CN110003442B - Housing and manufacturing method thereof, modified epoxy resin, epoxy resin board and electronic equipment - Google Patents

Housing and manufacturing method thereof, modified epoxy resin, epoxy resin board and electronic equipment Download PDF

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Publication number
CN110003442B
CN110003442B CN201910337064.3A CN201910337064A CN110003442B CN 110003442 B CN110003442 B CN 110003442B CN 201910337064 A CN201910337064 A CN 201910337064A CN 110003442 B CN110003442 B CN 110003442B
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epoxy resin
layer
polyimide
housing
modified
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CN110003442A (en
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杨光明
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Guangdong Oppo Mobile Telecommunications Corp Ltd
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Guangdong Oppo Mobile Telecommunications Corp Ltd
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Priority to CN201910337064.3A priority Critical patent/CN110003442B/en
Publication of CN110003442A publication Critical patent/CN110003442A/en
Priority to PCT/CN2020/081315 priority patent/WO2020215975A1/en
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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

Abstract

The invention relates to a shell, a manufacturing method of the shell, modified epoxy resin, an epoxy resin board and electronic equipment. The modified epoxy resin has an epoxy value of 0.25-0.45, is modified by a modifier, is selected from at least one of organic silicon, polyurethane prepolymer and polyimide, and has a mass ratio of 1: 5-1: 10 to the epoxy resin. The modified epoxy resin has good wear resistance, good scratch resistance and good tensile property.

Description

Housing and manufacturing method thereof, modified epoxy resin, epoxy resin board and electronic equipment
Technical Field
The invention relates to the technical field of electronic equipment, in particular to a shell and a manufacturing method thereof, modified epoxy resin, an epoxy resin board and electronic equipment.
Background
At present, shells of electronic devices (such as mobile phones) are generally made of composite boards and pure PC boards made of PC (polycarbonate) and PMMA (polymethyl methacrylate), however, the tensile resistance of the composite boards is poor, if bending forming is adopted, the composite boards are easy to crack when being stretched in a bending process, and the pure PC boards have good tensile resistance, so that the problem of cracking in the forming and stretching process of the composite boards can be solved to a certain extent, but the hardness of the PC boards is low, so that the wear resistance and the scratch resistance of the PC boards are poor, and the experience of consumers is affected.
Because the PET (polyethylene terephthalate) sheet has better wear resistance and scratch resistance, some terminal companies also try to use the PET sheet to manufacture the housing of the electronic device at present, but the PET sheet is easy to warp in the bending process, which limits the application of the PET sheet on the rear cover.
Disclosure of Invention
Based on the above, there is a need for a modified epoxy resin having good wear resistance, good scratch resistance and good tensile resistance.
In addition, an epoxy resin plate, a shell manufacturing method and electronic equipment are also provided.
The modified epoxy resin has an epoxy value of 0.25-0.45, is modified by a modifier, is selected from at least one of organic silicon, polyurethane prepolymer and polyimide, and has a mass ratio of 1: 5-1: 10 to the epoxy resin.
The epoxy value of the modified epoxy resin is controlled to be 0.25-0.45, and the mass ratio of the modifier to the epoxy resin for preparing the modified epoxy resin is 1: 5-1: 10, so that the hardness of the modified epoxy resin can reach HB-H, and the modified epoxy resin has good wear resistance and good scratch resistance; the modified epoxy resin also has good tensile resistance, the tensile strength is more than 60MPa, and the modified epoxy resin can be directly bent and formed; the modified epoxy resin has a softening temperature of 100-130 ℃ and good high-temperature resistance.
The epoxy resin plate is made of modified epoxy resin, the epoxy value of the modified epoxy resin is 0.25-0.45, the modified epoxy resin is modified by a modifier, the modifier is at least one selected from organic silicon, polyurethane prepolymer and polyimide, and the mass ratio of the modifier to the epoxy resin is 1: 5-1: 10.
Because the epoxy resin plate is prepared from the modified epoxy resin, the hardness of the epoxy resin plate can reach HB-H, and the epoxy resin plate has better wear resistance and better scratch resistance; the epoxy resin plate also has better tensile resistance, the tensile strength is more than 60MPa, and the epoxy resin plate can be directly bent and formed; the softening temperature of the modified epoxy resin is 100-130 ℃, and the modified epoxy resin has better high-temperature resistance.
The shell comprises an epoxy resin layer, the epoxy resin layer is made of modified epoxy resin, the epoxy value of the modified epoxy resin is 0.25-0.45, the modified epoxy resin is modified by a modifier, the modifier is at least one of organic silicon, polyurethane prepolymer and polyimide, and the mass ratio of the modifier to the epoxy resin is 1: 5-1: 10.
Because above-mentioned shell includes the epoxy layer of above-mentioned material, this epoxy layer has better wear resistance and better scratch resistance ability, and still has better high temperature resistance and ageing resistance for above-mentioned shell not only has better performance, still is favorable to reducing its cost.
A manufacturing method of a shell comprises the following steps:
preparing an epoxy resin plate, wherein the epoxy resin plate is made of modified epoxy resin, the epoxy value of the modified epoxy resin is 0.25-0.45, the modified epoxy resin is modified by a modifier, the modifier is at least one of organic silicon, polyurethane prepolymer and polyimide, and the mass ratio of the modifier to the epoxy resin is 1: 5-1: 10; and
and bending and molding the epoxy resin plate to obtain the shell.
Because the epoxy resin plate is prepared from the modified epoxy resin, the epoxy resin plate also has better tensile property and can be directly bent and formed; the hardness of the epoxy resin plate can reach HB-H, the epoxy resin plate has good wear resistance and scratch resistance, the softening temperature is 100-130 ℃, the epoxy resin plate has good high temperature resistance, and meanwhile, the modified epoxy resin also has good aging resistance.
Although the existing method for preparing the integrated shell with different thicknesses by adopting the epoxy resin injection molding mode easily generates stress lines during cold and hot shrinkage, so that the rainbow phenomenon is easily generated at corners or wake flow positions, and the stress lines are likely to appear in the shell, so that the shell cannot be repaired again, and the appearance is greatly influenced; in addition, the sample after injection molding needs a polishing process to obtain a better appearance surface, so compared with the epoxy resin injection molding mode, the manufacturing method of the shell has the advantages that the epoxy resin plate is bent and molded, the process of the bent and molded epoxy resin plate is not needed, and the rainbow phenomenon can be avoided, so the manufacturing method of the shell can simplify the manufacturing process, improve the yield and reduce the manufacturing cost of the shell.
An electronic device comprises the shell or the shell manufactured by the shell manufacturing method.
Because the electronic equipment adopts the shell, the service life of the electronic equipment is prolonged, and the production cost of the electronic equipment is reduced.
Drawings
Fig. 1 is a flowchart of a method of manufacturing a housing of a first embodiment;
FIG. 2 is a schematic structural view of the housing of the first embodiment;
FIG. 3 is a partial cross-sectional view of the housing shown in FIG. 2;
FIG. 4 is a flow chart of a method of making a housing of the second embodiment;
FIG. 5 is a partial cross-sectional view of a housing of the second embodiment;
FIG. 6 is a flow chart of a method of making a housing of the third embodiment;
fig. 7 is a partial sectional view of the housing of the third embodiment.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The modified epoxy resin of an embodiment can be used for manufacturing a shell, such as a shell of an electronic device, in particular a back cover of a mobile phone, a tablet computer and the like. The epoxy value of the modified epoxy resin is 0.25-0.45, the modified epoxy resin is modified by a modifier, the modifier is at least one selected from organic silicon, polyurethane prepolymer and polyimide, and the mass ratio of the modifier to the epoxy resin is 1: 5-1: 10.
The epoxy value referred to herein means the amount (i.e., molar amount) of the substance having an epoxy group contained in 100g of the modified epoxy resin, and the mass percentage content of the epoxy group in the modified epoxy resin can be determined based on the epoxy value. The relationship between epoxy value and epoxy equivalent is: the epoxy value was 100/epoxy equivalent, the molecular weight of the epoxy group was 43, and the mass percentage of the epoxy group in the modified epoxy resin was 43 × 100/epoxy equivalent. For example, when the epoxy equivalent of a bisphenol a type epoxy resin is 180 g/eq, the epoxy group content of the resin is 43 × 100/180 ═ 23.88 by mass, and the epoxy value of the resin is 100/180 ═ 0.555.
The epoxy resin is modified by adding the modifier in the proportion, so that the tensile strength and the impact resistance of the epoxy resin can be improved and the risk of cracking of the material in the manufacturing process can be well reduced on the premise of ensuring higher hardness of the epoxy resin.
A method for producing a modified epoxy resin according to an embodiment is a method for producing the above-described modified epoxy resin, and the method for producing the modified epoxy resin includes the steps of: mixing the modifier, the epoxy resin and a catalyst according to the epoxy value of the modified epoxy resin of 0.25-0.45 to obtain a mixture, wherein the mass ratio of the modifier to the epoxy resin is 1: 5-1: 10; adding a curing agent into the mixture, and then reacting at 80-120 ℃ to obtain the modified epoxy resin.
The epoxy resin may be an epoxy resin commonly used in the art, such as a bisphenol a type epoxy resin. In one embodiment, the epoxy resin is selected from at least one of E-51 epoxy, E-55 epoxy, and E-44 epoxy.
The silicone may be a silicone monomer commonly used in the art. In one embodiment, the silicone is selected from at least one of polydimethylsiloxane, dimethyldimethoxysiloxane, methylvinyldimethoxysiloxane, and methylphenyldimethoxysiloxane.
The polyurethane prepolymer can be a polyurethane prepolymer commonly used in the field for modifying epoxy resin, and is obtained by reacting diisocyanate or polyisocyanate with polyol according to a certain proportion. In one embodiment, the polyisocyanate is selected from one of IPDI (isophorone diisocyanate), TDI (toluene diisocyanate), MDI (diphenylmethane-4, 4' -diisocyanate), and HDI (hexamethylene diisocyanate); the polyalcohol is polyethylene glycol or polypropylene glycol; the mass ratio of the polyisocyanate to the polyol is 1 (0.5-1.5). Polyurethane prepolymers are also commercially available, such as those made by Jining HuaKa resin, model No. KHP-456, and those made by Dow, U.S. model No. N434.
The polyimide is selected from at least one of pyromellitic polyimide, fluoroanhydride polyimide, ketoanhydride polyimide, NA-group-terminated polyimide, ethynyl-terminated polyimide and polybenzimidazole polyimide.
The catalyst may be a catalyst commonly used in the art. In one embodiment, the catalyst is dibutyltin dilaurate.
The curing agent may be one commonly used in the art. In one embodiment, the curing agent is dicyandiamide.
If the modified epoxy resin is required to have higher optical transmittance (the optical transmittance is more than 85%), the modified substance is selected from at least one of organic silicon and polyurethane prepolymer; or the modifier consists of polyimide and polyurethane prepolymer, wherein the mass percentage of the polyurethane prepolymer in the modifier is more than 60%; or the modifier consists of organic silicon and polyimide with the mass ratio of 1 (0.1-0.2).
