a flowchart of a manufacturing method of a housing of the first embodiment
  • FIG. 2 is a schematic diagram of the structure of the housing of the first embodiment
  • Figure 3 is a partial cross-sectional view of the housing shown in Figure 2;
  • FIG. 4 is a flowchart of the manufacturing method of the housing of the second embodiment
  • Figure 5 is a partial cross-sectional view of the housing of the second embodiment
  • Fig. 6 is a flow chart of the manufacturing method of the housing of the third embodiment
  • Fig. 7 is a partial cross-sectional view of the housing of the third embodiment.
  • the modified epoxy resin of an embodiment can be used to make housings, such as housings of electronic devices, especially back covers of mobile phones, tablet computers, and the like.
  • the epoxy value of the modified epoxy resin is 0.25-0.45
  • the modified epoxy resin is the epoxy resin modified by the modified product
  • the modified product is selected from at least one of silicone, polyurethane prepolymer and polyimide One type
  • the mass ratio of the modified product to the epoxy resin is 1:5-1:10.
  • the epoxy value referred to herein refers to the amount (ie, molar amount) of the epoxy group contained in 100g of the modified epoxy resin, and the epoxy value of the modified epoxy resin can be determined according to the epoxy value. Quality percentage.
  • Modification of epoxy resin can improve the tensile strength and impact resistance of epoxy resin and reduce the risk of material cracking during the manufacturing process while ensuring that the epoxy resin has a higher hardness.
  • the method for preparing the modified epoxy resin in one embodiment is a method for preparing the above-mentioned modified epoxy resin.
  • the method for preparing the modified epoxy resin includes the following steps: according to the epoxy value of the modified epoxy resin 0.25-0.45, mix the above modified substance, epoxy resin and catalyst to obtain a mixture, wherein the mass ratio of the modified substance to epoxy resin is 1:5-1:10; add curing agent to the mixture, and then React at 80°C-120°C to obtain the above-mentioned modified epoxy resin.
  • the epoxy resin may be an epoxy resin commonly used in the art, such as bisphenol A epoxy resin.
  • the epoxy resin is selected from at least one of E-51 epoxy resin, E-55 epoxy resin and E-44 epoxy resin.
  • the organosilicon can be an organosilicon monomer commonly used in the field.
  • the silicone is selected from polydimethylsiloxane, dimethyldimethoxysiloxane, methylvinyldimethoxysiloxane and methylphenyldimethoxysiloxane At least one of siloxanes.
  • the polyurethane prepolymer can be a polyurethane prepolymer commonly used in the field for modifying epoxy resins, and the polyurethane prepolymer is obtained by reacting diisocyanate or polyisocyanate and polyol in a certain proportion.
  • the polyisocyanate is selected from IPDI (isophorone diisocyanate), TDI (toluene diisocyanate), MDI (diphenylmethane-4,4'-diisocyanate) and HDI (hexamethylene diisocyanate) One of them; the polyol is polyethylene glycol or polypropylene glycol; the mass ratio of polyisocyanate to polyol is 1:(0.5-1.5).
  • Polyurethane prepolymers can also be purchased on the market, such as the polyurethane prepolymer model KHP-456 produced by Jining Huakai Resin, and the MDI polyurethane prepolymer model N434 of Dow USA.
  • the polyimide is selected from benzene type polyimide, fluorinated anhydride type polyimide, ketone anhydride type polyimide, NA group-terminated polyimide, ethynyl-terminated polyimide, polyphenylene At least one of bisimidazole polyimides.
  • the catalyst may be a catalyst commonly used in the field.
  • the catalyst is dibutyl tin dilaurate.
  • the curing agent may be a curing agent commonly used in the field.
  • the curing agent is dicyandiamide.
  • the modified product is selected from at least one of silicone and polyurethane prepolymer; or, the modified product is made of It is composed of polyimide and polyurethane prepolymer.
  • the mass percentage of the polyurethane prepolymer is more than 60%; or, the modification is made of silicone with a mass ratio of 1:(0.1-0.2) And polyimide composition.
  • the step of preparing the modified epoxy resin includes: mixing the modified product, epoxy resin, and catalyst at room temperature for 1 hour to 4 hours, and then adding a curing agent at 80°C to 120°C React for 1 hour to 2 hours to obtain modified epoxy resin.
  • the mass ratio of modified substance and epoxy resin is 1:5-1:10
  • the mass ratio of catalyst to epoxy resin is 1:100-5:100
  • the mass ratio of curing agent to epoxy resin is 10: 100-30:100.
  • the room temperature referred to herein is 10°C-40°C.
  • the method for preparing the above-mentioned modified epoxy resin is not limited to using the materials and steps in the above-mentioned steps, and the above-mentioned modified epoxy resin can also be prepared by using a traditional modified epoxy resin preparation process.
  • the controlled epoxy value of the modified epoxy resin is 0.25-0.45, and the mass ratio of the modified epoxy resin to the epoxy resin is 1:5-1:10, so that the modified epoxy resin
  • the hardness can reach HB-H, and it has good wear resistance and good scratch resistance; the above modified epoxy resin also has good tensile properties, tensile strength above 60MPa, and can be directly bent and formed; And the softening temperature of the above modified epoxy resin is 100°C-130°C, which has good high temperature resistance.
  • the softening temperature of the above modified epoxy resin is 100°C-130°C, which has good high temperature resistance.
  • Modified epoxy resin can also not yellow under ultraviolet light for 48H, has good aging resistance, and also has impact resistance.
  • the material of the epoxy resin board is the above-mentioned modified epoxy resin. That is, the epoxy resin board is obtained by the above-mentioned modified epoxy resin molding process.
  • the epoxy resin board can be used to make shells, such as the shells of electronic devices, especially the back covers of mobile phones or tablet computers.
  • the thickness of the epoxy resin board is 0.4 mm-0.8 mm, and the epoxy resin board of this thickness is suitable for making a shell with a decorative layer (such as a pattern, a texture, etc.). It can be understood that the thickness of the epoxy resin board can be adjusted according to the required thickness and performance.
  • the optical transmittance of the epoxy resin board is 83%-88%, so as to make other decorative layers (such as patterns, textures, etc.) on the epoxy resin board subsequently to obtain vibrant products.
  • the preparation step of the epoxy resin board includes: melting the modified epoxy resin at 140° C.-190° C. and then extruding to obtain the epoxy resin board.
  • the epoxy resin board is prepared from the modified epoxy resin, the epoxy resin board has a hardness of up to HB-H, and has good abrasion resistance and scratch resistance; and the epoxy resin board It also has good tensile properties, and can be directly bent and formed; and the softening temperature of the modified epoxy resin is 100°C-130°C, which has good high temperature resistance.
  • the traditional epoxy resin board has poor high temperature resistance and is easy to age, which limits its scope of use.
  • the material of the epoxy resin board is the modified epoxy resin, and the softening temperature of the modified epoxy resin is 100°C. -130°C, has good high temperature resistance, does not turn yellow under ultraviolet radiation for 48H, and has good aging resistance, so that the above epoxy resin board can be used for making shells.
  • the housing manufactured by this method can be used as the housing of an electronic device, such as a housing of a tablet computer, a mobile phone, etc., especially a back cover of a mobile phone or a tablet computer.
  • the manufacturing method of the housing of this embodiment includes the following steps S11-S15:
  • Step S11 preparing an epoxy resin board.
  • the material of the epoxy resin board is modified epoxy resin
  • the epoxy value of the modified epoxy resin is 0.25-0.45
  • the modified epoxy resin is the epoxy resin modified by the modification
  • the modification is selected from At least one of organosilicon, polyurethane prepolymer and polyimide
  • the mass ratio of the modified product and the epoxy resin is 1:5-1:10.
  • the epoxy resin board is the above-mentioned epoxy resin board, and the preparation method is as described above, which will not be repeated here.
  • the housing is the back cover of the mobile phone, and the thickness of the epoxy resin board is 0.4 mm-0.8 mm. It can be understood that the thickness of the epoxy resin board can be adjusted according to the required thickness and performance.
  • optical transmittance of the epoxy resin board is 83%-88%.
  • Step S12 forming a pattern layer on one side of the epoxy resin board.
  • the pattern of the pattern layer may be, for example, a LOGO, a symbol, an animal pattern, and the like.
  • the pattern layer is printed by mirror silver ink and dried. More specifically, the step of forming a pattern layer on one side of the epoxy resin board is: use 300-420 mesh screen printing mirror silver ink on one side of the epoxy resin board, and then statically at 15°C-30°C Let it stand for 30 minutes-60 minutes, and then bake at 60°C-80°C for 30 minutes-90 minutes.
  • the mirror ink is, for example, the 06B mirror silver ink from Shenzhen Lianyiwang Ink Technology Co., Ltd.
  • the corrosion-resistant layer is UV glue
  • the UV glue is urethane acrylate glue. This type of glue has good chemical resistance, good adhesion, and excellent weather resistance. Polyurethane acrylate glue such as Bethel New Material Co., Ltd.'s model is 633-75 UV glue.
  • the thickness of the pattern layer is 1 ⁇ m-4 ⁇ m. It is understood that the thickness of the pattern layer can be set as required.
  • Step S13 setting a decoration unit on the epoxy resin board.
  • a decoration unit is provided on the side of the epoxy resin board where the pattern layer is formed, and the pattern layer is covered.
  • the decoration unit includes an adhesive layer, a reflective layer and an ink layer.
  • the step of arranging a decorative unit on the epoxy resin board includes: forming a transparent adhesive layer on the side of the epoxy resin board where the pattern layer is formed, and the adhesive layer covers the pattern layer; A reflective layer is formed on one side; an ink layer is formed on the side of the reflective layer away from the adhesive layer.
  • the adhesive layer is obtained by UV (ultraviolet light) glue transfer, and the adhesive layer has a texture pattern, so that the shell has a textured appearance.
  • the UV glue can be a transparent UV glue that is commonly used in the field after curing.
  • the UV glue is urethane acrylate glue, for example, the UV glue of the model 633-75 from Bethel New Material Co., Ltd.
  • the curing energy of UV glue is 600mj/cm 2 -1500mj/cm 2 .
  • the UV glue is not limited to the above-mentioned glue, and may also be a glue that is commonly used in the field and becomes transparent after curing; the adhesive layer may not have a texture pattern, at this time, the shell does not have a texture appearance.
  • the thickness of the adhesive layer is 5 ⁇ m-20 ⁇ m. It can be understood that the thickness of the adhesive layer is not limited to the above-mentioned thickness, and the thickness of the adhesive layer can be set as required.
  • the reflective layer is obtained by vacuum non-conductive electroplating (NCVM), so that the reflective layer can not only impart color to the shell, but also improve the gloss and reflectivity of the shell.
  • NCVM vacuum non-conductive electroplating
  • the reflective layer formed on the adhesive layer can improve the reflective layer and adhesion.
  • the reflective layer is selected from at least an indium tin oxide layer, a titanium dioxide layer, a niobium dioxide layer, a niobium trioxide layer, a niobium dioxide layer, a niobium pentoxide layer, a silicon dioxide layer, and a zirconium dioxide layer.
  • the reflective layer may have a single-layer structure or a multilayer structure.
  • the total thickness of the reflective layer is 5 nanometers to 300 nanometers, that is, when the reflective layer is a single layer structure, the thickness of the reflective layer is 5 nanometers to 300 nanometers, and when the reflective layer is a multilayer structure, the multilayer The total thickness of the reflective layer is 5 nm to 300 nm. It can be understood that the thickness of the reflective layer is not limited to the above-mentioned thickness, and the thickness of the reflective layer can be set as required.
  • the ink layer is prepared by screen printing. Further, the ink layer is formed by multiple printings and multiple dryings, and multiple printings and multiple dryings are performed alternately. Each printing has a thickness of 5-8 microns.
  • the ink layer can be made more flat and relatively smooth through multiple printings. Reliable, if the thickness of a single printing is too thick, appearance quality problems such as bubbles may occur during baking.
  • the ink layer includes a white ink layer, a white ink layer or a gray ink layer. The ink layer can not only protect the reflective layer, but also provide the background color and shield the light. The internal structure and components of the product can be seen through the shell.
  • the thickness of the ink layer is 10 ⁇ m-20 ⁇ m. It can be understood that the thickness of the ink layer is not limited to the above-mentioned thickness, and the thickness of the ink layer can be set as required.
  • Step S14 The epoxy resin board is bent and formed.
  • the epoxy resin board with the decorative unit and the pattern layer is about to be bent and formed. After the epoxy resin board is bent and formed, the epoxy resin board has an inner concave surface and an outer convex surface opposite to the inner concave surface. Both the decoration unit and the pattern layer are located on the concave surface.
  • the method of bending and forming the epoxy resin board is high pressure forming.
  • High pressure molding refers to a process in which raw materials are processed and shaped under a pressure of more than 14 kg/cm, which is approximately 1.4 ⁇ 10 Pa.
  • the process parameters of high-pressure molding include: the temperature of the molding die is 90°C-150°C, the temperature of the heating plate is 150°C-300°C, the inflation pressure is 10Bar-30Bar, and the molding time is 60sec-150sec. Among them, the temperature of the molding die and the temperature of the heating plate must be appropriate and matched with each other. If the temperature is too high, the surface of the epoxy resin board (especially the convex surface) is easy to fold and foam. If the temperature is too low, it will cause the epoxy resin The board cracks, especially the curved part of the convex surface.
  • the method of bending and forming the epoxy resin board is hot pressing, and the step of hot pressing includes: first placing the epoxy resin board in the lower mold, and the temperature of the heating plate is 250°C-380°C. Heat 15 seconds-30 seconds under the condition of °C, and the lower mold temperature is 90°C-140°C; then close the upper mold and the lower mold, and hold the pressure for 10 seconds-30 seconds, the upper mold temperature is 90°C-130°C .
  • the temperature of the heating plate, the temperature of the upper mold, and the temperature of the lower mold must be appropriate and matched. If the temperature is too high, the epoxy resin board is easy to fold and foam (especially the convex surface). If the temperature is too low, it will cause ringing. The oxy resin board cracked, especially the curved part of the convex surface.
  • Step S15 forming a hardened layer on the convex surface of the epoxy resin board to obtain a shell.
  • the step of forming a hardened layer on the convex surface of the epoxy resin board includes: spraying a hardening solution on the convex surface of the epoxy resin board, and then baking at 60°C-80°C 3 Minutes to 10 minutes, and then irradiated with ultraviolet light to cure to obtain a hardened layer.
  • the main component liquid hardening resin is added a silicone acrylate and perfluorinated polyether urethane acrylate, e.g. PPG's 304 model hardening liquid; curing energy 400mj / cm 2 -1200mj / cm 2 .
  • the hardening liquid is not limited to the above-mentioned substances, and may be a hardening liquid commonly used in the art.
  • the hardened layer prepared by the above hardening liquid has good wear resistance and good scratch resistance.
  • the thickness of the hardened layer is 3 ⁇ m-20 ⁇ m. It can be understood that the thickness of the hardened layer can be adjusted as required.
  • the hardness of the hardened layer is 3H-5H. If the hardness is too small, the wear resistance and scratch resistance will be poor; if the hardness is too large, the hardened layer will become more brittle and reduce production efficiency.
  • the hardness of the hardened layer can be adjusted by adjusting the thickness and curing energy of the hardened layer.
  • the manufacturing method of the housing is not limited to the above steps, the hardened layer can be omitted, then step S15 can be omitted; the decoration unit is not limited to the above structure, for example, the decoration unit does not have an ink layer, that is, the ink layer can be omitted; Alternatively, the decoration unit does not have a reflective layer.
  • the ink layer is directly printed on the side of the adhesive layer away from the epoxy resin board.
  • the pattern layer can be omitted.
  • step S12 can be omitted.
  • a decorative unit is formed on one side of the epoxy resin board, and a transparent adhesive layer is formed on one side of the epoxy resin board.
  • the unit can only be an ink layer, and the ink layer can be directly printed on one side of the epoxy resin board.
  • the decoration unit can also be omitted, and step S13 is omitted in this case.
  • the shell can also be obtained by bending and molding only an epoxy resin plate, and the manufacturing method of the shell does not have steps S12, S13 and S15; or, the shell does not have a pattern layer.
