CN110003442A - Shell and preparation method thereof, modified epoxy, epoxy resin board and electronic equipment - Google Patents

Shell and preparation method thereof, modified epoxy, epoxy resin board and electronic equipment Download PDF

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Publication number
CN110003442A
CN110003442A CN201910337064.3A CN201910337064A CN110003442A CN 110003442 A CN110003442 A CN 110003442A CN 201910337064 A CN201910337064 A CN 201910337064A CN 110003442 A CN110003442 A CN 110003442A
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epoxy resin
layer
resin board
shell
modifier
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CN201910337064.3A
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CN110003442B (en
Inventor
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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to a kind of shell and preparation method thereof, modified epoxy, epoxy resin board and electronic equipments.A kind of modified epoxy, the epoxide number of modified epoxy is 0.25~0.45, modified epoxy is the modified epoxy resin of modifier, and modifier is selected from least one of organosilicon, base polyurethane prepolymer for use as and polyimides, and the mass ratio of modifier and epoxy resin is 1:5~1:10.The modified epoxy has both preferable wear-resisting property, preferable adhesion strength and preferable tensile property.

Description

Shell and preparation method thereof, modified epoxy, epoxy resin board and electronic equipment
Technical field
The present invention relates to technical field of electronic equipment, more particularly to a kind of shell and preparation method thereof, modified epoxy tree Rouge, epoxy resin board and electronic equipment.
Background technique
Currently, the material of the shell of electronic equipment (such as mobile phone) generallys use PC (polycarbonate) and PMMA (poly- methyl Methyl acrylate) composite board, the pure PC plate material etc. that are fabricated to, however, the tensile resistance of composite board is poor, according to curved Song molding, is stretched easy cracking during bending, and although pure PC plate material has preferable tensile resistance, Neng Gou The problem of Cracking in composite board molding drawing process is solved to a certain extent, but the hardness of PC plate material is lower, causes its resistance to It grinds performance and adhesion strength is poor, influence the experience of consumer.
Since PET (polyethylene terephthalate) plate has preferable wear-resisting property and adhesion strength, have at present A little terminal companies also attempt the shell using PET sheet material production electronic equipment, but PET sheet material is easy during brake forming Warpage limits its application covered after.
Summary of the invention
Based on this, it is necessary to provide one kind and have both preferable wear-resisting property, preferable adhesion strength and preferable tension Stretch the modified epoxy of performance.
In addition, also providing the production method and electronic equipment of a kind of epoxy resin board, shell and shell.
A kind of modified epoxy, the epoxide number of the modified epoxy are 0.25~0.45, the modified epoxy tree Rouge is the modified epoxy resin of modifier, the modifier in organosilicon, base polyurethane prepolymer for use as and polyimides at least One kind, and the mass ratio of the modifier and the epoxy resin is 1:5~1:10.
Above-mentioned modified epoxy control epoxide number is 0.25~0.45, and prepares the above-mentioned modifier of modified epoxy Mass ratio with epoxy resin is 1:5~1:10, so that the hardness of modified epoxy has preferable wearability up to HB~H It can be with preferable adhesion strength；Above-mentioned modified epoxy also has a preferable tensile resistance, tensile strength 60MPa with On, and can directly be manually bent；The softening temperature of above-mentioned modified epoxy is 100 DEG C~130 DEG C, is had preferable High temperature resistance.
A kind of epoxy resin board, the material of the epoxy resin board are modified epoxy, the modified epoxy Epoxide number is 0.25~0.45, and the modified epoxy is the modified epoxy resin of modifier, and the modifier is selected from organic At least one of silicon, base polyurethane prepolymer for use as and polyimides, and the mass ratio of the modifier and the epoxy resin is 1:5 ~1:10.
Since above-mentioned epoxy resin board is prepared by above-mentioned modified epoxy, the hardness of the epoxy resin board is reachable HB-H has preferable wear-resisting property and preferable adhesion strength；The epoxy resin board also has preferable tensile resistance, tension Intensity 60MPa or more is stretched, and can be directly manually bent；And the softening temperature of above-mentioned modified epoxy be 100 DEG C~ 130 DEG C, there is preferable high temperature resistance.
A kind of shell, including epoxy resin layer, the material of the epoxy resin layer are modified epoxy, the modified ring The epoxide number of oxygen resin is 0.25~0.45, and the modified epoxy is the modified epoxy resin of modifier, the modifier Selected from least one of organosilicon, base polyurethane prepolymer for use as and polyimides, and the matter of the modifier and the epoxy resin Amount is than being 1:5~1:10.
Since above-mentioned shell includes the epoxy resin layer of above-mentioned material, the epoxy resin layer have preferable wear-resisting property and compared with Good adhesion strength, and also there is preferable high temperature resistance and ageing-resistant performance, so that above-mentioned shell not only has preferably Performance, also help and reduce its cost.
A kind of production method of shell, includes the following steps:
Epoxy resin board is prepared, the material of the epoxy resin board is modified epoxy, the modified epoxy Epoxide number is 0.25~0.45, and the modified epoxy is the modified epoxy resin of modifier, and the modifier is selected from organic At least one of silicon, base polyurethane prepolymer for use as and polyimides, and the mass ratio of the modifier and the epoxy resin is 1:5 ~1:10；And
By the epoxy resin board brake forming, shell is obtained.
Since above-mentioned epoxy resin board is prepared by above-mentioned modified epoxy, which also has preferable drawing Performance is stretched, can be directly manually bent；And the hardness of the epoxy resin board is up to HB~H, have preferable wear-resisting property and Preferable adhesion strength, softening temperature are 100 DEG C~130 DEG C, have preferable high temperature resistance, meanwhile, above-mentioned modified ring Oxygen resin also has preferable ageing-resistant performance.
Although the current method for preparing one by the way of epoxy resin injection molding and not waiting thick shells, in cold and hot contraction When be easy to produce stress line so that being easy to appear rainbow phenomena at turning or wake flow, and occur being likely to appear in shell Inside leads to not modify it again, produce bigger effect to appearance；In addition, injection molding after sample also need into Row polishing process can just obtain preferable appearance, accordingly, with respect to the mode of above-mentioned epoxy resin injection molding, the system of above-mentioned shell Make method by the way that by epoxy resin board brake forming, the epoxy resin board after brake forming is not necessarily to process, and can also avoid coloured silk Rainbow phenomenon, therefore, the production method of above-mentioned shell can simplify production process, improve yield rate, reduce the cost of manufacture of shell.
A kind of electronic equipment, the prepared shell of production method including above-mentioned shell or above-mentioned shell.
Since above-mentioned electronic equipment uses above-mentioned shell, be conducive to the service life for increasing electronic equipment, reduce electronics and set Standby production cost.
Detailed description of the invention
Fig. 1 is the flow chart of the production method of the shell of first embodiment；
Fig. 2 is the structural schematic diagram of the shell of first embodiment；
Fig. 3 is the partial cutaway view of shell shown in Fig. 2；
Fig. 4 is the flow chart of the production method of the shell of second embodiment；
Fig. 5 is the partial cutaway view of the shell of second embodiment；
Fig. 6 is the flow chart of the production method of the shell of third embodiment；
Fig. 7 is the partial cutaway view of the shell of third embodiment.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing Give preferred embodiment of the invention.But the invention can be realized in many different forms, however it is not limited to herein Described embodiment.On the contrary, purpose of providing these embodiments is keeps the understanding to the disclosure more saturating It is thorough comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool The purpose of the embodiment of body, it is not intended that in the limitation present invention.
The modified epoxy of one embodiment, the modified epoxy can be used for making shell, such as electronic equipment Shell, the especially rear cover of mobile phone, tablet computer etc..The epoxide number of modified epoxy is 0.25~0.45, modified epoxy Resin is the modified epoxy resin of modifier, modifier in organosilicon, base polyurethane prepolymer for use as and polyimides at least one Kind, and the mass ratio of modifier and epoxy resin is 1:5~1:10.
Epoxide number as referred to herein refers to the amount of the substance of contained epoxy group in 100g modified epoxy (i.e. mole Amount), the mass percentage of the epoxy group in modified epoxy can be determined according to the epoxide number.Epoxide number and epoxide equivalent Relationship are as follows: epoxide number=100/ epoxide equivalent, the molecular weight of epoxy group are 43, the quality hundred of the epoxy group of modified epoxy Divide content=43 × 100/ epoxide equivalent.For example, the epoxide equivalent of certain bisphenol A type epoxy resin is 180 grams/equivalent, then should The mass percentage of the epoxy group of resin is 43 × 100/180=23.88, and the epoxide number of the resin is 100/180= 0.555。
Wherein, epoxide number is higher, and epoxy resin is harder, and wear-resisting property and adhesion strength are better, but will lead to asphalt mixtures modified by epoxy resin The brittleness of rouge is excessive, and material is caused to be easy cracking, and the modifier by adding aforementioned proportion is modified epoxy resin, can Under the premise of guaranteeing epoxy resin hardness with higher, the tensile strength of epoxy resin, impact resistance and are improved very much The risk that material cracks in the production process is reduced well.
The preparation method of the modified epoxy of one embodiment is a kind of preparation method of above-mentioned modified epoxy, The preparation method of the modified epoxy includes the following steps: according to the epoxide number of modified epoxy to be 0.25~0.45, incite somebody to action Above-mentioned modifier, epoxy resin and catalyst mixing, obtain mixture, wherein the mass ratio of modifier and epoxy resin is 1:5 ~1:10；Curing agent is added in the mixture, is then reacted at 80 DEG C~120 DEG C, obtains above-mentioned modified epoxy.
Epoxy resin can be epoxy resin commonly used in the art, such as bisphenol A type epoxy resin.An implementation wherein In example, epoxy resin is selected from least one of E-51 epoxy resin, E-55 epoxy resin and E-44 epoxy resin.
Organosilicon can be organic silicon monomer commonly used in the art.Organosilicon is selected from poly- two in one of the embodiments, Methylsiloxane, dimethylformamide dimethyl oxygroup siloxanes, methyl ethylene dimethoxysiloxane and aminomethyl phenyl dimethoxy silicon At least one of oxygen alkane.
Base polyurethane prepolymer for use as can be the base polyurethane prepolymer for use as modified epoxy commonly used in the art, and polyurethane is pre- Aggressiveness is that diisocyanate or polyisocyanates and polyalcohol are obtained according to there is certain proportion to react.One embodiment wherein In, polyisocyanates is selected from IPDI (isophorone diisocyanate), TDI (toluene di-isocyanate(TDI)), MDI (diphenyl methane- 4,4'- diisocyanate) and HDI (hexamethylene diisocyanate) in it is a kind of；Polyalcohol is polyethylene glycol or polypropylene glycol；Polyisocyanic acid The mass ratio of ester and polyalcohol is 1:(0.5~1.5).Base polyurethane prepolymer for use as can also be commercially available by market, such as Jining The MDI polyurethane prepolymer of the base polyurethane prepolymer for use as of the model KHP-456 of Hua Kai production of resins, Dow model N434 Body.