In one embodiment, the step of preparing the modified epoxy resin comprises: the modified epoxy resin is obtained by stirring and mixing the modified substance, the epoxy resin and the catalyst for 1 to 4 hours at room temperature, and then adding the curing agent to react for 1 to 2 hours at a temperature of between 80 and 120 ℃. Wherein the mass ratio of the modifier to the epoxy resin is 1: 5-1: 10, the mass ratio of the catalyst to the epoxy resin is 1: 100-5: 100, and the mass ratio of the curing agent to the epoxy resin is 10: 100-30: 100. Wherein the room temperature referred to herein is 10 ℃ to 40 ℃.
It is to be understood that the method for preparing the above modified epoxy resin is not limited to the use of the substances and steps in the above steps, and the above modified epoxy resin may be prepared by a conventional preparation process of modified epoxy resin.
The epoxy value of the modified epoxy resin is controlled to be 0.25-0.45, and the mass ratio of the modifier to the epoxy resin for preparing the modified epoxy resin is 1: 5-1: 10, so that the hardness of the modified epoxy resin can reach HB-H, and the modified epoxy resin has good wear resistance and good scratch resistance; the modified epoxy resin also has better tensile property, the tensile strength is more than 60MPa, and the modified epoxy resin can be directly bent and formed; the softening temperature of the modified epoxy resin is 100-130 ℃, and the modified epoxy resin has better high-temperature resistance.
The traditional epoxy resin plate has poor high-temperature resistance and easy aging, so that the application range of the epoxy resin plate is limited, the softening temperature of the modified epoxy resin is 100-130 ℃, the modified epoxy resin has good high-temperature resistance, and meanwhile, the modified epoxy resin can be prevented from yellowing by irradiating for 48H under ultraviolet rays, has good aging resistance and also has impact resistance.
In the epoxy resin board of an embodiment, the material of the epoxy resin board is the modified epoxy resin. Namely, the epoxy resin plate is obtained by molding the modified epoxy resin. The epoxy board can be used for manufacturing a shell, such as a shell of an electronic device, in particular a back cover of a mobile phone or a tablet computer.
In one embodiment, the thickness of the epoxy resin plate is 0.4 mm to 0.8 mm, and the epoxy resin plate with the thickness is suitable for manufacturing a shell with a decorative layer (such as patterns, textures and the like). It will be appreciated that the thickness of the epoxy board can be adjusted according to the desired thickness and performance.
Further, the optical transmittance of the epoxy resin plate is 83% -88%, so that other decorative layers (such as patterns, textures and the like) can be manufactured on the epoxy resin plate in a subsequent process, and a fine product can be obtained.
In one embodiment, the epoxy board is prepared by the steps of: and melting the modified epoxy resin at 140-190 ℃, and then extruding to obtain the epoxy resin plate.
Because the epoxy resin plate is prepared from the modified epoxy resin, the hardness of the epoxy resin plate can reach HB-H, and the epoxy resin plate has better wear resistance and better scratch resistance; the epoxy resin plate also has better tensile resistance and can be directly bent and formed; the softening temperature of the modified epoxy resin is 100-130 ℃, and the modified epoxy resin has better high-temperature resistance.
The traditional epoxy resin plate is poor in high-temperature resistance and easy to age, so that the application range of the traditional epoxy resin plate is limited, the epoxy resin plate is made of the modified epoxy resin, the softening temperature of the modified epoxy resin is 100-130 ℃, the modified epoxy resin has good high-temperature resistance, the modified epoxy resin is not yellowed when irradiated under ultraviolet rays for 48H, and the modified epoxy resin has good aging resistance, so that the epoxy resin plate can be used for manufacturing a shell.
As shown in fig. 1, the method for manufacturing a housing according to the first embodiment can be used as a housing of an electronic device, such as a housing of a tablet computer, a mobile phone, and the like, and particularly as a back cover of a mobile phone or a tablet computer. The method for manufacturing the housing according to this embodiment includes steps S11 to S15:
step S11: an epoxy board was prepared.
The epoxy resin plate is made of modified epoxy resin, the epoxy value of the modified epoxy resin is 0.25-0.45, the modified epoxy resin is modified by a modifier, the modifier is at least one of organic silicon, polyurethane prepolymer and polyimide, and the mass ratio of the modifier to the epoxy resin is 1: 5-1: 10. Specifically, the epoxy resin board is the epoxy resin board, and the preparation method is as described above, which is not described herein again.
In one embodiment, the shell is a mobile phone rear cover, and the thickness of the epoxy resin plate is 0.4-0.8 mm. It will be appreciated that the thickness of the epoxy board can be adjusted according to the desired thickness and performance.
Further, the optical transmittance of the epoxy resin plate is 83% to 88%.
Step S12: a pattern layer is formed on one side of the epoxy resin plate.
The pattern of the pattern layer may be LOGO, symbol, animal pattern, or the like, for example.
Specifically, the pattern layer is obtained by printing mirror silver ink and then drying. More specifically, the step of forming a pattern layer on one side of the epoxy resin plate is: adopting a 300-420 mesh silk screen printing plate silk screen mirror surface silver ink on one side of an epoxy resin plate, standing for 30-60 minutes at 15-30 ℃, and baking for 30-90 minutes at 60-80 ℃. The mirror ink is, for example, 06B mirror silver ink of Shenzhen Jiwang ink science and technology Limited.
If the mirror-like silver ink used is an ink having corrosiveness, a transparent corrosion-resistant layer is formed on one side of the epoxy resin plate before the step of forming the pattern layer on one side of the epoxy resin plate, and then the pattern layer is formed on the corrosion-resistant layer. In one embodiment, the corrosion-resistant layer is UV glue, the UV glue is polyurethane acrylate glue, the glue has good chemical resistance, good adhesion and excellent weather resistance, and the polyurethane acrylate glue is UV glue with the model number of 633-75 of New Bitili Material Co.
In one embodiment, the patterned layer has a thickness of 1 to 4 microns. It is to be understood that the thickness of the pattern layer may be set as desired.
Step S13: a decoration unit is arranged on the epoxy resin plate.
In the present embodiment, a decorative unit is provided on the side of the epoxy resin plate on which the pattern layer is formed, and covers the pattern layer.
In one embodiment, the decorative unit includes a bonding layer, a reflective layer, and an ink layer. The step of providing the decorative unit on the epoxy resin plate includes: forming a transparent bonding layer on one side of the epoxy resin plate on which the pattern layer is formed, wherein the bonding layer covers the pattern layer; forming a reflecting layer on one side of the bonding layer, which is far away from the epoxy resin plate; and forming an ink layer on one side of the reflecting layer away from the bonding layer.
Further, the adhesive layer is obtained by UV (ultraviolet) glue transfer printing, and the adhesive layer has a texture pattern, so that the shell has a texture appearance. The UV glue can be transparent UV glue which is commonly used in the field after being cured. In one embodiment, the UV glue is a urethane acrylate glue, such as UV glue model 633-75 from New fibrate materials, Inc. The curing energy of the UV glue is 600mj/cm2～1500mj/cm2. It can be understood that the UV glue is not limited to the above glue, but may also be a glue that is transparent after being cured, which is commonly used in the art; the adhesive layer may also have no textured pattern, in which case the shell has no textured appearance.
In one embodiment, the bonding layer has a thickness of 5 to 20 microns. It is understood that the thickness of the adhesive layer is not limited to the above thickness, and the thickness of the adhesive layer may be set as desired.
The reflective layer is obtained by vacuum non-conductive plating (NCVM) so that the reflective layer not only can impart a color to the case, but also can enhance the gloss and reflectance of the case. And the reflecting layer is formed on the bonding layer, so that the reflecting layer and the adhesive force can be improved.
Specifically, the reflective layer is at least one selected from an indium tin oxide layer, a titanium dioxide layer, a niobium trioxide layer, a niobium dioxide layer, a niobium pentoxide layer, a silicon dioxide layer, and a zirconium dioxide layer. That is, the reflective layer may have a single-layer structure or a multilayer structure.
In one embodiment, the total thickness of the reflective layer is 5 nm to 300 nm, that is, when the reflective layer has a single-layer structure, the thickness of the reflective layer is 5 nm to 300 nm, and when the reflective layer has a multi-layer structure, the total thickness of the multi-layer reflective layer is 5 nm to 300 nm. It is to be understood that the thickness of the reflective layer is not limited to the above thickness, and the thickness of the reflective layer may be set as desired.
The ink layer is prepared by screen printing. Further, the printing ink layer is formed through printing many times and drying many times, and many times printing and many times drying go on in turn, and printing thickness is 5 microns ~ 8 microns at every turn, can make the printing ink layer level and smooth more through printing many times, and comparatively reliable, if the thickness of single printing is too thick, appearance quality problems such as bubble may appear during the stoving. Specifically, the ink layer includes a white ink layer, or a gray ink layer. The printing ink layer not only can protect the reflection stratum, can also provide background colour and shelter from light, places internal structure and components and parts etc. of seeing the product through the shell.
In one embodiment, the thickness of the ink layer is 10 to 20 microns. It is to be understood that the thickness of the ink layer is not limited to the above thickness, and the thickness of the ink layer may be set as desired.
Step S14: and bending and molding the epoxy resin plate.
Namely, the epoxy resin plate with the decorative units and the pattern layer is formed by bending. And after the epoxy resin plate is bent and formed, the epoxy resin plate is provided with an inner concave surface and an outer convex surface opposite to the inner concave surface. The decoration unit and the pattern layer are both positioned on the inner concave surface.
In one embodiment, the method of bending the epoxy resin plate is high pressure molding. High pressure forming refers to a process in which the material is shaped at a pressure of greater than 14 kg/cm, approximately 1.4X 10 Pa. The technological parameters of high-pressure forming comprise: the temperature of the forming die is 90-150 ℃, the temperature of the heating plate is 150-300 ℃, the inflation pressure is 10-30 Bar, and the forming time is 60-150 seconds. The temperature of the forming mold and the temperature of the heating plate need to be appropriate and matched with each other, if the temperature is too high, the surface (especially the outer convex surface) of the epoxy resin plate is prone to wrinkle and bubble, and if the temperature is too low, the epoxy resin plate is cracked, especially the arc-shaped part of the outer convex surface.
In another embodiment, the method for bending and molding the epoxy resin plate is hot press molding, and the step of hot press molding comprises the following steps: firstly, placing an epoxy resin plate in a lower die, heating for 15-30 seconds under the condition that the temperature of a heating plate is 250-380 ℃, and controlling the temperature of the lower die to be 90-140 ℃; and then closing the upper die and the lower die, and keeping the pressure for 10-30 seconds, wherein the temperature of the upper die is 90-130 ℃. The temperature of the heating plate, the temperature of the upper die and the temperature of the lower die are required to be proper and matched with each other, if the temperature is too high, the epoxy resin plate is prone to wrinkle and bubble (particularly to form an outer convex surface), and if the temperature is too low, the epoxy resin plate is prone to crack, particularly to form an arc-shaped part of the outer convex surface.