  • the epoxy resin board also has at least one of a hardened layer and a decorative layer, that is, the manufacturing method of the housing does not have steps S12 and S15, or the manufacturing method of the housing does not have steps S12 and S13.
  • the epoxy resin board Since the above-mentioned epoxy resin board is prepared from the above-mentioned modified epoxy resin, the epoxy resin board has good tensile performance (tensile strength above 60MPa) and can be directly bent and formed; and the epoxy resin board The hardness can reach HB-H, it has good wear resistance and good scratch resistance, and the softening temperature is 110°C-130°C. It has good high temperature resistance, and also has good aging resistance and Impact resistance.
  • the current method of using epoxy resin injection molding to prepare one-piece unequal-thickness shells is prone to stress lines (cracks) during cold and hot shrinkage, making the corners or wakes prone to rainbow phenomenon, and it is likely to occur Inside the shell, it cannot be trimmed again, which has a greater impact on the appearance; in addition, the samples after injection need to be polished to get a better appearance. Therefore, compared to the above-mentioned epoxy resin injection molding method , The manufacturing method of the above-mentioned casing is formed by bending the epoxy resin plate, the epoxy resin plate after bending and molding does not require any process, and can also avoid the rainbow phenomenon. Therefore, the manufacturing method of the above-mentioned casing can simplify the manufacturing process, improve the yield, and reduce The production cost of the shell.
  • the housing 100 of the first embodiment can be produced by the manufacturing method of the housing of the first embodiment described above.
  • the housing 100 can be used as a housing of an electronic device, such as a tablet computer, a mobile phone, etc. It is the back cover of a mobile phone or tablet.
  • the housing 100 of the first embodiment includes an epoxy resin layer 110, a pattern layer 120, a decoration unit 130 and a hardened layer 140.
  • the material of the epoxy resin layer 110 is the above modified epoxy resin, which will not be repeated here.
  • the epoxy resin layer 110 is obtained by bending the above-mentioned epoxy resin board.
  • the epoxy resin layer 110 has a first surface 112 and a second surface 114 opposite to the first surface 112.
  • the first surface 112 is an inner concave surface
  • the second surface 114 is an outer convex surface.
  • the housing 100 is a back cover of a mobile phone, and the thickness of the epoxy resin layer 110 is 0.4 mm-0.8 mm. It can be understood that the thickness of the epoxy resin layer 110 can be adjusted as required.
  • the pattern layer 120 is disposed on the first surface 112.
  • the pattern of the pattern layer 120 may be, for example, a logo, a symbol, an animal pattern, and the like.
  • the material of the pattern layer 120 is mirror silver; the pattern silver is prepared by screen printing mirror silver ink.
  • the thickness of the pattern layer 120 is 1 ⁇ m-4 ⁇ m. It can be understood that the thickness of the pattern layer 120 can be set as required.
  • the decoration unit 130 is disposed on the first surface 112 of the epoxy resin layer 110 and covers the pattern layer 120. Specifically, in the illustrated embodiment, the decoration unit 130 includes an adhesive layer 132, a reflective layer 134, and an ink layer 136 stacked in sequence.
  • the adhesive layer 132 is a transparent material.
  • the adhesive layer 132 is disposed on the first surface 112 of the epoxy resin layer 110, and the adhesive layer 132 covers the pattern layer 120.
  • the adhesive layer 132 is a UV transfer layer with a texture pattern, so that the outer shell 100 has a texture appearance.
  • the adhesive layer 132 is a urethane acrylate glue layer.
  • Betteli New Material Co., Ltd.'s model is 633-75 UV glue. It can be understood that the adhesive layer 132 is not limited to the above-mentioned glue layer, and may also be a transparent glue that is commonly used in the art after curing; the adhesive layer 132 may not have a texture pattern. In this case, the housing 100 does not have a texture appearance.
  • the thickness of the adhesive layer 132 is 5 ⁇ m-20 ⁇ m. It can be understood that the thickness of the adhesive layer 132 is not limited to the above-mentioned thickness, and the thickness of the adhesive layer 132 can be set as required.
  • the reflective layer 134 is laminated on the side of the adhesive layer 132 away from the epoxy resin layer 110. Specifically, the reflective layer 134 is a vacuum non-conductive electroplated layer.
  • the reflective layer 134 is selected from the group consisting of an indium tin oxide layer, a titanium dioxide layer, a niobium dioxide layer, a niobium trioxide layer, a niobium dioxide layer, a niobium pentoxide layer, a silicon dioxide layer, and a zirconium dioxide layer. At least one. That is, the reflective layer 134 may have a single-layer structure or a multilayer structure.
  • the total thickness of the reflective layer 134 is 5 nanometers to 300 nanometers, that is, when the reflective layer 134 is a single layer structure, the thickness of the reflective layer 134 is 5 nanometers to 300 nanometers, and the reflective layer 134 has a multilayer structure. At this time, the total thickness of the multilayer reflective layer 134 is 5 nm to 300 nm. It can be understood that the thickness of the reflective layer 134 is not limited to the above-mentioned thickness, and the thickness of the reflective layer 134 can be set as required.
  • the ink layer 136 is laminated on the side of the reflective layer 134 away from the adhesive layer 132. Specifically, the ink layer 136 includes a white ink layer, a white ink layer, or a gray ink layer. The ink layer 136 can not only protect the reflective layer 134, but also provide a background color and shield light, and the internal structure and components of the product can be seen through the housing 100.
  • the thickness of the ink layer 136 is 10 ⁇ m-20 ⁇ m. It can be understood that the thickness of the ink layer 136 is not limited to the above-mentioned thickness, and the thickness of the ink layer 136 can be set as required.
  • the hardening layer 140 is disposed on the second surface 114 of the epoxy resin layer 110.
  • the hardened layer 140 can increase the wear resistance and scratch resistance of the housing 100.
  • the hardening layer 140 is prepared from hardening liquid, and the main components of the hardening liquid are urethane acrylate, silicone resin and perfluoropolyether acrylate, such as PPG304 hardening liquid. It can be understood that the hardening liquid is not limited to the above-mentioned substances, and may be a hardening liquid commonly used in the art.
  • the hardened layer 140 prepared by the above hardening liquid has good wear resistance and good scratch resistance.
  • the hardness of the hardened layer 140 is 3H-5H. If the hardness is too small, the wear resistance and scratch resistance will be poor; if the hardness is too large, the hardened layer 140 will become more brittle and reduce production efficiency.
  • the thickness of the hardened layer 140 is 3 ⁇ m-20 ⁇ m. It can be understood that the thickness of the hardened layer 140 can be adjusted as required.
  • the structure of the housing 100 is not limited to a structure.
  • the hardened layer 140 may be omitted.
  • the second surface 114 of the epoxy resin layer 110 is the outer surface of the housing 100.
  • the pattern layer 120 may also be omitted, and the decoration unit 130 is directly laminated on the first surface 112 of the epoxy resin layer 110.
  • the decoration unit 130 is not limited to the above structure.
  • the adhesive layer 132 of the decoration unit 130 can be replaced with other coatings that can facilitate the adhesion of the reflective layer 134, such as spraying a semi-transparent color layer, inkjet printing to achieve a semi-transparent color; or
  • the decoration unit 130 does not have the ink layer 136, that is, the reflective layer 134 of the decoration unit 130 does not have the ink layer 136 on the side away from the adhesive layer 132; or, the decoration unit 130 does not have the adhesive layer 132 and the reflective layer 134 at the same time.
  • the layer 136 is directly disposed on the first surface 112 of the epoxy resin layer 110; or, the decoration unit 130 does not have the reflective layer 134, and the ink layer 136 is directly laminated on the side of the adhesive layer 132 away from the epoxy resin layer 110.
  • the decoration unit 130 can also be omitted.
  • a protective layer can be provided on the first surface 112 of the epoxy resin layer 110, and the protective layer covers the pattern layer 120 to protect the pattern layer 120.
  • the protective layer can be a UV glue layer.
  • the decoration unit 130, the pattern layer 120, and the hardened layer 140 may also be omitted at the same time.
  • the housing 100 may only have the epoxy resin layer 110.
  • the aforementioned housing 100 has at least the following advantages:
  • the housing 100 includes the epoxy resin layer 110 of the above material, the epoxy resin layer 110 has better wear resistance and better scratch resistance, and also has better high temperature resistance, aging resistance and resistance The impact performance makes the aforementioned housing 100 not only have better performance, but also help reduce its cost.
  • the second embodiment of the manufacturing method of the housing, the housing manufactured by this method can be used as the housing of an electronic device, for example, a housing of a tablet computer, a mobile phone, etc., especially a back cover of a mobile phone or a tablet computer.
  • the manufacturing method of the housing of this embodiment includes the following steps S21-S26:
  • Step S21 preparing an epoxy resin board.
  • step S11 The steps of preparing the epoxy resin board in this embodiment are the same as step S11, and will not be repeated here.
  • Step S22 forming a pattern layer on one side of the epoxy resin board.
  • the method for forming a patterned layer in this embodiment is the same as that for forming a patterned layer in step S12 of the first embodiment, and will not be repeated here.
  • Step S23 forming a protective layer on the side of the epoxy resin board where the pattern layer is formed, and the protective layer covers the pattern layer.
  • the protective layer is a UV glue layer.
  • the protective layer is a polyurethane acrylate glue layer.
  • Betteli New Material Co., Ltd.'s model is 633-75 UV glue. It can be understood that the protective layer is not limited to the above-mentioned glue layer.
  • the thickness of the protective layer is 8-20 microns. It can be understood that the thickness of the protective layer is not limited to the above-mentioned thickness, and the thickness of the protective layer can be set as required.
  • Step S24 setting a decoration unit on the side of the protective layer away from the epoxy resin board.
  • the step of arranging a decorative unit on the side of the protective layer away from the epoxy resin board includes: forming a transparent adhesive layer on the base film, forming a reflective layer on the adhesive layer, and forming an ink layer on the reflective layer to obtain Decoration unit; bonding the side of the base film of the decoration unit away from the adhesive layer with the side of the protective layer away from the epoxy resin board.
  • the base film is a polycarbonate (PC) film or a TPU film. It can be understood that the base film is not limited to the above base film, and the base film may be a transparent base film commonly used in the art. Specifically, the thickness of the base film is 50 micrometers to 125 micrometers. It can be understood that the thickness of the base film is not limited to the above-mentioned thickness, and the thickness of the base film can be set as required.
  • the manufacturing method of the bonding layer is similar to the manufacturing method of the bonding layer of the first embodiment, except that the bonding layer of this embodiment is manufactured on the base film, which will not be repeated here.
  • the manufacturing method of the reflective layer is the same as the manufacturing method of the reflective layer of the first embodiment, and will not be repeated here.
  • the manufacturing method of the ink layer is the same as the manufacturing method of the ink layer of the first embodiment, and will not be repeated here.
  • the step of bonding the side of the base film of the decoration unit away from the adhesive layer and the side of the protective layer away from the epoxy resin board includes: using a UV adhesive to move the base film away from the side of the adhesive layer to the protective layer.
  • the side of the layer away from the epoxy board is bonded.
  • the UV adhesive is Bethel 805-16 glue.
  • Step S25 bending the epoxy resin board into shape.
  • the epoxy resin board with the protective layer, pattern layer and decoration unit will be bent and formed. Specifically, the method of bending the epoxy resin board in this embodiment is the same as that in the first embodiment, and will not be repeated here.
  • Step S26 forming a hardened layer on the convex surface of the epoxy resin board to obtain a shell.
  • the step of forming the hardened layer of this embodiment is the same as the step of forming the hardened layer of the first embodiment, and will not be repeated here.
  • the manufacturing method of the casing of this embodiment is not limited to the above steps.
  • This embodiment is also similar to the manufacturing method of the casing of the first embodiment, and the production of the hardened layer in step S26 can be omitted; step S22 and steps S23 can be omitted, that is, the pattern layer and the protective layer are not made, and the decoration unit is directly adhered to the epoxy resin board through the UV adhesive; or, step S23 is omitted, that is, the protective layer is not made, and the decoration unit is directly adhered through the UV adhesive. Adhere to the epoxy resin board and cover the pattern layer.
  • the decoration unit can also be made as required, for example, the ink layer is omitted, and so on.
  • the manufacturing method of the housing of this embodiment is similar to the manufacturing method of the housing of the first embodiment, it also has the effect similar to the manufacturing method of the housing of the first embodiment, which will not be repeated here.
  • the housing 200 of the second embodiment can be produced by the manufacturing method of the housing of the second embodiment described above.
  • the housing 200 can be used as a housing of an electronic device, such as a tablet computer, a mobile phone, etc. It is the back cover of a mobile phone or tablet.
  • the structure of the housing 200 of this embodiment is similar to the structure of the housing 100 of the first embodiment, with the following differences:
  • the housing 200 further includes a protective layer 250 disposed on the first surface 212 of the epoxy resin layer 210 and covering the pattern layer 220.
  • the first surface 212 is a concave surface.
  • the protective layer 250 is a UV glue layer.
  • the protective layer 250 is a urethane acrylate glue layer.
  • Betteli New Material Co., Ltd.'s model is 633-75 UV glue. It can be understood that the protective layer 250 is not limited to the aforementioned glue layer.
  • the decoration unit 230 further includes a base film 238, which is disposed on the first surface 212
  • the housing 200 further includes an adhesive layer 260, which is disposed between the base film 238 and the first surface 212, and the adhesive layer 260 fixes and bonds the base film 238 and the first surface 212.
  • the side of the adhesive layer 232 away from the reflective layer 234 and the side of the base film 238 away from the first surface 212 are laminated, that is, the adhesive layer 232, the reflective layer 234, and the ink layer 236 are sequentially formed on the base film 238.
  • the base film 238 is a polycarbonate (PC) film or a TPU film. It can be understood that the base film 238 is not limited to the above-mentioned base film 238, and the base film 238 may be a transparent base film commonly used in the art.
  • PC polycarbonate
  • TPU TPU
  • the material of the adhesive layer 260 is a UV adhesive
  • the UV adhesive is a UV glue with a model of 805-16 from Bethel New Material Co., Ltd.
  • the housing 200 of the second embodiment Since the structure of the housing 200 of the second embodiment is similar to the structure of the housing 100 of the first embodiment, the housing 200 of the second embodiment also has similar effects to the housing 100 of the first embodiment, which will not be repeated here.
  • the manufacturing method of the housing of the third embodiment can be used as the housing of an electronic device, for example, a housing of a tablet computer, a mobile phone, etc., especially a back cover of a mobile phone or a tablet computer.
  • the manufacturing method of the housing of this embodiment includes the following steps S31-S35:
  • Step S31 preparing an epoxy resin board.
  • step S11 The steps of preparing the epoxy resin board in this embodiment are the same as step S11, and will not be repeated here.
  • Step S32 forming a pattern layer on one side of the epoxy resin board.
  • the method of forming a patterned layer in this embodiment is similar to that of forming a patterned layer in step S12 of the first embodiment, and will not be repeated here.
  • Step S33 The epoxy resin board is bent and formed.
  • the epoxy resin board with the patterned layer is about to be bent and molded. Specifically, the method of bending the epoxy resin board in this embodiment is the same as that in the first embodiment, and will not be repeated here.
  • Step S34 setting a decoration unit on the concave surface of the epoxy resin.
  • the step of providing a decorative layer on the concave surface of the epoxy resin is after the step of bending the epoxy resin board.
  • the step of arranging a decorative unit on the concave surface of the epoxy resin includes: forming a transparent adhesive layer on the base film, forming a reflective layer on the adhesive layer, and forming an ink layer on the reflective layer to obtain the decorative unit ; Bond the side of the base film of the decoration unit away from the adhesive layer with the concave surface of the epoxy resin board.
  • the step of forming the decoration unit can be before or at the same time as step S33, that is, the decoration unit can be made in step S33 or at the same time as step S33, and then the base film of the decoration unit can be connected to the epoxy resin board on the side away from the adhesive layer.
  • the concave surface is bonded.
  • the base film is a polycarbonate film or a TPU film. It can be understood that the base film is not limited to the above base film, and the base film may be a transparent base film commonly used in the art.
