Transparent abrasion-resistant film layer, method for modifying plastic surface and product

Abstract

A transparent abrasion-resistant film layer, a method for modifying a plastic substrate, and a product, the method for modifying a plastic substrate includes bombarding at least one plastic substrate in a chamber of a PECVD coating apparatus with plasma to clean and activate the plastic substrate, and forming a transparent abrasion-resistant film layer on the surface of the activated plastic substrate by plasma-enhanced chemical vapor deposition using a siloxane monomer as a reactant.

Description

[Technical Field]

[0001] The present invention relates to the field of surface modification of plastic materials, and in particular to a transparent abrasion-resistant film layer, a method for modifying the surface of plastics, and a product thereof. [Background technology]

[0002] Plastics are a very familiar material in our daily lives, and transparent plastics are one such example. Compared to ordinary plastics, transparent plastics can be used as optical materials. Currently, there are hundreds of types of transparent plastics, among which polymethyl methacrylate (PMMA), polycarbonate (PC), polystyrene (PS), etc. are widely used. These transparent plastics have excellent properties such as low density, easy processing and molding, good impact resistance, and foldability. Therefore, in the field of display materials, transparent plastics are replacing the original glass substrate, especially in the field of portable and wearable electronic displays.

[0003] However, transparent plastics have drawbacks such as poor solvent resistance, poor weather resistance, low hardness, and susceptibility to scratches, especially from friction, which limits the application of transparent plastics in the field of displays, especially in touch-sensitive displays.

[0004] There are two main methods for improving the hardness of plastics: one is to modify the plastic itself, such as by adding a hardening additive to make the entire plastic harder, and the other is to form a film layer on the surface of the plastic to increase its surface hardness. The two methods have different applications; the former must be performed during the plastic manufacturing process and cannot modify the finished plastic, while the latter has the advantage of being able to modify the finished plastic product.

[0005] To increase the hardness of plastics, surface modification of transparent plastics is commonly used. The solution method is commonly used, in which an organic monomer is pre-coated on the plastic surface, followed by thermal or UV curing to form a hard film layer. This process is tedious, and the industrial production process is relatively laborious. It is difficult to control the product quality during industrial production, and it is prone to raw material waste and environmental pollution.

[0006] Patent CN110760256A describes a method in which various acrylates, fluorine-containing monomers, nanodiamond particles and organic solvents are mixed by ultrasonic stirring to form a solution, and then a coating layer is applied to the surface of the PC material by spraying technology, which is then dried in an oven, and finally the coating layer is applied at 1000mJ / cm 2 The entire process is complicated, and industrial production requires the installation of various processes, which increases production costs and makes quality control difficult. At the same time, the use of a solution spraying method inevitably causes environmental pollution and human health problems. Summary of the Invention

[0007] The advantage of the present invention is that it provides a transparent wear-resistant film layer, a method for surface modification of plastic, and a product thereof, and the plastic modification method can harden the plastic, resulting in a plastic material that is wear-resistant, while the transparent wear-resistant film layer formed by the plastic modification method does not significantly affect the light transmission performance of the plastic material itself.

[0008] Another advantage of the present invention is that it provides a transparent wear-resistant film layer, a method for surface modification of plastics, and a product thereof, and by using the plastic modification method, the preparation process of the transparent wear-resistant film layer does not require the use of large amounts of organic solvents, and the entire preparation process is very clean and pollution-free.

[0009] Another advantage of the present invention is that it provides a transparent abrasion-resistant film layer, a method for surface modification of plastics, and a product thereof, and the plastic modification method allows the amount of monomer supplied in the preparation process of the transparent abrasion-resistant film layer to be controlled, which is advantageous for stabilizing the quality of the vapor-deposited film.

[0010] Another advantage of the present invention is that it provides a transparent, abrasion-resistant film layer, a method for surface modification of plastics, and a product thereof, and the plastic modification method allows for control of film layer growth at the nano-level, which is advantageous for producing the transparent, abrasion-resistant film layer in fields requiring high precision, such as precision electronics.