Step S15: a hardened layer is formed on the outer convex surface of the epoxy resin plate to obtain a case.
In one embodiment, the step of forming the hardened layer on the outer convex surface of the epoxy resin board includes: and spraying a hardening liquid on the convex surface of the epoxy resin plate, baking for 3-10 minutes at 60-80 ℃, and then irradiating by ultraviolet light for curing to obtain a hardened layer.
In one embodiment, the hardening liquid is mainly composed of urethane acrylate, silicone resin and perfluoropolyether acrylate, such as the hardening liquid of type 304 from PPG company; curing energy 400mj/cm2～1200mj/cm2. It is to be understood that the hardening liquid is not limited to the above-mentioned ones, and may be one commonly used in the art. The hardened layer prepared by the hardening liquid has better wear resistance and scratch resistance.
In one embodiment, the thickness of the hardened layer is 3 microns to 20 microns. It will be appreciated that the thickness of the hardened layer may be adjusted as desired.
Specifically, the hardness of the hardened layer is 3H-5H, and if the hardness is too low, the wear resistance and the scratch resistance are poor; if the hardness is too high, the brittleness of the hardened layer increases, and the production efficiency is lowered. The hardness of the hardened layer can be adjusted by adjusting the thickness and the curing energy of the hardened layer.
It should be noted that the manufacturing method of the housing is not limited to the above steps, and the hardened layer may be omitted, and then step S15 may be omitted; the decoration unit is not limited to the above structure, for example, the decoration unit does not have the ink layer, that is, the ink layer may be omitted; or, the decorative unit does not have a reflecting layer, and in this case, the ink layer is directly printed on the side of the bonding layer away from the epoxy resin plate. Alternatively, the pattern layer may be omitted, in which case step S12 may be omitted, and in this case, the decorative element may be formed on one side of the epoxy resin plate, and the transparent adhesive layer may be formed on one side of the epoxy resin plate, in which case, the decorative element may be only an ink layer, and the ink layer may be directly printed on one side of the epoxy resin plate. Alternatively, the decoration unit may be omitted, in which case step S13 is omitted. Alternatively, in other embodiments, the housing may be obtained by only bending and molding an epoxy resin plate, and the manufacturing method of the housing does not include steps S12, S13, and S15; alternatively, the housing does not have a pattern layer, and in this case, the housing has at least one of a hardened layer and a decorative layer in addition to the epoxy resin plate, that is, the housing is not manufactured in the steps S12 and S15, or the housing is not manufactured in the steps S12 and S13.
The manufacturing method of the shell has at least the following advantages:
because the epoxy resin plate is prepared from the modified epoxy resin, the epoxy resin plate has better tensile resistance (tensile strength is more than 60 MPa), and can be directly bent and formed; the hardness of the epoxy resin plate can reach HB-H, and the epoxy resin plate has good wear resistance and scratch resistance, the softening temperature is 110-130 ℃, and the epoxy resin plate has good high temperature resistance, aging resistance and impact resistance.
Although, in the existing method for preparing the integrated shell with different thicknesses by adopting the epoxy resin injection molding mode, stress lines (cracks) are easily generated during cold and hot shrinkage, so that rainbow phenomena are easily generated at corners or wake positions, and the rainbow phenomena are likely to occur in the shell, so that the shell cannot be repaired again, and the appearance is greatly influenced; in addition, the sample after injection molding needs a polishing process to obtain a better appearance surface, so compared with the epoxy resin injection molding mode, the manufacturing method of the shell has the advantages that the epoxy resin plate is bent and molded, the process of the bent and molded epoxy resin plate is not needed, and the rainbow phenomenon can be avoided, so the manufacturing method of the shell can simplify the manufacturing process, improve the yield and reduce the manufacturing cost of the shell.
As shown in fig. 2, the housing 100 of the first embodiment can be manufactured by the method for manufacturing the housing of the first embodiment, and the housing 100 can be used as a housing of an electronic device, for example, a housing of a tablet computer, a mobile phone, and the like, and especially, a rear cover of a mobile phone or a tablet computer. As shown in fig. 3, the case 100 of the first embodiment includes an epoxy resin layer 110, a pattern layer 120, a decoration unit 130, and a hardening layer 140.
The material of the epoxy resin layer 110 is the modified epoxy resin, and is not described herein again. The epoxy resin layer 110 is formed by bending the epoxy resin plate. The epoxy layer 110 has a first surface 112 and a second surface 114 opposite the first surface 112. The first surface 112 is an inner concave surface, and the second surface 114 is an outer convex surface.
In one embodiment, the housing 100 is a mobile phone rear cover, and the thickness of the epoxy layer 110 is 0.4 mm to 0.8 mm. It is understood that the thickness of the epoxy layer 110 may be adjusted as desired.
The patterned layer 120 is disposed on the first surface 112. The pattern of the pattern layer 120 may be, for example, LOGO, symbol, animal pattern, etc. In one embodiment, the material of the pattern layer 120 is mirror silver; the pattern silver is prepared by screen printing mirror silver ink.
In one embodiment, the thickness of the patterned layer 120 is 1 micron to 4 microns. It is understood that the thickness of the pattern layer 120 may be set as desired.
The decoration unit 130 is disposed on the first surface 112 of the epoxy 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, which are sequentially stacked.
The adhesive layer 132 is made of a transparent material. The adhesive layer 132 is disposed on the first surface 112 of the epoxy layer 110, and the adhesive layer 132 covers the pattern layer 120. Further, the adhesive layer 132 is a UV transfer layer having a textured pattern to give the housing 100 a textured appearance. Specifically, the adhesive layer 132 is a urethane acrylate glue layer. Such as UV glues with model number 633-75 from new fibrate materials limited. It is understood that the adhesive layer 132 is not limited to the glue layer, but may be glue that is transparent after being cured, which is commonly used in the art; the adhesive layer 132 may also have no textured pattern, in which case the housing 100 does not have a textured appearance.
In one embodiment, the bonding layer 132 has a thickness of 5 microns to 20 microns. It is to 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 may be set as desired.
The reflective layer 134 is laminated on the side of the adhesive layer 132 away from the epoxy layer 110. Specifically, the reflective layer 134 is a vacuum non-conductive plating layer.
Specifically, the reflective layer 134 is selected from at least one of an indium tin oxide layer, a titanium dioxide layer, a niobium trioxide layer, a niobium dioxide layer, a niobium pentoxide layer, a silicon dioxide layer, and a zirconium dioxide layer. That is, the reflective layer 134 may have a single-layer structure or a multi-layer structure.
In one embodiment, the total thickness of the reflective layer 134 is 5 nm to 300 nm, that is, when the reflective layer 134 has a single-layer structure, the thickness of the reflective layer 134 is 5 nm to 300 nm, and when the reflective layer 134 has a multi-layer structure, the total thickness of the multi-layer reflective layer 134 is 5 nm to 300 nm. It is to be understood that the thickness of the reflective layer 134 is not limited to the above thickness, and the thickness of the reflective layer 134 may be set as desired.
An ink layer 136 is laminated to the side of the reflective layer 134 remote from the adhesive layer 132. Specifically, the ink layer 136 includes a white ink layer, or a gray ink layer. The ink layer 136 can not only protect the reflective layer 134, but also provide background color and shade to place internal structures and components of the product viewed through the housing 100.
In one embodiment, the thickness of the ink layer 136 is 10 microns to 20 microns. It is understood that the thickness of the ink layer 136 is not limited to the above thickness, and the thickness of the ink layer 136 may be set as desired.
The hardened layer 140 is disposed on the second surface 114 of the epoxy layer 110. The hardened layer 140 can increase the wear resistance and scratch resistance of the housing 100.
In one embodiment, the stiffening layer 140 is prepared from a stiffening liquid, the main components of which are urethane acrylate, silicone resin and perfluoropolyether acrylate, such as PPG 304 stiffening liquid. It is to be understood that the hardening liquid is not limited to the above-mentioned ones, and may be one commonly used in the art. The hardened layer 140 prepared from the hardening liquid has good wear resistance and scratch resistance.
Specifically, the hardness of the hardened layer 140 is 3H to 5H, and if the hardness is too low, the wear resistance and the scratch resistance are poor; if the hardness is too high, the brittleness of the hardened layer 140 increases, and the production efficiency is lowered.
In one embodiment, the thickness of the hardened layer 140 is 3 microns to 20 microns. It is understood that the thickness of the hardened layer 140 can be adjusted as desired.
Note that the structure of the housing 100 is not limited to a structure, for example, the hardened layer 140 may be omitted, and in this case, the second surface 114 of the epoxy resin layer 110 is an outer surface of the housing 100.
The pattern layer 120 may be omitted and the decoration unit 130 is directly laminated on the first surface 112 of the epoxy layer 110.
The decoration unit 130 is not limited to the above structure, and the adhesive layer 132 of the decoration unit 130 may be replaced by other coating layers capable of facilitating the adhesion of the reflection layer 134, such as spraying a semi-transparent color layer, and inkjet printing to a semi-transparent color; alternatively, the decoration unit 130 does not have the ink layer 136, that is, the side of the reflective layer 134 of the decoration unit 130 away from the bonding layer 132 does not have the ink layer 136; alternatively, the decoration unit 130 does not have the adhesive layer 132 and the reflective layer 134 at the same time, and the ink layer 136 is directly disposed on the first surface 112 of the epoxy layer 110; alternatively, the decoration unit 130 does not have the reflection layer 134, and the ink layer 136 is directly laminated on the side of the adhesive layer 132 away from the epoxy layer 110.
The decoration unit 130 may be omitted, and in the case that the pattern layer 120 is disposed, the pattern layer 120 may be protected by disposing a protective layer on the first surface 112 of the epoxy layer 110, the protective layer covering the pattern layer 120, and the protective layer may be, for example, a UV glue layer.
The decoration unit 130, the pattern layer 120, and the hardening layer 140 may be simultaneously omitted, and in this case, the case 100 may have only the epoxy resin layer 110.
The housing 100 described above has at least the following advantages:
because the shell 100 comprises the epoxy resin layer 110 made of the material, the epoxy resin layer 110 has good wear resistance, good scratch resistance, good high temperature resistance, good aging resistance and good shock resistance, so that the shell 100 not only has good performance, but also is beneficial to reducing the cost.
As shown in fig. 4, the housing of the second embodiment can be used as a housing of an electronic device, for example, a housing of a tablet computer, a mobile phone, and the like, and especially, a back cover of a mobile phone or a tablet computer. The method for manufacturing the housing of the present embodiment includes steps S21 to S26:
step S21: an epoxy board was prepared.
The step of preparing the epoxy resin board in this embodiment is the same as step S11, and is not described herein again.
Step S22: a pattern layer is formed on one side of the epoxy resin plate.
Specifically, the method for forming the pattern layer in this embodiment is the same as that for forming the pattern layer in step S12 in the first embodiment, and is not repeated herein.