Polyimides is selected from polypyromelliticimide, fluorine acid anhydride type polyimides, ketone acid anhydride type polyimides, NA base and blocks polyamides At least one of imines, acetenyl capped polyimides, polybenzimidazoles polyimides.
Catalyst can be catalyst commonly used in the art.Catalyst is tin dilaurate two in one of the embodiments, Butyl tin.
Curing agent can be curing agent commonly used in the art.Curing agent is dicyandiamide in one of the embodiments,.
If desired modified epoxy optical transmittance with higher (optical transmittance is 85% or more), modifier choosing From at least one of organosilicon and base polyurethane prepolymer for use as；Alternatively, modifier is polyimides and base polyurethane prepolymer for use as by being made of, In modifier, the mass percentage of base polyurethane prepolymer for use as is 60% or more；Alternatively, modifier by mass ratio be 1:(0.1~ 0.2) organosilicon and polyimides composition.
The step of preparing modified epoxy in one of the embodiments, includes: by modifier, epoxy resin, catalysis Mixing 1 hour~4 hours is stirred at room temperature in agent, and then adding curing agent, that 1 hour~2 are reacted at 80 DEG C~120 DEG C is small When, obtain modified epoxy.Wherein, the mass ratio of modifier and epoxy resin is 1:5~1:10, catalyst and epoxy resin Mass ratio be 1:100~5:100, the mass ratio of curing agent and epoxy resin is 10:100~30:100.Wherein, referred to herein Room temperature be 10 DEG C~40 DEG C.
It is appreciated that the method for preparing above-mentioned modified epoxy is not limited to using the substance and step in above-mentioned steps, Preparing above-mentioned modified epoxy can also be prepared using the preparation process of traditional modified epoxy.
Above-mentioned modified epoxy control epoxide number is 0.25~0.45, and prepares the above-mentioned modifier of modified epoxy Mass ratio with epoxy resin is 1:5~1:10, so that the hardness of modified epoxy has preferable wearability up to HB~H It can be with preferable adhesion strength；Above-mentioned modified epoxy also has a preferable tensile property, tensile strength 60MPa or more, And it can directly be manually bent；And the softening temperature of above-mentioned modified epoxy is 100 DEG C~130 DEG C, is had preferable High temperature resistance.
It is easy to aging since traditional epoxy resin board high temperature resistance is poor, limit its use scope, and above-mentioned modification The softening temperature of epoxy resin is 100 DEG C~130 DEG C, has preferable high temperature resistance, meanwhile, above-mentioned modified epoxy is also 48H non yellowing can be irradiated under ultraviolet light, and there is preferable ageing-resistant performance, also there is shock resistance.
The epoxy resin board of one embodiment, the material of epoxy resin board are above-mentioned modified epoxy.That is the asphalt mixtures modified by epoxy resin Rouge plate is obtained by above-mentioned modified epoxy forming processes.The epoxy resin board can be used for making shell, such as electronic equipment Shell, the especially rear cover of mobile phone or tablet computer.
In one of the embodiments, epoxy resin board with a thickness of 0.4 millimeter~0.8 millimeter, the asphalt mixtures modified by epoxy resin of the thickness Rouge plate is suitable for making the shell with decorative layer (such as pattern, texture etc.).It is appreciated that the thickness of epoxy resin board can be with It is adjusted according to required thickness and performance.
Further, the optical transmittance of epoxy resin board is 83%~88%, in order to subsequent on epoxy resin board Other decorative layers (such as pattern, texture etc.) is made, to obtain exquisite product.
The preparation step of epoxy resin board includes: by above-mentioned modified epoxy at 140 DEG C in one of the embodiments, It melts at~190 DEG C, then squeezes out, obtain epoxy resin board.
Since above-mentioned epoxy resin board is prepared by above-mentioned modified epoxy, the hardness of the epoxy resin board is up to HB ~H has preferable wear-resisting property and preferable adhesion strength；And the epoxy resin board also has preferable tensile resistance, and And it can directly be manually bent；And the softening temperature of above-mentioned modified epoxy is 100 DEG C~130 DEG C, is had preferable High temperature resistance.
It is easy to aging since traditional epoxy resin board high temperature resistance is poor, limit its use scope, and above-mentioned epoxy The material of resin plate is above-mentioned modified epoxy, and the softening temperature of above-mentioned modified epoxy is 100 DEG C~130 DEG C, is had Preferable high temperature resistance irradiates 48H non yellowing under ultraviolet light, has preferable ageing-resistant performance, so that above-mentioned asphalt mixtures modified by epoxy resin Rouge plate can be used in making shell.
As shown in Figure 1, the production method of the shell of first embodiment, the shell of this method production can be set as electronics The rear cover of the shell of standby shell, such as tablet computer, mobile phone etc., especially mobile phone or tablet computer.Outside the embodiment The production method of shell includes the following steps S11~S15:
Step S11: epoxy resin board is prepared.
Wherein, the material of epoxy resin board is modified epoxy, and the epoxide number of modified epoxy is 0.25~0.45, Modified epoxy is the modified epoxy resin of modifier, and modifier is in organosilicon, base polyurethane prepolymer for use as and polyimides At least one, and the mass ratio of modifier and the epoxy resin is 1:5~1:10.Specifically, epoxy resin board is above-mentioned Epoxy resin board, and preparation method is as described above, details are not described herein.
In one of the embodiments, shell be cell phone rear cover, epoxy resin board with a thickness of 0.4 millimeter~0.8 millimeter. It is appreciated that the thickness of epoxy resin board can be adjusted according to required thickness and performance.
Further, the optical transmittance of epoxy resin board is 83%~88%.
Step S12: pattern layer is formed in the side of epoxy resin board.
Wherein, the pattern of pattern layer can be for example LOGO, symbol, animal pattern etc..
Specifically, it is dried to obtain after pattern layer is printed by mirror-like silver ink.More specifically, in the side shape of epoxy resin board The step of at pattern layer are as follows: 300 mesh~420 mesh silk-screen halftone silk-screen mirror-like silver ink is used in the side of epoxy resin board, Then 30 minutes~60 minutes are stood at 15 DEG C~30 DEG C, then is toasted 30 minutes~90 minutes at 60 DEG C~80 DEG C.Wherein, Ink with mirror effect is, for example, the 06B mirror-like silver ink of Lian Yiwang ink Science and Technology Ltd., Shenzhen.
If the mirror-like silver ink used is to form the step of pattern layer in the side of epoxy resin board with corrosive ink Before rapid, transparent anti-corrosion layer is first formed in the side of epoxy resin board, then forms pattern layer in anti-corrosion layer.Wherein In one embodiment, anti-corrosion layer is UV glue, and UV glue is urethane acrylate glue, this kind of glue chemical-resistance It is good, there is good adhesive force, weather resistance is excellent, urethane acrylate glue such as Bei Teli new material Co., Ltd The UV glue of model 633-75.
In one of the embodiments, pattern layer with a thickness of 1 micron~4 microns.To understand, the thickness of pattern layer can be with It is configured as needed.
Step S13: decorating unit is set on epoxy resin board.
In the present embodiment, decorating unit, and overlay pattern are set in the side that epoxy resin board is formed with pattern layer Layer.
Decorating unit includes adhesive layer, reflecting layer and ink layer in one of the embodiments,.It is set on epoxy resin board The step of setting decorating unit includes: that transparent adhesive layer is formed in the side that epoxy resin board is formed with pattern layer, and adhesive layer Coverage diagram pattern layer；Reflecting layer is formed far from the side of epoxy resin board in adhesive layer；In side shape of the reflecting layer far from adhesive layer At ink layer.
Further, adhesive layer is to transfer to obtain by UV (ultraviolet light) glue, and adhesive layer has textured pattern, thus with Make shell that there is texture appearance.Wherein, UV glue can be to be transparent UV glue after solidification commonly used in the art.Wherein one In a embodiment, UV glue is urethane acrylate glue, such as the model 633-75 of Bei Teli new material Co., Ltd UV glue.The solidification energy of UV glue is 600mj/cm2~1500mj/cm2.It is appreciated that UV glue is not limited to above-mentioned glue Water, or be transparent glue after solidification commonly used in the art；Adhesive layer can also not have textured pattern, at this point, outside Shell does not have texture appearance.
In one of the embodiments, adhesive layer with a thickness of 5 microns~20 microns.It is appreciated that the thickness of adhesive layer It is not limited to above-mentioned thickness, the thickness of adhesive layer, which can according to need, to be configured.
Reflecting layer is obtained by the non-conductive plating (NCVM) of vacuum, so that reflecting layer can not only assign color of shell, also It is able to ascend the gloss and reflectivity of shell.And reflecting layer is formed on adhesive layer and can be improved reflecting layer and adhesive force.
Specifically, reflecting layer is selected from indium tin oxide layer, titanium dioxide layer, columbium dioxide layer, columbium sesquioxide layer, titanium dioxide At least one of two niobium layers, niobium pentaoxide layer, silicon dioxide layer and titanium dioxide zirconium layer.I.e. reflecting layer can be single layer knot Structure, or multilayered structure.
The overall thickness in reflecting layer is 5 nanometers~300 nanometers in one of the embodiments, i.e., when reflecting layer is single layer knot When structure, reflecting layer with a thickness of 5 nanometers~300 nanometers, when reflecting layer is multilayered structure, the overall thickness of multilayer reflective layers is 5 to receive Rice~300 nanometers.It is appreciated that the thickness in reflecting layer is not limited to above-mentioned thickness, the thickness in reflecting layer can according to need into Row setting.
Ink layer is prepared by silk-screen printing.Further, ink layer is formed by repeatedly printing and repeatedly drying, And repeatedly alternately, each print thickness is 5 microns~8 microns for printing and multiple drying, can make oil by repeatedly printing Layer of ink is more smooth, and more reliable, if the thickness of single printing is too thick, it is possible that the presentation qualities such as bubble are asked when baking Topic.Specifically, ink layer includes white ink layer, white ink layer or gray oil layer of ink.Ink layer can not only protect reflection Layer, additionally it is possible to background color and shield lights are provided, shell is placed through and sees internal structure and component of product etc..
In one of the embodiments, ink layer with a thickness of 10 microns~20 microns.It is appreciated that the thickness of ink layer It is not limited to above-mentioned thickness, the thickness of ink layer, which can according to need, to be configured.
Step S14: by epoxy resin board brake forming.
