CN114059016A

CN114059016A - Coating film pretreatment method and device, appearance part preparation method and electronic equipment

Info

Publication number: CN114059016A
Application number: CN202111291853.1A
Authority: CN
Inventors: 周亮; 莫亚杰; 蒋正南
Original assignee: Guangdong Oppo Mobile Telecommunications Corp Ltd
Current assignee: Guangdong Oppo Mobile Telecommunications Corp Ltd
Priority date: 2021-11-02
Filing date: 2021-11-02
Publication date: 2022-02-18

Abstract

The application provides a method for pretreatment of coating, which comprises the steps of placing a substrate in a pretreatment device for coating, wherein the pretreatment device for coating comprises a shell, a target, a substrate seat, a magnet and a power supply unit, the shell is provided with an accommodating space, the target and the substrate seat are oppositely arranged in the accommodating space, the target is made of graphite, the shell is provided with a vent hole, the magnet is arranged on the surface of one side, away from the substrate seat, of the target, the power supply unit is electrically connected with the target, the substrate is provided with an organic layer, the substrate is placed on the substrate seat, and the organic layer is arranged on one side, close to the target, of the substrate; and introducing oxygen and inert gas into the accommodating space through the vent hole and starting the power supply unit to ionize the oxygen and the inert gas so as to pretreat the base material. Thus, the surface modification is carried out on the organic layer of the base material, which is beneficial to the improvement of the binding force and the binding reliability between the organic layer and the coating layer. The application also provides a coating film pretreatment device, an appearance piece, a preparation method of the appearance piece and electronic equipment.

Description

Coating film pretreatment method and device, appearance part preparation method and electronic equipment

Technical Field

The application belongs to the technical field of electronic equipment, and particularly relates to a coating pretreatment method and device, an appearance part preparation method and electronic equipment.

Background

With the increase of the consumption level, consumers have pursued not only the diversification of functions but also the higher and higher requirements for the appearance effect of electronic products, and the monotonous appearance cannot meet the user requirements. Therefore, the appearance effect of more and more electronic products is being diversified.

Disclosure of Invention

In view of the above, the present application provides a coating pretreatment method, a coating pretreatment apparatus, an appearance piece, a manufacturing method thereof, and an electronic device.

In a first aspect, the present application provides a method for pretreatment of plating, comprising:

placing a substrate in a coating pretreatment device, wherein the coating pretreatment device comprises a shell, a target, a substrate seat, a magnet and a power supply unit, the shell is provided with an accommodating space, the target and the substrate seat are oppositely arranged in the accommodating space, the material of the target comprises graphite, the shell is provided with a vent hole, the magnet is arranged on the surface of one side, away from the substrate seat, of the target, the power supply unit is electrically connected with the target, the substrate is provided with an organic layer, the substrate is placed on the substrate seat, and the organic layer is arranged on one side, close to the target, of the substrate;

and introducing oxygen and inert gas into the accommodating space through the vent hole and starting the power supply unit to ionize the oxygen and the inert gas so as to pretreat the base material.

In a second aspect, the application provides a processing apparatus before coating film, including shell, target, substrate seat, magnet and power supply unit, the shell has accommodating space, the target with the substrate seat sets up relatively in the accommodating space, the material of target includes graphite, the substrate seat is used for placing the substrate that has organic layer, the air vent has on the shell, the air vent be used for to let in oxygen and inert gas in the accommodating space, the magnet sets up the target deviates from a side surface of substrate seat, power supply unit with the target electricity is connected.

In a third aspect, the present application provides a method for manufacturing an appearance piece, comprising:

introducing oxygen and inert gas into the accommodating space through the vent hole and starting the power supply unit to ionize the oxygen and the inert gas so as to pretreat the base material;

and forming a coating layer on the surface of the organic layer after the pretreatment to obtain the appearance piece.

In a fourth aspect, the present application provides an appearance piece prepared by the preparation method of the third aspect, wherein the appearance piece comprises a base material and a coating layer, the base material comprises an organic layer, and the coating layer is arranged on the surface of the organic layer.

In a fifth aspect, the present application provides an electronic device including the appearance piece of the fourth aspect.

The application provides a coating pretreatment method, which is characterized in that a substrate to be coated is placed in a coating pretreatment device for pretreatment, so that an organic layer of the substrate is subjected to physical and chemical modification, the surface roughness of the organic layer and the content of surface active groups are improved, and the improvement of the binding force and the binding reliability between the organic layer and a coating layer is facilitated. The application provides a processing apparatus before coating film can carry out the pretreatment to the substrate that has the organic layer, promotes the cohesion between organic layer and the coating film layer. The preparation method of the appearance piece is simple, convenient to operate and suitable for industrial production, the prepared appearance piece is excellent in internal bonding force, reliability and stability, and the electronic equipment with the appearance piece is good in reliability and capable of meeting user requirements.

Drawings

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

Fig. 1 is a schematic structural diagram of a plating pretreatment apparatus according to an embodiment of the present disclosure.

Fig. 2 is a schematic structural diagram of a plating pretreatment apparatus according to another embodiment of the present application.

Fig. 3 is a schematic structural diagram of a plating pretreatment apparatus according to yet another embodiment of the present application.

Fig. 4 is a schematic structural diagram of a plating pretreatment apparatus according to yet another embodiment of the present application.

Fig. 5 is a schematic flow chart of a plating pretreatment method according to an embodiment of the present disclosure.

Fig. 6 is a schematic view illustrating an installation manner of a substrate in a plating pretreatment apparatus according to an embodiment of the present application.

Fig. 7 is a schematic flow chart illustrating a manufacturing method of an appearance piece according to an embodiment of the present disclosure.

Fig. 8 is a schematic cross-sectional view of an appearance member according to an embodiment of the present application.

Fig. 9 is a schematic cross-sectional view of an appearance piece according to another embodiment of the present application.

Fig. 10 is a schematic structural diagram of an electronic device according to an embodiment of the present application.

Fig. 11 is an atomic force microscope image of the surface of the UV glue layer, wherein a, b, c and d in fig. 11 correspond to the blank control, comparative example 1, comparative example 2 and example, respectively.