Step S23: and forming a protective layer on one side of the epoxy resin plate on which the pattern layer is formed, wherein the protective layer covers the pattern layer.
Specifically, the protective layer is a UV glue layer. In one embodiment, the protective layer is a urethane acrylate glue layer. Such as UV glues with model number 633-75 from new fibrate materials limited. It is to be understood that the protective layer is not limited to the glue layer described above.
In one embodiment, the protective layer has a thickness of 8 to 20 microns. It is to be understood that the thickness of the protective layer is not limited to the above thickness, and the thickness of the protective layer may be set as desired.
Step S24: and arranging a decoration unit on one side of the protection layer, which is far away from the epoxy resin plate.
Specifically, the step of providing the decorative unit on the side of the protective layer away from the epoxy resin plate includes: forming a transparent bonding layer on the base film, forming a reflecting layer on the bonding layer, and forming an ink layer on the reflecting layer to obtain a decorative unit; and bonding one side of the base film of the decoration unit, which is far away from the bonding layer, with one side of the protection layer, which is far away from the epoxy resin plate.
In one embodiment, the base film is a Polycarbonate (PC) film or a TPU film. It is to 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 to 125 micrometers. It is to be understood that the thickness of the base film is not limited to the above-described thickness, and the thickness of the base film may be set as needed.
The method for fabricating the adhesive layer is similar to that of the first embodiment, except that the adhesive layer of this embodiment is fabricated on the base film, and thus is not described herein again.
The manufacturing method of the reflective layer is the same as that of the reflective layer of the first embodiment, and is not described herein again.
The manufacturing method of the ink layer is the same as that of the ink layer of the first embodiment, and is not described herein again.
Specifically, the step of bonding the side of the base film of the decoration unit away from the bonding layer with the side of the protection layer away from the epoxy resin plate comprises the following steps: and adhering the side of the base film, which is far away from the adhesive layer, to the side of the protective layer, which is far away from the epoxy resin plate by using a UV adhesive. In one embodiment, the UV adhesive is fibrate 805-16 glue.
Step S25: and bending and molding the epoxy resin plate.
Namely, the epoxy resin plate with the protective layer, the pattern layer and the decoration unit is bent and molded. Specifically, the method for bending and molding the epoxy resin plate in this embodiment is the same as that in the first embodiment, and will not be described again.
Step S26: a hardened layer is formed on the outer convex surface of the epoxy resin plate to obtain a case.
The step of forming the hardened layer in this embodiment is the same as the step of forming the hardened layer in the first embodiment, and is not described herein again.
The method for manufacturing the housing of the present embodiment is not limited to the above steps, and the present embodiment is also similar to the method for manufacturing the housing of the first embodiment, and the manufacturing of the hardened layer in step S26 may be omitted; the steps S22 and S23 may 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 plate by the UV adhesive; alternatively, step S23 is omitted, i.e., no protective layer is made, and the decorative unit is directly adhered to the epoxy board by the UV adhesive and covered with the pattern layer. The decorative element can also be made as desired, for example omitting the ink layer, etc.
Since the manufacturing method of the housing of the present embodiment is similar to the manufacturing method of the housing of the first embodiment, the same effects as the manufacturing method of the housing of the first embodiment are obtained, and the description thereof is omitted.
As shown in fig. 5, the housing 200 of the second embodiment can be manufactured by the manufacturing method of the housing of the second embodiment, and the housing 200 can be used as a housing of an electronic device, for example, a housing of a tablet computer, a mobile phone, and the like, and especially, a rear cover of a mobile phone or a tablet computer. The structure of the housing 200 of the present embodiment is similar to that of the housing 100 of the first embodiment, except that:
the housing 200 further includes a protective layer 250, the protective layer 250 being disposed on the first surface 212 of the epoxy layer 210 and covering the pattern layer 220. The first surface 212 is an inner concave surface. Specifically, the protective layer 250 is a UV glue layer. In one embodiment, the protective layer 250 is a urethane acrylate glue layer. Such as UV glues with model number 633-75 from new fibrate materials limited. It is understood that the protective layer 250 is not limited to the glue layer described above.
The decoration unit 230 further includes a base film 238, the base film 238 is disposed on the first surface 212, the housing 200 further includes an adhesive layer 260, the adhesive layer 260 is disposed between the base film 238 and the first surface 212, and the adhesive layer 260 fixedly bonds the base film 238 and the first surface 212. The side of the adhesive layer 232 away from the reflective layer 234 is laminated to the side of the base film 238 away from the first surface 212, i.e., the adhesive layer 232, the reflective layer 234, and the ink layer 236 are sequentially formed on the base film 238.
In one embodiment, the base film 238 is a Polycarbonate (PC) film or a TPU film. It is to be understood that the base film 238 is not limited to the above-described base film 238, and the base film 238 may be a transparent base film commonly used in the art.
In one embodiment, the adhesive layer 260 is made of a UV adhesive, which is a UV glue with model number 805-16 manufactured by new fibrate material ltd.
Since the structure of the housing 200 of the second embodiment is similar to that 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, and thus, detailed description thereof is omitted.
As shown in fig. 6, the housing according to the third embodiment can be used as a housing of an electronic device, for example, a housing of a tablet computer, a mobile phone, and the like, and especially, a back cover of a mobile phone or a tablet computer. The method for manufacturing the housing according to this embodiment includes steps S31 to S35:
step S31: an epoxy board was prepared.
The step of preparing the epoxy resin board in this embodiment is the same as step S11, and is not described herein again.
Step S32: a pattern layer is formed on one side of the epoxy resin plate.
Specifically, the method for forming the pattern layer in this embodiment is similar to that for forming the pattern layer in step S12 in the first embodiment, and is not repeated herein.
Step S33: and bending and molding the epoxy resin plate.
Namely, the epoxy resin plate with the pattern layer is bent and molded. Specifically, the method for bending and molding the epoxy resin plate in this embodiment is the same as that in the first embodiment, and will not be described again.
Step S34: a decorative unit is disposed on the interior concave surface of the epoxy resin.
That is, in the present embodiment, the step of providing the decorative layer on the inner concave surface of the epoxy resin is after the step of bending the epoxy resin sheet.
Specifically, the step of providing the decoration unit on the inner concave surface of the epoxy resin includes: forming a transparent bonding layer on the base film, forming a reflecting layer on the bonding layer, and forming an ink layer on the reflecting layer to obtain a decorative unit; and bonding one side of the base film of the decoration unit, which is far away from the bonding layer, with the inner concave surface of the epoxy resin plate. It is understood that the step of forming the decorative element may be performed before or at the same time as step S33, that is, the decorative element may be manufactured at step S33 or at the same time as step S33, and then the side of the base film of the decorative element away from the adhesive layer is adhered to the inner concave surface of the epoxy resin plate.
In one embodiment, the substrate film is a polycarbonate film or a TPU film. It is to 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 method for fabricating the adhesive layer is similar to that of the first embodiment, except that the adhesive layer of this embodiment is fabricated on the base film, and thus is not described herein again.
The manufacturing method of the reflective layer is the same as that of the reflective layer of the first embodiment, and is not described herein again.
The manufacturing method of the ink layer is the same as that of the ink layer of the first embodiment, and is not described herein again.
Specifically, the step of bonding the side of the base film of the decoration unit, which is far away from the bonding layer, with the inner concave surface of the epoxy resin plate comprises the following steps: and adopting an adhesive to bond one side of the base film, which is far away from the adhesive layer, with the inner concave surface of the epoxy resin plate. In the present embodiment, the adhesive is a thermosetting adhesive or a UV adhesive. The thermosetting adhesive is OCA glue, such as Olympic OCA glue; the UV adhesive is UV glue with model number of 805-16 of New fibrate material company Limited.
Step S35: a hardened layer is formed on the outer convex surface of the epoxy resin plate to obtain a case.
The step of forming the hardened layer in this embodiment is the same as the step of forming the hardened layer in the first embodiment, and is not described herein again.
Note that the method for manufacturing the case of the present embodiment is not limited to the above steps, and the manufacturing of the hardened layer in step S35 may be omitted in the present embodiment similarly to the method for manufacturing the case of the first embodiment; step S32 may be omitted, and at this time, the pattern layer is not produced, and one side of the base film of the decoration unit, which is far away from the adhesive layer, is adhered to the inner concave surface of the epoxy resin plate, that is, the decoration unit is directly adhered to the inner concave surface of the epoxy resin plate by the UV adhesive; the decorative element can also be made as desired, for example omitting the ink layer, etc.
Since the manufacturing method of the housing of the present embodiment is similar to the manufacturing method of the housing of the first embodiment, the same effects as the manufacturing method of the housing of the first embodiment are obtained, and the description thereof is omitted. Since the bending step of the manufacturing method of the housing of the third embodiment precedes the setting of the decorative unit, the glue by which the manufacturing method of the housing of this embodiment sets the decorative unit on the epoxy resin plate may use a thermosetting type adhesive in addition to the UV adhesive.
As shown in fig. 7, the housing 300 of the third embodiment can be manufactured by the method for manufacturing the housing of the third embodiment, and the housing 300 can be used as a housing of an electronic device, for example, a housing of a tablet computer, a mobile phone, and the like, and especially, a rear cover of a mobile phone or a tablet computer. The structure of the housing 300 of the present embodiment is similar to that of the housing 100 of the first embodiment, except that:
the decoration unit 330 further includes a base film 338, the base film 338 is disposed on the inner concave surface 312 of the epoxy layer 310, the housing 300 further includes an adhesive layer 350, the adhesive layer 350 is disposed between the base film 338 and the inner concave surface 312, the base film 338 and the inner concave surface 312 are fixedly bonded by the adhesive layer 350, one side of the bonding layer 332 away from the reflection layer is laminated with the inner concave surface 312 of the epoxy layer 310, that is, the bonding layer 332, the reflection layer 334 and the ink layer 336 are sequentially formed on the base film 338.
In one embodiment, the base film 338 is a PC film or a TPU film. It is to be understood that the base film 338 is not limited to the above-described base film, and the base film 338 may be a transparent base film commonly used in the art.
In one embodiment, the adhesive layer 360 is made of a UV adhesive or a thermosetting adhesive. Wherein the UV adhesive is UV with model number of 805-16 of Biteli New Material Co; the thermosetting adhesive is OCA glue, such as AOJIAOphotoelectricity OCA glue.
Since the structure of the housing 300 of the third embodiment is similar to that 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, and thus, detailed description thereof is omitted.
An electronic device according to an embodiment, for example, a tablet computer, a mobile phone, or the like, includes a housing, and the housing is a housing manufactured by the method for manufacturing a housing according to the first embodiment, a housing manufactured by the method for manufacturing a housing according to the second embodiment, a housing manufactured by the method for manufacturing a housing according to the third embodiment, or a housing according to the third embodiment.
In one embodiment, the electronic device is a mobile phone or a tablet computer, and the housing is a rear cover.