  • the manufacturing method of the bonding layer is similar to the manufacturing method of the bonding layer of the first embodiment, except that the bonding layer of this embodiment is manufactured on the base film, which will not be repeated here.
  • the manufacturing method of the reflective layer is the same as the manufacturing method of the reflective layer of the first embodiment, and will not be repeated here.
  • the manufacturing method of the ink layer is the same as the manufacturing method of the ink layer of the first embodiment, and will not be repeated here.
  • the step of bonding the side of the base film of the decoration unit away from the adhesive layer to the concave surface of the epoxy resin board includes: using an adhesive to connect the side of the base film away from the adhesive layer to the epoxy resin board.
  • the concave surface is bonded.
  • the adhesive is a thermosetting adhesive or a UV adhesive.
  • the thermosetting adhesive is OCA glue, such as OCA glue from Aojia Optoelectronics; the UV adhesive is UV glue with the model of 805-16 from Bethel New Material Co., Ltd.
  • Step S35 forming a hardened layer on the convex surface of the epoxy resin board to obtain a shell.
  • the step of forming the hardened layer of this embodiment is the same as the step of forming the hardened layer of the first embodiment, and will not be repeated here.
  • the manufacturing method of the casing of this embodiment is not limited to the above steps. In this embodiment, it is also similar to the manufacturing method of the casing of the first embodiment.
  • the production of the hardened layer in step S35 can be omitted; step S32 It can be omitted.
  • step S32 It can be omitted.
  • no pattern layer is made, and the side of the base film of the decoration unit away from the adhesive layer is bonded to the concave surface of the epoxy resin board, that is, the decoration unit is directly adhered to the ring through the UV adhesive.
  • the decoration unit can also be made as required, for example, the ink layer is omitted, and so on.
  • the manufacturing method of the housing of this embodiment is similar to the manufacturing method of the housing of the first embodiment, it also has the effect similar to the manufacturing method of the housing of the first embodiment, which will not be repeated here. Since the bending step of the manufacturing method of the housing of the third embodiment is before the decoration unit is set, the glue of the manufacturing method of the housing of this embodiment to set the decoration unit to the epoxy resin board can not only use UV adhesive, but also Use thermosetting adhesive.
  • the housing 300 of the third embodiment can be manufactured by the manufacturing method of the housing of the third embodiment described above.
  • the housing 300 can be used as a housing of an electronic device, such as a tablet computer, a mobile phone, etc. It is the back cover of a mobile phone or tablet.
  • the structure of the housing 300 of this embodiment is similar to the structure of the housing 100 of the first embodiment, with the following differences:
  • the decoration unit 330 further includes a base film 338, which is disposed on the concave surface 312 of the epoxy resin layer 310, and the housing 300 further includes an adhesive layer 350, which is disposed between the base film 338 and the concave surface 312.
  • the adhesive layer 350 fixes and bonds the base film 338 and the concave surface 312, and the side of the adhesive layer 332 away from the reflective layer is laminated with the concave surface 312 of the epoxy resin layer 310, that is, the adhesive layer 332, the reflective layer 334 and the ink layer 336 are sequentially formed on the base film 338.
  • the base film 338 is a PC film or a TPU film. It can be understood that the base film 338 is not limited to the aforementioned base film, and the base film 338 may be a transparent base film commonly used in the art.
  • the material of the adhesive layer 360 is UV adhesive or thermosetting adhesive.
  • the UV adhesive is, for example, a UV model of 805-16 from Bethel New Material Co., Ltd.
  • the thermosetting adhesive is OCA glue, such as OCA glue of Aojia Optoelectronics.
  • the housing 300 of the third embodiment Since the structure of the housing 300 of the third embodiment is similar to the structure of the housing 100 of the first embodiment, the housing 300 of the third embodiment also has similar effects to the housing 100 of the first embodiment, which will not be repeated here.
  • An electronic device of an embodiment for example, a tablet computer, a mobile phone, etc., includes a casing, wherein the outer casing is the casing produced by the method of manufacturing the casing of the first embodiment, the casing of the first embodiment, and the casing of the second embodiment The shell produced by the manufacturing method, the shell of the second embodiment, the shell of the third embodiment, or the shell of the third embodiment.
  • the electronic device is a mobile phone or a tablet computer
  • the housing is a back cover.
  • the above-mentioned electronic device adopts the housing produced by the housing manufacturing method of the first embodiment, the housing of the first embodiment, the housing produced by the housing of the second embodiment, the housing of the second embodiment, and the third embodiment
  • the housing produced by the method of manufacturing the housing or the housing of the third embodiment is beneficial to increase the service life of the electronic device and reduce the production cost of the electronic device.
  • housing is not limited to the housing of the electronic device, and may also be the housing of other products.
  • the preparation methods of modified epoxy resin as an example to illustrate the preparation of modified epoxy resin, but the preparation method of modified epoxy resin of the present invention does not It is not limited to the following steps and the following materials, that is, the technical solution of the present invention is not limited to the following examples.
  • the catalyst adopts dibutyltin dilaurate
  • the curing agent adopts dicyandiamide
  • the polyurethane prepolymer adopts the United States.
  • Dow's MDI polyurethane prepolymer with the model number N434 is an example and does not limit the scope of the present invention):
  • modified epoxy resin According to Table 1, according to the mass ratio of modified product and epoxy resin as A:B, the modified product, epoxy resin and catalyst were stirred and mixed for t 1 hour at room temperature, then Add the curing agent and stir uniformly, and then react at T 1 °C for t 2 hours to obtain a modified epoxy resin.
  • the mass ratio of the catalyst to the epoxy resin is C:B
  • the mass ratio of the curing agent to the epoxy resin is D:B
  • the catalyst is dibutyltin dilaurate
  • the curing agent is dicyandiamide.
  • E-51, E-55 and E-44 represent E-51 epoxy resin, E-55 epoxy resin and E-44 epoxy resin respectively, and this The ":" in the column indicates the mass ratio.
  • E-51:E-44 means that the epoxy resin of this example is composed of E-51 epoxy resin and E-44 epoxy resin, and E-51:E The ratio indicated by -44 is mass ratio.
  • Example 1 0.33 122 168 0.6
  • Example 2 0.32 115 165 0.4
  • Example 3 0.34 124 170 0.8
  • Example 4 0.33 120 155 0.5
  • Example 5 0.32 121 148 0.7
  • Example 6 0.36 126 142 0.6
  • Example 7 0.33 123 170 0.4
  • Example 8 0.31 109 150 0.8 Example 9 0.37 127 180 0.6
  • Example 10 0.34 124 177 0.5
  • Example 11 0.32 116 155 0.7
  • Example 12 0.33 120 160 0.4
  • Example 13 0.36 125 158 0.6
  • Example 14 0.45 130 190 0.8
  • Example 15 0.25 100 140 0.7
  • Example 16 0.42 128 174 0.6
  • Example 17 0.45 129 188 0.4
  • Example 18 0.36 125 172 0.5
  • Example 19 0.38 128 181 0.7
  • Example 20 0.43 120 155 0.6
  • Example 21 0.35 124 178 0.6 Comparative example 1 0.24 100 140 0.6 Comparative example 2 0.46 130 190 0.6 Comparative example 3 0.33 122 168 0.6 Comparative example 4 0.33 122 168 0.6 Comparative example 5 0.35 125 180 0.6
  • Comparative Example 5 is a conventional 3240 epoxy resin board with a thickness of 0.6 mm and an epoxy value of 0.35.
  • Comparative Example 6 is a conventional composite substrate of polycarbonate (PC) and polymethyl methacrylate (PMMA), with a total thickness of 0.6 mm.
  • Comparative Example 7 is a conventional pure polycarbonate (PC) board with a thickness of 0.6 mm.
  • Comparative Example 8 is a conventional polyethylene terephthalate (PET) board with a thickness of 0.6 mm.
  • Hot press bending test the epoxy resin board of Example 1-21 and Comparative Example 1-4, the 3240 epoxy resin board of Comparative Example 5, the composite substrate of Comparative Example 6 and the pure polycarbonate of Comparative Example 7
  • the ester board and the polyethylene terephthalate board of Comparative Example 8 are used as the template to be bent by hot pressing.
  • the specific steps are: first place the template in the lower mold and set the heating plate temperature to 300°C.
  • the optical transmittance of the epoxy resin board of Example 1-21 is 83%-88%, which has a relatively high optical transmittance, and the epoxy resin board of Example 1-21
  • the tensile strength is at least 60MPa, the tensile strength is better, the hardness is HB-H, and the hardness is greater, so that it has better wear resistance, better scratch resistance, and
  • the above epoxy resin board does not turn yellow under ultraviolet light for 48H, and has good aging resistance. Its performance is equivalent to that of the composite substrate of Comparative Example 6. It can be used as a shell, thereby providing a new material for the manufacture of the shell. .
  • the epoxy resin board of Examples 1-21 can be bent into a predetermined shape after hot press bending and high pressure bending molding without cracks. It can be directly formed by bending, which simplifies the production process, improves the yield, and reduces The production cost of the shell.
  • the epoxy resin board of Comparative Example 1 not only has low tensile strength, but also has low hardness. It turns yellow slightly after 48H of ultraviolet radiation and cannot be bent into a predetermined shape; the epoxy resin of Comparative Example 2 and Comparative Example 3 Although the resin board has greater hardness, its tensile strength is low, and there will be cracks after the bending test, so it cannot be directly bent into shape; although the epoxy resin board of Comparative Example 4 has greater tensile strength, But the hardness is too low; although the epoxy resin board of Comparative Example 5 has greater hardness and better tensile strength, it is severely yellowed after 48 hours of ultraviolet radiation, and there are cracks on the surface after bending and forming, and it cannot be bent directly.
  • the hardness of the pure polycarbonate plate of Comparative Example 7 is too low, and the wear resistance and scratch resistance are too poor; the tensile strength of the polyethylene terephthalate plate of Comparative Example 8 is too large, and the curvature after bending Smaller, it cannot be bent into a predetermined shape, and it is more difficult to make a shell with a predetermined arc.
  • the epoxy resin board produced in Example 1 was subjected to high-pressure molding to bend the epoxy resin board, and then CNC processing was performed to mill off the excess leftover material to obtain a shell.
  • the process parameters of high-pressure molding include: the temperature of the molding die is 120°C, the temperature of the heating plate is 200°C, the inflation pressure is 20 Bar, and the molding time is 100 seconds.
  • the epoxy resin board produced in Example 4 was subjected to high-pressure molding to bend the epoxy resin board, and then CNC processing was performed to mill out the excess scrap to obtain the shell.
  • the process parameters of high-pressure molding include: the temperature of the molding die is 90°C, the temperature of the heating plate is 300°C, the inflation pressure is 10 Bar, and the molding time is 60 seconds.
  • the epoxy resin board produced in Example 7 was subjected to high-pressure molding to bend the epoxy resin board, and then CNC processing was performed to mill out the excess leftover material to obtain the shell.
  • the process parameters of high-pressure molding include: the temperature of the molding die is 150°C, the temperature of the heating plate is 150°C, the inflation pressure is 30 Bar, and the molding time is 150 seconds.
  • the epoxy resin board produced in Example 2 was subjected to thermocompression molding to bend the epoxy resin board, and then CNC processing was performed to mill out the excess leftover material to obtain the shell.
  • the step of hot pressing is as follows: first put the epoxy resin board in the lower mold, heat it for 25 seconds under the condition that the temperature of the heating plate is 320°C, and the temperature of the lower mold is 120°C, remove the heating plate , And then close the upper film and the lower mold, and hold the pressure for 20 seconds, the upper mold temperature is 110 °C.
  • the epoxy resin board produced in Example 5 was subjected to thermo-compression molding to bend the epoxy resin board, and then CNC processing was performed to mill off excess leftover material to obtain a shell.
  • the step of hot pressing is as follows: first put the epoxy resin board in the lower mold, heat for 30 seconds under the condition that the temperature of the heating plate is 250°C, and the temperature of the lower mold is 140°C, remove the heating plate , And then close the upper film and the lower mold, and hold the pressure for 30 seconds, the upper mold temperature is 130 °C.
  • the epoxy resin board produced in Example 8 was subjected to thermocompression molding to bend the epoxy resin board, and then CNC processing was performed to mill out the excess leftover material to obtain the shell.
  • the step of hot pressing is as follows: first put the epoxy resin board in the lower mold, heat it for 15 seconds under the condition of the temperature of the heating plate is 380°C, and the temperature of the lower mold is 90°C, remove the heating plate , And then close the upper film and the lower mold, and hold the pressure for 10 seconds, the upper mold temperature is 90 °C.
  • UV glue Bity New Material Co., Ltd., Model 633-75
  • the layer covers the pattern layer; on the side of the adhesive layer away from the epoxy resin board, vacuum non-conductive electroplating forms a reflective layer with a thickness of 15 nanometers, the reflective layer is an indium tin oxide layer; on the side of the indium tin oxide layer away from the adhesive layer Print black ink to form an ink layer with a thickness of 15 microns to form a decorative unit.
  • step (3) The epoxy resin board with the decoration unit formed in step (2) is subjected to high pressure molding to bend the epoxy resin board.
  • the process parameters of high-pressure molding include: the temperature of the molding die is 140°C, the temperature of the heating plate is 250°C, the inflation pressure is 15 Bar, and the molding time is 120 seconds.
  • UV glue Bity New Material Co., Ltd., model 633-75
  • the layer covers the pattern layer; on the side of the adhesive layer away from the epoxy resin board, vacuum non-conductive electroplating forms a reflective layer with a thickness of 50 nanometers, the reflective layer is a niobium dioxide layer; on the side of the niobium dioxide layer away from the adhesive layer Print black ink to form an ink layer with a thickness of 20 microns to form a decorative unit.
  • step (3) The epoxy resin board with the decoration unit formed in step (2) is subjected to high pressure molding to bend the epoxy resin board.
  • the process parameters of high-pressure molding include: the temperature of the molding die is 100°C, the temperature of the heating plate is 280°C, the inflation pressure is 200 Bar, and the molding time is 80 seconds.
  • step (3) The epoxy resin board with the decoration unit formed in step (2) is subjected to high pressure molding to bend the epoxy resin board.
  • the process parameters of high-pressure molding include: the temperature of the molding die is 90°C, the temperature of the heating plate is 200°C, the inflation pressure is 30Bar, and the molding time is 150 seconds.
  • the difference is that the preparation process of the reflective layer is different: vacuum non-conductive electroplating is formed on the side of the adhesive layer away from the epoxy resin board to form niobium pentoxide with a thickness of 50 nm Layer, and then a silicon dioxide layer with a thickness of 50 nm is formed on the niobium pentoxide layer. The ink layer is formed on the side of the silicon dioxide layer away from the niobium pentoxide layer.
  • step (3) The epoxy resin board with the decorative unit formed in step (2) is subjected to thermo-compression molding to bend the epoxy resin board.
  • step of hot press molding is: first place the epoxy resin board in the lower mold, heat it for 18 seconds under the condition that the temperature of the heating plate is 300°C, and the temperature of the lower mold is 100°C, remove the heating plate , And then close the upper film and the lower mold, and hold the pressure for 30 seconds, the upper mold temperature is 130 °C.
  • step (1) of Example 29 is similar to step (1) of Example 29, except that the epoxy resin board used is the epoxy resin board prepared in Example 13.
  • the difference is that the preparation process of the reflective layer is different: vacuum non-conductive electroplating is formed on the side of the adhesive layer away from the epoxy resin board to form a thickness of 40 nanometers of niobium pentoxide Layer, then vacuum non-conductive electroplating on the niobium pentoxide layer to form a silicon dioxide layer with a thickness of 60 nanometers, and then vacuum non-conductive electroplating on the side of the silicon dioxide layer away from the niobium pentoxide layer to form a thickness of 70 nanometers Zirconium dioxide layer.
  • the ink layer is formed on the side of the zirconium dioxide layer away from the silicon dioxide layer.
  • step (3) The epoxy resin board with the decorative unit formed in step (2) is subjected to thermo-compression molding to bend the epoxy resin board.
  • step of hot pressing is as follows: first put the epoxy resin board in the lower mold, heat it for 20 seconds under the condition that the temperature of the heating plate is 350°C, and the lower mold temperature is 110°C, remove the heating plate , Then the upper film and the lower mold are closed, and the pressure is kept for 20 seconds, and the upper mold temperature is 110°C.