The epoxy resin board brake forming of decorating unit and pattern layer will be formed with.And epoxy resin board brake forming it Afterwards, epoxy resin board has concave surface and the convex surface opposite with concave surface.In decorating unit and pattern layer are respectively positioned on In concave surface.
It is in one of the embodiments, high-pressure molding by the method for epoxy resin board brake forming.High-pressure molding refers to It is being greater than 14 kilograms per centimeters, is being roughly equal to a kind of molding technique of Raw material processing under the pressure of 1.4 × 10 pas.The work of high-pressure molding Skill parameter includes: that the temperature of molding die is 90 DEG C~150 DEG C, and the temperature of heating plate is 150 DEG C~300 DEG C, and the blowing pressure is 10Bar~30Bar, molding time are 60 seconds~150 seconds.Wherein, the temperature of the temperature, heating plate of molding die needs suitable and phase Mutually collocation, if temperature is excessively high, the easily fold blistering of the surface (especially convex surface) of epoxy resin board if temperature is too low, can be led Cause epoxy resin board cracking, the especially arch section of convex surface.
It in another embodiment, is hot-forming, hot-forming step by the method for epoxy resin board brake forming Include: that first epoxy resin board is placed in lower die, the temperature of heating plate be 250 DEG C~380 DEG C under conditions of heating 15 seconds~ 30 seconds, and lower die temperature is 90 DEG C~140 DEG C；Then upper mold and lower die are molded, and pressure maintaining 10 seconds~30 seconds, upper mold temperature is 90 DEG C ~130 DEG C.Wherein, the temperature of the temperature of heating plate, the temperature of upper mold and lower die is needed suitable and is collocated with each other, if temperature is excessively high The easy fold blistering (especially convex surface) of epoxy resin board will lead to epoxy resin board cracking if temperature is too low, especially outer The arch section of nonreentrant surface.
Step S15: hardened layer is formed in the convex surface of epoxy resin board, obtains shell.
It include: in one of the embodiments, in ring the step of forming hardened layer in the convex surface of epoxy resin board Then showering hardening bath in the convex surface of oxygen resin plate toasts 3 minutes~10 minutes at 60 DEG C~80 DEG C, then through ultraviolet Light is irradiated to solidify, and obtains hardened layer.
Hardening bath main component is that urethane acrylate adds organic siliconresin and perfluor in one of the embodiments, Polyether acrylate, for example, PPG company model 304 hardening bath；Solidification energy 400mj/cm2~1200mj/cm2.It can be with Understand, it can be hardening bath commonly used in the art that hardening bath, which is not limited to above-mentioned substance,.The hardening that above-mentioned hardening bath is prepared Layer has preferable wear-resisting property and preferable adhesion strength.
In one of the embodiments, hardened layer with a thickness of 3 microns~20 microns.It is appreciated that the thickness of hardened layer It can according to need and be adjusted.
Specifically, hardness 3H~5H of hardened layer, if hardness is too small, wear-resisting property and adhesion strength are poor；If hardness Excessive, hardened layer brittleness increases, and can reduce production efficiency.Hardening can be adjusted by adjusting the thickness and solidification energy of hardened layer The hardness of layer.
It should be noted that the production method of shell is not limited to above-mentioned steps, hardened layer be can be omitted, then, step S15 can be omitted；Decorating unit is not limited to above structure, for example, decorating unit does not have ink layer, i.e. ink layer can save Slightly；Alternatively, decorating unit does not have reflecting layer, at this point, ink layer is directly printed on side of the adhesive layer far from epoxy resin board. Alternatively, pattern layer can be omitted, step S12 be can be omitted at this time, at this point, being in the side of epoxy resin board formation decorating unit Can, transparent adhesive layer is formed in the side of epoxy resin board, at this point, decorating unit can be only ink layer, then in ink layer It is directly printed on the side of epoxy resin board.Alternatively, decorating unit also can be omitted, step S13 is omitted at this time.Alternatively, In other embodiments, shell obtains after can moreover be only epoxy resin board brake forming, and the production method of shell does not have step Rapid S12, S13 and step S15；Alternatively, shell does not have pattern layer, at this point, shell is in addition to also having hard with epoxy resin board Change at least one of layer and decorative layer, i.e. the production method of shell does not have step S12 and step S15, alternatively, the system of shell Make method without step S12 and step S13.
The production method of above-mentioned shell at least has the advantage that
Since above-mentioned epoxy resin board is prepared by above-mentioned modified epoxy, which has preferable tension Stretching performance, (tensile strength can directly be manually bent in 60MPa or more)；And the hardness of the epoxy resin board is up to HB ~H has preferable wear-resisting property and preferable adhesion strength, and softening temperature is 110 DEG C~130 DEG C, has preferable resistance to height Warm nature energy, while also there is preferable ageing-resistant performance and shock resistance.
Although the current method for preparing one by the way of epoxy resin injection molding and not waiting thick shells, in cold and hot contraction When be easy to produce stress line (crackle) so that being easy to appear rainbow phenomena at turning or wake flow, and occur being likely to occur Inside housings, lead to not modify it again, appearance is produced bigger effect；In addition, the sample after injection molding is also Preferable appearance can just be obtained by needing to carry out polishing process, above-mentioned outer accordingly, with respect to the mode of above-mentioned epoxy resin injection molding The production method of shell is by the way that by epoxy resin board brake forming, the epoxy resin board after brake forming is not necessarily to process, and can also Rainbow phenomena is avoided, therefore, the production method of above-mentioned shell can simplify production process, improve yield rate, reduce the system of shell Make cost.
As shown in Fig. 2, the shell 100 of first embodiment, can pass through the production side of the shell of above-mentioned first embodiment Legal system obtains, which can be used as the shell of electronic equipment, for example, the shell of tablet computer, mobile phone etc., especially The rear cover of mobile phone or tablet computer.As shown in figure 3, the shell 100 of first embodiment includes epoxy resin layer 110, pattern layer 120, decorating unit 130 and hardened layer 140.
The material of epoxy resin layer 110 is above-mentioned modified epoxy, and details are not described herein.Wherein, epoxy resin layer 110 It is obtained for above-mentioned epoxy resin board brake forming.Epoxy resin layer 110 is opposite with first surface 112 and with first surface 112 Second surface 114.Wherein, first surface 112 is concave surface, and second surface 114 is convex surface.
In one of the embodiments, shell 100 be cell phone rear cover, epoxy resin layer 110 with a thickness of 0.4 millimeter~ 0.8 millimeter.It is appreciated that the thickness of epoxy resin layer 110 can according to need and be adjusted.
Pattern layer 120 is arranged on first surface 112.The pattern of pattern layer 120 for example can be LOGO, symbol, animal Pattern etc..The material of pattern layer 120 is mirror-like silver in one of the embodiments,；Pattern silver passes through silk-screen printing mirror-like silver oil Ink is prepared.
In one of the embodiments, pattern layer 120 with a thickness of 1 micron~4 microns.It is appreciated that pattern layer 120 Thickness, which can according to need, to be configured.
Decorating unit 130 is arranged on the first surface 112 of epoxy resin layer 110, and coverage diagram pattern layer 120.Specifically exist In the embodiment of diagram, decorating unit 130 includes adhesive layer 132, reflecting layer 134 and the ink layer 136 stacked gradually.
Adhesive layer 132 is transparent material.Adhesive layer 132 is arranged on the first surface 112 of epoxy resin layer 110, bonding 132 coverage diagram pattern layer 120 of layer.Further, adhesive layer 132 is the UV transfer printing layer with textured pattern, thus so that shell 100 With texture appearance.Specifically, adhesive layer 132 is urethane acrylate glue layer.Such as Bei Teli new material Co., Ltd Model 633-75 UV glue.It is appreciated that adhesive layer 132 is not limited to above-mentioned glue layer, or this field is normal It is transparent glue after solidification；Adhesive layer 132 can also not have textured pattern, at this point, shell 100 does not have outside texture It sees.
In one of the embodiments, adhesive layer 132 with a thickness of 5 microns~20 microns.It is appreciated that adhesive layer 132 Thickness be not limited to above-mentioned thickness, the thickness of adhesive layer 132, which can according to need, to be configured.
Reflecting layer 134 is layered in side of the adhesive layer 132 far from epoxy resin layer 110.Specifically, reflecting layer 134 is true Empty non-conductive electroplated layer.
Specifically, reflecting layer 134 is selected from indium tin oxide layer, titanium dioxide layer, columbium dioxide layer, columbium sesquioxide layer, two Aoxidize at least one of two niobium layers, niobium pentaoxide layer, silicon dioxide layer and titanium dioxide zirconium layer.I.e. reflecting layer 134 can be Single layer structure, or multilayered structure.
The overall thickness in reflecting layer 134 is 5 nanometers~300 nanometers in one of the embodiments, i.e., when reflecting layer 134 is When single layer structure, reflecting layer 134 with a thickness of 5 nanometers~300 nanometers, when reflecting layer 134 is multilayered structure, multilayer reflective layers 134 overall thickness is 5 nanometers~300 nanometers.It is appreciated that the thickness in reflecting layer 134 is not limited to above-mentioned thickness, reflecting layer 134 thickness, which can according to need, to be configured.
Ink layer 136 is layered in side of the reflecting layer 134 far from adhesive layer 132.Specifically, ink layer 136 includes white Ink layer, white ink layer or gray oil layer of ink.Ink layer 136 can not only protect reflecting layer 134, additionally it is possible to provide background face Color and shield lights are placed through shell 100 and see internal structure and component of product etc..
In one of the embodiments, ink layer 136 with a thickness of 10 microns~20 microns.It is appreciated that ink layer 136 Thickness be not limited to above-mentioned thickness, the thickness of ink layer 136, which can according to need, to be configured.
Hardened layer 140 is arranged on the second surface 114 of epoxy resin layer 110.Hardened layer 140 can increase shell 100 Wear-resisting property and adhesion strength.
Hardened layer 140 is prepared by hardening bath in one of the embodiments, and the main component of hardening bath is polyurethane Acrylate, organic siliconresin and perfluoropolyether acrylate, such as 304 hardening bath of PPG.It is appreciated that hardening bath is not limited to It can be hardening bath commonly used in the art for above-mentioned substance.The hardened layer 140 that above-mentioned hardening bath is prepared has preferable resistance to Grind performance and preferable adhesion strength.
Specifically, hardness 3H~5H of hardened layer 140, if hardness is too small, wear-resisting property and adhesion strength are poor；If hard It spends greatly, 140 brittleness of hardened layer increases, and can reduce production efficiency.
In one of the embodiments, hardened layer 140 with a thickness of 3 microns~20 microns.It is appreciated that hardened layer 140 Thickness can according to need and be adjusted.