FIG. 12 is a carbon chromatogram of the X-ray photoelectron spectrum of the surface of the UV glue layer.

Fig. 13 shows zeta potential results for the UV glue layer, where a and b in fig. 13 correspond to example and comparative example 1, respectively.

Description of reference numerals:

the device comprises a shell-10, a containing space-11, a vent hole-12, a target-20, a base material seat-30, a magnet-40, a power supply unit-50, a vent pipe-60, a cooling unit-70, a coating pretreatment device-100, a base material-201, a coating layer-202, an organic layer-203, a base material body-204, an appearance piece-200 and electronic equipment-300.

Detailed Description

The following is a preferred embodiment of the present application, and it should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present application, and these improvements and modifications are also considered as the protection scope of the present application.

The following disclosure provides many different embodiments or examples for implementing different features of the application. In order to simplify the disclosure of the present application, specific example components and arrangements are described below. Of course, they are merely examples and are not intended to limit the present application. Moreover, the present application may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, examples of various specific processes and materials are provided herein, but one of ordinary skill in the art may recognize applications of other processes and/or use of other materials.

Referring to fig. 1, which is a schematic structural diagram of a pre-processing apparatus for coating film according to an embodiment of the present disclosure, the pre-processing apparatus 100 for coating film includes a housing 10, a target 20, a substrate holder 30, a magnet 40, and a power supply unit 50, where the housing 10 has an accommodating space 11, the target 20 and the substrate holder 30 are oppositely disposed in the accommodating space 11, the target 20 is made of graphite, the substrate holder 30 is used for placing a substrate 201 having an organic layer 203, the housing 10 has a vent hole 12, the vent hole 12 is used for introducing oxygen and an inert gas into the accommodating space 11, the magnet 40 is disposed on a side surface of the target 20 away from the substrate holder 30, and the power supply unit 50 is electrically connected to the target 20. The coating pretreatment device 100 is used for treating the substrate 201 with the organic layer 203 and physically and chemically modifying the organic layer 203, so as to activate the organic layer 203, improve the dyne value of the organic layer 203, and facilitate the improvement of the bonding force and the bonding reliability between the layer structure arranged on the organic layer 203 and the organic layer 203.

In the present application, the power supply unit 50 is electrically connected to the target 20, and the target 20 is used as an electrode to excite glow discharge, so that oxygen and inert gas entering the accommodating space 11 through the vent hole 12 are ionized to generate plasma; under the action of an electric field generated by electrifying the target 20, a magnetic field generated by the magnet 40 and collision energy, cations in the plasma bombard the target 20 to generate secondary electrons, electrons and secondary electrons collide with oxygen and inert gas which are not ionized, so that ionization is generated, glow discharge is maintained, the plasma concentration is ensured, anions bombard the organic layer 203 in the substrate 201, and the oxygen in the plasma, oxygen anions, oxygen radicals and excited states are collided and moved by the collision of the cations, the anions, the electrons or the secondary electrons, so that the electrons can collide with the surface of the organic layer 203 and are embedded into the organic layer 203, the material of the organic layer 203 is oxidized, polar groups such as C-O, C-O, O-C-O are generated on the surface of the organic layer 203, and the purpose of activating the surface of the organic layer 203 is achieved, meanwhile, in the process of bombarding the organic layer 203, the roughness of the surface of the organic layer 203 is increased, the roughness uniformity is improved, and the purpose of physical modification is achieved; by the chemical modification and the physical modification, the bonding force and the bonding reliability between the layer structure provided on the surface of the organic layer 203 and the organic layer 203 are improved.

In the present embodiment, the housing 10 is an insulating housing, so as to avoid the influence of the housing 10 on the movement of the plasma. Specifically, the housing 10 may be, but is not limited to, a plastic case or the like. In the present application, the housing 10 has the accommodating space 11, so that the surface of the organic layer 203 can be subjected to a film plating pretreatment in a pollution-free and vacuum environment, and the accommodating space 11 serves as an ionization chamber to ensure a modification effect of the surface of the organic layer 203. In the present application, the housing 10 has a vent hole 12, and the vent hole 12 introduces oxygen and inert gas into the housing space 11. In the embodiment of the present application, the pre-coating treatment device 100 further includes a vent pipe 60 connected to the vent hole 12, so as to facilitate the introduction of oxygen and inert gas into the pre-coating treatment device 100 during the use process. Further, the breather pipe 60 has two opposite ends, one of which is connected to the breather hole 12 and the other of which is connected to a gas device having oxygen and inert gas. It is understood that the pre-coating treatment device 100 may have one or more vent holes 12 and a vent pipe 60, and the positions of the vent holes 12 on the housing 10 may be selected according to the needs.

In the present application, the target material 20 includes graphite, the sputtering rate of graphite is low, carbon atoms rarely sputter out in the process of bombarding the target material 20 by ions, and the introduced oxygen can inhibit the sputtering rate of the target material 20, so that even if the target material 20 sputters out and reacts with oxygen to generate other products, the other products cannot sputter onto the surface of the organic layer 203, further the surface modification of the organic layer 203 cannot be affected, and the original performance of the substrate 201 cannot be affected; moreover, the target material 20 serving as an electrode has a good glow discharge effect and can generate more plasmas, so that strong chemical modification is generated on the surface of the organic layer 203, the content of polar groups generated on the surface of the organic layer 203 is increased, and the adhesion and the maintenance of other layer structures are facilitated; meanwhile, the graphite target has wide working power range and wide process window, and is suitable for being used in industry. In one embodiment, the target 20 is a graphite target. In the present embodiment, the pre-coating treatment apparatus 100 includes at least one target 20. Referring to fig. 1, the pre-coating treatment apparatus 100 includes a plurality of targets 20, the targets 20 are disposed in a housing 10 at intervals, and the targets 20 are disposed corresponding to a substrate holder 30. Referring to fig. 2, a schematic structural diagram of a pre-coating treatment apparatus according to another embodiment of the present disclosure is substantially the same as that shown in fig. 1, except that the pre-coating treatment apparatus 100 is provided with a target 20. In the present application, the target 20 may be, but is not limited to, a cylindrical target, a planar target, and the like.