[0011] Another advantage of the present invention is to provide a transparent abrasion-resistant film layer, a method for modifying the surface of plastics, and a product thereof, in which the method for modifying plastics uses plasma to clean and activate the plastic substrate and improve the surface energy of the plastic substrate, thereby improving the bonding strength between the transparent abrasion-resistant film layer and the surface of the plastic substrate, and thereby improving the stability and abrasion resistance life of the transparent abrasion-resistant film layer.

[0012] Another advantage of the present invention is that it provides a transparent wear-resistant film layer, a method for surface modification of plastics, and a product thereof, which allows the plastic substrate to be cooled, reducing the possibility of damage to some precision components due to lack of heat resistance and expanding the range of applications of the plastic modification method.

[0013] In one aspect of the present invention, the present invention provides A method for modifying the surface of plastics is provided, which includes the steps of introducing a siloxane monomer as a reaction raw material into a chamber of a PECVD coating apparatus and forming a transparent, abrasion-resistant film layer on the surface of at least one plastic substrate by plasma-enhanced chemical vapor deposition.

[0014] In one embodiment of the present invention, the modification method includes, before the step of forming the transparent abrasion-resistant film layer, The method further includes bombarding the plastic substrate with plasma to activate the plastic substrate.

[0015] In one embodiment of the present invention, in the step of forming the transparent abrasion-resistant film layer, an auxiliary gas is introduced while introducing the siloxane monomer, and the auxiliary gas is one or more selected from the group consisting of an inert gas and an oxygen gas.

[0016] In one embodiment of the present invention, the plasma bombardment step includes introducing an activated gas and initiating a plasma discharge, the activated gas comprising one selected from the group consisting of oxygen gas and hydrogen gas.

[0017] In one embodiment of the present invention, in the plasma bombardment step, before the activation gas is introduced, an inert gas is introduced to initiate plasma discharge, and the inert gas comprises one or more selected from the group consisting of He, Ar, and Kr.

[0018] In one embodiment of the present invention, in the step of forming the transparent abrasion-resistant film layer, siloxane, an inert gas, and oxygen gas are introduced as reaction raw materials.

[0019] In one embodiment of the present invention, the step of forming the transparent abrasion-resistant film layer includes introducing siloxane and oxygen gas as reaction raw materials.

[0020] In one embodiment of the present invention, in the above method, the PECVD apparatus uses an ICP source as the plasma source.

[0021] In one embodiment of the present invention, in the above method, a bias voltage is applied within the chamber of the PECVD apparatus.

[0022] In one embodiment of the present invention, in the above method, the plastic substrate is placed on a turntable and coated while moving.

[0023] In one embodiment of the invention, the plastic substrate is cleaned with a cleaning agent prior to the plasma bombardment step.

[0024] In one embodiment of the present invention, the plasma bombardment step comprises: The vacuum level of the chamber is 1×10 -1 Vacuum the area to a pressure of 0.1 Pa or less. Inert gas is introduced into the chamber, a bias of 10 to 1000 V is applied, the ICP source power is controlled to 50 to 1000 W, and the degree of vacuum is controlled to 0.1 to 50 Pa to perform plasma impact activation; and The method includes the following steps: introducing an activation gas, applying a bias of 10 to 1000 V into the chamber, controlling the ICP source power to 100 to 1000 W, and controlling the degree of vacuum to 0.1 to 50 Pa to perform plasma impact activation.

[0025] In one embodiment of the present invention, the step of forming the transparent abrasion-resistant film layer comprises: Siloxane monomer vapor is introduced into the chamber, a bias of 100 to 1000 V is applied, the ICP source power is controlled to 100 to 1000 W, and the degree of vacuum is controlled to 0.5 to 80 Pa to grow a deposited film.

[0026] In one embodiment of the present invention, the siloxane monomer vapor enters the chamber through a vacuum liquid-phase evaporator, and the liquid-phase siloxane monomer passes through a diaphragm valve in a quantitatively controlled manner into the evaporation chamber of the vacuum liquid-phase evaporator, where it evaporates into vapor and enters the chamber.