It should be noted that the structure of shell 100 is not limited to structure, for example, hardened layer 140 can be omitted, at this point, ring The second surface 114 of oxygen resin layer 110 is the outer surface of shell 100.
Pattern layer 120 also can be omitted, and decorating unit 130 is directly layered in the first surface 112 of epoxy resin layer 110 On.
Decorating unit 130 is not limited to above structure, the adhesive layer 132 of decorating unit 130 can with it is other can be advantageous It is replaced in the coating that reflecting layer 134 is adhered to, coating for example sprays semi-transparent color layers, and inkjet printing reaches semi-transparent color；Alternatively, dress It adorns unit 130 and does not have ink layer 136, is i.e. the reflecting layer 134 of decorating unit 130 does not have oil far from the side of adhesive layer 132 Layer of ink 136；Alternatively, decorating unit 130 does not have adhesive layer 132 and reflecting layer 134 simultaneously, ink layer 136 is set up directly on ring On the first surface 112 of oxygen resin layer 110；Alternatively, decorating unit 130 does not have reflecting layer 134, ink layer 136 is directly laminated In side of the adhesive layer 132 far from epoxy resin layer 110.
Decorating unit 130 also can be omitted, can be by epoxy resin layer in the case where being provided with pattern layer 120 Protective layer is set on 110 first surface 112, and protective layer coverage diagram pattern layer 120, to protect pattern layer 120, protective layer for example may be used Think UV glue layer.
Decorating unit 130, pattern layer 120 and hardened layer 140 can also be omitted all simultaneously, at this point, shell 100 can only have There is epoxy resin layer 110.
Above-mentioned shell 100 at least has the advantage that
Since above-mentioned shell 100 includes the epoxy resin layer 110 of above-mentioned material, which has preferably resistance to Performance and preferable adhesion strength are ground, and also there is preferable high temperature resistance, ageing-resistant performance and shock resistance, so that Above-mentioned shell 100 not only has preferable performance, also helps and reduces its cost.
As shown in figure 4, the production method of the shell of second embodiment, the shell of this method production can be set as electronics Standby shell, for example, the rear cover of the shell of tablet computer, mobile phone etc., especially mobile phone or tablet computer.Outside present embodiment The production method of shell includes the following steps S21~S26:
Step S21: epoxy resin board is prepared.
Present embodiment it is identical as step S11 the step of preparing epoxy resin board, details are not described herein.
Step S22: pattern layer is formed in the side of epoxy resin board.
Specifically, the step S12 of the method for the formation pattern layer of present embodiment and first embodiment forms pattern layer It is identical, details are not described herein.
Step S23: protective layer, protective layer coverage diagram pattern layer are formed in the side that epoxy resin board is formed with pattern layer.
Specifically, protective layer is UV glue layer.Protective layer is urethane acrylate glue in one of the embodiments, Layer.Such as the UV glue of the model 633-75 of Bei Teli new material Co., Ltd.It is appreciated that protective layer be not limited to it is above-mentioned Glue layer.
In one of the embodiments, protective layer with a thickness of 8 microns~20 microns.It is appreciated that the thickness of protective layer It is not limited to above-mentioned thickness, the thickness of protective layer, which can according to need, to be configured.
Step S24: decorating unit is set far from the side of epoxy resin board in protective layer.
It specifically, include: on basilar memebrane the step of decorating unit is arranged far from the side of epoxy resin board in protective layer Transparent adhesive layer is formed, forms reflecting layer on adhesive layer, forms ink layer on reflecting layer, obtains decorating unit；It will dress The basilar memebrane for adoring unit is bonded far from the side of adhesive layer and protective layer far from the side of epoxy resin board.
Basilar memebrane is polycarbonate (PC) film or TPU membrane in one of the embodiments,.It is appreciated that basilar memebrane is unlimited In for above-mentioned basilar memebrane, basilar memebrane can be transparent basilar memebrane commonly used in the art.Specifically, basilar memebrane is micro- with a thickness of 50 Rice~125 microns.It is appreciated that the thickness of basilar memebrane is not limited to above-mentioned thickness, the thickness of basilar memebrane can according to need into Row setting.
The production method of adhesive layer of production method and first embodiment of adhesive layer is similar, and difference is, this implementation The adhesive layer of mode is produced on basilar memebrane, and details are not described herein.
The production method in reflecting layer of production method and first embodiment in reflecting layer is identical, and details are not described herein.
The production method of ink layer of production method and first embodiment of ink layer is identical, and details are not described herein.
Specifically, the side of the side by the basilar memebrane of decorating unit far from adhesive layer and protective layer far from epoxy resin board The step of bonding includes: one of side and protective layer using UV binder by basilar memebrane far from adhesive layer far from epoxy resin board Side bonding.UV binder is Bei Teli 805-16 glue in one of the embodiments,.
Step S25: by epoxy resin board brake forming.
The epoxy resin board that matcoveredn, pattern layer and decorating unit will be formed is manually bent.Specifically, this reality The method by epoxy resin board brake forming for applying mode is identical with first embodiment, and details are not described herein.
Step S26: hardened layer is formed in the convex surface of epoxy resin board, obtains shell.
The forming step of hardened layer of forming step and first embodiment of the hardened layer of present embodiment is identical, herein It repeats no more.
It should be noted that the production method of the shell of present embodiment is also not necessarily limited to as above-mentioned steps, present embodiment Also similar to the production method of the shell of first embodiment, the production of the hardened layer of step S26 can be omitted；Step S22 and Step S23 can be omitted, i.e., not pattern-making layer and protective layer, decorating unit are adhered directly to epoxy resin by UV binder On plate；Alternatively, step S23 is omitted, i.e., protective layer is not made, decorating unit is adhered directly to epoxy resin board by UV binder On, and coverage diagram pattern layer.Decorating unit also can according to need and be made, such as omit ink layer, etc..
Since the production method of the shell of present embodiment is similar to the production method of the shell of first embodiment, because This, it may have the similar effect of the production method of the shell of first embodiment, details are not described herein.
As shown in figure 5, the shell 200 of second embodiment, can pass through the production side of the shell of above-mentioned second embodiment Legal system obtains, which can be used as the shell of electronic equipment, for example, the shell of tablet computer, mobile phone etc., especially The rear cover of mobile phone or tablet computer.The structure phase of the shell 100 of the structure and first embodiment of the shell 200 of present embodiment Seemingly, difference is:
Shell 200 further includes protective layer 250, and protective layer 250 is arranged on the first surface 212 of epoxy resin layer 210, and Coverage diagram pattern layer 220.Wherein, first surface 212 is concave surface.Specifically, protective layer 250 is UV glue layer.Wherein one In a embodiment, protective layer 250 is urethane acrylate glue layer.Such as the model of Bei Teli new material Co., Ltd The UV glue of 633-75.It is appreciated that protective layer 250 is not limited to above-mentioned glue layer.
Decorating unit 230 further includes basilar memebrane 238, and basilar memebrane 238 is arranged on first surface 212, and shell 200 further includes Adhesive layer 260, adhesive layer 260 are arranged between basilar memebrane 238 and first surface 212, and the fixed bond substrates film of adhesive layer 260 238 and first surface 212.Side of the adhesive layer 232 far from reflecting layer 234 and side of the basilar memebrane 238 far from first surface 212 Stacking, i.e., adhesive layer 232, reflecting layer 234 and ink layer 236 are sequentially formed on basilar memebrane 238.
Basilar memebrane 238 is polycarbonate (PC) film or TPU membrane in one of the embodiments,.It is appreciated that basilar memebrane 238 are not limited to above-mentioned basilar memebrane 238, and basilar memebrane 238 can be transparent basilar memebrane commonly used in the art.
The material of adhesive layer 260 is UV binder in one of the embodiments, and UV binder is that Bei Teli new material has The UV glue of the model 805-16 of limit company.
Since the structure of the shell 200 of second embodiment is similar to the structure of shell 100 of first embodiment, because This, the shell 200 of second embodiment is also with the similar effect of shell 100 of first embodiment, and details are not described herein.
As shown in fig. 6, the production method of the shell of third embodiment, the shell of this method production can be set as electronics Standby shell, for example, the rear cover of the shell of tablet computer, mobile phone etc., especially mobile phone or tablet computer.Outside the embodiment The production method of shell includes the following steps S31~S35:
Step S31: epoxy resin board is prepared.
Present embodiment it is identical as step S11 the step of preparing epoxy resin board, details are not described herein.
Step S32: pattern layer is formed in the side of epoxy resin board.
Specifically, the step S12 of the method for the formation pattern layer of present embodiment and first embodiment forms pattern layer It is similar, details are not described herein.
Step S33: by epoxy resin board brake forming.
The epoxy resin board that pattern layer will be formed with is manually bent.Specifically, present embodiment by asphalt mixtures modified by epoxy resin The molding method of rouge plate benging is identical with first embodiment, and details are not described herein.
Step S34: decorating unit is set on the concave surface of epoxy resin.
I.e. in the present embodiment, by epoxy resin board the step of decorative layer is arranged on the concave surface of epoxy resin After the step of brake forming.
It specifically, include: to be formed thoroughly on basilar memebrane the step of decorating unit is set on the concave surface of epoxy resin Bright adhesive layer, forms reflecting layer on adhesive layer, and ink layer is formed on reflecting layer, obtains decorating unit；By decorating unit Side and epoxy resin board of the basilar memebrane far from adhesive layer concave surface bonding.It is appreciated that forming the step of decorating unit It suddenly can be before or while step S33, it can make decorating unit in step S33 or while step S33, then The concave surface of side and epoxy resin board by the basilar memebrane of decorating unit far from adhesive layer bonds.
Basilar memebrane is polycarbonate membrane or TPU membrane in one of the embodiments,.It is appreciated that basilar memebrane is not limited to Above-mentioned basilar memebrane, basilar memebrane can be transparent basilar memebrane commonly used in the art.
The production method of adhesive layer of production method and first embodiment of adhesive layer is similar, and difference is, this implementation The adhesive layer of mode is produced on basilar memebrane, and details are not described herein.
The production method in reflecting layer of production method and first embodiment in reflecting layer is identical, and details are not described herein.
The production method of ink layer of production method and first embodiment of ink layer is identical, and details are not described herein.
Specifically, the concave surface of the side by the basilar memebrane of decorating unit far from adhesive layer and epoxy resin board bonds Step includes: the concave surface bonding of the side and epoxy resin board using binder by basilar memebrane far from adhesive layer.In this reality It applies in example, binder is thermoset binder or UV binder.Thermoset binder is OCA glue, such as the OCA of good photoelectricity difficult to understand Glue；UV binder is the UV glue of the model 805-16 of Bei Teli new material Co., Ltd.
Step S35: hardened layer is formed in the convex surface of epoxy resin board, obtains shell.