In the present application, the substrate holder 30 is used to place the substrate 201 when the plating pretreatment apparatus 100 is used. Specifically, the substrate 201 may be hung on the substrate holder 30, or may be laid on the substrate holder 30; the material, shape and size of the substrate holder 30 may be selected as needed, but are not limited thereto. In the present application, the substrate holder 30 and the target 20 are positioned relative to each other to facilitate bombardment of the organic layer 203 by the plasma. It is understood that the surface of the substrate holder 30 is disposed opposite to the surface of the target 20 to be bombarded by ions, such as two surfaces disposed in parallel or two surfaces extending at an angle, so long as the plasma can bombard the organic layer 203. In the present application, the substrate holder 30 may be coupled to the housing 10 to secure the substrate holder 30.

In the present application, the magnet 40 is used to generate a magnetic field, thereby affecting the moving direction of ions and electrons in cooperation with the electric field, and further modifying the surface of the organic layer 203. In the present embodiment, the magnet 40 includes at least one of a permanent magnet and an electromagnet. The permanent magnet can continuously generate a magnetic field, so that the magnetic field is more convenient to generate, and the generated magnetic field has high intensity and good stability, such as a neodymium iron boron magnet and the like; the electromagnet generates a magnetic field under the electrified condition, and the controllability is good. In the present embodiment, the plating pretreatment apparatus 100 includes at least one magnet 40. In the embodiment, the coating pretreatment apparatus 100 includes a plurality of magnets 40, and the magnets 40 corresponding to the same target 20 have opposite polarities from each other among the magnets 40. Referring to fig. 2, the pre-coating treatment apparatus 100 includes a target 20 and a plurality of magnets 40, wherein the adjacent magnets 40 have opposite magnetic properties; that is, the south (S) to north (N) poles of adjacent magnets 40 are in opposite directions. Referring to fig. 3, a schematic structural diagram of a pre-coating treatment apparatus according to another embodiment of the present disclosure is shown, wherein the pre-coating treatment apparatus 100 includes a plurality of targets 20 and a plurality of magnets 40, the targets 20 are disposed at intervals, and the magnetic properties of the adjacent magnets 40 corresponding to the same target 20 are opposite; that is, a plurality of magnets 40 are provided for each target 20, and the south pole to north pole directions of adjacent magnets 40 are opposite among the plurality of magnets 40 corresponding to the same target 20. In the present embodiment, the south-to-north direction of the magnet 40 is a first direction, and the first direction may be parallel to or at an angle with respect to the extending direction of the length of the target 20, such as perpendicular. In an embodiment of the present invention, when the pre-coating treatment apparatus 100 is in use, the direction of the electric field and the direction of the magnetic field form an included angle, such as perpendicular, which is beneficial for the plasma to bombard the organic layer 203.

In the present embodiment, the power supply unit 50 is electrically connected to the target 20 so that the target 20 becomes an electrode, and generates an electric field in the housing space 11 to ignite glow discharge. In the present application, the type of the power supply unit 50 may be selected as required, so that the target 20 can be used as an electrode to ionize oxygen and inert gas, and the generated plasma bombards the organic layer 203. In the embodiment of the present application, the power supply unit 50 includes at least one of a direct current unit, an intermediate frequency unit, a radio frequency unit, and a pulse unit. In one embodiment, the power supply unit 50 is a dc unit, and the cathode of the dc unit is connected to the target 20 and the anode is connected to the substrate holder 30. In another embodiment, referring to fig. 1, the pre-coating treatment apparatus 100 includes at least two targets 20, the power supply unit 50 is an intermediate frequency unit, and the intermediate frequency unit is respectively connected to the two targets 20, so that the two targets 20 periodically alternate as a cathode and an anode; at this time, the two target materials 20 may be referred to as twin targets.

Referring to fig. 4, a schematic structural diagram of a pre-coating treatment apparatus according to another embodiment of the present disclosure is substantially the same as that shown in fig. 1, except that the pre-coating treatment apparatus 100 further includes a cooling unit 70, the cooling unit 70 is disposed between the target 20 and the magnet 40, and the cooling unit 70 is used for cooling the target 20. In this way, it is avoided that the temperature of the target 20 is too high during the pre-treatment process, which may affect the use of the target 20 and the modification of the organic layer 203. In one embodiment of the present application, the cooling unit 70 is a water-cooled pipe, which reduces the temperature of the target 20 by flowing water. In an embodiment of the present application, the cooling unit 70 is disposed outside the accommodating space 11.

In the embodiment of the present application, the pre-coating treatment apparatus 100 further includes a target holder for placing the target 20. In the embodiment of the present application, the pre-coating treatment apparatus 100 further includes a transfer unit connected to the target holder and/or the substrate holder 30, and the transfer unit is configured to transfer the target 20 and/or the substrate 201. Therefore, the coating pretreatment process can be more automated. Specifically, the conveying unit may be, but is not limited to, a conveyor belt or the like.

The coating film pretreatment device 100 can be used independently, modifies the organic layer 203, can also be connected with a coating device to form a complete system, directly conveys the substrate 201 to the coating device for coating after the coating film pretreatment device 100 treats the substrate, is more convenient and is suitable for industry use, wherein the coating device can be but not limited to a magnetron monomer furnace, a magnetron continuous line, electron gun evaporation plating and the like, and can be specifically selected according to the forming mode of the coating film layer 202.

Referring to fig. 5, a schematic flow chart of a method for pre-processing a plated film according to an embodiment of the present application includes:

s101: the substrate is placed in a coating pretreatment device, the coating pretreatment device comprises a shell, a target, a substrate seat, a magnet and a power supply unit, the shell is provided with an accommodating space, the target and the substrate seat are oppositely arranged in the accommodating space, the target is made of graphite, the shell is provided with a vent hole, the magnet is arranged on the surface of one side, deviating from the substrate seat, of the target, the power supply unit is electrically connected with the target, the substrate is provided with an organic layer, the substrate is placed on the substrate seat, and the organic layer is arranged on one side, close to the target, of the substrate.