[0027] In one embodiment of the present invention, the siloxane is one or more selected from the group consisting of octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, trimethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, decamethylcyclopentasiloxane, dimethylsiloxane, tetraethoxysilane, tetramethoxysilane, hexamethyldisiloxane, tetramethyldisiloxane, and hexaethyldisiloxane.

[0028] In one embodiment of the present invention, the plastic substrate is one or more selected from the group consisting of substrates made of plastic and substrates having a plastic surface.

[0029] In another aspect of the present invention, the present invention provides an article having a transparent abrasion-resistant film layer on at least one surface, the surface of the article being made of a plastic material, and the transparent abrasion-resistant film layer being formed on the surface of the article by plasma-enhanced chemical vapor deposition using a siloxane monomer as a reactive raw material.

[0030] In one embodiment of the present invention, the product is one or more selected from the group consisting of a plastic product, a printed circuit board, an electronic product, an electronic assembly semi-finished product, and an electrical component. DETAILED DESCRIPTION OF THE INVENTION

[0031] The following description is intended to disclose the present invention so that those skilled in the art can achieve it. The preferred embodiments in the following description are merely examples, and other obvious modifications may be readily apparent to those skilled in the art. The basic principles of the present invention defined in the following description may be applied to other embodiments, modifications, improvements, equivalents, and other technical forms without departing from the spirit and scope of the present invention.

[0032] Those skilled in the art should understand that in the present disclosure, the term "1" should be understood as "at least one" or "one or more," i.e., in one embodiment, the number of an element may be one, but in another embodiment, the number of this element may be multiple, and the term "1" should not be understood as a numerical limitation.

[0033] The present invention provides a transparent abrasion-resistant film layer, a method for modifying the surface of plastics, and a product thereof, and the transparent abrasion-resistant film layer can contain Si, O, or Si, O, and H.

[0034] The transparent abrasion-resistant film layer has good scratch resistance and light transmittance. When the transparent abrasion-resistant film layer is attached to the surface of a substrate, particularly a plastic substrate, the transparent abrasion-resistant film layer provides the substrate with good abrasion resistance and light transmittance. When the substrate is a plastic substrate, particularly a transparent plastic substrate, the transparent abrasion-resistant film layer does not excessively affect the light transmittance of the plastic substrate itself, that is, even after the transparent abrasion-resistant film layer is formed on the transparent plastic substrate, the original light transmittance or a light transmittance close to the original light transmittance can be maintained.

[0035] These features of the transparent abrasion-resistant film layer can widen the range of applications of the transparent abrasion-resistant film layer.

[0036] The present invention provides a product having the transparent abrasion-resistant film layer, which includes the plastic substrate, and it is understood that the plastic substrate can refer to a product made entirely of plastic or a product with a plastic surface and a non-plastic interior.

[0037] In some embodiments of the present invention, the product is one or more selected from the group consisting of plastic products, printed circuit boards, electronic products, semi-finished electronic assemblies, and electrical components. When the product is an electronic device with a plastic surface, examples include, but are not limited to, devices such as mobile phones, tablets, keyboards, e-readers, wearable devices, displays, earphones, and PSPs. When the product is an electrical component, the electrical component may be a resistor, capacitor, transistor, diode, amplifier, relay, transformer, battery, fuse, integrated circuit, switch, LED, LED display, piezoelectric element, optoelectronic component, antenna, oscillator, etc. Of course, those skilled in the art will understand that the above description is illustrative and not intended to limit the present invention.

[0038] When the product having the transparent abrasion-resistant film layer was wiped with a dust-free cloth, it was found that there was no scratch even after several thousand rubs.With the product having the transparent abrasion-resistant film layer, the color of the plastic substrate itself can be observed through the transparent abrasion-resistant film layer within a certain thickness range.

[0039] The present invention provides a method for surface modification of plastics, which forms the transparent abrasion-resistant film layer on the surface of the plastic substrate by a plasma-enhanced chemical vapor deposition (PECVD) process. That is, in the preparation process, the plastic substrate is exposed to a chamber of a plasma-enhanced chemical vapor deposition coating device, plasma is formed in the chamber, and the transparent abrasion-resistant film layer is formed on the surface of the plastic substrate by a chemical growth reaction of reactive raw materials.