The forming step of hardened layer of forming step and first embodiment of the hardened layer of present embodiment is identical, herein It repeats no more.
It should be noted that the production method of the shell of present embodiment is also not necessarily limited to as above-mentioned steps, in this embodiment party Also similar to the production method of the shell of first embodiment in formula, the production of the hardened layer of step S35 can be omitted；Step S32 can be omitted, the layer of not pattern-making at this time, side and epoxy resin by the basilar memebrane of decorating unit far from the adhesive layer The concave surface of plate bonds, i.e., decorating unit is adhered directly on the concave surface of epoxy resin board by UV binder；Decoration Unit also can according to need and be made, such as omit ink layer, etc..
Since the production method of the shell of present embodiment is similar to the production method of the shell of first embodiment, because This, it may have the similar effect of the production method of the shell of first embodiment, details are not described herein.Due to third embodiment Shell production method bending step before decorating unit is set so that the shell of the embodiment production method will Decorating unit is arranged to the glue on epoxy resin board in addition to UV binder can be used, and can also use thermoset binder.
As shown in fig. 7, the shell 300 of third embodiment, can pass through the production side of the shell of above-mentioned third embodiment Legal system obtains, which can be used as the shell of electronic equipment, for example, the shell of tablet computer, mobile phone etc., especially The rear cover of mobile phone or tablet computer.The structure phase of the shell 100 of the structure and first embodiment of the shell 300 of present embodiment Seemingly, difference is:
Decorating unit 330 further includes basilar memebrane 338, and the concave surface 312 of epoxy resin layer 310 is arranged in basilar memebrane 338 On, shell 300 further includes adhesive layer 350, and adhesive layer 350 is arranged between basilar memebrane 338 and concave surface 312, and adhesive layer 350 fixed bond substrates films 338 and concave surface 312, side of the adhesive layer 332 far from reflecting layer and epoxy resin layer 310 Concave surface 312 is laminated, i.e., adhesive layer 332, reflecting layer 334 and ink layer 336 are sequentially formed on basilar memebrane 338.
Basilar memebrane 338 is PC film or TPU membrane in one of the embodiments,.It is appreciated that basilar memebrane 338 is not limited to Above-mentioned basilar memebrane, basilar memebrane 338 can be transparent basilar memebrane commonly used in the art.
The material of adhesive layer 360 is UV bonding agent or heat curing type bonding agent in one of the embodiments,.Wherein, UV is viscous Meet the UV that agent is, for example, the model 805-16 of Bei Teli new material Co., Ltd；Heat curing type bonding agent is OCA glue, such as difficult to understand The OCA glue of good photoelectricity.
Since the structure of the shell 300 of third embodiment is similar to the structure of shell 100 of first embodiment, because This, the shell 300 of third embodiment is also with the similar effect of shell 100 of first embodiment, and details are not described herein.
The electronic equipment of one embodiment, for example, tablet computer, mobile phone etc., including shell, wherein shell is first The prepared shell of the production method of the shell of embodiment, the shell of first embodiment, second embodiment shell The prepared shell of production method, the shell of second embodiment, third embodiment shell production method production The shell of obtained shell or third embodiment.
Electronic equipment is mobile phone or tablet computer in one of the embodiments, and shell is rear cover.
The prepared shell of production method, the first reality due to above-mentioned electronic equipment using the shell of first embodiment Apply the shell of mode, the prepared shell of production method of the shell of second embodiment, the shell of second embodiment, The shell of the prepared shell of the production method of the shell of three embodiments or third embodiment is conducive to increase electronics and sets Standby service life reduces the production cost of electronic equipment.
It should be noted that above-mentioned shell is not limited to the shell of electronic equipment, or the shell of other products.
The following are specific embodiment part (following embodiment by taking one of preparation method of modified epoxy as an example, The preparation of modified epoxy is illustrated, but the preparation method of modified epoxy of the invention be not limited to for Following steps and following substance, i.e. technical solution of the present invention is also not necessarily limited to as following embodiment, for example, urging in following embodiment Agent uses dibutyl tin dilaurate, and curing agent uses dicyandiamide, and base polyurethane prepolymer for use as uses the model of Dow The MDI base polyurethane prepolymer for use as of N434 is for example, not limiting the scope of the invention):
Embodiment 1
The preparation process of the epoxy resin board of the present embodiment is as follows:
(1) it prepares modified epoxy: according to table 1, being A:B according to the mass ratio of modifier and epoxy resin, will be modified Mixed t is stirred at room temperature in object, epoxy resin and catalyst1Hour, curing agent is then added and stirs evenly, then in T1It is anti-at DEG C Answer t2Hour, obtain modified epoxy.The quality of catalyst and the mass ratio of epoxy resin are C:B, curing agent and asphalt mixtures modified by epoxy resin The mass ratio of rouge is D:B, and catalyst is dibutyl tin dilaurate, and curing agent is dicyandiamide.
According to the epoxide number for the modified epoxy that GB 1677-1981 " hydrochloric acid-acetone method " test is prepared；According to The softening temperature of modified epoxy that ISO306-2013 test is prepared, wherein the epoxide number of modified epoxy and Softening temperature is as shown in table 2.
(2) according to table 2, the modified epoxy that step (1) is prepared is in T2It melts at DEG C, then squeezes out, obtain With a thickness of D millimeters of epoxy resin board.
Table 1
Wherein, in table 1 in " epoxy resin " column, E-51, E-55 and E-44 respectively indicate E-51 epoxy resin, E-55 ring Oxygen resin and E-44 epoxy resin, and ": " in this column indicates mass ratio, for example, E-51:E-44 indicates the epoxy of the embodiment Resin is made of the epoxy resin of E-51 epoxy resin and E-44, and the ratio that E-51:E-44 is indicated is mass ratio.
Table 2
Comparative example 5
Comparative example 5 is 3240 conventional epoxy resin boards, with a thickness of 0.6 millimeter, epoxide number 0.35.
Comparative example 6
Comparative example 6 is the composite substrate of conventional polycarbonate (PC) and polymethyl methacrylate (PMMA), overall thickness It is 0.6 millimeter.
Comparative example 7
Comparative example 7 is conventional pure polycarbonate (PC) plate, with a thickness of 0.6 millimeter.
Comparative example 8
Comparative example 8 is conventional polyethylene terephthalate (PET) plate, with a thickness of 0.6 millimeter.
Test:
(1) using the FTS-3000 FTIR spectrum tester testing example 1~21 of DIGILA company and comparison The epoxy resin board of example 1~4,3240 epoxy resin boards of comparative example 5, the composite substrate of comparative example 6, comparative example 7 pure poly- carbon The optical transmittance of acid esters plate and the polyethylene terephthalate plate of comparative example 8；
(2) using the epoxy resin board of the AG-IS universal testing machine Examples 1 to 21 of Shimadzu and comparative example 1~4, comparison 3240 epoxy resin boards of example 5, the composite substrate of comparative example 6, poly- pair of the pure polycarbonate plate of comparative example 7 and comparative example 8 The tensile resistance of polyethylene terephthalate plate；
(3) using ASTM D3363 method testing example 1~21 and epoxy resin board, the comparative example 5 of comparative example 1~4 3240 epoxy resin boards, the composite substrate of comparative example 6, the pure polycarbonate plate of comparative example 7 and comparative example 8 it is poly- to benzene two The hardness of formic acid second diester plate；
(4) using ASTM G-151 method testing example 1~21 and epoxy resin board, the comparative example 5 of comparative example 1~4 3240 epoxy resin boards, the composite substrate of comparative example 6, the pure polycarbonate plate of comparative example 7 and comparative example 8 it is poly- to benzene two The ageing-resistant performance of formic acid second diester plate；
(5) hot pressing bend test: by the epoxy resin board of Examples 1 to 21 and comparative example 1~4,3240 rings of comparative example 5 Oxygen resin plate, the composite substrate of comparative example 6, the pure polycarbonate plate of comparative example 7 and comparative example 8 poly terephthalic acid second two Ester plate is exemplarily bent by hot-forming mode, specific steps are as follows: first template is placed in lower die, and is being heated Plate temperature heats 22 seconds under conditions of being 300 DEG C, and lower die temperature is 90 DEG C~140 DEG C；Then upper film and lower die are molded, and protected Pressure 20 seconds, upper mold temperature are 120 DEG C, and whether the effect that template after bending is then observed under light (is bent into predetermined arc Whether degree, convex surface crack).
(6) high pressure bend test: by the epoxy resin board of Examples 1 to 21 and comparative example 1~4,3240 rings of comparative example 5 Oxygen resin plate, the composite substrate of comparative example 6, the pure polycarbonate plate of comparative example 7 and comparative example 8 poly terephthalic acid second two Ester plate is exemplarily bent by way of high-pressure molding, specific process parameter are as follows: and the temperature of molding die is 120 DEG C, The temperature of heating plate is 220 DEG C, the blowing pressure 20Bar, and molding time is 100 seconds.Then it is observed under light after bending The effect of template.
Wherein, the epoxy resin board of Examples 1 to 21 and comparative example 1~4,3240 epoxy resin boards of comparative example 5, comparison The optical lens of the polyethylene terephthalate plate of the composite substrate of example 6, the pure polycarbonate plate of comparative example 7 and comparative example 8 Cross the bending effect difference of rate, tensile resistance, hardness, ageing-resistant performance, hot-forming bending effect and high-pressure molding As shown in table 3.
Table 3
From table 3 it is observed that the optics light transmittance of the epoxy resin board of Examples 1 to 21 is 83%~88%, have Higher optical transmittance, and the tensile strength of the epoxy resin board of Examples 1 to 21 is at least 60MPa, has preferable Tensile strength, hardness are HB~H, have greater hardness, to make it have preferable wear-resisting property, preferable resistance to marring Can, meanwhile, above-mentioned epoxy resin board irradiates 48H non yellowing under ultraviolet light, has preferable ageing-resistant performance, performance and comparison The composite substrate of example 6 is suitable, can do shell use, so that the production to shell provides a kind of new material.Meanwhile implementing The epoxy resin board of example 1~21 is bent into preboarding, and equal flawless, energy after hot pressing bending and high pressure brake forming It is enough directly to be formed by curved mode, simplify production process, improves yield rate, reduce the cost of manufacture of shell.