S102: and introducing oxygen and inert gas into the accommodating space through the vent hole and starting the power supply unit to ionize the oxygen and the inert gas so as to pretreat the base material.

In the application, a substrate 201 with an organic layer 203 is placed in a coating pretreatment device 100, and after oxygen and inert gas are introduced, a power supply unit 50 is started to excite glow discharge, so that the oxygen and the inert gas are ionized to generate plasma, wherein the plasma comprises electrons, inert gas ions, oxygen positive ions, oxygen negative ions, oxygen free radicals, excited oxygen and the like; oxygen-containing ions, oxygen-containing groups and the like generated under the action of the electric field and the magnetic field generated by the magnet 40 can bombard the organic layer 203, so that the surface contamination of the organic layer 203 can be removed, the surface roughness and roughness uniformity of the organic layer 203 can be improved, and the organic layer 203 can be physically modified; meanwhile, the organic material in the organic layer 203 can be embedded in the organic layer 203 to oxidize the organic material, polar groups such as C-O, C-O, O-C-O are generated on the surface of the organic layer 203, and the organic layer 203 can be chemically modified to increase the dyne value on the surface of the organic layer 203. In the related art, in order to improve the appearance effect of the appearance piece 200 of the electronic device 300, such as the rear cover, the middle frame, the key cap, the dial cover, and the like, the coating layer 202 is often required to be arranged to realize a colorful appearance, however, most of the coating layer 202 is an inorganic material layer, the coating layer 202 is often required to be arranged in cooperation with the organic layer 203, the two layers have large difference in performance, the bonding force between the two layers is weak, the bonding stability is not good, and the resistance to photo-oxidation aging is weak, so that the phenomenon that the coating layer 202 falls off occurs to the electronic device 300, and the use and the user experience of the electronic device 300 are affected; when the substrate 201 is cleaned by the inert gas, the dirt on the surface of the substrate 201 can be removed, the substrate 201 cannot be chemically modified, the stable combination between the coating layer 202 and the organic layer 203 cannot be ensured, the problem that the coating layer 202 falls off still exists, the cleaning time is too long, the surface of the organic layer 203 is damaged, and the adhesion of the coating layer 202 is not facilitated. Therefore, through carrying out coating pretreatment to the substrate 201 with the organic layer 203 in this application, carry out physics and chemical modification to the organic layer 203 surface through inert gas, oxygen plasma, show the surface activity who promotes the organic layer 203, can not harm the organic layer 203 simultaneously again to guarantee the combination between follow-up coating layer 202 and the organic layer 203, promote the combination reliability of outward appearance piece 200 and electronic equipment 300.

In S101, the substrate 201 is placed in the pre-coating treatment apparatus 100, and the organic layer 203 is directed toward the target 20, so that the plasma generated by the glow discharge can bombard the surface of the organic layer 203, thereby physically and chemically modifying the surface of the organic layer 203. Referring to fig. 6, a schematic view of an arrangement manner of the substrate in the pre-processing apparatus for coating film according to an embodiment of the present disclosure is shown, wherein a plurality of substrates 201 may be arranged and fixed on the substrate holder 30 at intervals.

In the present application, the material of the organic layer 203 is an organic material, and the organic layer 203 may be, but not limited to, an ultraviolet curing glue layer (UV glue layer). In one embodiment of the present disclosure, the substrate 201 includes a substrate body 204 and an organic layer 203 disposed on a surface of the substrate body 204; the material of the substrate body 204 can be selected according to the use requirement of the substrate 201, and the material of the substrate body 204 can include, but is not limited to, plastics, such as polycarbonate, polyphenylene sulfide, polyethylene terephthalate, polymethyl methacrylate, and the like. In the present application, the thickness and material of the substrate body 204 and the organic layer 203 may be selected as needed, but are not limited thereto.

In the embodiment of the present application, the distance between the target 20 and the substrate 201 is 10mm to 50 mm; thus, more plasma acts on the organic layer 203, and the surface modification effect of the plasma is improved. Further, the distance between the target 20 and the substrate 201 is 15mm-40 mm. Specifically, the distance between the target 20 and the substrate 201 may be, but not limited to, 10mm, 20mm, 25mm, 30mm, 35mm, 40mm, or 50 mm.

In the present embodiment, the magnetic field strength generated by the magnet 40 is 200 gauss to 500 gauss; thus, the magnetic field generates a strong magnetic force effect on the plasma, so that more plasmas bombard the organic layer 203 in the collision process, and the surface modification effect of the organic layer 203 is improved. Further, the magnet 40 generates a magnetic field strength of 250 gauss to 480 gauss. Specifically, the magnetic field strength generated by the magnet 40 may be, but is not limited to, 200 gauss, 220 gauss, 270 gauss, 300 gauss, 390 gauss, 450 gauss, or 460 gauss, etc.

In S102, oxygen and inert gas are introduced into the coating pretreatment apparatus 100, and the power supply unit 50 is turned on, so that glow discharge occurs, and the oxygen and inert gas are ionized to generate plasma, wherein electrons move to the anode, while the magnetic field near the target 20 restricts the movement range of the electrons, and the electrons perform a compound movement of cycloidal movement and spiral movement under the action of the magnetic field and the electric field, and can collide with the inert gas and oxygen that are not ionized in the process, thereby further obtaining plasma; the positive ions bombard the target material 20, so that secondary electrons are emitted from the surface of the target material 20, move under the constraint action of a magnetic field and collide with gas to be ionized, and the plasma concentration is maintained; the generated anions and electrons bombard the surface of the organic layer 203, and oxygen cations, oxygen radicals and excited oxygen are collided to bombard the surface of the organic layer 203, remove dirt on the surface of the organic layer 203 and improve the roughness and roughness uniformity of the surface of the organic layer 203, and are chemically bonded with the surface of the organic layer 203 to form polar groups to activate the surface of the organic layer 203; meanwhile, the target material 20 made of graphite is adopted in the application, so that when cations bombard the target material 20, the sputtering rate of the target material 20 is low, and even if the target material 20 sputters, sputtered carbon atoms react with oxygen ions to generate gas products, so that the gas products cannot be sputtered onto the surface of the organic layer 203, and the performance of the organic layer 203 is further ensured. In the application, the organic layer 203 is modified under the interaction of the electric field and the magnetic field, if only the electric field exists, the electron motion track is short, gas cannot be collided repeatedly, glow discharge and plasma concentration cannot be maintained, and the physical and chemical modification effects on the organic layer 203 cannot be guaranteed.