  • UV glue (Bettery New Material Co., Ltd., Model 633-75) to transfer the base film to form an adhesive layer with texture and thickness of 8 microns.
  • the adhesive layer is far from the epoxy resin board.
  • the side vacuum non-conductive electroplating forms a reflective layer with a thickness of 80 nanometers, and the reflective layer is a niobium dioxide layer; black ink is printed on the side of the niobium dioxide layer away from the bonding layer to form an ink layer with a thickness of 18 microns.
  • To form a decorative unit use the UV adhesive on the side of the base film of the decorative unit away from the adhesive layer and the side of the protective layer away from the epoxy resin board (Better New Material Co., Ltd. model is 805-16 UV Glue) bonding.
  • the base film is a polycarbonate film with a thickness of 50 microns.
  • the epoxy resin board provided with the decoration unit in step (3) is subjected to high pressure molding to bend the epoxy resin board.
  • the process parameters of high-pressure molding include: the temperature of the molding die is 150°C, the temperature of the heating plate is 250°C, the inflation pressure is 20 Bar, and the molding time is 120 seconds.
  • UV glue (Bettery New Material Co., Ltd., Model 633-75) to transfer the base film to form an adhesive layer with a texture and a thickness of 12 microns.
  • the adhesive layer is far from the epoxy resin board.
  • Side vacuum non-conductive electroplating forms a reflective layer with a thickness of 200 nanometers, and the reflective layer is a niobium dioxide layer; black ink is printed on the side of the indium tin oxide layer away from the adhesive layer to form an ink layer with a thickness of 12 microns to form Decoration unit; use UV adhesive on the side of the base film of the decoration unit away from the adhesive layer and the side of the protective layer away from the epoxy resin board (Better New Material Co., Ltd.'s model is 805-16 UV glue) Bonding.
  • the base film is a polycarbonate film with a thickness of 100 microns.
  • the epoxy resin board provided with the decoration unit in step (3) is subjected to high pressure molding to bend the epoxy resin board.
  • the process parameters of high-pressure molding include: the temperature of the molding die is 90°C, the temperature of the heating plate is 300°C, the inflation pressure is 15 Bar, and the molding time is 60 seconds.
  • step (1) of Example 33 the difference is that the epoxy resin board is the epoxy resin board prepared in Example 4.
  • step (3) It is similar to step (3) of Embodiment 33, except that the light reflecting layer is a zirconium dioxide layer with a thickness of 20 nanometers.
  • step (3) The epoxy resin board provided with the decoration unit in step (3) is subjected to thermocompression molding to bend the epoxy resin board.
  • step of hot press molding is: first put the epoxy resin board in the lower mold, heat it for 28 seconds under the condition of the temperature of the heating plate is 280°C, and the temperature of the lower mold is 90°C, remove the heating plate , Then the upper film and the lower mold are closed, and the pressure is maintained for 30 seconds, and the upper mold temperature is 90°C.
  • step (1) of Example 34 the difference is that the epoxy resin board is the epoxy resin board prepared in Example 18.
  • step (3) It is similar to step (3) of embodiment 34, except that the reflective layer is a niobium pentoxide layer with a thickness of 100 nm.
  • the epoxy resin board provided with the decoration unit in step (3) is subjected to thermocompression molding to bend the epoxy resin board.
  • the step of hot press molding is: first put the epoxy resin board in the lower mold, heat it for 20 seconds under the condition of the temperature of the heating plate at 370°C, and the temperature of the lower mould is 120°C, remove the heating plate, and then Clamp the upper film and the lower mold, and hold the pressure for 15 seconds.
  • the upper mold temperature is 120°C.
  • the epoxy resin board forming the pattern layer is subjected to high pressure molding to bend the epoxy resin board.
  • the process parameters of high-pressure molding include: the temperature of the molding die is 100°C, the temperature of the heating plate is 180°C, the inflation pressure is 15 Bar, and the molding time is 120 seconds.
  • UV glue (Bettery New Material Co., Ltd., Model 633-75) to transfer the base film to form an adhesive layer with a texture and a thickness of 16 microns.
  • the adhesive layer is far from the epoxy resin board.
  • Side vacuum non-conductive electroplating forms a reflective layer with a thickness of 120 nanometers, and the reflective layer is an indium tin oxide layer; black ink is printed on the side of the indium tin oxide layer away from the adhesive layer to form an ink layer with a thickness of 15 microns to form a decoration Unit;
  • the side of the base film of the decorative unit away from the adhesive layer and the concave surface of the epoxy resin board are bonded with OCA glue (OCA glue from Aojia Optoelectronics), and the decorative unit covers the pattern layer.
  • the base film is a TPU film with a thickness of 125 microns.
  • the epoxy resin board forming the pattern layer is subjected to high pressure molding to bend the epoxy resin board.
  • the process parameters of high-pressure molding include: the temperature of the molding die is 120°C, the temperature of the heating plate is 200°C, the inflation pressure is 10 Bar, and the molding time is 150 seconds.
  • the adhesive layer is far from the epoxy resin board.
  • the side vacuum non-conductive electroplating forms a reflective layer with a thickness of 30 nanometers, and the reflective layer is a silicon dioxide layer; black ink is printed on the side of the silicon dioxide layer away from the adhesive layer to form an ink layer with a thickness of 10 microns to form a decoration Unit;
  • the side of the base film of the decorative unit away from the adhesive layer and the concave surface of the epoxy resin board are bonded with OCA glue (OCA glue from Aojia Optoelectronics), and the decorative unit covers the pattern layer.
  • the base film is a TPU film with a thickness of 75 microns.
  • the epoxy resin board forming the pattern layer is thermocompressed to bend the epoxy resin board.
  • the steps of hot press molding are: first place the epoxy resin board in the lower mold, heat it for 15 seconds under the condition of the temperature of the heating plate at 280°C and the temperature of the lower mold at 140°C, remove the heating plate, and then Clamp the upper film and the lower mold, and hold the pressure for 130 seconds.
  • the temperature of the upper mold is 130°C.
  • step (1) of embodiment 38 the difference is that the epoxy resin board of this embodiment is the epoxy resin board prepared in embodiment 16.
  • the epoxy resin board forming the pattern layer is thermocompressed to bend the epoxy resin board.
  • the step of hot press molding is: first place the epoxy resin board in the lower mold, heat it for 30 seconds under the condition of the temperature of the heating plate at 300°C, and the temperature of the lower mold is 90°C, remove the heating plate, and then Clamp the upper film and the lower mold, and hold the pressure for 10 seconds.