[0040] The plasma-enhanced chemical vapor deposition (PECVD) process has many advantages over other existing growth processes: (1) it is a dry process, and the resulting thin films are uniform and pinhole-free; (2) the plasma-polymerized films have stable chemical and physical properties, such as solvent resistance, chemical resistance, heat resistance, and abrasion resistance; (3) the plasma-polymerized films have good adhesion to the substrate; (4) uniform thin films can be formed even on highly irregular substrate surfaces; (5) the coating layer can be produced at low temperatures, effectively avoiding damage to temperature-sensitive devices; and (6) the plasma process can produce not only micron-scale coating layers, but also ultrathin nanoscale coating layers.

[0041] The present invention provides a method for surface modification of plastics, comprising the following steps: (1) Cleaning of plastic substrates The plastic substrate is washed with a detergent to remove oily stains from the surface.

[0042] (2) Surface activation of plastic substrates Inert gas atmosphere: The washed and dried plastic substrate is placed in the chamber of the PECVD coating device, and after evacuation, an inert gas is introduced. The chamber is discharged under a certain vacuum and a certain voltage to perform plasma impact activation; Under activated gas atmosphere: An activated gas is introduced, and plasma impact activation is performed by discharging in the chamber under a certain degree of vacuum and a certain voltage.

[0043] (3) Formation of the transparent abrasion-resistant coating layer Siloxane monomer, inert gas and activated gas are introduced and controlled to form the transparent abrasion-resistant coating layer on the surface of the plastic substrate under a certain vacuum and voltage.

[0044] According to one embodiment of the present invention, in the step of cleaning the plastic substrate, the cleaning agent may be an organic solvent such as ethanol or isopropanol, or deionized water, and the oily stains on the surface of the plastic substrate can be removed with the aid of ultrasound.

[0045] If the plastic substrate is likely to be damaged by ultrasound, it may be possible to first clean it with an organic solvent and then activate it by cleaning it with plasma in the plastic substrate activation step.

[0046] According to one embodiment of the present invention, in the step of cleaning the plastic substrate, the plastic substrate is ultrasonically cleaned in deionized water and industrial high-purity ethanol or isopropanol for 10 to 20 minutes, respectively, to remove impurities on the surface of the plastic substrate.

[0047] According to one embodiment of the present invention, the method for modifying the surface of plastic can be carried out at a lower temperature, for example, 20 to 30°C.

[0048] According to one embodiment of the present invention, in the step of activating the plastic substrate, the inert gas is one or more selected from the group consisting of He, Ar, and Kr.

[0049] According to one embodiment of the present invention, in the step of activating the plastic substrate, after the inert gas is introduced, the degree of vacuum in the chamber in the PECVD coating apparatus is controlled to 0.1 to 50 Pa, further, for example, 0.5 to 5 Pa. After the activation gas is introduced, the degree of vacuum in the chamber in the PECVD coating apparatus is controlled to 0.1 to 50 Pa, further, for example, 0.1 to 1 Pa.

[0050] The plastic substrate may be fixedly disposed at a predetermined position in the chamber, or the plastic substrate may be movably disposed at a predetermined position in the chamber.

[0051] According to one embodiment of the present invention, the PECVD coating apparatus includes a carrier, which is disposed in the chamber and may be a turntable. The plastic substrate is disposed on the turntable. When the turntable moves about an axis relative to the chamber, the plastic substrate can move relative to the chamber. In this way, the plastic substrate can be in sufficient contact with the plasma in the chamber, promoting uniformity of the deposited film.

[0052] In the plasma-enhanced chemical vapor deposition (PECVD) process employed in the present invention, plasma is generated by glow discharge, and the discharge method may be, but is not limited to, micro-discharge, high-frequency discharge, ultraviolet discharge, electric spark discharge, etc.