In the present embodiment, the vacuum degree of the film formation pretreatment apparatus 100 before introducing oxygen and inert gas was 6X 10^-3Pa or less. In this way, the ionization of the gas in the housing space 11 can be better ensured. In one embodiment, the substrate 201 is placed in the pre-coating treatment apparatus 100 and pumped to a backing vacuum of 6 × 10^-3Pa, and then oxygen and inert gas are introduced into the housing space 11 through the vent hole 12.

In the embodiment of the present application, the flow ratio of oxygen to inert gas is (1-4): 1. thus, the oxygen can be pressed to sputter the target material 20 onto the surface of the organic layer 203, target poisoning can be avoided, and the discharge process can be maintained, so that the organic layer 203 can be better modified. In one embodiment, the amount of oxygen introduced is greater than the amount of inert gas introduced. Further, the flow ratio of the oxygen gas to the inert gas is (1.5-3.5): 1. specifically, the flow ratio of oxygen to inert gas may be, but is not limited to, 1.5:1, 2:1, 2.3:1, 2.6:1, 3:1, 3.5:1, or 4:1, etc. In the present embodiment, the inert gas includes at least one of argon, helium, neon, krypton, and xenon; in this manner, the surface modification of the organic layer 203 can be ensured.

In the embodiment of the present application, the power of the power supply unit 50 is 8kW to 20 kW. In the present application, the sputtering rate of the target 20 is low, so that the power selection range of the power supply unit 50 is wide, the process window is wide, thereby facilitating the use in industry, and more plasmas can be generated to ensure the surface modification effect on the organic layer 203. Specifically, the power of the power supply unit 50 may be, but is not limited to, 8kW, 10kW, 13kW, 15kW, 19kW, or 20 kW. In the embodiment of the present application, the pretreatment time is 3min to 10 min. Therefore, the organic layer 203 can be physically and chemically modified, damage to the surface of the organic layer 203 is avoided, and combination of the organic layer 203 and the coating layer 202 is facilitated. Specifically, the pretreatment time may be, but is not limited to, 3min, 4min, 5.5min, 6min, 7min, or 9 min.

In the application, after pretreatment, a plurality of polar groups are generated on the surface of the organic layer 203, so that the electron adsorption effect between the organic layer and the coating layer 202 is increased, the adhesive force of the coating layer 202 is further improved, the photo-oxidation aging resistance is strong, and the combination stability is high. In the embodiment of the present application, the dyne value of the surface of the organic layer 203 after the pretreatment is 64 or more. Further, the dyne value of the surface of the organic layer 203 after the pretreatment is 64 to 68. The pretreatment method provided by the application can enable the organic layer 203 to have high surface energy, strong surface activity and excellent binding performance.

Referring to fig. 7, a schematic flow chart of a method for manufacturing an appearance piece according to an embodiment of the present application includes:

s201: the substrate is placed in a coating pretreatment device, the coating pretreatment device comprises a shell, a target, a substrate seat, a magnet and a power supply unit, the shell is provided with an accommodating space, the target and the substrate seat are oppositely arranged in the accommodating space, the target is made of graphite, the shell is provided with a vent hole, the magnet is arranged on the surface of one side, deviating from the substrate seat, of the target, the power supply unit is electrically connected with the target, the substrate is provided with an organic layer, the substrate is placed on the substrate seat, and the organic layer is arranged on one side, close to the target, of the substrate.

S202: and introducing oxygen and inert gas into the accommodating space through the vent hole and starting the power supply unit to ionize the oxygen and the inert gas so as to pretreat the base material.

S203: and forming a coating layer on the surface of the organic layer after pretreatment to obtain the appearance piece.

In the application, the organic layer 203 of the substrate 201 is pretreated, and the organic layer 203 is physically and chemically modified, so that the surface roughness and the dyne value of the organic layer 203 are improved, the combination between the organic layer 203 and the coating layer 202 is improved, and the reliability between the organic layer 203 and the coating layer 202 is improved. For S201 and S202, reference may be made to the description of S101 and S102, which is not described herein again.

In S203, the plating layer 202 may be formed on the surface of the organic layer 203 by, but not limited to, physical vapor deposition, such as evaporation, sputtering, ion plating, and the like. It can be understood that when the coating layer 202 is arranged on the surface of the organic layer 203, due to the performance difference between the organic material and the inorganic material, the bonding force between the two layers of structures cannot be generated, and by the method, the polar group content and the surface roughness of the surface of the organic layer 203 are improved, so that the strong bonding force is generated between the organic layer 203 and the coating layer 202, and the bonding force can be stably maintained for a long time, and the reliability of the whole structure is improved.

Referring to fig. 8, which is a schematic cross-sectional view of an appearance member 200 according to an embodiment of the present disclosure, the appearance member includes a substrate 201 and a coating layer 202, the substrate 201 includes an organic layer 203, and the coating layer 202 is disposed on a surface of the organic layer 203. Through setting up coating film layer 202, promoted outward appearance effect of outward appearance piece 200, organic layer 203 is good with coating film layer 202's associative property simultaneously, has improved the life of outward appearance. Referring to fig. 9, which is a schematic cross-sectional view of an appearance piece according to another embodiment of the present disclosure, an appearance piece 200 includes a substrate 201 and a coating layer 202, the substrate 201 includes a substrate body 204 and an organic layer 203 disposed on a surface of the substrate body 204, and the coating layer 202 is disposed on a surface of the organic layer 203.