And the epoxy resin board of comparative example 1 not only has lesser tensile strength, and hardness is also smaller, shines in ultraviolet light The slight xanthochromia of 48H is penetrated, predetermined shape can not be bent to；Although the epoxy resin board of comparative example 2 and comparative example 3 has biggish Hardness, but tensile strength is smaller, and crackle is had after bend test, it is thus impossible to direct brake forming；Comparative example 4 Although epoxy resin board has biggish tensile strength, hardness is too low；Although the epoxy resin board of comparative example 5 have compared with Big hardness and preferable tensile strength, but the serious xanthochromia of 48H is irradiated in ultraviolet light, and brake forming rear surface has and splits Line, cannot direct brake forming.The hardness of the pure polycarbonate plate of comparative example 7 is too low, and wear-resisting property and adhesion strength are too poor； The tensile strength of the polyethylene terephthalate plate of comparative example 8 is excessive, and radian is smaller after bending, fails to bend to predetermined Shape, it is more difficult to be fabricated to the shell of predetermined arc.
Embodiment 22
The manufacturing process of the shell of the present embodiment is as follows:
The epoxy resin board that embodiment 1 is made carries out high-pressure molding, so that epoxy resin plate benging, then carries out CNC Processing, mills extra leftover pieces, obtains shell.Wherein, the technological parameter of high-pressure molding includes: that the temperature of molding die is 120 DEG C, the temperature of heating plate is 200 DEG C, the blowing pressure 20Bar, and molding time is 100 seconds.
Embodiment 23
The manufacturing process of the shell of the present embodiment is as follows:
The epoxy resin board that embodiment 4 is made carries out high-pressure molding, so that epoxy resin plate benging, then carries out CNC Processing, mills extra leftover pieces, obtains shell.Wherein, it is 90 that the technological parameter of high-pressure molding, which includes: the temperature of molding die, DEG C, the temperature of heating plate is 300 DEG C, the blowing pressure 10Bar, and molding time is 60 seconds.
Embodiment 24
The manufacturing process of the shell of the present embodiment is as follows:
The epoxy resin board that embodiment 7 is made carries out high-pressure molding, so that epoxy resin plate benging, then carries out CNC Processing, mills extra leftover pieces, obtains shell.Wherein, the technological parameter of high-pressure molding includes: that the temperature of molding die is 150 DEG C, the temperature of heating plate is 150 DEG C, the blowing pressure 30Bar, and molding time is 150 seconds.
Embodiment 25
The manufacturing process of the shell of the present embodiment is as follows:
The epoxy resin board progress that embodiment 2 is made is hot-forming, so that epoxy resin plate benging, then carries out CNC Processing, mills extra leftover pieces, obtains shell.Wherein, hot-forming step are as follows: be first placed in down the epoxy resin board It in mould, heats 25 seconds under conditions of the temperature of heating plate is 320 DEG C, and lower die temperature is 120 DEG C, removes heating plate, then will Upper film and lower die mold, and pressure maintaining 20 seconds, and upper mold temperature is 110 DEG C.
Embodiment 26
The manufacturing process of the shell of the present embodiment is as follows:
The epoxy resin board progress that embodiment 5 is made is hot-forming, so that epoxy resin plate benging, then carries out CNC Processing, mills extra leftover pieces, obtains shell.Wherein, hot-forming step are as follows: be first placed in down the epoxy resin board It in mould, heats 30 seconds under conditions of the temperature of heating plate is 250 DEG C, and lower die temperature is 140 DEG C, removes heating plate, then will Upper film and lower die mold, and pressure maintaining 30 seconds, and upper mold temperature is 130 DEG C.
Embodiment 27
The manufacturing process of the shell of the present embodiment is as follows:
The epoxy resin board progress that embodiment 8 is made is hot-forming, so that epoxy resin plate benging, then carries out CNC Processing, mills extra leftover pieces, obtains shell.Wherein, hot-forming step are as follows: be first placed in down the epoxy resin board It in mould, is heated 15 seconds under conditions of the temperature of heating plate is 380 DEG C, and lower die temperature is 90 DEG C, removes heating plate, it then will be upper Film and lower die mold, and pressure maintaining 10 seconds, and upper mold temperature is 90 DEG C.
Embodiment 28
The manufacturing process of the shell of the present embodiment is as follows:
(1) side for the epoxy resin board being prepared in embodiment 3 is oily using the silk-screen halftone silk-screen mirror-like silver of 350 mesh Then ink stands 45 minutes at 25 DEG C, then toast 60 minutes at 70 DEG C, forms the pattern layer with a thickness of 3 microns.
(2) side UV glue (Bei Teli new material Co., Ltd, the model of pattern layer are formed in epoxy resin board 633-75) transfer, which is formed, has texture, with a thickness of 10 microns of adhesive layers, and adhesive layer coverage diagram pattern layer；It is separate in adhesive layer The non-conductive plating of the side vacuum of epoxy resin board forms the reflecting layer with a thickness of 15 nanometers, and reflecting layer is indium tin oxide layer；? Side process black ink of the indium tin oxide layer far from adhesive layer forms the ink layer with a thickness of 15 microns, single to form decoration Member.
(3) epoxy resin board that step (2) is formed with decorating unit is subjected to high-pressure molding, so that epoxy resin board is curved It is bent.The technological parameter of high-pressure molding includes: that the temperature of molding die is 140 DEG C, and the temperature of heating plate is 250 DEG C, the blowing pressure For 15Bar, molding time is 120 seconds.
(4) in side showering PPG 304 hardening bath of the curved epoxy resin board far from decorating unit, then at 70 DEG C Baking 6 minutes, then solidify under ultraviolet light, solidification energy 800mj/cm2, the hardened layer with a thickness of 10 microns is formed, Then CNC processing is carried out, extra leftover pieces is milled, obtains shell.
Embodiment 29
The manufacturing process of the shell of the present embodiment is as follows:
(1) side for the epoxy resin board being prepared in embodiment 6 is oily using the silk-screen halftone silk-screen mirror-like silver of 300 mesh Then ink stands 60 minutes at 15 DEG C, then toast 90 minutes at 60 DEG C, forms the pattern layer with a thickness of 4 microns.
(2) side UV glue (Bei Teli new material Co., Ltd, the model of pattern layer are formed in epoxy resin board 633-75) transfer, which is formed, has texture, with a thickness of 5 microns of adhesive layers, and adhesive layer coverage diagram pattern layer；In adhesive layer far from ring The non-conductive plating of the side vacuum of oxygen resin plate forms the reflecting layer with a thickness of 50 nanometers, and reflecting layer is columbium dioxide layer；Two Side process black ink of the niobium oxide layer far from adhesive layer forms the ink layer with a thickness of 20 microns, to form decorating unit.
(3) epoxy resin board that step (2) is formed with decorating unit is subjected to high-pressure molding, so that epoxy resin board is curved It is bent.The technological parameter of high-pressure molding includes: that the temperature of molding die is 100 DEG C, and the temperature of heating plate is 280 DEG C, the blowing pressure For 200Bar, molding time is 80 seconds.
(4) in side showering PPG 304 hardening bath of the curved epoxy resin board far from decorating unit, then at 60 DEG C Baking 10 minutes, then solidify under ultraviolet light, solidification energy 400mj/cm2, the hardened layer with a thickness of 3 microns is formed, Then CNC processing is carried out, extra leftover pieces is milled, obtains shell.
Embodiment 30
The manufacturing process of the shell of the present embodiment is as follows:
(1) side for the epoxy resin board being prepared in embodiment 10 uses the silk-screen halftone silk-screen mirror-like silver of 420 mesh Then ink stands 30 minutes at 30 DEG C, then toast 30 minutes at 80 DEG C, forms the pattern layer with a thickness of 1 micron.
(2) side UV glue (Bei Teli new material Co., Ltd, the model of pattern layer are formed in epoxy resin board 633-75) transfer, which is formed, has texture, with a thickness of 20 microns of adhesive layers, and adhesive layer coverage diagram pattern layer；It is separate in adhesive layer The non-conductive plating of the side vacuum of epoxy resin board forms the reflecting layer with a thickness of 300 nanometers, and reflecting layer is columbium sesquioxide Layer；In side process black ink of the columbium sesquioxide layer far from adhesive layer, the ink layer with a thickness of 10 microns is formed, to be formed Decorating unit.
(3) epoxy resin board that step (2) is formed with decorating unit is subjected to high-pressure molding, so that epoxy resin board is curved It is bent.The technological parameter of high-pressure molding includes: that the temperature of molding die is 90 DEG C, and the temperature of heating plate is 200 DEG C, and the blowing pressure is 30Bar, molding time are 150 seconds.
(4) in side showering PPG 304 hardening bath of the curved epoxy resin board far from decorating unit, then at 80 DEG C Baking solidifies under ultraviolet light for 3 minutes again, solidification energy 1200mj/cm2, the hardened layer with a thickness of 20 microns is formed, Then CNC processing is carried out, extra leftover pieces is milled, obtains shell.
Embodiment 31
The manufacturing process of the shell of the present embodiment is as follows:
(1) similar to (1) the step of embodiment 28, difference is, the epoxy resin board used is that embodiment 11 is prepared into The epoxy resin board arrived.
(2) similar to (2) the step of embodiment 28, difference is, the preparation process in reflecting layer is different: separate in adhesive layer The non-conductive plating of the side vacuum of epoxy resin board forms the niobium pentaoxide layer with a thickness of 50 nanometers, then in niobium pentaoxide The silicon dioxide layer with a thickness of 50 nanometers is formed on layer.Ink layer is formed in one of silicon dioxide layer far from niobium pentaoxide layer Side.
(3) the epoxy resin board progress for step (2) being formed with decorating unit is hot-forming, so that epoxy resin board is curved It is bent.Wherein, hot-forming step are as follows: first the epoxy resin board is placed in lower die, is 300 DEG C in the temperature of heating plate Under the conditions of heat 18 seconds, and lower die temperature is 100 DEG C, removes heating plate, is then molded upper film and lower die, and pressure maintaining 30 seconds, on Mould temperature is 130 DEG C.
(4) identical as (4) the step of embodiment 28.
Embodiment 32
The manufacturing process of the shell of the present embodiment is as follows:
(1) similar to (1) the step of embodiment 29, difference is, the epoxy resin board used is that embodiment 13 is prepared into The epoxy resin board arrived.
(2) similar to (2) the step of embodiment 29, difference is, the preparation process in reflecting layer is different: separate in adhesive layer The non-conductive plating of the side vacuum of epoxy resin board forms the niobium pentaoxide layer with a thickness of 40 nanometers, then in niobium pentaoxide The non-conductive plating of vacuum forms the silicon dioxide layer with a thickness of 60 nanometers on layer, then in silicon dioxide layer far from niobium pentaoxide layer The non-conductive plating of side vacuum formed with a thickness of 70 nanometers of titanium dioxide zirconium layer.Ink layer is formed in titanium dioxide zirconium layer far from two The side of silicon oxide layer.
(3) the epoxy resin board progress for step (2) being formed with decorating unit is hot-forming, so that epoxy resin board is curved It is bent.Wherein, hot-forming step are as follows: first the epoxy resin board is placed in lower die, is 350 DEG C in the temperature of heating plate Under the conditions of heat 20 seconds, and lower die temperature is 110 DEG C, removes heating plate, is then molded upper film and the lower die, and pressure maintaining 20 Second, upper mold temperature is 110 DEG C.