The electronic device is advantageous in that the service life of the electronic device can be prolonged and the production cost of the electronic device can be reduced by adopting the housing manufactured by the method for manufacturing the housing of the first embodiment, the housing manufactured by the method for manufacturing the housing of the second embodiment, the housing manufactured by the method for manufacturing the housing of the third embodiment, or the housing manufactured by the housing of the third embodiment.
The housing is not limited to a housing of an electronic device, and may be a housing of another product.
The following specific examples (the following examples illustrate the preparation of the modified epoxy resin by taking one of the preparation methods of the modified epoxy resin as an example, but the preparation method of the modified epoxy resin of the present invention is not limited to the following steps and the following substances, i.e., the technical solution of the present invention is not limited to the following examples, for example, dibutyltin dilaurate is used as a catalyst, dicyandiamide is used as a curing agent, MDI polyurethane prepolymer with model N434 of dow, usa is used as a polyurethane prepolymer, and the scope of the present invention is not limited by the following examples):
example 1
The epoxy resin board of this example was prepared as follows:
(1) preparing modified epoxy resin: according to Table 1, the modified product, the epoxy resin and the catalyst were mixed at room temperature under stirring at a mass ratio of A to B of the modified product to the epoxy resin of t1H, adding curing agent, stirring, and adding1Reaction at DEG C t2And (4) obtaining the modified epoxy resin after hours. 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, and the curing agent is dicyandiamide.
The epoxy value of the prepared modified epoxy resin is tested according to GB 1677-; the softening temperature of the modified epoxy resin prepared was tested according to ISO306-2013, wherein the epoxy value and softening temperature of the modified epoxy resin are shown in Table 2.
(2) According to Table 2, the modified epoxy resin prepared in step (1) was added to T2Melted at a temperature of DEG C and then extruded to obtain an epoxy resin plate having a thickness of D mm.
TABLE 1
Figure BDA0002039479780000111
Figure BDA0002039479780000121
Wherein, in the column of "epoxy resin" in Table 1, E-51, E-55 and E-44 represent E-51 epoxy resin, E-55 epoxy resin and E-44 epoxy resin, respectively, and ": in this column, represents a mass ratio, for example, E-51: E-44 represents that the epoxy resin of this example is composed of E-51 epoxy resin and E-44 epoxy resin, and the ratio represented by E-51: E-44 is a mass ratio.
TABLE 2
Figure BDA0002039479780000122
Figure BDA0002039479780000131
Comparative example 5
Comparative example 5 is a conventional 3240 epoxy panel having a thickness of 0.6 mm and an epoxy value of 0.35.
Comparative example 6
Comparative example 6 is a conventional composite substrate of Polycarbonate (PC) and Polymethylmethacrylate (PMMA) with a total thickness of 0.6 mm.
Comparative example 7
Comparative example 7 is a conventional pure Polycarbonate (PC) plate with a thickness of 0.6 mm.
Comparative example 8
Comparative example 8 is a conventional polyethylene terephthalate (PET) sheet having a thickness of 0.6 mm.
And (3) testing:
(1) FTS-3000 Fourier Infrared Spectroscopy (FTS-3000 FTS) instruments of DIGILA corporation were used to test the optical transmittances of the epoxy resin sheets of examples 1-21 and comparative examples 1-4, the 3240 epoxy resin sheet of comparative example 5, the composite substrate of comparative example 6, the pure polycarbonate sheet of comparative example 7, and the polyethylene terephthalate sheet of comparative example 8;
(2) tensile properties of the epoxy resin sheets of examples 1 to 21 and comparative examples 1 to 4, the 3240 epoxy resin sheet of comparative example 5, the composite substrate of comparative example 6, the pure polycarbonate sheet of comparative example 7, and the polyethylene terephthalate sheet of comparative example 8 were measured using an AG-IS Universal tester from Shimadzu;
(3) the epoxy resin sheets of examples 1 to 21 and comparative examples 1 to 4, the 3240 epoxy resin sheet of comparative example 5, the composite substrate of comparative example 6, the pure polycarbonate sheet of comparative example 7, and the polyethylene terephthalate sheet of comparative example 8 were tested for hardness using the ASTM D3363 method;
(4) the epoxy resin sheets of examples 1 to 21 and comparative examples 1 to 4, the 3240 epoxy resin sheet of comparative example 5, the composite substrate of comparative example 6, the pure polycarbonate sheet of comparative example 7 and the polyethylene terephthalate sheet of comparative example 8 were tested for aging resistance by the ASTM G-151 method;
(5) hot-press bending test: the epoxy resin plates of examples 1 to 21 and comparative examples 1 to 4, the 3240 epoxy resin plate of comparative example 5, the composite substrate of comparative example 6, the pure polycarbonate plate of comparative example 7 and the polyethylene terephthalate plate of comparative example 8 were bent by hot press molding as a template, and the specific steps were as follows: firstly, placing a sample plate in a lower die, and heating for 22 seconds under the condition that the temperature of a heating plate is 300 ℃, wherein the temperature of the lower die is 90-140 ℃; and then closing the upper film and the lower film, maintaining the pressure for 20 seconds, keeping the temperature of the upper die at 120 ℃, and observing the effect of the bent sample plate (whether the sample plate can be bent to a preset radian or not and whether cracks are generated on the outer convex surface or not) under the light.
(6) High-pressure bending test: the epoxy resin plates of examples 1 to 21 and comparative examples 1 to 4, the 3240 epoxy resin plate of comparative example 5, the composite substrate of comparative example 6, the pure polycarbonate plate of comparative example 7 and the polyethylene terephthalate plate of comparative example 8 were bent by high pressure molding using as a template, and the specific process parameters were: the temperature of the forming die is 120 ℃, the temperature of the heating plate is 220 ℃, the inflation pressure is 20Bar, and the forming time is 100 seconds. The effect of the bent template was then observed under light.
The optical transmittance, tensile strength, hardness, aging resistance, bending effect by hot press molding and bending effect by high pressure molding of the epoxy resin sheets of examples 1 to 21 and comparative examples 1 to 4, the 3240 epoxy resin sheet of comparative example 5, the composite substrate of comparative example 6, the pure polycarbonate sheet of comparative example 7 and the polyethylene terephthalate sheet of comparative example 8 are shown in table 3, respectively.
TABLE 3
Figure BDA0002039479780000141
Figure BDA0002039479780000151
As can be seen from table 3, the epoxy resin sheets of examples 1 to 21 have optical transmittance of 83% to 88% and higher optical transmittance, and the epoxy resin sheets of examples 1 to 21 have tensile strength of at least 60MPa, better tensile strength, hardness of HB to H, and higher hardness, so that they have better wear resistance and better scratch resistance, and at the same time, the epoxy resin sheets do not yellow when irradiated by ultraviolet light for 48H, have better aging resistance, and the properties are equivalent to those of the composite substrate of comparative example 6, and can be used as a housing, thereby providing a new material for the manufacture of the housing. Meanwhile, the epoxy resin boards in the embodiments 1 to 21 can be bent to be pre-shaped after being subjected to hot press bending and high pressure bending molding, have no cracks, can be directly molded in a bending mode, simplify the manufacturing process, improve the yield and reduce the manufacturing cost of the shell.
The epoxy resin plate of comparative example 1 has not only a small tensile strength but also a small hardness, is slightly yellowed by ultraviolet irradiation of 48H, and cannot be bent into a predetermined shape; the epoxy resin sheets of comparative examples 2 and 3, although having a large hardness, had a small tensile strength and cracks after the bending test, and thus could not be directly bent; the epoxy resin sheet of comparative example 4 has a large tensile strength, but the hardness is too low; the epoxy resin sheet of comparative example 5, although having a large hardness and a good tensile strength, was severely yellowed by the ultraviolet irradiation of 48H, and had cracks on the surface after bending molding, and could not be directly bent-molded. The hardness of the pure polycarbonate sheet of comparative example 7 was too low, and the abrasion resistance and scratch resistance were too poor; the polyethylene terephthalate sheet of comparative example 8 has an excessively high tensile strength and a small camber after bending, and is not bent into a predetermined shape, and is difficult to be manufactured into a case of a predetermined camber.
Example 22
The manufacturing process of the housing of this embodiment is as follows:
the epoxy resin board manufactured in example 1 was subjected to high-pressure molding to bend the epoxy resin board, and then subjected to CNC processing to mill off excess edge trims, thereby obtaining a housing. Wherein, the technological parameters of the high-pressure forming comprise: the temperature of the forming die is 120 ℃, the temperature of the heating plate is 200 ℃, the inflation pressure is 20Bar, and the forming time is 100 seconds.
Example 23
The manufacturing process of the housing of this embodiment is as follows:
the epoxy resin board manufactured in example 4 was subjected to high-pressure molding to bend the epoxy resin board, and then subjected to CNC processing to mill off excess edge trims, thereby obtaining a housing. Wherein, the technological parameters of the high-pressure forming comprise: the temperature of the forming die is 90 ℃, the temperature of the heating plate is 300 ℃, the inflation pressure is 10Bar, and the forming time is 60 seconds.
Example 24
The manufacturing process of the housing of this embodiment is as follows:
the epoxy resin board manufactured in example 7 was subjected to high-pressure molding to bend the epoxy resin board, and then subjected to CNC processing to mill off excess edge trims, thereby obtaining a housing. Wherein, the technological parameters of the high-pressure forming comprise: the temperature of the forming die is 150 ℃, the temperature of the heating plate is 150 ℃, the inflation pressure is 30Bar, and the forming time is 150 seconds.
Example 25
The manufacturing process of the housing of this embodiment is as follows:
the epoxy resin board manufactured in example 2 was subjected to hot press molding to bend the epoxy resin board, and then subjected to CNC processing to mill off excess edge materials, thereby obtaining a housing. Wherein, the hot-press molding step is as follows: the epoxy resin plate is placed in a lower die, the epoxy resin plate is heated for 25 seconds under the condition that the temperature of a heating plate is 320 ℃, the temperature of the lower die is 120 ℃, the heating plate is removed, then an upper die and the lower die are assembled, the pressure is maintained for 20 seconds, and the temperature of an upper die is 110 ℃.
Example 26
The manufacturing process of the housing of this embodiment is as follows:
the epoxy resin board manufactured in example 5 was subjected to hot press molding to bend the epoxy resin board, and then subjected to CNC processing to mill off excess edge materials, thereby obtaining a housing. Wherein, the hot-press molding step is as follows: the epoxy resin plate is placed in a lower die, the epoxy resin plate is heated for 30 seconds under the condition that the temperature of a heating plate is 250 ℃, the temperature of the lower die is 140 ℃, the heating plate is removed, then an upper die and the lower die are assembled, the pressure is maintained for 30 seconds, and the temperature of an upper die is 130 ℃.