In the embodiment of the application, the ultraviolet limit test time between the organic layer 203 and the coating layer 202 is not less than 168h, the xenon lamp limit test time is not less than 72h, and the double 85 limit test time is not less than 7 days, so that the service life of the appearance piece 200 is prolonged. Further, the ultraviolet limit test time between the organic layer 203 and the coating layer 202 is not less than 175h, the xenon lamp limit test time is not less than 80h, and the double 85 limit test time is not less than 8 days.

In this application embodiment, organic layer 203 includes the ultraviolet curing glue film, so, can set up the ultraviolet curing glue film that has texture, promotes the outward appearance effect of outward appearance piece 200. In an embodiment of the present application, the surface of the substrate body 204 is coated with the uv-curable adhesive, and then the mold with the texture is attached to the surface of the uv-curable adhesive, and after curing, the mold is removed, so as to obtain the uv-curable adhesive layer with the texture structure.

In the present embodiment, the material of the coating layer 202 includes SiO₂、TiO₂、Ti₃O₅、NbO₂、Nb₂O₃、NbO、Nb₂O₅And ZrO₂At least one of (1). Thus, the film coating layer 202 can change refraction, reflection and the like of light, thereby realizing the effect of changing light and shadow flowing and improving the visual effect of the appearance piece 200. In one embodiment, the coating 202 includes a plurality of optical layers, and the refractive index of adjacent optical layers is different, so as to improve the light and shadow variation effect of the coating 202. Specifically, the number of layers and the material of the optical film layer can be selected according to the needs.

In the present embodiment, the thickness of the coating layer 202 is 200nm to 700 nm. Thus, the appearance effect of the appearance piece 200 can be improved, the thickness of the appearance piece 200 is not excessively increased, and the appearance piece can be well combined with the organic layer 203. Further, the thickness of the plating layer 202 is 380nm-450 nm. Specifically, the thickness of the plating layer 202 may be, but is not limited to, 250nm, 300nm, 390nm, 400nm, 420nm, 440nm, 500nm, 630nm, 690nm, or the like.

In the embodiment of the present application, the exterior member 200 further includes a color layer, so that the exterior member 200 can have different colors. In the present application, the substrate body 204 may be a light-transmitting layer, and in this case, the organic layer 203, the film coating layer 202 and the color layer may be disposed on the outer surface of the substrate body 204, or may be disposed on the inner surface of the substrate body 204; when the substrate body 204 is a non-transparent layer, the organic layer 203, the coating layer 202 and the color layer are disposed on the outer surface of the substrate body 204.

In the embodiment of the application, the appearance piece 200 further includes a light shielding layer, the visible light transmittance of the light shielding layer is less than 5%, and the light shielding layer is disposed on the inner surface of the substrate body 204, so that when the appearance piece 200 is used in the electronic device 300, components inside the electronic device 300 are shielded, and the appearance effect of the appearance piece 200 is ensured. In the embodiment of the present application, the exterior member 200 further includes a protective layer disposed on an outer surface of the exterior member 200, so that the exterior member 200 can be protected. Specifically, the protective layer is a light-transmitting protective layer, such as an anti-fingerprint layer, a hardened layer, and the like. It can be understood that the setting positions of the light shielding layer and the protective layer do not affect the appearance of the organic layer 203, the film plating layer 202 and the color layer.

The present application provides an electronic device 300 including the exterior piece 200 of any of the above embodiments. It is understood that the electronic device 300 can be, but is not limited to, a mobile phone, a tablet computer, a notebook computer, a watch, an MP3, an MP4, a GPS navigator, a digital camera, etc., and the exterior part 200 can be a housing, a battery cover, a front cover, a middle frame, a key cap, a dial, a watch cover, etc. of the electronic device 300. In the embodiment of the present application, the market failure feedback index (FFR) of the electronic apparatus 300 is within 10ppm, wherein the market failure feedback index is a percentage of a failure due to the falling of the coating layer 202 of the exterior member 200 in one million pieces of electronic apparatuses 300. Referring to fig. 10, a schematic structural diagram of an electronic device according to an embodiment of the present disclosure is shown, in which an electronic device 300 includes an appearance member 200 and a display device, and the appearance member 200 is connected to the display device. The appearance piece 200 can endow the electronic device 300 with changeable visual effects, and meanwhile, the service life of the electronic device 300 is prolonged.

The technical solution of the present application is further described below by specific examples.

Example 1

Providing a coating pretreatment device, referring to fig. 3, the coating pretreatment device comprises a housing, two targets, a plurality of permanent magnets, a substrate holder and a power supply, the housing is provided with an accommodating space, the targets and the substrate holder are oppositely arranged in the accommodating space, the targets are graphite targets, the housing is provided with vent holes, the magnets are arranged on one side surface of the targets departing from the substrate holder, south poles or north poles of the magnets are oppositely arranged with the targets, the directions of two poles of adjacent magnets are opposite, and the two targets are arranged at intervals and connected with the intermediate frequency power supply.

A substrate is provided that includes a polycarbonate layer and a UV glue layer disposed on the polycarbonate layer. And placing the substrate on a substrate seat in a coating pretreatment device, wherein the UV adhesive layer is positioned between the polycarbonate layer and the target material.

Pumping the coating pretreatment device to 6 multiplied by 10^-3Pa vacuum degree, introducing 500sccm oxygen and 250sccm argon, starting a power supply, wherein the power supply is a medium-frequency power supply, the power is 15kW, the two targets are alternately used as a cathode and an anode, an electric field is generated, glow discharge is generated, and the UV adhesive layer is pretreated by plasma for 8 min.

And sequentially evaporating a first niobium oxide layer with the thickness of 90nm, a first silicon dioxide layer with the thickness of 90nm, a second niobium oxide layer with the thickness of 90nm, a second silicon dioxide layer with the thickness of 90nm and a third niobium oxide layer with the thickness of 90nm on the surface of the treated UV glue layer through an electron gun evaporation device to form a coating film layer with the thickness of 450nm, so as to obtain the appearance piece.

Comparative example 1

The difference is that the UV glue layer is pretreated by a Hall source in an electron gun evaporation system, wherein the anode voltage is 130V, the current is 6.5A, the filament current is 40A, the argon flow is 40sccm, and the treatment time is 7 min.