  • the temperature of the upper mold is 90°C.
  • the manufacturing process of the casing of this embodiment is similar to that of Embodiment 23, except that the temperature of the heating plate is 310°C.
  • the manufacturing process of the housing of this embodiment is similar to that of Embodiment 24, except that the temperature of the molding die is 80°C.
  • the manufacturing process of the shell of this embodiment is similar to that of Embodiment 24, except that the temperature of the heating plate is 140°C.
  • the manufacturing process of the housing of this embodiment is similar to that of Embodiment 26, except that the temperature of the heating plate is 240°C.
  • the manufacturing process of the shell of this embodiment is similar to that of Embodiment 27, except that the temperature of the heating plate is 390°C.
  • the epoxy resin layer of the shell of Examples 22-40 has no cracks and is bent into a predetermined bending arc, while the surface of the epoxy resin layer of Example 41 and Example 45 is blistered.
  • the reason is that the heating temperature is too high.
  • the epoxy resin layer of Example 42 and Example 43 is not bent into a predetermined bending arc because the temperature of the molding die or heating plate is too low, resulting in insufficient molding temperature.
  • the epoxy resin of Example 44 The cracking of the layer occurs because the temperature of the heating plate is too low, which causes the epoxy resin layer to crack during the clamping and holding pressure process, resulting in cracks.

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Abstract

一种外壳及其制作方法、改性环氧树脂、环氧树脂板和电子设备。改性环氧树脂的环氧值为0.25-0.45，改性环氧树脂为改性物改性的环氧树脂，改性物选自有机硅、聚氨酯预聚体及聚酰亚胺中的至少一种，且改性物与环氧树脂的质量比为1∶5-1∶10。

Description

外壳及其制作方法、改性环氧树脂、环氧树脂板和电子设备 技术领域
本发明涉及电子设备技术领域，特别是涉及一种外壳及其制作方法、改性环氧树脂、环氧树脂板和电子设备。
背景技术
目前，电子设备(例如手机)的外壳的材质通常采用PC(聚碳酸酯)和PMMA(聚甲基丙烯酸甲酯)制作成的复合板材、纯PC板材等，然而，复合板材的抗拉伸性能较差，若采用弯曲成型，在弯曲过程中受到拉伸容易开裂，而纯PC板材虽然具备较好的抗拉伸性能，能够在一定程度上解决复合板材成型拉伸过程中的开裂问题，但是PC板材的硬度较低，导致其耐磨性能和抗划伤性能均较差，影响消费者的体验。
由于PET(聚对苯二甲酸乙二酯)板材具有较好的耐磨性能和抗划伤性能，目前有些终端公司也尝试采用PET板材制作电子设备的壳体，但是PET板材在弯曲成型过程中容易翘曲，限制了其在后盖上的应用。
发明内容
基于此，有必要提供一种外壳及其制作方法、改性环氧树脂、环氧树脂板和电子设备。
一种改性环氧树脂，所述改性环氧树脂的环氧值为0.25-0.45，所述改性环氧树脂为改性物改性的环氧树脂，所述改性物选自有机硅、聚氨酯预聚体及聚酰亚胺中的至少一种，且所述改性物与所述环氧树脂的质量比为1:5-1:10。
一种环氧树脂板，所述环氧树脂板的材料为改性环氧树脂，所述改性环氧树脂的环氧值为0.25-0.45，所述改性环氧树脂为改性物改性的环氧树脂，所述改性物选自有机硅、聚氨酯预聚体及聚酰亚胺中的至少一种，且所述改性物与所述环氧树脂的质量比为1:5-1:10。
一种外壳，包括环氧树脂层，所述环氧树脂层的材料为改性环氧树脂，所述改性环氧树脂的环氧值为0.25-0.45，所述改性环氧树脂为改性物改性的环氧树脂，所述改性物选自有机硅、聚氨酯预聚体及聚酰亚胺中的至少一种，且所述改性物与所述环氧树脂的质量比为1:5-1:10。
一种外壳的制作方法，包括如下步骤：
制备环氧树脂板，所述环氧树脂板的材料为改性环氧树脂，所述改性环氧树脂的环氧值为0.25-0.45，所述改性环氧树脂为改性物改性的环氧树脂，所述改性物选自有机硅、聚氨酯预聚体及聚酰亚胺中的至少一种，且所述改性物与所述环氧树脂的质量比为1:5-1:10；及
将所述环氧树脂板弯曲成型，得到外壳。
一种电子设备，包括上述外壳或上述外壳的制作方法制作得到的外壳。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他实施例的附图。
图1为第一实施方式的外壳的制作方法的流程图；
图2为第一实施方式的外壳的结构示意图；
图3为图2所示的外壳的局部剖面图；
图4为第二实施方式的外壳的制作方法的流程图；
图5为第二实施方式的外壳的局部剖面图；
图6为第三实施方式的外壳的制作方法的流程图；
图7为第三实施方式的外壳的局部剖面图。
具体实施方式
为了便于理解本发明，下面将参照相关附图对本发明进行更全面的描述。附图中给出了本发明的较佳的实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
一实施方式的改性环氧树脂，该改性环氧树脂可以用于制作外壳，例如电子设备的外壳，特别是手机、平板电脑等的后盖。改性环氧树脂的环氧值为0.25-0.45，改性环氧树脂为改性物改性的环氧树脂，改性物选自有机硅、聚氨酯预聚体及聚酰亚胺中的至少一种，且改性物与环氧树脂的质量比为1:5-1:10。
本文所指的环氧值指的是100g改性环氧树脂中所含环氧基的物质的量(即摩尔量)，根据该环氧值可以确定改性环氧树脂中的环氧基的质量百分含量。环氧值与环氧当量的关系为：环氧值＝100/环氧当量，环氧基的分子量为43，改性环氧树脂的环氧基的质量百分含量＝43×100/环氧当量。例如，某双酚A型环氧树脂的环氧当量为180克/当量，那么该树脂的环氧基的质量百分含量为43×100/180＝23.88，该树脂的环氧值为100/180＝0.555。
其中，环氧值越高，环氧树脂越硬，耐磨性能和抗划伤性能越好，但会导致环氧树脂的脆性过大，导致材料容易开裂，通过添加上述比例的改性物对环氧树脂进行改性，能够在保证环氧树脂具有较高的硬度的前提下，提高环氧树脂的抗拉伸强度、耐冲击性以及很好地降低材料在制作过程中开裂的风险。
一实施方式的改性环氧树脂的制备方法，为上述改性环氧树脂的一种制备方法，该改性环氧树脂的制备方法包括如下步骤：根据改性环氧树脂的环氧值为0.25-0.45，将上述改性物、环氧树脂和催化剂混合，得到混合物，其中，改性物与环氧树脂的质量比为1:5-1:10；在混合物中加入固化剂，然后在80℃-120℃下反应，得到上述改性环氧树脂。
环氧树脂可以为本领域常用的环氧树脂，例如双酚A型环氧树脂。在其中一个实施例中，环氧树脂选自E-51环氧树脂、E-55环氧树脂及E-44环氧树脂中的至少一种。
有机硅可以为本领域常用的有机硅单体。在其中一个实施例中，有机硅选自聚二甲基硅氧烷、二甲基二甲氧基硅氧烷、甲基乙烯基二甲氧基硅氧烷及甲基苯基二甲氧基硅氧烷中的至少一种。
聚氨酯预聚体可以为本领域常用的用于改性环氧树脂的聚氨酯预聚体，聚氨酯预聚体为二异氰酸酯或多异氰酸酯和多元醇按照有一定比例反应而得。在其中一个实施例中，多异氰酸酯选自IPDI(异佛尔酮二异氰酸酯)、TDI(甲苯二异氰酸酯)、MDI(二苯基甲烷-4,4'-二异氰酸酯)及HDI(己二异氰酸酯)中一种；多元醇为聚乙二醇或聚丙二醇；多异氰酸酯与多元醇的质量比为1:(0.5-1.5)。聚氨酯预聚体也可以通过市面购买得到，例如济宁华凯树脂生产的型号为KHP-456的聚氨酯预聚体、美国陶氏型号为N434的MDI聚氨酯预聚体。
聚酰亚胺选自均苯型聚酰亚胺、氟酐型聚酰亚胺、酮酐型聚酰亚胺、NA基封端聚酰亚胺、乙炔基封端聚酰亚胺、聚苯并咪唑聚酰亚胺中的至少一种。
催化剂可以为本领域常用的催化剂。在其中一个实施例中，催化剂为二月桂酸二丁基锡。
固化剂可以为本领域常用的固化剂。在其中一个实施例中，固化剂为双氰胺。
若需要改性环氧树脂具有较高的光学透过率(光学透过率在85％以上)，改性物选自有机硅及聚氨酯预聚体中的至少一种；或者，改性物由有聚酰亚胺和聚氨酯预聚体组成，改性物中，聚氨酯预聚体的质量百分含量为60％以上；或者，改性物由质量比为1:(0.1-0.2)的有机硅和聚酰亚胺组成。
在其中一个实施例中，制备改性环氧树脂的步骤包括：将改性物、环氧树脂、催化剂在室温下搅拌混合1小时-4小时，然后再加入固化剂在80℃-120℃下反应1小时-2小时，得到改性环氧树脂。其中，改性物与环氧树脂的质量比为1:5-1:10，催化剂与环氧树脂的质量比为1:100-5:100，固化剂与环氧树脂的质量比为10:100-30:100。其中，本文所指的室温为10℃-40℃。
可以理解，制备上述改性环氧树脂的方法不限于采用上述步骤中的物质和步骤，制备上述改性环氧树脂也可以采用传统的改性环氧树脂的制备工艺进行制备。
上述改性环氧树脂控制环氧值为0.25-0.45，且制备改性环氧树脂的上述改性物与环氧树脂的质量比为1:5-1:10，使得改性环氧树脂的硬度可达HB-H，具有较好耐磨性能和较好的抗划伤性能；上述改性环氧树脂还具有较好拉伸性能，抗拉伸强度60MPa以上，且能够直接进行弯曲成型；且上述改性环氧树脂的软化温度为100℃-130℃，具有较好的耐高温性能。
由于传统的环氧树脂板耐高温性能较差，易老化，限制了其使用范围，而上述改性环氧树脂的软化温度为100℃-130℃，具有较好的耐高温性能，同时，上述改性环氧树脂还能够在紫外线下照射48H不黄变，具有较好的耐老化性能，还具有抗冲击性能。
一实施方式的环氧树脂板，环氧树脂板的材料为上述改性环氧树脂。即该环氧树脂板由上述改性环氧树脂成型处理得到。该环氧树脂板可以用于制作外壳，例如电子设备的外壳，尤其是手机或平板电脑的后盖。
在其中一个实施例中，环氧树脂板的厚度为0.4毫米-0.8毫米，该厚度的环氧树脂板适用于制作具有装饰层(例如图案、纹理等)的外壳。可以理解，环氧树脂板的厚度可以根据所需厚度以及性能进行调整。
进一步地，环氧树脂板的光学透过率为83％-88％，以便于后续在环氧树脂板上制作其它装饰层(例如图案、纹理等)，以获得精美的制品。
在其中一个实施例中，环氧树脂板的制备步骤包括：将上述改性环氧树脂在140℃-190℃下熔融，然后挤出，得到环氧树脂板。
由于上述环氧树脂板由上述改性环氧树脂制备得到，该环氧树脂板的硬度可达HB-H，具有较好耐磨性能和较好的抗划伤性能；且该环氧树脂板还具有较好抗拉伸性能，并且能够直接进行弯曲成型；且上述改性环氧树脂的软化温度为100℃-130℃，具有较好的耐高温性能。
由于传统的环氧树脂板耐高温性能较差，易老化，限制了其使用范围，而上述环氧树脂板的材料为上述改性环氧树脂，上述改性环氧树脂的软化温度为100℃-130℃，具有较好的耐高温性能，在紫外线下照射48H不黄变，具有较好的耐老化性能，以使上述环氧树脂板能够用于制作外壳。
如图1所示，第一实施方式的外壳的制作方法，该方法制作的外壳能够作为电子设备的外壳，例如平板电脑、手机等的外壳，尤其是手机或平板电脑的后盖。该实施方式的外壳的制作方法包括如下步骤S11-S15：
步骤S11：制备环氧树脂板。
其中，环氧树脂板的材料为改性环氧树脂，改性环氧树脂的环氧值为0.25-0.45，改性环氧树脂为改性物改性的环氧树脂，改性物选自有机硅、聚氨酯预聚体及聚酰亚胺中的至少一种，且改性物与所述环氧树脂的质量比为1:5-1:10。具体地，环氧树脂板为上述环氧树脂板，且制备方法如上述所述，在此不再赘述。
在其中一个实施例中，外壳为手机后盖，环氧树脂板的厚度为0.4毫米-0.8毫米。可以理解，环氧树脂板的厚度可以根据所需厚度及性能进行调整。
进一步地，环氧树脂板的光学透过率为83％-88％。
步骤S12：在环氧树脂板的一侧形成图案层。
其中，图案层的图案例如可以为LOGO、符号、动物图案等。
具体地，图案层由镜面银油墨印刷后干燥得到。更具体地，在环氧树脂板的一侧形成图案层的步骤为：在环氧树脂板的一侧采用300目-420目的丝印网版丝印镜面银油墨，然后在15℃-30℃下静置30分钟-60分钟，再在60℃-80℃下烘烤30分钟-90分钟。其中，镜面油墨例如为深圳市连亿旺油墨科技有限公司的06B镜面银油墨。
若使用的镜面银油墨为具有腐蚀性的油墨，在环氧树脂板的一侧形成图案层的步骤之前，先在环氧树脂板的一侧形成透明的耐腐蚀层，然后在耐腐蚀层形成图案层。在其中一个实施例中，耐腐蚀层为UV胶水，UV胶水为聚氨酯丙烯酸酯胶水，这类胶水耐化学性能好，具有良好的附着力，耐候性能优异， 聚氨酯丙烯酸酯胶水例如贝特利新材料有限公司的型号为633-75的UV胶水。
在其中一个实施例中，图案层的厚度为1微米-4微米。以理解，图案层的厚度可以根据需要进行设置。
步骤S13：在环氧树脂板上设置装饰单元。
在本实施方式中，在环氧树脂板形成有图案层的一侧设置装饰单元，并覆盖图案层。
在其中一个实施例中，装饰单元包括粘结层、反射层和油墨层。在环氧树脂板上设置装饰单元的步骤包括：在环氧树脂板形成有图案层的一侧形成透明的粘结层，且粘结层覆盖图案层；在粘结层远离环氧树脂板的一侧形成反射层；在反射层远离粘结层的一侧形成油墨层。
进一步地，粘结层为通过UV(紫外光)胶水转印得到，粘结层具有纹理图案，从而以使外壳具有纹理外观。其中，UV胶水可以为本领域常用的固化后为透明的UV胶水。在其中一个实施例中，UV胶水为聚氨酯丙烯酸酯胶水，例如贝特利新材料有限公司的型号为633-75的UV胶水。UV胶水的固化能量为600mj/cm 2-1500mj/cm 2。可以理解，UV胶水不限于为上述胶水，也可以为本领域常用的固化后为透明的胶水；粘结层也可以不具有纹理图案，此时，外壳不具有纹理外观。
在其中一个实施例中，粘结层的厚度为5微米-20微米。可以理解，粘结层的厚度不限于为上述厚度，粘结层的厚度可以根据需要进行设置。
反射层通过真空不导电电镀(NCVM)得到，以使反射层不仅能够赋予外壳颜色，还能够提升外壳的光泽和反射率。而在粘结层上形成反射层能够提高反射层与附着力。
具体地，反射层选自氧化铟锡层、二氧化钛层、二氧化铌层、三氧化二铌层、二氧化二铌层、五氧化二铌层、二氧化硅层及二氧化锆层中的至少一种。即反射层可以为单层结构，也可以为多层结构。
在其中一个实施例中，反射层的总厚度为5纳米-300纳米，即当反射层为单层结构时，反射层的厚度为5纳米-300纳米，反射层为多层结构时，多层反射层的总厚度为5纳米-300纳米。可以理解，反射层的厚度不限于为上述厚度，反射层的厚度可以根据需要进行设置。
油墨层通过丝网印刷制备得到。进一步地，油墨层通过多次印刷和多次干燥形成，且多次印刷和多次干燥交替进行，每次印刷厚度为5微米-8微米，通过多次印刷能够使油墨层更加平整，且较为可靠，若单次印刷的厚度太厚，烘烤时可能会出现气泡等外观质量问题。具体地，油墨层包括白色油墨层、白色油墨层或灰色油墨层。油墨层不仅能够保护反射层，还能够提供背景颜色和遮蔽光线，放置通过外壳看到产品的内部结构和元器件等。
在其中一个实施例中，油墨层的厚度为10微米-20微米。可以理解，油墨层的厚度不限于为上述厚度，油墨层的厚度可以根据需要进行设置。