[0053] According to one embodiment of the present invention, the PECVD coating apparatus provides one or more energy sources capable of converting one or more gases into a plasma, which may include ionized and neutral feed gases / precursors, ions, electrons, atoms, free radicals, and / or other plasma-generated neutrals.

[0054] The energy source may include an ICP (inductively coupled plasma) excitation source or a bias power supply. The carrier may be made of a conductive material, and the bias power supply may be conductively connected to the carrier so as to discharge at the carrier. The ICP plasma excitation source is mounted outside the chamber. It should be understood that the installation locations of the energy source described herein are exemplary. The energy source may be mounted on the inner wall of the chamber or at other locations.

[0055] According to one embodiment of the present invention, in the step of activating the plastic substrate, after the inert gas is introduced, the voltage of the bias power supply may be controlled to 10 V to 1000 V and the power of the ICP may be controlled to 50 W to 1000 W. In the step of cleaning and activating the plastic substrate, after the activation gas is introduced, the voltage of the bias power supply may be controlled to 10 V to 1000 V and the power of the ICP may be controlled to 100 W to 1000 W.

[0056] According to one embodiment of the present invention, a high-frequency power source can be used as the power source for the ICP, and an alternating magnetic field can be generated by inductive coupling of a coil to convert the gas into plasma. The rapidly changing magnetic field promotes sufficient and uniform plasma generation. The bias power source can be a pulsed bias power source that converts the gas into plasma through the effect of glow discharge and simultaneously exerts directional attraction and acceleration effects on positive ions. The process of forming the transparent abrasion-resistant film layer has an impact effect, allowing the formation of a dense, highly hard transparent abrasion-resistant film layer.

[0057] The ICP and the bias power supply can be used simultaneously to obtain a highly plasma-enhanced plasma, thereby increasing the energy of the plasma reaching the surface of the plastic substrate and facilitating the obtaining of a dense transparent abrasion-resistant film layer.

[0058] The simultaneous use of the ICP and the bias power supply can improve growth efficiency, allowing the transparent wear-resistant film layer to be effectively grown and formed on the surface of the plastic substrate, and shortening the required preparation time, which is very advantageous for industrial production of the transparent wear-resistant film layer and can improve its production efficiency.

[0059] According to one embodiment of the present invention, in the step of cleaning and activating the plastic substrate, the flow rates of the inert gas and the activation gas can be controlled to 10 sccm to 1000 sccm, respectively.

[0060] In one embodiment of the present invention, the activation gas may be oxygen gas, hydrogen gas, or a mixture of oxygen gas and hydrogen gas. In the step of cleaning and activating the plastic substrate, contaminants, such as oil stains, adhering to the surface of the plastic substrate can be effectively removed by generating plasma bombardment under the action of the energy source. It is worth noting that when the activation gas is oxygen gas, oxygen ions can form dangling bonds on the surface of the plastic substrate, which is advantageous for increasing the bonding strength between the later-formed transparent abrasion-resistant film layer and the plastic substrate.

[0061] According to one embodiment of the present invention, the siloxane monomer may be a chain siloxane compound or a cyclic siloxane compound.

[0062] According to one embodiment of the present invention, the siloxane monomer has the following structure: TIFF0007797467000001.tif2550 where R1 to R6 each independently represent a C1 to C6 alkyl group, a C2 to C6 alkenyl group, or hydrogen, and at least one of R1 to R6 does not represent hydrogen. Optionally, R1 to R6 each independently represent a C1 to C3 alkyl group, a C2 to C4 alkenyl group, or hydrogen, for example, a methyl group, an ethyl group, a vinyl group, an allyl group, or hydrogen, provided that at least one of R1 to R6 does not represent hydrogen. Optionally, at least two or three (e.g., four, five, or six) of R1 to R6 do not represent hydrogen. Examples that may be selected include hexamethyldisiloxane (HMDSO), hexaethyldisiloxane, tetramethyldisiloxane (TMDSO), 1,3-divinyltetramethyldisiloxane (DVTMDSO), and hexavinyldisiloxane (HVDSO).