Example 27
The manufacturing process of the housing of this embodiment is as follows:
the epoxy resin board manufactured in example 8 was subjected to hot press molding to bend the epoxy resin board, and then subjected to CNC processing to mill off excess edge materials, thereby obtaining a housing. Wherein, the hot-press molding step is as follows: the epoxy resin plate is placed in a lower die, the epoxy resin plate is heated for 15 seconds under the condition that the temperature of a heating plate is 380 ℃, the temperature of the lower die is 90 ℃, the heating plate is removed, then an upper die and the lower die are assembled, the pressure is maintained for 10 seconds, and the temperature of an upper die is 90 ℃.
Example 28
The manufacturing process of the housing of this embodiment is as follows:
(1) one side of the epoxy resin plate prepared in example 3 was printed with mirror-surface silver ink using a 350-mesh screen printing plate, and then left to stand at 25 ℃ for 45 minutes and then baked at 70 ℃ for 60 minutes to form a pattern layer having a thickness of 3 μm.
(2) Transferring and printing a bonding layer with textures and a thickness of 10 micrometers on one side of the epoxy resin plate on which the pattern layer is formed by using UV glue (New fibrate material Co., Ltd., model 633-75), wherein the bonding layer covers the pattern layer; vacuum non-conducting electroplating is carried out on one side, away from the epoxy resin plate, of the bonding layer to form a reflecting layer with the thickness of 15 nanometers, wherein the reflecting layer is an indium tin oxide layer; and printing black ink on the side of the indium tin oxide layer far away from the bonding layer to form an ink layer with the thickness of 15 microns so as to form the decorative unit.
(3) And (3) performing high-pressure forming on the epoxy resin plate with the decoration units formed in the step (2) to bend the epoxy resin plate. The technological parameters of high-pressure forming comprise: the temperature of the forming die is 140 ℃, the temperature of the heating plate is 250 ℃, the inflation pressure is 15Bar, and the forming time is 120 seconds.
(4) Spraying PPG 304 hardening liquid on the side of the bent epoxy resin plate far away from the decoration unit, baking at 70 ℃ for 6 minutes, and curing under the irradiation of ultraviolet light, wherein the curing energy is 800mj/cm2And forming a hardened layer with the thickness of 10 microns, then carrying out CNC machining, and milling off redundant leftover materials to obtain the shell.
Example 29
The manufacturing process of the housing of this embodiment is as follows:
(1) a 300-mesh silk-screen plate was used to screen-print mirror silver ink on one side of the epoxy resin plate prepared in example 6, and then the epoxy resin plate was allowed to stand at 15 ℃ for 60 minutes and then baked at 60 ℃ for 90 minutes to form a pattern layer having a thickness of 4 μm.
(2) Transferring and printing a bonding layer with textures and a thickness of 5 microns by using UV glue (New fibrate material Co., Ltd., model 633-75) on one side of the epoxy resin plate on which the pattern layer is formed, wherein the bonding layer covers the pattern layer; vacuum non-conducting electroplating is carried out on one side, away from the epoxy resin plate, of the bonding layer to form a reflecting layer with the thickness of 50 nanometers, wherein the reflecting layer is a niobium dioxide layer; and printing black ink on the side of the niobium dioxide layer far away from the bonding layer to form an ink layer with the thickness of 20 microns so as to form a decorative unit.
(3) And (3) performing high-pressure forming on the epoxy resin plate with the decoration units formed in the step (2) to bend the epoxy resin plate. The technological parameters of high-pressure forming comprise: the temperature of the forming die is 100 ℃, the temperature of the heating plate is 280 ℃, the inflation pressure is 200Bar, and the forming time is 80 seconds.
(4) Spraying PPG 304 hardening liquid on the side of the bent epoxy resin plate far away from the decoration unit, baking at 60 ℃ for 10 minutes, and curing under the irradiation of ultraviolet light, wherein the curing energy is 400mj/cm2And forming a hardened layer with the thickness of 3 microns, then carrying out CNC machining, and milling off redundant leftover materials to obtain the shell.
Example 30
The manufacturing process of the housing of this embodiment is as follows:
(1) one side of the epoxy resin plate prepared in example 10 was subjected to screen printing using a 420-mesh screen printing plate and mirror-like silver ink, and then the epoxy resin plate was allowed to stand at 30 ℃ for 30 minutes and baked at 80 ℃ for 30 minutes to form a pattern layer having a thickness of 1 μm.
(2) Transferring and printing a bonding layer with textures and a thickness of 20 microns by using UV glue (New fibrate material Co., Ltd., model 633-75) on one side of the epoxy resin plate on which the pattern layer is formed, wherein the bonding layer covers the pattern layer; vacuum non-conducting electroplating is carried out on one side, away from the epoxy resin plate, of the bonding layer to form a reflecting layer with the thickness of 300 nanometers, and the reflecting layer is a niobium trioxide layer; and printing black ink on the side of the niobium trioxide layer far away from the bonding layer to form an ink layer with the thickness of 10 microns so as to form a decorative unit.
(3) And (3) performing high-pressure forming on the epoxy resin plate with the decoration units formed in the step (2) to bend the epoxy resin plate. The technological parameters of high-pressure forming comprise: the temperature of the forming die is 90 ℃, the temperature of the heating plate is 200 ℃, the inflation pressure is 30Bar, and the forming time is 150 seconds.
(4) Spraying PPG 304 hardening liquid on the side of the bent epoxy resin plate far away from the decoration unit, baking at 80 ℃ for 3 minutes, and curing under the irradiation of ultraviolet light, wherein the curing energy is 1200mj/cm2And forming a hardened layer with the thickness of 20 microns, then carrying out CNC machining, and milling off redundant leftover materials to obtain the shell.
Example 31
The manufacturing process of the housing of this embodiment is as follows:
(1) similar to step (1) of example 28, except that the epoxy resin sheet used was the epoxy resin sheet prepared in example 11.
(2) Similar to step (2) of example 28, except that the reflective layer was prepared by a different procedure: and forming a niobium pentoxide layer with the thickness of 50 nanometers on the side, away from the epoxy resin plate, of the bonding layer by vacuum non-conducting electroplating, and then forming a silicon dioxide layer with the thickness of 50 nanometers on the niobium pentoxide layer. The ink layer is formed on the side of the silicon dioxide layer far away from the niobium pentoxide layer.
(3) And (3) performing hot press molding on the epoxy resin board with the decoration units formed in the step (2) to bend the epoxy resin board. Wherein, the hot-press molding step is as follows: the epoxy resin plate is placed in a lower die, the epoxy resin plate is heated for 18 seconds under the condition that the temperature of a heating plate is 300 ℃, the temperature of the lower die is 100 ℃, the heating plate is removed, then an upper die and the lower die are assembled, the pressure is maintained for 30 seconds, and the temperature of an upper die is 130 ℃.
(4) Same as in step (4) of example 28.
Example 32
The manufacturing process of the housing of this embodiment is as follows:
(1) similar to step (1) of example 29, except that the epoxy resin sheet used was the epoxy resin sheet prepared in example 13.
(2) Similar to step (2) of example 29, except that the reflective layer was prepared by a different procedure: and performing vacuum non-conducting electroplating on one side of the bonding layer, which is far away from the epoxy resin plate, to form a niobium pentoxide layer with the thickness of 40 nanometers, performing vacuum non-conducting electroplating on the niobium pentoxide layer to form a silicon dioxide layer with the thickness of 60 nanometers, and performing vacuum non-conducting electroplating on one side of the silicon dioxide layer, which is far away from the niobium pentoxide layer, to form a zirconium dioxide layer with the thickness of 70 nanometers. The ink layer is formed on the side of the zirconium dioxide layer far away from the silicon dioxide layer.
(3) And (3) performing hot press molding on the epoxy resin board with the decoration units formed in the step (2) to bend the epoxy resin board. Wherein, the hot-press molding step is as follows: the epoxy resin plate is placed in a lower die, the epoxy resin plate is heated for 20 seconds under the condition that the temperature of a heating plate is 350 ℃, the temperature of the lower die is 110 ℃, the heating plate is removed, then an upper film and the lower die are assembled, the pressure is maintained for 20 seconds, and the temperature of an upper die is 110 ℃.
(4) Same as in step (4) of example 29.
Example 33
The manufacturing process of the housing of this embodiment is as follows:
(1) one side of the epoxy resin plate prepared in example 14 was subjected to screen printing with a 350-mesh screen printing plate and mirror-like silver ink, and then the plate was allowed to stand at 20 ℃ for 50 minutes and then baked at 75 ℃ for 50 minutes to form a pattern layer having a thickness of 2 μm.
(2) A protective layer having a thickness of 8 μm was formed on the side of the epoxy resin plate on which the pattern layer was formed using UV glue (beitili new materials ltd., model 633-75), and the protective layer covered the pattern layer.
(3) Transferring and printing UV glue (New fibrate material Co., Ltd., model 633-75) on the base film to form a bonding layer with textures and the thickness of 8 microns, and performing vacuum non-conducting electroplating on one side of the bonding layer, which is far away from the epoxy resin plate, to form a reflecting layer with the thickness of 80 nanometers, wherein the reflecting layer is a niobium dioxide layer; printing black ink on one side of the niobium dioxide layer away from the bonding layer to form an ink layer with the thickness of 18 microns so as to form a decorative unit; the side of the base film of the decorative unit remote from the adhesive layer and the side of the protective layer remote from the epoxy plate were bonded with a UV adhesive (UV glue model 805-16 of new fibrate material ltd). Wherein, the basement membrane is polycarbonate membrane with the thickness of 50 microns.
(4) And (4) carrying out high-pressure forming on the epoxy resin plate provided with the decoration units in the step (3) so as to bend the epoxy resin plate. The technological parameters of high-pressure forming comprise: the temperature of the forming die is 150 ℃, the temperature of the heating plate is 250 ℃, the inflation pressure is 20Bar, and the forming time is 120 seconds.
(5) Spraying PPG 304 hardening liquid on the side of the bent epoxy resin plate far away from the decoration unit, baking at 65 ℃ for 8 minutes, and curing under the irradiation of ultraviolet light, wherein the curing energy is 600mj/cm2And forming a hardened layer with the thickness of 8 microns, then carrying out CNC machining, and milling off redundant leftover materials to obtain the shell.
Example 34
The manufacturing process of the housing of this embodiment is as follows:
(1) one side of the epoxy resin plate prepared in example 15 was printed with mirror-surface silver ink using a 400-mesh screen printing plate, and then left to stand at 25 ℃ for 40 minutes and then baked at 70 ℃ for 70 minutes to form a pattern layer having a thickness of 3 μm.
(2) A protective layer having a thickness of 20 μm was formed on the side of the epoxy resin plate on which the pattern layer was formed using UV glue (beitili new materials ltd., model 633-75), and the protective layer covered the pattern layer.
(3) Transferring and printing UV glue (New fibrate material Co., Ltd., model 633-75) on the base film to form a bonding layer with textures and 12 microns in thickness, and performing vacuum non-conducting electroplating on one side of the bonding layer away from the epoxy resin plate to form a reflecting layer with the thickness of 200 nanometers, wherein the reflecting layer is a niobium dioxide layer; printing black ink on one side of the indium tin oxide layer, which is far away from the bonding layer, to form an ink layer with the thickness of 12 microns so as to form a decorative unit; the side of the base film of the decorative unit remote from the adhesive layer and the side of the protective layer remote from the epoxy plate were bonded with a UV adhesive (UV glue model 805-16 of new fibrate material ltd). Wherein, the basement membrane is polycarbonate membrane with the thickness of 100 microns.