步骤S14：将环氧树脂板弯曲成型。
即将形成有装饰单元和图案层的环氧树脂板弯曲成型。且环氧树脂板弯曲成型之后，环氧树脂板具有内凹表面及与内凹表面相对的外凸表面。装饰单元和图案层均位于内凹表面上。
在其中一个实施例中，将环氧树脂板弯曲成型的方法为高压成型。高压成型是指在大于14公斤/厘米，约合1.4×10帕的压力下将原料加工成型的一种工艺。高压成型的工艺参数包括：成型模具的温度为90℃-150℃，加热板的温度为150℃-300℃，充气压力为10Bar-30Bar，成型时间为60秒-150秒。其中，成型模具的温度、加热板的温度需合适且相互搭配，若温度过高，环氧树脂板的表面(特别是外凸表面)易褶皱起泡，若温度过低，会导致环氧树脂板开裂，特别是外凸表面的弧形部分。
在另一个实施例中，将环氧树脂板弯曲成型的方法为热压成型，热压成型的步骤包括：先将环氧树脂板置于下模中，在加热板的温度为250℃-380℃的条件下加热15秒-30秒，且下模温为90℃-140℃；然后将上模与下模合模，并保压10秒-30秒，上模温为90℃-130℃。其中，加热板的温度、上模的温度以及下模的温度需合适且相互搭配，若温度过高环氧树脂板易褶皱起泡(特别是外凸表面)，若温度过低，会导致环氧树脂板开裂，特别是外凸表面的弧形部分。
步骤S15：在环氧树脂板的外凸表面上形成硬化层，得到外壳。
在其中一个实施例中，在环氧树脂板的外凸表面上形成硬化层的步骤包括：在环氧树脂板的外凸表面上淋涂硬化液，然后在60℃-80℃下烘烤3分钟-10分钟，然后经紫外光照射以固化，得到硬化层。
在其中一个实施例中，硬化液主要成分为聚氨酯丙烯酸酯添加有机硅树脂和全氟聚醚丙烯酸酯，例如PPG公司的型号为304的硬化液；固化能量400mj/cm 2-1200mj/cm 2。可以理解，硬化液不限于为上述物质，可以为本领域常用的硬化液。上述硬化液制备得到的硬化层具有较好的耐磨性能和较好的抗划伤性能。
在其中一个实施例中，硬化层的厚度为3微米-20微米。可以理解，硬化层的厚度可以根据需要进行调整。
具体地，硬化层的硬度3H-5H，若硬度过小，耐磨性能和抗划伤性能较差；若硬度过大，硬化层脆性增大，会降低生产效率。通过调整硬化层的厚度和固化能量能够调整硬化层的硬度。
需要说明的是，外壳的制作方法不限于为上述步骤，硬化层可以省略，那么，步骤S15可以省略；装饰单元不限于为上述结构，例如，装饰单元不具有油墨层，即油墨层可以省略；或者，装饰单元不具有反射层，此时，油墨层直接印刷在粘结层远离环氧树脂板的一侧。或者，图案层可以省略，此时步骤S12可以省略，此时，在环氧树脂板的一侧形成装饰单元即可，在环氧树脂板的一侧形成透明的粘结层，此时，装饰单元可以仅为油墨层，则在油墨层直接印刷在环氧树脂板的一侧即可。或者，装饰单元也可以省略，此时步骤S13省略。或者，在其它实施例中，外壳还可以仅为环氧树脂板弯曲成型后得到，外壳的制作方法不具有步骤S12、S13及步骤S15；或者，外壳不具有图案层，此时，外壳除了具有环氧树脂板，还具有硬化层及装饰层中的至少一个，即外壳的制作方法不具有步骤S12和步骤S15，或者，外壳的制作方法不具有步骤S12和步骤S13。
上述外壳的制作方法至少有以下优点：
由于上述环氧树脂板由上述改性环氧树脂制备得到，该环氧树脂板具有较好抗拉伸性能(抗拉伸强度在60MPa以上)，能够直接进行弯曲成型；且该环氧树脂板的硬度可达HB-H，具有较好耐磨性能和较好的抗划伤性能，软化温度为110℃-130℃，具有较好的耐高温性能，同时还具有较好的耐老化性能和抗冲击性能。
虽然，目前的采用环氧树脂注塑的方式制备一体不等厚壳体的方法，在冷热收缩时容易产生应力纹(裂纹)，使得拐角或者尾流处容易出现彩虹现象，而且出现很可能出现在壳体内部，导致无法对其进行再次修整，对外观产生较大影响；另外，注塑之后的样品还需要进行抛光工序才能得到较好的外观面，因此，相对于上述环氧树脂注塑的方式，上述外壳的制作方法通过将环氧树脂板弯曲成型，弯曲成型后的环氧树脂板无需工序，且还能够避免彩虹现象，因此，上述外壳的制作方法能够简化制作流程，提高成品率，降低外壳的制作成本。
如图2所示，第一实施方式的外壳100，可通过上述第一实施方式的外壳的制作方法制作获得，该外壳100可以作为电子设备的外壳，例如，平板电脑、手机等的外壳，尤其是手机或平板电脑的后盖。如图3所示，第一实施方式的外壳100包括环氧树脂层110、图案层120、装饰单元130和硬化层140。
环氧树脂层110的材质为上述改性环氧树脂，在此不再赘述。其中，环氧树脂层110为上述环氧树脂板弯曲成型得到。环氧树脂层110具有第一表面112及与第一表面112相对的第二表面114。其中，第一表面112为内凹表面，第二表面114为外凸表面。
在其中一个实施例中，外壳100为手机后盖，环氧树脂层110的厚度为0.4毫米-0.8毫米。可以理解，环氧树脂层110的厚度可以根据需要进行调整。
图案层120设置在第一表面112上。图案层120的图案例如可以为LOGO、符号、动物图案等。在其中一个实施例中，图案层120的材质为镜面银；图案银通过丝网印刷镜面银油墨制备得到。
在其中一个实施例中，图案层120的厚度为1微米-4微米。可以理解，图案层120的厚度可以根据需要进行设置。
装饰单元130设置在环氧树脂层110的第一表面112上，并覆盖图案层120。具体在图示的实施例中，装饰单元130包括依次层叠的粘结层132、反射层134和油墨层136。
粘结层132为透明材质。粘结层132设置在环氧树脂层110的第一表面112上，粘结层132覆盖图案层120。进一步地，粘结层132为具有纹理图案的UV转印层，从而以使外壳100具有纹理外观。 具体地，粘结层132为聚氨酯丙烯酸酯胶水层。例如贝特利新材料有限公司的型号为633-75的UV胶水。可以理解，粘结层132不限于为上述胶水层，也可以为本领域常用的固化后为透明的胶水；粘结层132也可以不具有纹理图案，此时，外壳100不具有纹理外观。
在其中一个实施例中，粘结层132的厚度为5微米-20微米。可以理解，粘结层132的厚度不限于为上述厚度，粘结层132的厚度可以根据需要进行设置。
反射层134层叠在粘结层132远离环氧树脂层110的一侧。具体地，反射层134为真空不导电电镀层。
具体地，反射层134选自氧化铟锡层、二氧化钛层、二氧化铌层、三氧化二铌层、二氧化二铌层、五氧化二铌层、二氧化硅层及二氧化锆层中的至少一种。即反射层134可以为单层结构，也可以为多层结构。
在其中一个实施例中，反射层134的总厚度为5纳米-300纳米，即当反射层134为单层结构时，反射层134的厚度为5纳米-300纳米，反射层134为多层结构时，多层反射层134的总厚度为5纳米-300纳米。可以理解，反射层134的厚度不限于为上述厚度，反射层134的厚度可以根据需要进行设置。
油墨层136层叠在反射层134远离粘结层132的一侧。具体地，油墨层136包括白色油墨层、白色油墨层或灰色油墨层。油墨层136不仅能够保护反射层134，还能够提供背景颜色和遮蔽光线，放置通过外壳100看到产品的内部结构和元器件等。
在其中一个实施例中，油墨层136的厚度为10微米-20微米。可以理解，油墨层136的厚度不限于为上述厚度，油墨层136的厚度可以根据需要进行设置。
硬化层140设置在环氧树脂层110的第二表面114上。硬化层140能够增加外壳100的耐磨性能和抗划伤性能。
在其中一个实施例中，硬化层140由硬化液制备得到，硬化液的主要成分为聚氨酯丙烯酸酯、有机硅树脂和全氟聚醚丙烯酸酯，例如PPG 304硬化液。可以理解，硬化液不限于为上述物质，可以为本领域常用的硬化液。上述硬化液制备得到的硬化层140具有较好的耐磨性能和较好的抗划伤性能。
具体地，硬化层140的硬度3H-5H，若硬度过小，耐磨性能和抗划伤性能较差；若硬度过大，硬化层140脆性增大，会降低生产效率。
在其中一个实施例中，硬化层140的厚度为3微米-20微米。可以理解，硬化层140的厚度可以根据需要进行调整。
需要说明的是，外壳100的结构不限于为结构，例如，硬化层140可以省略，此时，环氧树脂层110的第二表面114为外壳100的外表面。
图案层120也可以省略，装饰单元130直接层叠在环氧树脂层110的第一表面112上。
装饰单元130不限于为上述结构，装饰单元130的粘结层132可以用其它能够有利于反射层134附着的涂层代替，涂层例如喷涂半透的颜色层，喷绘打印达半透颜色；或者，装饰单元130不具有油墨层136，即装饰单元130的反射层134远离粘结层132的一侧不具有油墨层136；或者，装饰单元130同时不具有粘结层132和反射层134，油墨层136直接设置在环氧树脂层110的第一表面112上；或者，装饰单元130不具有反射层134，油墨层136直接层叠在粘结层132远离环氧树脂层110的一侧。
装饰单元130也可以省略，在设置有图案层120的情况下，可以通过在环氧树脂层110的第一表面112上设置保护层，保护层覆盖图案层120，以保护图案层120，保护层例如可以为UV胶水层。
装饰单元130、图案层120和硬化层140也可以同时都省略，此时，外壳100可以仅具有环氧树脂层110。
上述外壳100至少有以下优点：
由于上述外壳100包括上述材质的环氧树脂层110，该环氧树脂层110具有较好耐磨性能且较好的抗划伤性能，且还具有较好的耐高温性能、耐老化性能和抗冲击性能，使得上述外壳100不仅具有较好的性能，还有利于降低其成本。
如图4所示，第二实施方式的外壳的制作方法，该方法制作的外壳能够作为电子设备的外壳，例如，平板电脑、手机等的外壳，尤其是手机或平板电脑的后盖。本实施方式的外壳的制作方法包括如下步骤S21-S26：
步骤S21：制备环氧树脂板。
本实施方式的制备环氧树脂板的步骤与步骤S11相同，在此不再赘述。
步骤S22：在环氧树脂板的一侧形成图案层。
具体地，本实施方式的形成图案层的方法与第一实施方式的步骤S12形成图案层的相同，在此不再赘述。
步骤S23：在环氧树脂板形成有图案层的一侧形成保护层，保护层覆盖图案层。
具体地，保护层为UV胶水层。在其中一个实施例中，保护层为聚氨酯丙烯酸酯胶水层。例如贝特利新材料有限公司的型号为633-75的UV胶水。可以理解，保护层不限于为上述胶水层。
在其中一个实施例中，保护层的厚度为8微米-20微米。可以理解，保护层的厚度不限于为上述厚度，保护层的厚度可以根据需要进行设置。
步骤S24：在保护层远离环氧树脂板的一侧设置装饰单元。
具体地，在保护层远离环氧树脂板的一侧设置装饰单元的步骤包括：在基底膜上形成透明的粘结层，在粘结层上形成反射层，在反射层上形成油墨层，得到装饰单元；将装饰单元的基底膜远离粘结层的一侧与保护层远离环氧树脂板的一侧粘结。
在其中一个实施例中，基底膜为聚碳酸酯(PC)膜或TPU膜。可以理解，基底膜不限于为上述基底膜，基底膜可以为本领域常用的透明的基底膜。具体地，基底膜的厚度为50微米-125微米。可以理解，基底膜的厚度不限于为上述厚度，基底膜的厚度可以根据需要进行设置。
粘结层的制作方法与第一实施方式的粘结层的制作方法相似，区别在于，本实施方式的粘结层制作在基底膜上，在此不再赘述。
反射层的制作方法与第一实施方式的反射层的制作方法相同，在此不再赘述。
油墨层的制作方法与第一实施方式的油墨层的制作方法相同，在此不再赘述。
具体地，将装饰单元的基底膜远离粘结层的一侧与保护层远离环氧树脂板的一侧粘结的步骤包括：采用UV粘结剂将基底膜远离粘结层的一侧与保护层远离环氧树脂板的一侧粘结。在其中一个实施例中，UV粘结剂为贝特利805-16胶水。
步骤S25：将环氧树脂板弯曲成型。
即将形成有保护层、图案层和装饰单元的环氧树脂板进行弯曲成型。具体地，本实施方式的将环氧树脂板弯曲成型的方法与第一实施方式相同，在此不再赘述。
步骤S26：在环氧树脂板的外凸表面上形成硬化层，得到外壳。
本实施方式的硬化层的形成步骤与第一实施方式的硬化层的形成步骤相同，在此不再赘述。
需要说明的是，本实施方式的外壳的制作方法也不限于为上述步骤，本实施方式也与第一实施方式的外壳的制作方法相似，步骤S26的硬化层的制作可以省略；步骤S22和步骤S23可以省略，即不制作图案层和保护层，装饰单元通过UV粘结剂直接粘附在环氧树脂板上；或者，步骤S23省略，即不制作保护层，装饰单元通过UV粘结剂直接粘附在环氧树脂板上，并覆盖图案层。装饰单元也可以根据需要进行制作，例如省略油墨层，等等。
由于本实施方式的外壳的制作方法与第一实施方式的外壳的制作方法相似，因此，也具有第一实施方式的外壳的制作方法相似的效果，在此不再赘述。
如图5所示，第二实施方式的外壳200，可通过上述第二实施方式的外壳的制作方法制作获得，该外壳200可以作为电子设备的外壳，例如，平板电脑、手机等的外壳，尤其是手机或平板电脑的后盖。本实施方式的外壳200的结构与第一实施方式的外壳100的结构相似，区别在于：
外壳200还包括保护层250，保护层250设置在环氧树脂层210的第一表面212上，并覆盖图案层220。其中，第一表面212为内凹表面。具体地，保护层250为UV胶水层。在其中一个实施例中， 保护层250为聚氨酯丙烯酸酯胶水层。例如贝特利新材料有限公司的型号为633-75的UV胶水。可以理解，保护层250不限于为上述胶水层。
装饰单元230还包括基底膜238，基底膜238设置在第一表面212上，外壳200还包括胶粘层260，胶粘层260设置在基底膜238和第一表面212之间，且胶粘层260固定粘结基底膜238和第一表面212。粘结层232远离反射层234的一侧与基底膜238远离第一表面212的一侧层叠，即粘结层232、反射层234及油墨层236依次形成在基底膜238上。
在其中一个实施例中，基底膜238为聚碳酸酯(PC)膜或TPU膜。可以理解，基底膜238不限于为上述基底膜238，基底膜238可以为本领域常用的透明的基底膜。
在其中一个实施例中，胶粘层260的材质为UV粘结剂，UV粘结剂为贝特利新材料有限公司的型号为805-16的UV胶水。
由于第二实施方式的外壳200的结构与第一实施方式的外壳100的结构相似，因此，第二实施方式的外壳200也具有第一实施方式的外壳100相似的效果，在此不再赘述。
如图6所示，第三实施方式的外壳的制作方法，该方法制作的外壳能够作为电子设备的外壳，例如，平板电脑、手机等的外壳，尤其是手机或平板电脑的后盖。该实施方式的外壳的制作方法包括如下步骤S31-S35：
步骤S31：制备环氧树脂板。
本实施方式的制备环氧树脂板的步骤与步骤S11相同，在此不再赘述。
步骤S32：在环氧树脂板的一侧形成图案层。
具体地，本实施方式的形成图案层的方法与第一实施方式的步骤S12形成图案层的相似，在此不再赘述。
步骤S33：将环氧树脂板弯曲成型。
即将形成有图案层的环氧树脂板进行弯曲成型。具体地，本实施方式的将环氧树脂板弯曲成型的方法与第一实施方式相同，在此不再赘述。
步骤S34：在环氧树脂的内凹表面上设置装饰单元。
即在本实施方式中，在环氧树脂的内凹表面上设置装饰层的步骤在将环氧树脂板弯曲成型的步骤之后。
具体地，在环氧树脂的内凹表面上设置装饰单元的步骤包括：在基底膜上形成透明的粘结层，在粘结层上形成反射层，在反射层上形成油墨层，得到装饰单元；将装饰单元的基底膜远离粘结层的一侧与环氧树脂板的内凹表面粘结。可以理解，形成装饰单元的步骤可以在步骤S33之前或者同时，即可以在步骤S33或在步骤S33的同时制作装饰单元，然后将装饰单元的基底膜远离粘结层的一侧与环氧树脂板的内凹表面粘结。
在其中一个实施例中，基底膜为聚碳酸酯膜或TPU膜。可以理解，基底膜不限于为上述基底膜，基底膜可以为本领域常用的透明的基底膜。
粘结层的制作方法与第一实施方式的粘结层的制作方法相似，区别在于，本实施方式的粘结层制作在基底膜上，在此不再赘述。
反射层的制作方法与第一实施方式的反射层的制作方法相同，在此不再赘述。
油墨层的制作方法与第一实施方式的油墨层的制作方法相同，在此不再赘述。
具体地，将装饰单元的基底膜远离粘结层的一侧与环氧树脂板的内凹表面粘结的步骤包括：采用粘结剂将基底膜远离粘结层的一侧与环氧树脂板的内凹表面粘结。在本实施例中，粘结剂为热固型粘结剂或UV粘结剂。热固型粘结剂为OCA胶水，例如奥佳光电的OCA胶水；UV粘结剂为贝特利新材料有限公司的型号为805-16的UV胶水。
步骤S35：在环氧树脂板的外凸表面上形成硬化层，得到外壳。
本实施方式的硬化层的形成步骤与第一实施方式的硬化层的形成步骤相同，在此不再赘述。
需要说明的是，本实施方式的外壳的制作方法也不限于为上述步骤，在本实施方式中也与第一实 施方式的外壳的制作方法相似，步骤S35的硬化层的制作可以省略；步骤S32可以省略，此时不制作图案层，将装饰单元的基底膜远离所述粘结层的一侧与环氧树脂板的内凹表面粘结，即装饰单元通过UV粘结剂直接粘附在环氧树脂板的内凹表面上；装饰单元也可以根据需要进行制作，例如省略油墨层，等等。
由于本实施方式的外壳的制作方法与第一实施方式的外壳的制作方法相似，因此，也具有第一实施方式的外壳的制作方法相似的效果，在此不再赘述。由于第三实施方式的外壳的制作方法的弯曲步骤在设置装饰单元之前，使得该实施方式的外壳的制作方法将装饰单元设置到环氧树脂板上的胶水除了可以使用UV粘结剂，还可以使用热固型粘结剂。