[0063] According to one embodiment of the present invention, the siloxane monomer has the following structural formula: TIFF0007797467000002.tif3338 However, R7~R 10are each independently a C1-C6 alkyl group, a C1-C6 alkyloxy group, a C2-C6 alkenyl group, or hydrogen, and R7 to R 10 At least one of R7 to R8 does not represent hydrogen. 10 At least one of R7 to R7 has oxygen and forms a silicon-oxygen bond. 10 are each independently a C1-C3 alkyl group, a C1-C3 alkyloxy group, a C2-C4 alkenyl group, or hydrogen, and R7 to R 10 At least one of R7 to R8 does not represent hydrogen. 10 At least two, for example, three or four, of the groups do not represent hydrogen. Alternative examples include allyltrimethoxysilane (ATMOS), tetraethyl orthosilicate (TEOS), 3-(diethylamino)propyl-trimethoxysilane, trimethylsiloxane and triisopropylsiloxane, tetramethoxysilane, and dimethylsiloxane.

[0064] According to one embodiment of the present invention, the siloxane monomer has the following structural formula: TIFF0007797467000003.tif4149 where n represents 3 or 4, and R 11 and R 12 each independently represents a C1-C6 alkyl group, a C2-C6 alkenyl group, or hydrogen, with the proviso that R 11 and R 12 At least one of R does not represent hydrogen. 11 and R 12 each independently represents a C1-C3 alkyl group, a C2-C4 alkenyl group, or hydrogen, for example, a methyl group, an ethyl group, a vinyl group, an allyl group, or hydrogen, provided that R 11 and R 12At least one of the groups does not represent hydrogen. Selected examples include trivinyltrimethylcyclotrisiloxane (V3D3), tetravinyltetramethylcyclotetrasiloxane (V4D4), tetramethylcyclotetrasiloxane (TMCS), octamethylcyclotetrasiloxane (OMCTS), hexamethylcyclotrisiloxane, trimethylcyclotrisiloxane, dodecamethylcyclohexasiloxane, and decamethylcyclopentasiloxane.

[0065] According to one embodiment of the present invention, the siloxane monomer is one or more selected from octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, trimethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, decamethylcyclopentasiloxane, dimethylsiloxane, tetraethoxysilane, tetramethoxysilane, hexamethyldisiloxane, tetramethyldisiloxane, and hexaethyldisiloxane.

[0066] According to one embodiment of the present invention, the siloxane monomer can be supplied through a vacuum liquid-phase evaporator, which can quantitatively control the amount of the siloxane monomer and evaporate the siloxane monomer at a relatively low temperature to form a vapor, which then enters the chamber of the PECVD coating device. The vacuum liquid-phase evaporator can be equipped with a diaphragm valve for quantitatively controlling the amount of the siloxane monomer. The ability to accurately control the amount of the siloxane monomer supplied during the preparation process is advantageous for improving the growth stability of the transparent abrasion-resistant film layer and the utilization rate of the siloxane monomer.

[0067] In particular, the PECVD coating apparatus is equipped with an exhaust gas filter device, and the exhaust gas generated after the reaction is filtered through the exhaust gas filter device, thereby reducing pollution to the external environment.

[0068] In particular, the plastic substrate only needs to be moved between the step (1) of cleaning the plastic substrate and the step (2) of cleaning and activating the surface of the plastic substrate, and does not need to be moved between other steps in the entire preparation process, which reduces industrial variables and is advantageous for mass production of the transparent abrasion-resistant film layer. [Example]

[0069] Example 1 1) The PC sheets were placed in deionized water and industrial high-purity ethanol or isopropanol and ultrasonically cleaned for 10 minutes to remove surface oil.

[0070] 2) After drying the PC sheet obtained above, it was placed in the chamber of the PECVD coating device and 1×10 -2 The system was evacuated to 100 Pa or less, and an inert gas (Ar or He) was introduced at a flow rate of 100 sccm, the degree of vacuum was maintained at 0.5 Pa, a bias of 500 V was applied to the turntable, the ICP power was set to 300 W, and plasma impact activation was performed for 10 minutes. Further, O2 was introduced at a flow rate of 100 sccm, the degree of vacuum was maintained at 0.5 Pa, a bias of 200 V was applied to the turntable, the ICP power was set to 500 W, and plasma impact activation was performed for 10 minutes to increase surface activity.