(4) And (4) carrying out high-pressure forming on the epoxy resin plate provided with the decoration units in the step (3) so as to bend the epoxy resin plate. The technological parameters of high-pressure forming comprise: the temperature of the forming die is 90 ℃, the temperature of the heating plate is 300 ℃, the inflation pressure is 15Bar, and the forming time is 60 seconds.
(5) Spraying PPG 304 hardening liquid on the side of the bent epoxy resin plate far away from the decoration unit, baking at 80 ℃ for 4 minutes, and curing under the irradiation of ultraviolet light, wherein the curing energy is 1000mj/cm2And forming a hardened layer with the thickness of 12 microns, then carrying out CNC machining, and milling off redundant leftover materials to obtain the shell.
Example 35
The manufacturing process of the housing of this embodiment is as follows:
(1) similar to step (1) of example 33, except that the epoxy resin sheet was the epoxy resin sheet prepared in example 4.
(2) Same as in step (2) of example 33.
(3) Similar to step (3) of example 33, except that the light-reflecting layer is a zirconium dioxide layer having a thickness of 20 nm.
(4) And (4) carrying out hot press molding on the epoxy resin board provided with the decoration units in the step (3) so as to bend the epoxy resin board. Wherein, the hot-press molding step is as follows: the epoxy resin plate is placed in a lower die, the epoxy resin plate is heated for 28 seconds under the condition that the temperature of a heating plate is 280 ℃, the temperature of the lower die is 90 ℃, the heating plate is removed, then an upper film and the lower die are assembled, the pressure is maintained for 30 seconds, and the temperature of an upper die is 90 ℃.
(5) Same as in step (5) of example 33.
Example 36
The manufacturing process of the housing of this embodiment is as follows:
(1) similar to step (1) of example 34, except that the epoxy resin sheet was the epoxy resin sheet prepared in example 18.
(2) Same as in step (2) of example 34.
(3) Similar to step (3) of example 34, except that the reflective optical layer was a niobium pentoxide layer having a thickness of 100 nm.
(4) And (4) carrying out hot press molding on the epoxy resin board provided with the decoration units in the step (3) so as to bend the epoxy resin board. Wherein, the hot-press molding step is as follows: the epoxy resin plate is placed in a lower die, the epoxy resin plate is heated for 20 seconds under the condition that the temperature of a heating plate is 370 ℃, the temperature of the lower die is 120 ℃, the heating plate is removed, then an upper die and the lower die are assembled, the pressure is maintained for 15 seconds, and the temperature of an upper die is 120 ℃.
(5) Same as in step (5) of example 34.
Example 37
The manufacturing process of the housing of this embodiment is as follows:
(1) one side of the epoxy resin plate prepared in example 5 was subjected to screen printing with a 320-mesh screen printing plate and mirror-like silver ink, and then the epoxy resin plate was allowed to stand at 15 ℃ for 60 minutes and then baked at 80 ℃ for 60 minutes to form a pattern layer having a thickness of 4 μm.
(2) And performing high-pressure molding on the epoxy resin plate with the pattern layer so as to bend the epoxy resin plate. The technological parameters of high-pressure forming comprise: the temperature of the forming die is 100 ℃, the temperature of the heating plate is 180 ℃, the inflation pressure is 15Bar, and the forming time is 120 seconds.
(3) Transferring and printing UV glue (New fibrate material Co., Ltd., model 633-75) on the base film to form a bonding layer with textures and 16 microns in thickness, and performing vacuum non-conducting electroplating on one side of the bonding layer away from the epoxy resin plate to form a reflecting layer with the thickness of 120 nanometers, wherein the reflecting layer is an indium tin oxide layer; printing black ink on one side of the indium tin oxide layer, which is far away from the bonding layer, to form an ink layer with the thickness of 15 microns so as to form a decorative unit; and adhering one side of the base film of the decoration unit, which is far away from the adhesive layer, with the inner concave surface of the epoxy resin plate by using OCA glue (Aojia photoelectric OCA glue), and covering the decoration unit with the pattern layer. Wherein, the basement membrane is the TPU membrane of thickness 125 microns.
(4) Spraying PPG 304 hardening liquid on the outer convex surface of the epoxy resin plate, baking at 60 ℃ for 10 minutes, and curing under the irradiation of ultraviolet light, wherein the curing energy is 800mj/cm2And forming a hardened layer with the thickness of 18 microns, then carrying out CNC machining, and milling off redundant leftover materials to obtain the shell.
Example 38
The manufacturing process of the housing of this embodiment is as follows:
(1) one side of the epoxy resin plate prepared in example 16 was subjected to screen printing using a 420-mesh screen printing plate and mirror-like silver ink, and then the epoxy resin plate was allowed to stand at 30 ℃ for 30 minutes and baked at 60 ℃ for 90 minutes to form a pattern layer having a thickness of 2 μm.
(2) And performing high-pressure molding on the epoxy resin plate with the pattern layer so as to bend the epoxy resin plate. The technological parameters of high-pressure forming comprise: the temperature of the forming die is 120 ℃, the temperature of the heating plate is 200 ℃, the inflation pressure is 10Bar, and the forming time is 150 seconds.
(3) Transferring and printing UV glue (New fibrate material Co., Ltd., model 633-75) on the base film to form a bonding layer with textures and the thickness of 8 microns, and performing vacuum non-conducting electroplating on one side of the bonding layer away from the epoxy resin plate to form a reflecting layer with the thickness of 30 nanometers, wherein the reflecting layer is a silicon dioxide layer; printing black ink on one side of the silicon dioxide layer, which is far away from the bonding layer, to form an ink layer with the thickness of 10 microns so as to form a decorative unit; and adhering one side of the base film of the decoration unit, which is far away from the adhesive layer, with the inner concave surface of the epoxy resin plate by using OCA glue (Aojia photoelectric OCA glue), and covering the decoration unit with the pattern layer. Wherein, the basement membrane is the TPU membrane of thickness 75 microns.
(4) Spraying PPG 304 hardening liquid on the outer convex surface of the epoxy resin plate, baking at 80 ℃ for 3 minutes, and curing under the irradiation of ultraviolet light, wherein the curing energy is 500mj/cm2And forming a hardened layer with the thickness of 5 microns, then carrying out CNC machining, and milling off redundant leftover materials to obtain the shell.
Example 39
The manufacturing process of the housing of this embodiment is as follows:
(1) similar to step (1) of example 37, except that the epoxy resin sheet of this example was the epoxy resin sheet prepared in example 10.
(2) And performing hot-press molding on the epoxy resin plate with the pattern layer to bend the epoxy resin plate. Wherein, the hot-press molding step is as follows: the epoxy resin plate is firstly placed in a lower die, the epoxy resin plate is heated for 15 seconds under the condition that the temperature of a heating plate is 280 ℃, the temperature of the lower die is 140 ℃, the heating plate is removed, then an upper die and the lower die are closed, the pressure is maintained for 130 seconds, and the temperature of an upper die is 130 ℃.
(3) Same as in step (3) of example 37.
(4) Same as in step (4) of example 37.
Example 40
The manufacturing process of the housing of this embodiment is as follows:
(1) similar to step (1) of example 38, except that the epoxy resin board of this example was the epoxy resin board prepared in example 16.
(2) And performing hot-press molding on the epoxy resin plate with the pattern layer to bend the epoxy resin plate. Wherein, the hot-press molding step is as follows: the epoxy resin plate is firstly placed in a lower die, the epoxy resin plate is heated for 30 seconds under the condition that the temperature of a heating plate is 300 ℃, the temperature of the lower die is 90 ℃, the heating plate is removed, then an upper die and the lower die are assembled, the pressure is maintained for 10 seconds, and the temperature of an upper die is 90 ℃.
(3) Same as in step (3) of example 38.
(4) Same as in step (4) of example 38.
EXAMPLE 41
The housing of this example was made in a similar manner to example 23 except that the temperature of the heating plate was 310 ℃.
Example 42
The housing of this example was fabricated in a similar manner to example 24, except that the temperature of the molding die was 80 ℃.
Example 43
The housing of this example was made in a similar manner to example 24 except that the temperature of the heating plate was 140 ℃.
Example 44
The housing of this example was made in a similar manner to example 26 except that the temperature of the heating plate was 240 ℃.
Example 45
The housing of this example was made in a similar process to example 27 except that the temperature of the hot plate was 390 ℃.
And (3) testing:
the effect of observing the epoxy resin layer of the cases prepared in examples 22 to 45 at an angle changed under strong light (for example, table lamp light) is shown in table 4:
TABLE 4
Figure BDA0002039479780000211
Figure BDA0002039479780000221
As can be seen from table 4, the epoxy resin layers of the cases of examples 22 to 40 are all free from cracks and are bent to a predetermined bending curvature, whereas the surface wrinkles and blisters of the epoxy resin layers of examples 41 and 45 are caused by an excessively high heating temperature, the epoxy resin layers of examples 42 and 43 are not bent to a predetermined bending curvature because the temperature of the forming mold or the heating plate is too low, so that the forming temperature is insufficient, and the epoxy resin layer of example 44 is cracked because the heating plate temperature is too low, so that the epoxy resin layer is cracked and cracked during the mold clamping and pressure maintaining processes, thereby causing cracks.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (27)

1. The modified epoxy resin is characterized in that the epoxy value of the modified epoxy resin is 0.25-0.45, the modified epoxy resin is modified by a modifier, and the mass ratio of the modifier to the epoxy resin is 1: 5-1: 10; the preparation method of the modified epoxy resin comprises the following steps: stirring and mixing the modifier, the epoxy resin and a catalyst for 1-4 hours at room temperature, and then adding a curing agent to react for 1-2 hours at 80-120 ℃ to obtain the modified epoxy resin, wherein the catalyst is dibutyltin dilaurate, the mass ratio of the catalyst to the epoxy resin is 1: 100-5: 100, the curing agent is dicyandiamide, and the mass ratio of the curing agent to the epoxy resin is 10: 100-30: 100;
the modified material consists of polyimide and polyurethane prepolymer, wherein the polyurethane prepolymer is obtained by reacting polyisocyanate and polyol according to a certain proportion, the polyisocyanate is selected from one of IPDI (isophorone diisocyanate), TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate) and HDI (hexamethylene diisocyanate), the polyol is polyethylene glycol or polypropylene glycol, the mass ratio of the polyisocyanate to the polyol is 1 (0.5-1.5), and the polyimide is selected from at least one of pyromellitic polyimide and ethynyl terminated polyimide;
or the modifier consists of organic silicon and polyimide in a mass ratio of 1 (0.1-0.2), wherein the organic silicon is polydimethylsiloxane, and the polyimide is selected from at least one of pyromellitic polyimide and ethynyl terminated polyimide.