如图7所示，第三实施方式的外壳300，可通过上述第三实施方式的外壳的制作方法制作获得，该外壳300可以作为电子设备的外壳，例如，平板电脑、手机等的外壳，尤其是手机或平板电脑的后盖。本实施方式的外壳300的结构与第一实施方式的外壳100的结构相似，区别在于：
装饰单元330还包括基底膜338，基底膜338设置在环氧树脂层310的内凹表面312上，外壳300还包括胶粘层350，胶粘层350设置在基底膜338和内凹表面312之间，且胶粘层350固定粘结基底膜338和内凹表面312，粘结层332远离反射层的一侧与环氧树脂层310的内凹表面312层叠，即粘结层332、反射层334及油墨层336依次形成在基底膜338上。
在其中一个实施例中，基底膜338为PC膜或TPU膜。可以理解，基底膜338不限于为上述基底膜，基底膜338可以为本领域常用的透明的基底膜。
在其中一个实施例中，胶粘层360的材质为UV粘接剂或热固型粘接剂。其中，UV粘接剂例如为贝特利新材料有限公司的型号为805-16的UV；热固型粘接剂为OCA胶水，例如奥佳光电的OCA胶水。
由于第三实施方式的外壳300的结构与第一实施方式的外壳100的结构相似，因此，第三实施方式的外壳300也具有第一实施方式的外壳100相似的效果，在此不再赘述。
一实施方式的电子设备，例如，平板电脑、手机等，包括外壳，其中，外外壳为第一实施方式的外壳的制作方法制作得到的外壳、第一实施方式的外壳、第二实施方式的外壳的制作方法制作得到的外壳、第二实施方式的外壳、第三实施方式的外壳的制作方法制作得到的外壳或第三实施方式的外壳。
在其中一个实施例中，电子设备为手机或平板电脑，外壳为后盖。
由于上述电子设备采用第一实施方式的外壳的制作方法制作得到的外壳、第一实施方式的外壳、第二实施方式的外壳的制作方法制作得到的外壳、第二实施方式的外壳、第三实施方式的外壳的制作方法制作得到的外壳或第三实施方式的外壳，有利于增加电子设备的使用寿命，降低电子设备的生产成本。
需要说明的是，上述外壳不限于为电子设备的外壳，也可以为其它产品的外壳。
以下为具体实施例部分(以下实施例以改性环氧树脂的其中一种制备方法为例，对改性环氧树脂的制备进行举例说明，但是本发明的改性环氧树脂的制备方法并不限于为以下步骤及以下物质，即本发明的技术方案也不限于为以下实施例，例如，以下实施例中催化剂采用二月桂酸二丁基锡，固化剂采用双氰胺,聚氨酯预聚体采用美国陶氏的型号为N434的MDI聚氨酯预聚体，均为举例说明，并不限制本发明的范围)：
实施例1
本实施例的环氧树脂板的制备过程如下：
(1)制备改性环氧树脂：根据表1，按照改性物和环氧树脂的质量比为A:B，将改性物、环氧树脂及催化剂在室温下搅拌混合t 1小时，然后加入固化剂搅拌均匀，再在T 1℃下反应t 2小时，得到改性环氧树脂。催化剂的质量与环氧树脂的质量比为C:B，固化剂与环氧树脂的质量比为D:B，催化剂为二月桂酸二丁基锡，固化剂为双氰胺。
根据GB 1677-1981“盐酸-丙酮法”测试制备得到的改性环氧树脂的环氧值；根据ISO 306-2013测试制备得到的改性环氧树脂的软化温度，其中，改性环氧树脂的环氧值以及软化温度如表2所示。
(2)按照表2，将步骤(1)制备得到的改性环氧树脂在T 2℃下熔融，然后挤出，得到厚度为D 毫米的环氧树脂板。
表1
Figure PCTCN2020081315-appb-000001
Figure PCTCN2020081315-appb-000002
其中，表1中“环氧树脂”一栏中，E-51、E-55及E-44分别表示E-51环氧树脂、E-55环氧树脂及E-44环氧树脂，且此栏中的“:”表示质量比，例如，E-51:E-44表示该实施例的环氧树脂由E-51环氧树脂和E-44的环氧树脂组成，且E-51:E-44表示的比例为质量比。
表2
  环氧值 软化温度(℃) T 2(℃) D(毫米)
实施例1 0.33 122 168 0.6
实施例2 0.32 115 165 0.4
实施例3 0.34 124 170 0.8
实施例4 0.33 120 155 0.5
实施例5 0.32 121 148 0.7
实施例6 0.36 126 142 0.6
实施例7 0.33 123 170 0.4
实施例8 0.31 109 150 0.8
实施例9 0.37 127 180 0.6
实施例10 0.34 124 177 0.5
实施例11 0.32 116 155 0.7
实施例12 0.33 120 160 0.4
实施例13 0.36 125 158 0.6
实施例14 0.45 130 190 0.8
实施例15 0.25 100 140 0.7
实施例16 0.42 128 174 0.6
实施例17 0.45 129 188 0.4
实施例18 0.36 125 172 0.5
实施例19 0.38 128 181 0.7
实施例20 0.43 120 155 0.6
实施例21 0.35 124 178 0.6
对比例1 0.24 100 140 0.6
对比例2 0.46 130 190 0.6
对比例3 0.33 122 168 0.6
对比例4 0.33 122 168 0.6
对比例5 0.35 125 180 0.6
对比例5
对比例5为常规的3240环氧树脂板，厚度为0.6毫米，环氧值为0.35。
对比例6
对比例6为常规的聚碳酸酯(PC)和聚甲基丙烯酸甲酯(PMMA)的复合基板，总厚度为0.6毫米。
对比例7
对比例7为常规的纯聚碳酸酯(PC)板，厚度为0.6毫米。
对比例8
对比例8为常规的聚对苯二甲酸乙二酯(PET)板，厚度为0.6毫米。
测试：
(1)采用DIGILA公司的FTS-3000傅里叶红外光谱测试仪测试实施例1-21及对比例1-4的环氧树脂板、对比例5的3240环氧树脂板、对比例6的复合基板、对比例7的纯聚碳酸酯板以及对比例8的聚对苯二甲酸乙二酯板的光学透过率；
(2)采用岛津的AG-IS万能试验机实施例1-21及对比例1-4的环氧树脂板、对比例5的3240环氧树脂板、对比例6的复合基板、对比例7的纯聚碳酸酯板以及对比例8的聚对苯二甲酸乙二酯板的抗拉伸性能；
(3)采用ASTM D3363方法测试实施例1-21及对比例1-4的环氧树脂板、对比例5的3240环氧树脂板、对比例6的复合基板、对比例7的纯聚碳酸酯板以及对比例8的聚对苯二甲酸乙二酯板的硬度；
(4)采用ASTM G-151方法测试实施例1-21及对比例1-4的环氧树脂板、对比例5的3240环氧 树脂板、对比例6的复合基板、对比例7的纯聚碳酸酯板以及对比例8的聚对苯二甲酸乙二酯板的耐老化性能；
(5)热压弯曲试验：将实施例1-21及对比例1-4的环氧树脂板、对比例5的3240环氧树脂板、对比例6的复合基板、对比例7的纯聚碳酸酯板以及对比例8的聚对苯二甲酸乙二酯板作为样板通过热压成型的方式进行弯曲，具体步骤为：先将样板置于下模中，并在加热板温度为300℃的条件下加热22秒，且下模温为90℃-140℃；然后将上膜与下模合模，并保压20秒，上模温为120℃，然后在灯光下观察弯曲后的样板的效果(是否能够弯曲成预定弧度，外凸表面是否产生裂纹)。
(6)高压弯曲试验：将实施例1-21及对比例1-4的环氧树脂板、对比例5的3240环氧树脂板、对比例6的复合基板、对比例7的纯聚碳酸酯板以及对比例8的聚对苯二甲酸乙二酯板作为样板通过高压成型的方式进行弯曲，具体工艺参数为：成型模具的温度为120℃，加热板的温度为220℃，充气压力为20Bar，成型时间为100秒。然后在灯光下观察弯曲后的样板的效果。
其中，实施例1-21及对比例1-4的环氧树脂板、对比例5的3240环氧树脂板、对比例6的复合基板、对比例7的纯聚碳酸酯板以及对比例8的聚对苯二甲酸乙二酯板的光学透过率、抗拉伸性能、硬度、耐老化性能、热压成型的弯曲效果以及高压成型的弯曲效果分别如表3所示。
表3
Figure PCTCN2020081315-appb-000003
Figure PCTCN2020081315-appb-000004
从表3中可以看出，实施例1-21的环氧树脂板的光学透光率为83％-88％，具有较高的光学透过率，且实施例1-21的环氧树脂板的抗拉伸强度至少为60MPa，具有较佳的抗拉伸强度，硬度为HB-H，具有较大的硬度，以使其具有较好的耐磨性能、较好的抗划伤性能，同时，上述环氧树脂板在紫外线下照射48H不黄变，具有较好的耐老化性能，性能与对比例6的复合基板相当，能够做外壳使用，从而给外壳的制作提供了一种新的材料。同时，实施例1-21的环氧树脂板经热压弯曲和高压弯曲成型后均能够弯曲成预定形，且均无裂纹，能够直接通过弯曲的方式成型，简化制作流程，提高成品率，降低外壳的制作成本。
而对比例1的环氧树脂板不仅具有较小的抗拉伸强度，且硬度也较小，在紫外线照射48H轻微黄变，也不能弯曲成预定形状；对比例2和对比例3的环氧树脂板虽然具有较大的硬度，但是抗拉伸强度较小，且弯曲试验后会有裂纹，因此，不能直接弯曲成型；对比例4的环氧树脂板虽然具有较大的抗拉伸强度，但是硬度太低；对比例5的环氧树脂板虽然具有较大的硬度和较好的抗拉伸强度，但是在紫外线照射48H严重黄变，且弯曲成型后表面有裂纹，不能直接弯曲成型。对比例7的纯聚碳酸酯板的硬度太低，耐磨性能和抗划伤性能太差；对比例8的聚对苯二甲酸乙二酯板的抗拉伸强度过大，且弯曲后弧 度较小，未能弯曲成预定形状，较难制作成预定弧度的外壳。
实施例22
本实施例的外壳的制作过程如下：
将实施例1制作的环氧树脂板进行高压成型，以使环氧树脂板弯曲，然后进行CNC加工，铣去多余的边角料，得到外壳。其中，高压成型的工艺参数包括：成型模具的温度为120℃，加热板的温度为200℃，充气压力为20Bar，成型时间为100秒。
实施例23
本实施例的外壳的制作过程如下：
将实施例4制作的环氧树脂板进行高压成型，以使环氧树脂板弯曲，然后进行CNC加工，铣去多余的边角料，得到外壳。其中，高压成型的工艺参数包括：成型模具的温度为90℃，加热板的温度为300℃，充气压力为10Bar，成型时间为60秒。
实施例24
本实施例的外壳的制作过程如下：
将实施例7制作的环氧树脂板进行高压成型，以使环氧树脂板弯曲，然后进行CNC加工，铣去多余的边角料，得到外壳。其中，高压成型的工艺参数包括：成型模具的温度为150℃，加热板的温度为150℃，充气压力为30Bar，成型时间为150秒。
实施例25
本实施例的外壳的制作过程如下：
将实施例2制作的环氧树脂板进行热压成型，以使环氧树脂板弯曲，然后进行CNC加工，铣去多余的边角料，得到外壳。其中，热压成型的步骤为：先将所述环氧树脂板置于下模中，在加热板的温度为320℃的条件下加热25秒，且下模温为120℃，移走加热板，然后将上膜与下模合模，并保压20秒，上模温为110℃。
实施例26
本实施例的外壳的制作过程如下：
将实施例5制作的环氧树脂板进行热压成型，以使环氧树脂板弯曲，然后进行CNC加工，铣去多余的边角料，得到外壳。其中，热压成型的步骤为：先将所述环氧树脂板置于下模中，在加热板的温度为250℃的条件下加热30秒，且下模温为140℃，移走加热板，然后将上膜与下模合模，并保压30秒，上模温为130℃。
实施例27
本实施例的外壳的制作过程如下：
将实施例8制作的环氧树脂板进行热压成型，以使环氧树脂板弯曲，然后进行CNC加工，铣去多余的边角料，得到外壳。其中，热压成型的步骤为：先将所述环氧树脂板置于下模中，在加热板的温度为380℃的条件下加热15秒，且下模温为90℃，移走加热板，然后将上膜与下模合模，并保压10秒，上模温为90℃。
实施例28
本实施例的外壳的制作过程如下：
(1)在实施例3制备得到的环氧树脂板的一侧采用350目的丝印网版丝印镜面银油墨，然后在25℃下静置45分钟，再在70℃下烘烤60分钟，形成厚度为3微米的图案层。
(2)在环氧树脂板形成有图案层的一侧用UV胶水(贝特利新材料有限公司，型号633-75)转印形成具有纹理、厚度为10微米的粘结层，且粘结层覆盖图案层；在粘结层远离环氧树脂板的一侧真空不导电电镀形成厚度为15纳米的反射层，反射层为氧化铟锡层；在氧化铟锡层远离粘结层的一侧印刷黑色油墨，形成厚度为15微米的油墨层，以形成装饰单元。
(3)将步骤(2)形成有装饰单元的环氧树脂板进行高压成型，以使环氧树脂板弯曲。高压成型的工艺参数包括：成型模具的温度为140℃，加热板的温度为250℃，充气压力为15Bar，成型时间为120秒。
(4)在弯曲的环氧树脂板远离装饰单元的一侧淋涂PPG 304硬化液，然后在70℃下烘烤6分钟，再在紫外光照射下固化，固化能量为800mj/cm 2，形成厚度为10微米的硬化层，然后进行CNC加工，铣去多余的边角料，得到外壳。
实施例29
本实施例的外壳的制作过程如下：
(1)在实施例6制备得到的环氧树脂板的一侧采用300目的丝印网版丝印镜面银油墨，然后在15℃下静置60分钟，再在60℃下烘烤90分钟，形成厚度为4微米的图案层。
(2)在环氧树脂板形成有图案层的一侧用UV胶水(贝特利新材料有限公司，型号633-75)转印形成具有纹理、厚度为5微米的粘结层，且粘结层覆盖图案层；在粘结层远离环氧树脂板的一侧真空不导电电镀形成厚度为50纳米的反射层，反射层为二氧化铌层；在二氧化铌层远离粘结层的一侧印刷黑色油墨，形成厚度为20微米的油墨层，以形成装饰单元。
(3)将步骤(2)形成有装饰单元的环氧树脂板进行高压成型，以使环氧树脂板弯曲。高压成型的工艺参数包括：成型模具的温度为100℃，加热板的温度为280℃，充气压力为200Bar，成型时间为80秒。
(4)在弯曲的环氧树脂板远离装饰单元的一侧淋涂PPG 304硬化液，然后在60℃下烘烤10分钟，再在紫外光照射下固化，固化能量为400mj/cm 2，形成厚度为3微米的硬化层，然后进行CNC加工，铣去多余的边角料，得到外壳。
实施例30
本实施例的外壳的制作过程如下：
(1)在实施例10制备得到的环氧树脂板的一侧采用420目的丝印网版丝印镜面银油墨，然后在30℃下静置30分钟，再在80℃下烘烤30分钟，形成厚度为1微米的图案层。
(2)在环氧树脂板形成有图案层的一侧用UV胶水(贝特利新材料有限公司，型号633-75)转印形成具有纹理、厚度为20微米的粘结层，且粘结层覆盖图案层；在粘结层远离环氧树脂板的一侧真空不导电电镀形成厚度为300纳米的反射层，且反射层为三氧化二铌层；在三氧化二铌层远离粘结层的一侧印刷黑色油墨，形成厚度为10微米的油墨层，以形成装饰单元。
(3)将步骤(2)形成有装饰单元的环氧树脂板进行高压成型，以使环氧树脂板弯曲。高压成型的工艺参数包括：成型模具的温度为90℃，加热板的温度为200℃，充气压力为30Bar，成型时间为150秒。
(4)在弯曲的环氧树脂板远离装饰单元的一侧淋涂PPG 304硬化液，然后在80℃下烘烤3分钟再在紫外光照射下固化，固化能量为1200mj/cm 2，形成厚度为20微米的硬化层，然后进行CNC加工，铣去多余的边角料，得到外壳。
实施例31
本实施例的外壳的制作过程如下：
(1)与实施例28的步骤(1)相似，区别在于，使用的环氧树脂板为实施例11制备得到的环氧树脂板。
(2)与实施例28的步骤(2)相似，区别在于，反射层的制备过程不同：在粘结层远离环氧树脂板的一侧真空不导电电镀形成厚度为50纳米的五氧化二铌层，然后在五氧化二铌层上形成厚度为50纳米的二氧化硅层。油墨层形成在二氧化硅层远离五氧化二铌层的一侧。
(3)将步骤(2)形成有装饰单元的环氧树脂板进行热压成型，以使环氧树脂板弯曲。其中，热压成型的步骤为：先将所述环氧树脂板置于下模中，在加热板的温度为300℃的条件下加热18秒，且下模温为100℃，移走加热板，然后将上膜与下模合模，并保压30秒，上模温为130℃。
(4)与实施例28的步骤(4)相同。
实施例32
本实施例的外壳的制作过程如下：
(1)与实施例29的步骤(1)相似，区别在于，使用的环氧树脂板为实施例13制备得到的环氧树脂板。
(2)与实施例29的步骤(2)相似，区别在于，反射层的制备过程不同：在粘结层远离环氧树脂板的一侧真空不导电电镀形成厚度为40纳米的五氧化二铌层，然后在五氧化二铌层上真空不导电电镀形成厚度为60纳米的二氧化硅层，再在二氧化硅层远离五氧化二铌层的一侧真空不导电电镀形成厚度为70纳米的二氧化锆层。油墨层形成在二氧化锆层远离二氧化硅层的一侧。
(3)将步骤(2)形成有装饰单元的环氧树脂板进行热压成型，以使环氧树脂板弯曲。其中，热压成型的步骤为：先将所述环氧树脂板置于下模中，在加热板的温度为350℃的条件下加热20秒，且下模温为110℃，移走加热板，然后将上膜与所述下模合模，并保压20秒，上模温为110℃。
(4)与实施例29的步骤(4)相同。
实施例33
本实施例的外壳的制作过程如下：
(1)在实施例14制备得到的环氧树脂板的一侧采用350目的丝印网版丝印镜面银油墨，然后在20℃下静置50分钟，再在75℃下烘烤50分钟，形成厚度为2微米的图案层。
(2)用UV胶水(贝特利新材料有限公司，型号633-75)在环氧树脂板形成有图案层的一侧形成厚度为8微米的保护层，保护层覆盖图案层。