Comparative example 2

The difference is that the pre-treatment of the UV glue layer is carried out in a magnetron monomer furnace by adopting an anode layer ion source, wherein the anode voltage is 1500V, the argon flow is 400sccm, and the treatment time is 15 min.

Comparative example 3

The process was carried out in substantially the same manner as in example 1, except that the graphite target was changed to a zirconium target, the power supply was 3kW, the argon flow was 100sccm, the oxygen flow was 200sccm, and the treatment time was 6 min.

Comparative example 4

The process was carried out in substantially the same manner as in example 1 except that the graphite target was changed to a titanium target, the power supply was 3kW, the argon flow was 100sccm, the oxygen flow was 200sccm, and the treatment time was 6 min.

Comparative example 5

The process was carried out in substantially the same manner as in example 1, except that the graphite target was changed to an aluminum target, the power supply was 2kW, the argon flow was 100sccm, the oxygen flow was 200sccm, and the treatment time was 6 min.

Performance detection

The surface of the pretreated UV glue layer was observed by an atomic force microscope, and the untreated UV glue layer was used as a blank control, and the result is shown in fig. 11, wherein a, b, c, d and e in fig. 11 correspond to the blank control, comparative example 1, comparative example 2, comparative example 3 and example, respectively, and it can be seen that the surface roughening of the UV glue in the pretreated examples and comparative examples is enhanced and the roughness of the surface of the UV glue layer in the examples is more uniform compared to the blank control.

The surface of the pretreated UV adhesive layer is detected by an X-ray photoelectron spectrometer to obtain the atom percentage content on the surface of the UV adhesive layer, the untreated UV adhesive layer is used as a blank control group, the result is shown in Table 1, the percentage contents of C, O and N are listed in Table 1, and the content ratio of O and C is calculated. It can be seen that, compared with the blank control group, the oxygen content of the surface of the UV adhesive layer after the pretreatment is increased, and the oxygen content of the surface of the UV adhesive layer in the embodiment is significantly increased; meanwhile, a carbon fine spectrum in the X-ray photoelectron spectroscopy result is obtained, and the result is shown in fig. 12, wherein a dotted line in the graph represents a peak value corresponding to each group, and it can be seen that compared with a comparative example and a blank control group, the surface of the UV adhesive layer provided in example 1 contains abundant polar groups such as C-O, O-C-O, C-O, and the like, which indicates that active oxygen in plasma is embedded into the UV adhesive layer to generate the polar groups, and the surface of the UV adhesive layer is modified; compared with the comparative example 3, the pretreatment mode provided by the embodiment has more remarkable modification effect on the UV glue layer.

TABLE 1 atomic percent content on UV adhesive layer surface

Testing the water contact angle of the pretreated UV adhesive layer by a contact angle tester, wherein the water contact angles of the UV adhesive layer after the pretreatment and the standing for 1 day and 7 days are respectively detected, the results of using the un-pretreated UV glue layer as a blank control are shown in table 2, and it can be seen that various polar groups are generated on the surface of the UV glue layer in the examples, the activating and chemical modifying effects on the UV adhesive layer are achieved, and the water contact angle of the example is still kept at a lower level after the UV adhesive layer is placed for a period of time, which shows that the activating effect on the UV adhesive layer can be stably kept for a long time through the pretreatment mode provided by the application, so that the aging attenuation of the surface energy of the UV adhesive layer is far lower than that of other groups, and furthermore, in the embodiment, the water contact angle of the UV adhesive layer can be kept at a lower level for a long time, and the smaller the water contact angle is, the larger the surface energy is, so that the adhesion force of the UV adhesive layer and the coating layer is favorably improved.

TABLE 2 Water contact Angle test results

Zeta potential of the pretreated UV glue layer in example and comparative example 1 was measured, and the results are shown in fig. 13, wherein a and b in fig. 13 correspond to example and comparative example 1, respectively, and four sets of parallel experiments were performed in each of example and comparative example 1, and the average value of the test results is shown. Compared with the comparative example 1, the absolute value of zeta potential of the surface of the UV adhesive layer is lower, the electrostatic adsorption effect among interface atoms is increased, and the adhesion of a coating film and the improvement of the adhesion between the UV adhesive layer and the coating film are facilitated; meanwhile, under acidic conditions, the zeta potentials of the example and the comparative example 1 are not greatly different, and the absolute value of the zeta potential of the example under alkaline conditions is reduced, which also shows that the polar bonds of C-O, C ═ O, O-C ═ O of the UV adhesive surface of the example are increased, the polar bonds of-OH and-OOH on the surface are more in the zeta potential detection process, the ionization of-OH and-OOH is inhibited under acidic conditions, the zeta potentials of the example and the comparative example are not greatly different, and the ionization of-OH and-OOH is increased under alkaline conditions, so that the UV adhesive surface of the example is more negatively charged, the capacity of adsorbing charges is strong, the charges are increased, the net charge density of an electric double layer is reduced, and the absolute value of the zeta potential is reduced; therefore, the zeta potential detection result and the X-ray photoelectron spectroscopy result prove that the surface of the UV adhesive layer can be rich in polar groups such as C-O, O-C-O, C-O and the like through the pretreatment provided by the application.