(4) identical as (4) the step of embodiment 29.
Embodiment 33
The manufacturing process of the shell of the present embodiment is as follows:
(1) side for the epoxy resin board being prepared in embodiment 14 uses the silk-screen halftone silk-screen mirror-like silver of 350 mesh Then ink stands 50 minutes at 20 DEG C, then toast 50 minutes at 75 DEG C, forms the pattern layer with a thickness of 2 microns.
(2) pattern layer is formed in epoxy resin board with UV glue (Bei Teli new material Co., Ltd, model 633-75) Side formed with a thickness of 8 microns of protective layer, protective layer coverage diagram pattern layer.
(3) being formed on basilar memebrane with UV glue (Bei Teli new material Co., Ltd, model 633-75) transfer has line It manages, with a thickness of 8 microns of adhesive layers, is formed in the non-conductive plating of side vacuum of the adhesive layer far from epoxy resin board with a thickness of 80 The reflecting layer of nanometer, reflecting layer are two niobium layer of titanium dioxide；In two niobium of titanium dioxide, the side process black far from adhesive layer is oily layer by layer Ink forms the ink layer with a thickness of 18 microns, to form decorating unit；Side by the basilar memebrane of decorating unit far from adhesive layer The side UV binder (UV of the model 805-16 of Bei Teli new material Co., Ltd with protective layer far from epoxy resin board Glue) bonding.Wherein, basilar memebrane is the polycarbonate membrane with a thickness of 50 microns.
(4) epoxy resin board that step (3) is provided with decorating unit is subjected to high-pressure molding, so that epoxy resin board is curved It is bent.The technological parameter of high-pressure molding includes: that the temperature of molding die is 150 DEG C, and the temperature of heating plate is 250 DEG C, the blowing pressure For 20Bar, molding time is 120 seconds.
(5) in side showering PPG 304 hardening bath of the curved epoxy resin board far from decorating unit, then at 65 DEG C Baking 8 minutes, then solidify under ultraviolet light, solidification energy 600mj/cm2, the hardened layer with a thickness of 8 microns is formed, so CNC processing is carried out afterwards, is milled extra leftover pieces, is obtained shell.
Embodiment 34
The manufacturing process of the shell of the present embodiment is as follows:
(1) side for the epoxy resin board being prepared in embodiment 15 uses the silk-screen halftone silk-screen mirror-like silver of 400 mesh Then ink stands 40 minutes at 25 DEG C, then toast 70 minutes at 70 DEG C, forms the pattern layer with a thickness of 3 microns.
(2) pattern layer is formed in epoxy resin board with UV glue (Bei Teli new material Co., Ltd, model 633-75) Side formed with a thickness of 20 microns of protective layer, protective layer coverage diagram pattern layer.
(3) being formed on basilar memebrane with UV glue (Bei Teli new material Co., Ltd, model 633-75) transfer has line Reason, with a thickness of 12 microns of adhesive layers, the non-conductive plating formation of side vacuum of the adhesive layer far from epoxy resin board with a thickness of 200 nanometers of reflecting layer, reflecting layer are two niobium layer of titanium dioxide；In side process black oil of the indium tin oxide layer far from adhesive layer Ink forms the ink layer with a thickness of 12 microns, to form decorating unit；Side by the basilar memebrane of decorating unit far from adhesive layer The side UV binder (UV of the model 805-16 of Bei Teli new material Co., Ltd with protective layer far from epoxy resin board Glue) bonding.Wherein, basilar memebrane is the polycarbonate membrane with a thickness of 100 microns.
(4) epoxy resin board that step (3) is provided with decorating unit is subjected to high-pressure molding, so that epoxy resin board is curved It is bent.The technological parameter of high-pressure molding includes: that the temperature of molding die is 90 DEG C, and the temperature of heating plate is 300 DEG C, and the blowing pressure is 15Bar, molding time are 60 seconds.
(5) in side showering PPG 304 hardening bath of the curved epoxy resin board far from decorating unit, then at 80 DEG C Baking 4 minutes, then solidify under ultraviolet light, solidification energy 1000mj/cm2, the hardened layer with a thickness of 12 microns is formed, Then CNC processing is carried out, extra leftover pieces is milled, obtains shell.
Embodiment 35
The manufacturing process of the shell of the present embodiment is as follows:
(1) similar to (1) the step of embodiment 33, difference is, epoxy resin board is the epoxy that embodiment 4 is prepared Resin plate.
(2) identical as (2) the step of embodiment 33.
(3) similar to (3) the step of embodiment 33, difference is, reflection photosphere is the zirconium dioxide with a thickness of 20 nanometers Layer.
(4) the epoxy resin board progress for step (3) being provided with decorating unit is hot-forming, so that epoxy resin board is curved It is bent.Wherein, hot-forming step are as follows: first the epoxy resin board is placed in lower die, is 280 DEG C in the temperature of heating plate Under the conditions of heat 28 seconds, and lower die temperature is 90 DEG C, removes heating plate, is then molded upper film and the lower die, and pressure maintaining 30 seconds, Upper mold temperature is 90 DEG C.
(5) identical as (5) the step of embodiment 33.
Embodiment 36
The manufacturing process of the shell of the present embodiment is as follows:
(1) similar to (1) the step of embodiment 34, difference is, epoxy resin board is the ring that embodiment 18 is prepared Oxygen resin plate.
(2) identical as (2) the step of embodiment 34.
(3) similar to (3) the step of embodiment 34, difference is, reflection photosphere is five oxidations two with a thickness of 100 nanometers Niobium layer.
(4) the epoxy resin board progress for step (3) being provided with decorating unit is hot-forming, so that epoxy resin board is curved It is bent.Wherein, hot-forming step are as follows: first epoxy resin board is placed in lower die, the condition for being 370 DEG C in the temperature of heating plate Lower heating 20 seconds, and lower die temperature is 120 DEG C, removes heating plate, is then molded upper film and lower die, and pressure maintaining 15 seconds, upper mold temperature It is 120 DEG C.
(5) identical as (5) the step of embodiment 34.
Embodiment 37
The manufacturing process of the shell of the present embodiment is as follows:
(1) side for the epoxy resin board being prepared in embodiment 5 is oily using the silk-screen halftone silk-screen mirror-like silver of 320 mesh Then ink stands 60 minutes at 15 DEG C, then toast 60 minutes at 80 DEG C, forms the pattern layer with a thickness of 4 microns.
(2) epoxy resin board for forming pattern layer is subjected to high-pressure molding, so that epoxy resin plate benging.High-pressure molding Technological parameter includes: that the temperature of molding die is 100 DEG C, and the temperature of heating plate is 180 DEG C, the blowing pressure 15Bar, when molding Between be 120 seconds.
(3) being formed on basilar memebrane with UV glue (Bei Teli new material Co., Ltd, model 633-75) transfer has line Reason, with a thickness of 16 microns of adhesive layers, the non-conductive plating formation of side vacuum of the adhesive layer far from epoxy resin board with a thickness of 120 nanometers of reflecting layer, reflecting layer are indium tin oxide layer；In side process black ink of the indium tin oxide layer far from adhesive layer, The ink layer with a thickness of 15 microns is formed, to form decorating unit；Side by the basilar memebrane of decorating unit far from adhesive layer with The concave surface of epoxy resin board OCA glue (the OCA glue of good photoelectricity difficult to understand) bonding, and decorating unit coverage diagram pattern layer.Its In, basilar memebrane is the TPU membrane with a thickness of 125 microns.
(4) it in 304 hardening bath of convex surface showering PPG of epoxy resin board, is then toasted 10 minutes at 60 DEG C, then Solidify under ultraviolet light, solidification energy 800mj/cm2, the hardened layer with a thickness of 18 microns is formed, CNC is then carried out and adds Work mills extra leftover pieces, obtains shell.
Embodiment 38
The manufacturing process of the shell of the present embodiment is as follows:
(1) side for the epoxy resin board being prepared in embodiment 16 uses the silk-screen halftone silk-screen mirror-like silver of 420 mesh Then ink stands 30 minutes at 30 DEG C, then toast 90 minutes at 60 DEG C, forms the pattern layer with a thickness of 2 microns.
(2) epoxy resin board for forming pattern layer is subjected to high-pressure molding, so that epoxy resin plate benging.High-pressure molding Technological parameter includes: that the temperature of molding die is 120 DEG C, and the temperature of heating plate is 200 DEG C, the blowing pressure 10Bar, when molding Between be 150 seconds.
(3) being formed on basilar memebrane with UV glue (Bei Teli new material Co., Ltd, model 633-75) transfer has line It manages, with a thickness of 8 microns of adhesive layers, is formed in the non-conductive plating of side vacuum of the adhesive layer far from epoxy resin board with a thickness of 30 The reflecting layer of nanometer, reflecting layer is silicon dioxide layer；In side process black ink of the silicon dioxide layer far from adhesive layer, formed With a thickness of 10 microns of ink layer, to form decorating unit；Side and epoxy by the basilar memebrane of decorating unit far from adhesive layer The concave surface of resin plate OCA glue (the OCA glue of good photoelectricity difficult to understand) bonding, and decorating unit coverage diagram pattern layer.Wherein, base Counterdie is the TPU membrane with a thickness of 75 microns.
(4) it in 304 hardening bath of convex surface showering PPG of epoxy resin board, is then toasted 3 minutes at 80 DEG C, then Solidify under ultraviolet light, solidification energy 500mj/cm2, the hardened layer with a thickness of 5 microns is formed, CNC processing is then carried out, Extra leftover pieces are milled, shell is obtained.
Embodiment 39
The manufacturing process of the shell of the present embodiment is as follows:
(1) similar to (1) the step of embodiment 37, difference is, the epoxy resin board of the present embodiment is the system of embodiment 10 Standby obtained epoxy resin board.
(2) the epoxy resin board progress for forming pattern layer is hot-forming, so that epoxy resin plate benging.Wherein, hot pressing The step of molding are as follows: first epoxy resin board is placed in lower die, is heated 15 seconds under conditions of the temperature of heating plate is 280 DEG C, And lower die temperature is 140 DEG C, removes heating plate, is then molded upper film and lower die, and pressure maintaining 130 seconds, upper mold temperature is 130 DEG C.
(3) identical as (3) the step of embodiment 37.
(4) identical as (4) the step of embodiment 37.
Embodiment 40
The manufacturing process of the shell of the present embodiment is as follows:
(1) similar to (1) the step of embodiment 38, difference is, the epoxy resin board of the present embodiment is the system of embodiment 16 Standby obtained epoxy resin board.