(3)在基底膜上用UV胶水(贝特利新材料有限公司，型号633-75)转印形成具有纹理、厚度为8微米的粘结层，在粘结层远离环氧树脂板的一侧真空不导电电镀形成厚度为80纳米的反射层，反射层为二氧化二铌层；在二氧化二铌层层远离粘结层的一侧印刷黑色油墨，形成厚度为18微米的油墨层，以形成装饰单元；将装饰单元的基底膜远离粘结层的一侧与保护层远离环氧树脂板的一侧用UV粘结剂(贝特利新材料有限公司的型号为805-16的UV胶水)粘结。其中，基底膜为厚度为50微米的聚碳酸酯膜。
(4)将步骤(3)设置有装饰单元的环氧树脂板进行高压成型，以使环氧树脂板弯曲。高压成型的工艺参数包括：成型模具的温度为150℃，加热板的温度为250℃，充气压力为20Bar，成型时间为120秒。
(5)在弯曲的环氧树脂板远离装饰单元的一侧淋涂PPG 304硬化液，然后在65℃下烘烤8分钟，再在紫外光照射下固化，固化能量为600mj/cm 2，形成厚度为8微米的硬化层，然后进行CNC加工，铣去多余的边角料，得到外壳。
实施例34
本实施例的外壳的制作过程如下：
(1)在实施例15制备得到的环氧树脂板的一侧采用400目的丝印网版丝印镜面银油墨，然后在25℃下静置40分钟，再在70℃下烘烤70分钟，形成厚度为3微米的图案层。
(2)用UV胶水(贝特利新材料有限公司，型号633-75)在环氧树脂板形成有图案层的一侧形成 厚度为20微米的保护层，保护层覆盖图案层。
(3)在基底膜上用UV胶水(贝特利新材料有限公司，型号633-75)转印形成具有纹理、厚度为12微米的粘结层，在粘结层远离环氧树脂板的一侧真空不导电电镀形成厚度为200纳米的反射层，反射层为二氧化二铌层；在氧化铟锡层远离粘结层的一侧印刷黑色油墨，形成厚度为12微米的油墨层，以形成装饰单元；将装饰单元的基底膜远离粘结层的一侧与保护层远离环氧树脂板的一侧用UV粘结剂(贝特利新材料有限公司的型号为805-16的UV胶水)粘结。其中，基底膜为厚度为100微米的聚碳酸酯膜。
(4)将步骤(3)设置有装饰单元的环氧树脂板进行高压成型，以使环氧树脂板弯曲。高压成型的工艺参数包括：成型模具的温度为90℃，加热板的温度为300℃，充气压力为15Bar，成型时间为60秒。
(5)在弯曲的环氧树脂板远离装饰单元的一侧淋涂PPG 304硬化液，然后在80℃下烘烤4分钟，再在紫外光照射下固化，固化能量为1000mj/cm 2，形成厚度为12微米的硬化层，然后进行CNC加工，铣去多余的边角料，得到外壳。
实施例35
本实施例的外壳的制作过程如下：
(1)与实施例33的步骤(1)相似，区别在于，环氧树脂板为实施例4制备得到的环氧树脂板。
(2)与实施例33的步骤(2)相同。
(3)与实施例33的步骤(3)相似，区别在于，反射光层为厚度为20纳米的二氧化锆层。
(4)将步骤(3)设置有装饰单元的环氧树脂板进行热压成型，以使环氧树脂板弯曲。其中，热压成型的步骤为：先将所述环氧树脂板置于下模中，在加热板的温度为280℃的条件下加热28秒，且下模温为90℃，移走加热板，然后将上膜与所述下模合模，并保压30秒，上模温为90℃。
(5)与实施例33的步骤(5)相同。
实施例36
本实施例的外壳的制作过程如下：
(1)与实施例34的步骤(1)相似，区别在于，环氧树脂板为实施例18制备得到的环氧树脂板。
(2)与实施例34的步骤(2)相同。
(3)与实施例34的步骤(3)相似，区别在于，反射光层为厚度为100纳米的五氧化二铌层。
(4)将步骤(3)设置有装饰单元的环氧树脂板进行热压成型，以使环氧树脂板弯曲。其中，热压成型的步骤为：先将环氧树脂板置于下模中，在加热板的温度为370℃的条件下加热20秒，且下模温为120℃，移走加热板，然后将上膜与下模合模，并保压15秒，上模温为120℃。
(5)与实施例34的步骤(5)相同。
实施例37
本实施例的外壳的制作过程如下：
(1)在实施例5制备得到的环氧树脂板的一侧采用320目的丝印网版丝印镜面银油墨，然后在15℃下静置60分钟，再在80℃下烘烤60分钟，形成厚度为4微米的图案层。
(2)将形成图案层的环氧树脂板进行高压成型，以使环氧树脂板弯曲。高压成型的工艺参数包括：成型模具的温度为100℃，加热板的温度为180℃，充气压力为15Bar，成型时间为120秒。
(3)在基底膜上用UV胶水(贝特利新材料有限公司，型号633-75)转印形成具有纹理、厚度为16微米的粘结层，在粘结层远离环氧树脂板的一侧真空不导电电镀形成厚度为120纳米的反射层，反射层为氧化铟锡层；在氧化铟锡层远离粘结层的一侧印刷黑色油墨，形成厚度为15微米的油墨层，以形成装饰单元；将装饰单元的基底膜远离粘结层的一侧与环氧树脂板的内凹表面用OCA胶水(奥佳光电的OCA胶水)粘结，且装饰单元覆盖图案层。其中，基底膜为厚度为125微米的TPU膜。
(4)在环氧树脂板的外凸表面淋涂PPG 304硬化液，然后在60℃下烘烤10分钟，再在紫外光照射下固化，固化能量为800mj/cm 2，形成厚度为18微米的硬化层，然后进行CNC加工，铣去多余的边角料，得到外壳。
实施例38
本实施例的外壳的制作过程如下：
(1)在实施例16制备得到的环氧树脂板的一侧采用420目的丝印网版丝印镜面银油墨，然后在30℃下静置30分钟，再在60℃下烘烤90分钟，形成厚度为2微米的图案层。
(2)将形成图案层的环氧树脂板进行高压成型，以使环氧树脂板弯曲。高压成型的工艺参数包括：成型模具的温度为120℃，加热板的温度为200℃，充气压力为10Bar，成型时间为150秒。
(3)在基底膜上用UV胶水(贝特利新材料有限公司，型号633-75)转印形成具有纹理、厚度为8微米的粘结层，在粘结层远离环氧树脂板的一侧真空不导电电镀形成厚度为30纳米的反射层，反射层为二氧化硅层；在二氧化硅层远离粘结层的一侧印刷黑色油墨，形成厚度为10微米的油墨层，以形成装饰单元；将装饰单元的基底膜远离粘结层的一侧与环氧树脂板的内凹表面用OCA胶水(奥佳光电的OCA胶水)粘结，且装饰单元覆盖图案层。其中，基底膜为厚度为75微米的TPU膜。
(4)在环氧树脂板的外凸表面淋涂PPG 304硬化液，然后在80℃下烘烤3分钟，再在紫外光照射下固化，固化能量为500mj/cm 2，形成厚度为5微米的硬化层，然后进行CNC加工，铣去多余的边角料，得到外壳。
实施例39
本实施例的外壳的制作过程如下：
(1)与实施例37的步骤(1)相似，区别在于，本实施例的环氧树脂板为实施例10制备得到的环氧树脂板。
(2)将形成图案层的环氧树脂板进行热压成型，以使环氧树脂板弯曲。其中，热压成型的步骤为：先将环氧树脂板置于下模中，在加热板的温度为280℃的条件下加热15秒，且下模温为140℃，移走加热板，然后将上膜与下模合模，并保压130秒，上模温为130℃。
(3)与实施例37的步骤(3)相同。
(4)与实施例37的步骤(4)相同。
实施例40
本实施例的外壳的制作过程如下：
(1)与实施例38的步骤(1)相似，区别在于，本实施例的环氧树脂板为实施例16制备得到的环氧树脂板。
(2)将形成图案层的环氧树脂板进行热压成型，以使环氧树脂板弯曲。其中，热压成型的步骤为：先将环氧树脂板置于下模中，在加热板的温度为300℃的条件下加热30秒，且下模温为90℃，移走加热板，然后将上膜与下模合模，并保压10秒，上模温为90℃。
(3)与实施例38的步骤(3)相同。
(4)与实施例38的步骤(4)相同。
实施例41
本实施例的外壳的制作过程与实施例23相似，区别在于，加热板的温度为310℃。
实施例42
本实施例的外壳的制作过程与实施例24相似，区别在于，成型模具的温度为80℃。
实施例43
本实施例的外壳的制作过程与实施例24相似，区别在于，加热板的温度为140℃。
实施例44
本实施例的外壳的制作过程与实施例26相似，区别在于，加热板的温度为240℃。
实施例45
本实施例的外壳的制作过程与实施例27相似，区别在于，加热板的温度为390℃。
测试：
在强光(例如台灯灯光)下变换角度观察实施例22-实施例45制备得到的外壳的环氧树脂层的效果，如表4所示：
表4
  环氧树脂层的效果
实施例22 无裂痕，且弯曲成预定的弯曲弧度
实施例23 无裂痕，且弯曲成预定的弯曲弧度
实施例24 无裂痕，且弯曲成预定的弯曲弧度
实施例25 无裂痕，且弯曲成预定的弯曲弧度
实施例26 无裂痕，且弯曲成预定的弯曲弧度
实施例27 无裂痕，且弯曲成预定的弯曲弧度
实施例28 无裂痕，且弯曲成预定的弯曲弧度
实施例29 无裂痕，且弯曲成预定的弯曲弧度
实施例30 无裂痕，且弯曲成预定的弯曲弧度
实施例31 无裂痕，且弯曲成预定的弯曲弧度
实施例32 无裂痕，且弯曲成预定的弯曲弧度
实施例33 无裂痕，且弯曲成预定的弯曲弧度
实施例34 无裂痕，且弯曲成预定的弯曲弧度
实施例35 无裂痕，且弯曲成预定的弯曲弧度
实施例36 无裂痕，且弯曲成预定的弯曲弧度
实施例37 无裂痕，且弯曲成预定的弯曲弧度
实施例38 无裂痕，且弯曲成预定的弯曲弧度
实施例39 无裂痕，且弯曲成预定的弯曲弧度
实施例40 无裂痕，且弯曲成预定的弯曲弧度
实施例41 弯曲成预定的弯曲弧度，但表面褶皱起泡
实施例42 未弯曲成预定弯曲弧度
实施例43 未弯曲成预定弯曲弧度
实施例44 外凸表面的弧形部处开裂
实施例45 弯曲成预定的弯曲弧度，但表面褶皱起泡
从表4中可以看出，实施例22-40的外壳的环氧树脂层均无裂痕，且弯曲成预定的弯曲弧度，而实施例41和实施例45的环氧树脂层的表面褶皱起泡是因为加热温度过高导致的，实施例42和实施例43的环氧树脂层未弯曲成预定弯曲弧度是因为成型模具或加热板温度过低，导致成型温度不够，实施例44的环氧树脂层发生开裂，是因为加热板温度过低致使在合模保压过程中导致环氧树脂层开裂而产生裂痕。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书 记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (27)

  1. 一种改性环氧树脂，所述改性环氧树脂的环氧值为0.25-0.45，所述改性环氧树脂为改性物改性的环氧树脂，所述改性物选自有机硅、聚氨酯预聚体及聚酰亚胺中的至少一种，且所述改性物与所述环氧树脂的质量比为1:5-1:10。
  2. 根据权利要求1所述的改性环氧树脂，其特征在于，所述改性物选自所述有机硅及所述聚氨酯预聚体中的至少一种；
    或者，所述改性物由所述聚酰亚胺和所述聚氨酯预聚体组成，且在所述改性物中，所述聚氨酯预聚体的质量百分含量为60％以上；
    或者，所述改性物由质量比为1:(0.1-0.2)的所述有机硅和所述聚酰亚胺组成。
  3. 一种环氧树脂板，所述环氧树脂板的材料为改性环氧树脂，所述改性环氧树脂的环氧值为0.25-0.45，所述改性环氧树脂为改性物改性的环氧树脂，所述改性物选自有机硅、聚氨酯预聚体及聚酰亚胺中的至少一种，且所述改性物与所述环氧树脂的质量比为1:5-1:10。
  4. 一种外壳，包括环氧树脂层，所述环氧树脂层的材料为改性环氧树脂，所述改性环氧树脂的环氧值为0.25-0.45，所述改性环氧树脂为改性物改性的环氧树脂，所述改性物选自有机硅、聚氨酯预聚体及聚酰亚胺中的至少一种，且所述改性物与所述环氧树脂的质量比为1:5-1:10。
  5. 根据权利要求4所述的外壳，其特征在于，所述环氧树脂层具有第一表面，所述外壳还包括设置在所述第一表面上的装饰单元。
  6. 根据权利要求5所述的外壳，其特征在于，所述装饰单元包括依次层叠的粘结层、反射层和油墨层，所述粘结层为透明材质，所述粘结层远离所述反射层的一侧与所述第一表面层叠。
  7. 根据权利要求6所述的外壳，其特征在于，所述粘结层为具有纹理图案的UV转印层。
  8. 根据权利要求6所述的外壳，其特征在于，所述反射层为真空不导电电镀层。
  9. 根据权利要求6所述的外壳，其特征在于，所述反射层选自氧化铟锡层、二氧化钛层、二氧化铌层、三氧化二铌层、二氧化二铌层、五氧化二铌层、二氧化硅层及二氧化锆层中的至少一种。
  10. 根据权利要求6所述的外壳，其特征在于，所述装饰单元还包括基底膜，所述基底膜设置在所述第一表面上，所述外壳还包括胶粘层，所述胶粘层设置在所述基底膜和所述第一表面之间，且所述胶粘层固定粘结所述基底膜和所述第一表面，其中，所述粘结层远离所述反射层的一侧与所述基底膜远离所述第一表面的一侧层叠。
  11. 根据权利要求5所述的外壳，其特征在于，还包括设置在所述环氧树脂的所述第一表面上的图案层，所述装饰单元覆盖所述图案层。
  12. 根据权利要求4-11任一项所述的外壳，其特征在于，所述改性物选自所述有机硅及所述聚氨酯预聚体中的一种；
    或者，所述改性物由所述有机硅及所述聚酰亚胺中的至少一种和所述聚氨酯预聚体组成，且在所述改性物中，所述聚氨酯预聚体的质量百分含量为60％以上；
    或者，所述改性物由质量比为1:(0.1-0.2)的所述有机硅和所述聚酰亚胺组成。
  13. 根据权利要求4-11任一项所述的外壳，其特征在于，所述环氧树脂层具有第二表面，所述外壳还包括设置在所述第二表面上的硬化层。
  14. 一种外壳的制作方法，包括如下步骤：
    制备环氧树脂板，所述环氧树脂板的材料为改性环氧树脂，所述改性环氧树脂的环氧值为0.25-0.45，所述改性环氧树脂为改性物改性的环氧树脂，所述改性物选自有机硅、聚氨酯预聚体及聚酰亚胺中的至少一种，且所述改性物与所述环氧树脂的质量比为1:5-1:10；及
    将所述环氧树脂板弯曲成型，得到外壳。
  15. 根据权利要求14所述的外壳的制作方法，其特征在于，还包括在所述环氧树脂板上设置装饰单元的步骤；且将所述环氧树脂板弯曲成型之后，所述环氧树脂板具有内凹表面，所述装饰单元位于所述内凹表面上。
  16. 根据权利要求15所述的外壳的制作方法，其特征在于，所述在所述环氧树脂板上设置装饰单 元的步骤在所述将所述环氧树脂板弯曲成型的步骤之前，所述在所述环氧树脂板上设置装饰单元的步骤包括：在所述环氧树脂板的一侧形成透明的粘结层；在所述粘结层远离所述环氧树脂板的一侧形成反射层；在所述反射层远离所述粘结层的一侧形成油墨层，得到所述装饰单元。
  17. 根据权利要求15所述的外壳的制作方法，其特征在于，所述在所述环氧树脂板上设置装饰单元的步骤在所述将所述环氧树脂板弯曲成型的步骤之前，所述在所述环氧树脂板上设置装饰单元的步骤包括：在基底膜上形成透明的粘结层，在所述粘结层上形成反射层，在所述反射层上形成油墨层，得到所述装饰单元；将所述装饰单元的所述基底膜远离所述粘结层的一侧与所述环氧树脂板的一侧粘结。
  18. 根据权利要求15所述的外壳的制作方法，其特征在于，所述在所述环氧树脂板上设置装饰单元的步骤在所述将所述环氧树脂板弯曲成型的步骤之后，所述在所述环氧树脂板上设置装饰单元的步骤包括：在基底膜上形成透明的粘结层，在所述粘结层上形成反射层，在所述反射层上形成油墨层，得到所述装饰单元；将所述装饰单元的所述基底膜远离所述粘结层的一侧与所述环氧树脂板的所述内凹表面粘结。
  19. 根据权利要求16-18任一项所述的外壳的制作方法，其特征在于，所述粘结层为通过UV胶水转印得到，所述粘结层具有纹理图案。
  20. 根据权利要求16-18任一项所述的外壳的制作方法，其特征在于，所述反射层通过真空不导电电镀得到。
  21. 根据权利要求15-18任一项所述的外壳的制作方法，其特征在于，所述在所述环氧树脂板上设置装饰单元的步骤之前，还包括在所述环氧树脂板的一侧形成图案层的步骤；所述在所述环氧树脂板上设置装饰单元的步骤包括：在所述环氧树脂板形成有所述图案层的一侧形成所述装饰单元，所述装饰单元覆盖所述图案层。
  22. 根据权利要求21所述的外壳的制作方法，其特征在于，所述图案层由镜面银油墨印刷后干燥得到。
  23. 根据权利要求14-18任一项所述外壳的制作方法，其特征在于，所述改性物选自所述有机硅及所述聚氨酯预聚体中的至少一种；
    或者，所述改性物由所述聚酰亚胺和所述聚氨酯预聚体组成，且在所述改性物中，所述聚氨酯预聚体的质量百分含量为60％以上；
    或者，所述改性物由质量比为1:(0.1-0.2)的所述有机硅和所述聚酰亚胺组成。
  24. 根据权利要求14-18任一项所述的外壳的制作方法，其特征在于，所述将所述环氧树脂板弯曲成型之后，所述环氧树脂板具有外凸表面；所述将所述环氧树脂板弯曲成型的步骤之后，还包括在所述环氧树脂的所述外凸表面上形成硬化层的步骤。
  25. 根据权利要求14-18任一项所述的外壳的制作方法，其特征在于，所述将所述环氧树脂板弯曲成型的方法为高压成型，所述高压成型的工艺参数包括：成型模具的温度为90℃-150℃，加热板的温度为150℃-300℃，充气压力为10Bar-30Bar，成型时间为60秒-150秒；
    或者，所述将所述环氧树脂板弯曲成型的方法为热压成型，所述热压成型步骤包括：先将所述环氧树脂板置于下模中，在加热板的温度为250℃-380℃的条件下加热15秒-30秒，且下模温为90℃-140℃；然后将上膜与所述下模合模，并保压10秒-30秒，上模温为90℃-130℃。
  26. 一种电子设备，包括权利要求4-13任一项所述的外壳或权利要求14-25任一项所述的外壳的制作方法制作得到的外壳。
  27. 根据权利要求26所述的电子设备，其特征在于，所述电子设备为手机或平板电脑，所述外壳为后盖。
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