2. The modified epoxy resin according to claim 1, wherein the epoxy resin is a bisphenol a type epoxy resin.
3. The epoxy resin plate is characterized in that the epoxy resin plate is made of modified epoxy resin, the epoxy value of the modified epoxy resin is 0.25-0.45, the modified epoxy resin is modified by a modifier, and the mass ratio of the modifier to the epoxy resin is 1: 5-1: 10; the preparation method of the modified epoxy resin comprises the following steps: stirring and mixing the modifier, the epoxy resin and a catalyst for 1-4 hours at room temperature, and then adding a curing agent to react for 1-2 hours at 80-120 ℃ to obtain the modified epoxy resin, wherein the catalyst is dibutyltin dilaurate, the mass ratio of the catalyst to the epoxy resin is 1: 100-5: 100, the curing agent is dicyandiamide, and the mass ratio of the curing agent to the epoxy resin is 10: 100-30: 100;
the modified material consists of polyimide and polyurethane prepolymer, wherein the polyurethane prepolymer is obtained by reacting polyisocyanate and polyol according to a certain proportion, the polyisocyanate is selected from one of IPDI (isophorone diisocyanate), TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate) and HDI (hexamethylene diisocyanate), the polyol is polyethylene glycol or polypropylene glycol, the mass ratio of the polyisocyanate to the polyol is 1 (0.5-1.5), and the polyimide is selected from at least one of pyromellitic polyimide and ethynyl terminated polyimide;
or the modifier consists of organic silicon and polyimide in a mass ratio of 1 (0.1-0.2), wherein the organic silicon is polydimethylsiloxane, and the polyimide is selected from at least one of pyromellitic polyimide and ethynyl terminated polyimide.
4. The shell is characterized by comprising an epoxy resin layer, wherein the epoxy resin layer is made of modified epoxy resin, the epoxy value of the modified epoxy resin is 0.25-0.45, the modified epoxy resin is modified by a modifier, and the mass ratio of the modifier to the epoxy resin is 1: 5-1: 10; the preparation method of the modified epoxy resin comprises the following steps: stirring and mixing the modifier, the epoxy resin and a catalyst for 1-4 hours at room temperature, and then adding a curing agent to react for 1-2 hours at 80-120 ℃ to obtain the modified epoxy resin, wherein the catalyst is dibutyltin dilaurate, the mass ratio of the catalyst to the epoxy resin is 1: 100-5: 100, the curing agent is dicyandiamide, and the mass ratio of the curing agent to the epoxy resin is 10: 100-30: 100;
the modified material consists of polyimide and polyurethane prepolymer, wherein the polyurethane prepolymer is obtained by reacting polyisocyanate and polyol according to a certain proportion, the polyisocyanate is selected from one of IPDI (isophorone diisocyanate), TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate) and HDI (hexamethylene diisocyanate), the polyol is polyethylene glycol or polypropylene glycol, the mass ratio of the polyisocyanate to the polyol is 1 (0.5-1.5), and the polyimide is selected from at least one of pyromellitic polyimide and ethynyl terminated polyimide;
or the modifier consists of organic silicon and polyimide in a mass ratio of 1 (0.1-0.2), wherein the organic silicon is polydimethylsiloxane, and the polyimide is selected from at least one of pyromellitic polyimide and ethynyl terminated polyimide.
5. The housing of claim 4, wherein the epoxy layer has a first surface, the housing further comprising a decorative element disposed on the first surface.
6. The shell according to claim 5, wherein the decoration unit comprises an adhesive layer, a reflective layer and an ink layer which are sequentially stacked, the adhesive layer is made of a transparent material, and one side of the adhesive layer, which is far away from the reflective layer, is stacked with the first surface.
7. The housing of claim 6, wherein the adhesive layer is a UV transfer layer having a textured pattern.
8. The housing of claim 6, wherein the reflective layer is a vacuum non-conductive plating.
9. The housing of claim 6, wherein the reflective layer is selected from at least one of an indium tin oxide layer, a titanium dioxide layer, a niobium trioxide layer, a niobium dioxide layer, a niobium pentoxide layer, a silicon dioxide layer, and a zirconium dioxide layer.
10. The housing of claim 6, wherein the decorative element further comprises a substrate film disposed on the first surface, the housing further comprising an adhesive layer disposed between the substrate film and the first surface and fixedly bonding the substrate film to the first surface, wherein a side of the adhesive layer remote from the reflective layer is laminated to a side of the substrate film remote from the first surface.
11. The housing of claim 5, further comprising a pattern layer disposed on the first surface of the epoxy, the decorative element covering the pattern layer.
12. The housing according to any one of claims 4 to 11, wherein the polyimide is selected from at least one of a pyromellitic polyimide, a fluoroanhydride polyimide, a ketoanhydride polyimide, a NA-group terminated polyimide, an ethynyl terminated polyimide, and a polybenzimidazole polyimide.
13. A casing according to any one of claims 4 to 11, wherein the epoxy layer has a second surface, the casing further comprising a hardened layer provided on the second surface.
14. A method for manufacturing a shell is characterized by comprising the following steps:
preparing an epoxy resin plate, wherein the epoxy resin plate is made of modified epoxy resin, the epoxy value of the modified epoxy resin is 0.25-0.45, the modified epoxy resin is modified by a modifier, and the mass ratio of the modifier to the epoxy resin is 1: 5-1: 10; the preparation method of the modified epoxy resin comprises the following steps: stirring and mixing the modifier, the epoxy resin and a catalyst for 1-4 hours at room temperature, and then adding a curing agent to react for 1-2 hours at 80-120 ℃ to obtain the modified epoxy resin, wherein the catalyst is dibutyltin dilaurate, the mass ratio of the catalyst to the epoxy resin is 1: 100-5: 100, the curing agent is dicyandiamide, and the mass ratio of the curing agent to the epoxy resin is 10: 100-30: 100; the modified material consists of polyimide and polyurethane prepolymer, wherein the polyurethane prepolymer is obtained by reacting polyisocyanate and polyol according to a certain proportion, the polyisocyanate is selected from one of IPDI (isophorone diisocyanate), TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate) and HDI (hexamethylene diisocyanate), the polyol is polyethylene glycol or polypropylene glycol, the mass ratio of the polyisocyanate to the polyol is 1 (0.5-1.5), and the polyimide is selected from at least one of pyromellitic polyimide and ethynyl terminated polyimide; or the modifier consists of organic silicon and polyimide in a mass ratio of 1 (0.1-0.2), wherein the organic silicon is polydimethylsiloxane, and the polyimide is selected from at least one of pyromellitic polyimide and ethynyl terminated polyimide; and
and bending and molding the epoxy resin plate to obtain the shell.
15. The method of making a housing of claim 14, further comprising the step of providing a decorative element on said epoxy board; and after the epoxy resin plate is bent and molded, the epoxy resin plate has an inner concave surface on which the decoration unit is located.
16. The method of manufacturing an enclosure according to claim 15, wherein the step of providing a decorative element on the epoxy board is performed before the step of bending the epoxy board, and the step of providing a decorative element on the epoxy board includes: forming a transparent adhesive layer on one side of the epoxy resin plate; forming a reflecting layer on one side of the bonding layer, which is far away from the epoxy resin plate; and forming an ink layer on one side of the reflecting layer, which is far away from the bonding layer, so as to obtain the decorative unit.
17. The method of manufacturing an enclosure according to claim 15, wherein the step of providing a decorative element on the epoxy board is performed before the step of bending the epoxy board, and the step of providing a decorative element on the epoxy board includes: forming a transparent bonding layer on a base film, forming a reflecting layer on the bonding layer, and forming an ink layer on the reflecting layer to obtain the decorative unit; and bonding one side of the base film of the decoration unit, which is far away from the bonding layer, with one side of the epoxy resin plate.
18. The method of manufacturing an enclosure according to claim 15, wherein the step of providing the decorative element on the epoxy board is subsequent to the step of bending the epoxy board, and the step of providing the decorative element on the epoxy board includes: forming a transparent bonding layer on a base film, forming a reflecting layer on the bonding layer, and forming an ink layer on the reflecting layer to obtain the decorative unit; and bonding one side of the base film of the decoration unit, which is far away from the bonding layer, with the inner concave surface of the epoxy resin plate.
19. The method of any one of claims 16 to 18, wherein the adhesive layer is formed by UV glue transfer printing, and the adhesive layer has a texture pattern.
20. A method of making a housing according to any one of claims 16 to 18, wherein the reflective layer is formed by vacuum non-conductive plating.
21. The method for manufacturing the casing according to any one of claims 15 to 18, further comprising a step of forming a pattern layer on one side of the epoxy resin plate before the step of providing the decorative element on the epoxy resin plate; the step of providing a decorative unit on the epoxy board includes: and forming the decoration unit on one side of the epoxy resin plate on which the pattern layer is formed, wherein the decoration unit covers the pattern layer.
22. A method of making a housing according to claim 21, wherein the patterned layer is printed from a specular silver ink and dried.
23. The method for manufacturing the shell according to any one of claims 14 to 18, wherein the epoxy resin is a bisphenol a type epoxy resin.
24. The method for manufacturing the shell according to any one of claims 14 to 18, wherein after the epoxy resin plate is bent, the epoxy resin plate has an outer convex surface; after the step of bending the epoxy resin board, a step of forming a hardened layer on the outer convex surface of the epoxy resin board is further included.
25. The method for manufacturing the shell according to any one of claims 14 to 18, wherein the method for bending and molding the epoxy resin plate is high-pressure molding, and the process parameters of the high-pressure molding include: the temperature of the forming die is 90-150 ℃, the temperature of the heating plate is 150-300 ℃, the inflation pressure is 10-30 Bar, and the forming time is 60-150 seconds;
or, the method for bending and molding the epoxy resin plate is hot press molding, and the hot press molding step includes: firstly, placing the epoxy resin plate in a lower die, heating for 15-30 seconds under the condition that the temperature of a heating plate is 250-380 ℃, and controlling the temperature of the lower die to be 90-140 ℃; and then closing the upper film and the lower die, keeping the pressure for 10-30 seconds, and keeping the temperature of the upper die at 90-130 ℃.
26. An electronic device comprising the housing according to any one of claims 4 to 13 or the housing manufactured by the method for manufacturing the housing according to any one of claims 14 to 25.
27. The electronic device of claim 26, wherein the electronic device is a mobile phone or a tablet computer, and the housing is a rear cover.
CN201910337064.3A 2019-04-25 2019-04-25 Housing and manufacturing method thereof, modified epoxy resin, epoxy resin board and electronic equipment Active CN110003442B (en)

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CN114571904A (en) * 2020-12-02 2022-06-03 Oppo广东移动通信有限公司 Sheet material, method for preparing sheet material, shell and electronic equipment
CN114536882B (en) * 2022-01-13 2023-09-29 深圳市亿铭粤科技有限公司 Multilayer structure decoration and manufacturing method thereof

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