(2) the epoxy resin board progress for forming pattern layer is hot-forming, so that epoxy resin plate benging.Wherein, hot pressing The step of molding are as follows: first epoxy resin board is placed in lower die, is heated 30 seconds under conditions of the temperature of heating plate is 300 DEG C, And lower die temperature is 90 DEG C, removes heating plate, is then molded upper film and lower die, and pressure maintaining 10 seconds, upper mold temperature is 90 DEG C.
(3) identical as (3) the step of embodiment 38.
(4) identical as (4) the step of embodiment 38.
Embodiment 41
The manufacturing process of the shell of the present embodiment is similar to embodiment 23, and difference is, the temperature of heating plate is 310 DEG C.
Embodiment 42
The manufacturing process of the shell of the present embodiment is similar to embodiment 24, and difference is, the temperature of molding die is 80 DEG C.
Embodiment 43
The manufacturing process of the shell of the present embodiment is similar to embodiment 24, and difference is, the temperature of heating plate is 140 DEG C.
Embodiment 44
The manufacturing process of the shell of the present embodiment is similar to embodiment 26, and difference is, the temperature of heating plate is 240 DEG C.
Embodiment 45
The manufacturing process of the shell of the present embodiment is similar to embodiment 27, and difference is, the temperature of heating plate is 390 DEG C.
Test:
In the shell that strong light (such as desk lamp light) down conversion angle observation 22~embodiment of embodiment 45 is prepared The effect of epoxy resin layer, as shown in table 4:
Table 4
As can be seen from Table 4, the epoxy resin layer of the shell of embodiment 22~40 is flawless, and bends to scheduled Crooked radian, and the blistering of the surface folding of the epoxy resin layer of embodiment 41 and embodiment 45 is caused because heating temperature is excessively high , it is because of molding die or heating plate temperature that the epoxy resin layer of embodiment 42 and embodiment 43, which does not bend to predefined curved radian, It spends low, causes forming temperature inadequate, the epoxy resin layer of embodiment 44 cracks, and is caused because temperature of heating plate is too low Cause epoxy resin layer to crack in molding pressure maintaining period and generates slight crack.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (27)

1. a kind of modified epoxy, which is characterized in that the epoxide number of the modified epoxy is 0.25~0.45, described to change Property epoxy resin be the modified epoxy resin of modifier, the modifier is selected from organosilicon, base polyurethane prepolymer for use as and polyimides At least one of, and the mass ratio of the modifier and the epoxy resin is 1:5~1:10.
2. modified epoxy according to claim 1, which is characterized in that the modifier is selected from the organosilicon and institute State at least one of base polyurethane prepolymer for use as；
Alternatively, the modifier is made of the polyimides and the base polyurethane prepolymer for use as, and in the modifier, it is described The mass percentage of base polyurethane prepolymer for use as is 60% or more；
Alternatively, the modifier by mass ratio be 1:(0.1~0.2) the organosilicon and the polyimides form.
3. a kind of epoxy resin board, which is characterized in that the material of the epoxy resin board is modified epoxy, the modified ring The epoxide number of oxygen resin is 0.25~0.45, and the modified epoxy is the modified epoxy resin of modifier, the modifier Selected from least one of organosilicon, base polyurethane prepolymer for use as and polyimides, and the matter of the modifier and the epoxy resin Amount is than being 1:5~1:10.
4. a kind of shell, which is characterized in that including epoxy resin layer, the material of the epoxy resin layer is modified epoxy, The epoxide number of the modified epoxy is 0.25~0.45, and the modified epoxy is the modified epoxy resin of modifier, The modifier is selected from least one of organosilicon, base polyurethane prepolymer for use as and polyimides, and the modifier and the ring The mass ratio of oxygen resin is 1:5~1:10.
5. shell according to claim 4, which is characterized in that the epoxy resin layer has first surface, the shell It further include the decorating unit of setting on the first surface.
6. shell according to claim 5, which is characterized in that the decorating unit includes the adhesive layer stacked gradually, anti- Layer and ink layer are penetrated, the adhesive layer is transparent material, side of the adhesive layer far from the reflecting layer and first table Surface layer is folded.
7. shell according to claim 6, which is characterized in that the adhesive layer is the UV transfer printing layer with textured pattern.
8. shell according to claim 6, which is characterized in that the reflecting layer is the non-conductive electroplated layer of vacuum.
9. the production method of shell according to claim 6, which is characterized in that the reflecting layer be selected from indium tin oxide layer, Titanium dioxide layer, columbium dioxide layer, columbium sesquioxide layer, two niobium layer of titanium dioxide, niobium pentaoxide layer, silicon dioxide layer and dioxy Change at least one of zirconium layer.
10. shell according to claim 6, which is characterized in that the decorating unit further includes basilar memebrane, the basilar memebrane On the first surface, the shell further includes adhesive layer for setting, and adhesive layer setting is in the basilar memebrane and described the Between one surface, and the adhesive layer fixed bonding basilar memebrane and the first surface, wherein the adhesive layer is far from institute The side and the basilar memebrane for stating reflecting layer are laminated far from the side of the first surface.
11. shell according to claim 5, which is characterized in that further include described first that the epoxy resin is arranged in Pattern layer on surface, the decorating unit cover the pattern layer.
12. shell according to any one of claim 4 to 11, which is characterized in that the modifier is selected from the organosilicon And one of described base polyurethane prepolymer for use as；
Alternatively, the modifier is by least one of the organosilicon and the polyimides and the base polyurethane prepolymer for use as group At, and in the modifier, the mass percentage of the base polyurethane prepolymer for use as is 60% or more；
Alternatively, the modifier by mass ratio be 1:(0.1~0.2) the organosilicon and the polyimides form.
13. shell according to any one of claim 4 to 11, which is characterized in that the epoxy resin layer has the second table Face, the shell further include the hardened layer being arranged on the second surface.
14. a kind of production method of shell, which comprises the steps of:
Epoxy resin board is prepared, the material of the epoxy resin board is modified epoxy, the epoxy of the modified epoxy Being worth is 0.25~0.45, and the modified epoxy is the modified epoxy resin of modifier, and the modifier is selected from organosilicon, gathers At least one of urethane performed polymer and polyimides, and the mass ratio of the modifier and the epoxy resin is 1:5~1: 10；And
By the epoxy resin board brake forming, shell is obtained.
15. the production method of shell according to claim 14, which is characterized in that further include on the epoxy resin board The step of decorating unit is set；And by after the epoxy resin board brake forming, the epoxy resin board has concave surface, The decorating unit is located on the concave surface.
16. the production method of shell according to claim 15, which is characterized in that described to be set on the epoxy resin board The step of setting decorating unit it is described by the epoxy resin board brake forming the step of before, it is described in the epoxy resin board The step of upper setting decorating unit includes: that transparent adhesive layer is formed in the side of the epoxy resin board；In the adhesive layer Side far from the epoxy resin board forms reflecting layer；Ink is formed far from the side of the adhesive layer in the reflecting layer Layer, obtains the decorating unit.
17. the production method of shell according to claim 15, which is characterized in that described to be set on the epoxy resin board The step of setting decorating unit it is described by the epoxy resin board brake forming the step of before, it is described in the epoxy resin board The step of upper setting decorating unit includes: that transparent adhesive layer is formed on basilar memebrane, forms reflecting layer on the adhesive layer, Ink layer is formed on the reflecting layer, obtains the decorating unit；By the basilar memebrane of the decorating unit far from described The side of adhesive layer and the side of the epoxy resin board bond.
18. the production method of shell according to claim 15, which is characterized in that described to be set on the epoxy resin board The step of setting decorating unit it is described by the epoxy resin board brake forming the step of after, it is described in the epoxy resin board The step of upper setting decorating unit includes: that transparent adhesive layer is formed on basilar memebrane, forms reflecting layer on the adhesive layer, Ink layer is formed on the reflecting layer, obtains the decorating unit；By the basilar memebrane of the decorating unit far from described The concave surface of the side of adhesive layer and the epoxy resin board bonds.
19. the production method of 6~18 described in any item shells according to claim 1, which is characterized in that the adhesive layer is logical It crosses UV glue to transfer to obtain, the adhesive layer has textured pattern.
20. the production method of 6~18 described in any item shells according to claim 1, which is characterized in that the reflecting layer passes through The non-conductive plating of vacuum obtains.
21. the production method of 5~18 described in any item shells according to claim 1, which is characterized in that described in the epoxy Before the step of decorating unit is arranged on resin plate, further include the steps that forming pattern layer in the side of the epoxy resin board； Described includes: to be formed with the pattern layer in the epoxy resin board the step of decorating unit is arranged on the epoxy resin board Side form the decorating unit, the decorating unit covers the pattern layer.
22. the production method of shell according to claim 21, which is characterized in that the pattern layer is printed by mirror-like silver ink It is dried to obtain after brush.
23. the production method of any one of 4~18 shells according to claim 1, which is characterized in that the modifier is selected from institute State at least one of organosilicon and the base polyurethane prepolymer for use as；
Alternatively, the modifier is made of the polyimides and the base polyurethane prepolymer for use as, and in the modifier, it is described The mass percentage of base polyurethane prepolymer for use as is 60% or more；
Alternatively, the modifier by mass ratio be 1:(0.1~0.2) the organosilicon and the polyimides form.
24. the production method of 4~18 described in any item shells according to claim 1, which is characterized in that described by the epoxy After resin plate brake forming, the epoxy resin board has convex surface；It is described by the epoxy resin board brake forming After step, further include the steps that forming hardened layer in the convex surface of the epoxy resin.
25. the production method of 4~18 described in any item shells according to claim 1, which is characterized in that described by the epoxy The method of resin plate brake forming is high-pressure molding, and the technological parameter of the high-pressure molding includes: that the temperature of molding die is 90 DEG C~150 DEG C, the temperature of heating plate is 150 DEG C~300 DEG C, and the blowing pressure is 10Bar~30Bar, molding time is 60 seconds~ 150 seconds；
Alternatively, the method by the epoxy resin board brake forming be it is hot-forming, the hot-forming step includes: elder generation The epoxy resin board is placed in lower die, the heating 15 seconds~30 under conditions of the temperature of heating plate is 250 DEG C~380 DEG C Second, and lower die temperature is 90 DEG C~140 DEG C；Then upper film and the lower die are molded, and pressure maintaining 10 seconds~30 seconds, upper mold temperature is 90 DEG C~130 DEG C.
26. a kind of electronic equipment, which is characterized in that including the described in any item shells of claim 4~13 or claim 14 The prepared shell of production method of~25 described in any item shells.
27. electronic equipment according to claim 26, which is characterized in that the electronic equipment be mobile phone or tablet computer, The shell is rear cover.
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