The appearance pieces provided in examples and comparative examples were subjected to adhesion property tests including an ultraviolet limit test, a xenon arc lamp limit test, and a double 85 limit test, and the results are shown in table 3. The detection equipment for ultraviolet limit test is a QUV ultraviolet tester, the test environment is room temperature 15-35 deg.C, humidity is 25% RH-75% RH, and is used for simulating aging effect of external member exposed to sunlight and condensed dew, the blackboard temperature in UV irradiation stage is 60 deg.C, and irradiance is 0.63W/m²The irradiation time is 4h, the temperature in the cavity is set to be 55 ℃ in the condensation stage, the duration time is 4h, and a complete cycle is 8h in total, and the UV irradiation stage and the condensation stage are included. And after the experiment specifies the cycle number, taking out the appearance piece, observing whether the coating layer on the appearance piece falls off, standing for 2 hours, detecting the adhesive force between the coating layer and the UV adhesive layer by a lattice method (3M 610 is selected for drawing the adhesive paper), if the adhesive force reaches more than 3B (namely the falling area of the coating layer is less than or equal to 15 percent), judging to be qualified, continuously testing until the adhesive force is unqualified, and recording the corresponding test duration when the adhesive force is unqualified. The detection equipment for the xenon arc lamp limit test is a Q-Sun xenon arc lamp tester which is used for simulating whether the reliability problem occurs under the irradiation of sunlight; irradiance is set to 1.1W/m by using windows Q filter²@420nm, a blackboard temperature BPT of 63 ℃, an in-test-box temperature of 38 ℃ and a humidity of 50% RH. After testing for a specified time, taking outAnd (3) observing whether the coating layer on the appearance piece falls off or not, detecting the adhesive force between the coating layer and the UV adhesive layer by a lattice method (3M 610 is selected for drawing the adhesive tape) after standing for 2 hours, if the adhesive force reaches more than 3B (namely the falling area of the coating layer is less than or equal to 15 percent), judging to be qualified, continuously testing until the adhesive force is unqualified, and recording the corresponding test duration when the adhesive force is unqualified. The double 85 limit test is to set the temperature of 85 +/-1 ℃ and the humidity of 85 +/-2% RH, take out the appearance piece after placing in a constant temperature and humidity box for a specified time, observe whether the coating layer on the appearance piece falls off, after standing for 2 hours, detect the adhesive force between the coating layer and the UV adhesive layer through a Baige method (drawing adhesive paper selects 3M610), judge the product to be qualified if the adhesive force reaches more than 3B (namely the falling area of the coating layer is less than or equal to 15%), continue the test until the adhesive force is unqualified, and record the corresponding test duration when the adhesive force is unqualified.

TABLE 3 results of adhesion test

As can be seen from table 3, the ion source pretreatment methods in comparative examples 1 to 2 still cannot improve the bonding force between the organic layer and the coating layer and the photo-oxidation aging resistance of the appearance piece, the pretreatment methods in examples and comparative examples 3 to 5 improve the adhesion force and the bonding reliability between the coating layer and the UV adhesive layer, and the pretreatment methods provided by examples enable the content of oxygen embedded in the UV adhesive layer to be large and the generated polar groups to be large, thereby significantly improving the adhesion force and the bonding reliability between the coating layer and the UV adhesive layer, and the coating layer and the UV adhesive layer can be bonded for a long time in the ultraviolet limit test, the xenon arc lamp limit test and the double 85 limit test. In addition, in the embodiment, the graphite target is adopted, reactant gas of the graphite target and oxygen is not easy to generate target poisoning, meanwhile, the plating rate is low, the adhesion of a coating layer cannot be influenced in the pre-treatment process, the power supply power selection range of the graphite target is wide, for example, 8kW-20kW can be set, the process window is wide, and the graphite target is suitable for being used in industry; in the comparative examples 3 to 5, the metal target is adopted, so that target poisoning is easy to occur, the metal target is easy to sputter on the surface of the UV adhesive layer, the improvement of the bonding force between the UV adhesive layer and the coating layer is influenced, and the plating rate of the metal target can be improved by overlarge power supply, so that the power supply setting range of the metal target is narrow, for example, the power supply can be set to 1kW-3kW, the process conditions are strict, and the metal target is not suitable for industrial use.

The appearance pieces prepared in the embodiment, the comparative example 1 and the comparative example 2 are used as battery covers of mobile phones, the complete machines with the same process are prepared and used, and market failure feedback indexes (FFR) of the complete machines are compared, wherein the market failure feedback indexes of the complete machines prepared from the appearance pieces provided in the embodiment are within 10ppm, namely, the complete machines within 10 parts of a million complete machine products are withdrawn due to falling of a coating layer; the market failure feedback index of the complete machine made of the appearance piece provided by the comparative example 1 and the comparative example 2 is about 500 ppm; it can be seen that the pretreatment mode that this application provided can show the bonding performance who promotes between organic layer and the coating film layer, is favorable to improving the life of outward appearance piece and electronic equipment.

The foregoing detailed description has provided for the embodiments of the present application, and the principles and embodiments of the present application have been presented herein for purposes of illustration and description only and to facilitate understanding of the methods and their core concepts; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.

Claims

1. A method for pretreatment of coating film is characterized by comprising the following steps:

2. The method of pretreatment for coating film according to claim 1, wherein a flow ratio of the oxygen gas to the inert gas is (1-4): 1.

3. the method of claim 1, wherein the power supply unit has a power of 8kW to 20kW and the pretreatment time is 3min to 10 min.

4. The method according to claim 1, wherein a distance between the organic layer and the target is 10mm to 50 mm.

5. The method of pretreatment for coating film according to claim 1, wherein the magnetic field intensity generated by said magnet is 200 gauss to 500 gauss.

6. The method of pretreatment for coating film according to claim 1, wherein said inert gas comprises at least one of argon, helium, neon, krypton and xenon.

7. The utility model provides a processing apparatus before coating film, its characterized in that, includes shell, target, substrate seat, magnet and power supply unit, the shell has accommodating space, the target with the substrate seat sets up relatively in the accommodating space, the material of target includes graphite, the substrate seat is used for placing the substrate that has the organic layer, the shell has the air vent, the air vent be used for to let in oxygen and inert gas in the accommodating space, the magnet sets up the target deviates from a side surface of substrate seat, power supply unit with the target electricity is connected.

8. A method of making an appearance piece, comprising:

9. An exterior member characterized by being produced by the production method according to claim 8, comprising a substrate and a coating layer, wherein the substrate comprises an organic layer, and the coating layer is provided on a surface of the organic layer.

10. The appearance article of claim 9 wherein said coating has a thickness of 200nm to 700 nm;

the material of the coating layer comprises SiO₂、TiO₂、Ti₃O₅、NbO₂、Nb₂O₃、NbO、Nb₂O₅And ZrO₂At least one of (1).

11. An electronic device, comprising the appearance member according to any one of claims 9 to 10.