[0071] 3) Hexamethyldisiloxane monomer vapor was introduced at a monomer flow rate of 300 μL / min. He and O2 were simultaneously introduced at flow rates of 100 sccm and 300 sccm, respectively. The butterfly valve was adjusted to maintain a vacuum pressure of 16 Pa. A bias of 300 V was applied to the turntable, the ICP power was set to 800 W, and the deposition time was 1800 s.

[0072] The thickness of the film layer produced in accordance with Example 1 was 280 nm, the transmittance of the PC material increased by 0.5% (94% before deposition, 94.5% after deposition), and no scratches were observed after 10,000 rubs with a dust-free cloth (500 g, 30 r / min, 3 cm stroke, rub tester: XM-860 type rub tester from Shenzhen Xiangmin Instruments and Equipment Co., Ltd.). Example 2

[0073] 1) The PC sheets were placed in deionized water and industrial high-purity ethanol or isopropanol and ultrasonically cleaned for 10 minutes to remove surface oil.

[0074] 2) After drying the PC material obtained above, it was placed in the chamber of the PECVD coating device and 1×10 -2 The system was evacuated to a pressure of 100 Pa or less, and Ar was introduced at a flow rate of 100 sccm, the degree of vacuum was maintained at 0.5 Pa, a bias of 500 V was applied to the turntable, the ICP power was set to 300 W, and plasma impact activation was performed for 10 minutes.Furthermore, H2 was introduced at a flow rate of 100 sccm, the degree of vacuum was maintained at 0.5 Pa, a bias of 200 V was applied to the turntable, the ICP power was set to 500 W, and plasma impact activation was performed for 10 minutes to increase the surface activity.

[0075] 3) Tetraethoxysilane (TEOS) monomer vapor was introduced at a monomer flow rate of 500 μL / min. Simultaneously, O2 was introduced at a flow rate of 300 sccm. The butterfly valve was adjusted to maintain a vacuum pressure of 15 Pa. A bias of 600 V was applied to the turntable, and the ICP power was set to 500 W. Film deposition was performed for 1800 s.

[0076] The film layer produced according to Example 2 had a thickness of 235 nm and was not scratched after 10,000 rubs with a dust-free cloth. Example 3

[0077] 1) The PC sheets were ultrasonically cleaned in deionized water and industrial high-purity ethanol or isopropanol for 10 minutes to remove oil from the surface.

[0078] 2) After drying the PC material obtained above, it was placed in the chamber of the PECVD coating device and 1×10 -2 The system was evacuated to 100 Pa or less, and an inert gas (Ar or He) was introduced at a flow rate of 100 sccm, the degree of vacuum was maintained at 0.5 Pa, a bias of 500 V was applied to the turntable, the ICP power was set to 300 W, and plasma impact activation was performed for 10 minutes. Further, O2 was introduced at a flow rate of 100 sccm, the degree of vacuum was maintained at 0.5 Pa, a bias of 200 V was applied to the turntable, the ICP power was set to 500 W, and plasma impact activation was performed for 10 minutes to increase surface activity.

[0079] 3) Tetramethoxysilane (TMOS) monomer vapor was introduced at a monomer flow rate of 550 μL / min. Simultaneously, Ar and O were introduced at flow rates of 100 sccm and 300 sccm, respectively. The butterfly valve was adjusted to maintain a vacuum pressure of 16 Pa. A bias of 400 V was applied to the turntable, and the ICP power was set to 500 W. Film deposition was performed for 1800 s.

[0080] The film prepared according to Example 3 had a thickness of 320 nm and was not damaged after 10,000 rubs with a dust-free cloth. Example 4

[0081] 1) The PC sheets were ultrasonically cleaned in deionized water and industrial high-purity ethanol or isopropanol for 10 minutes to remove oil from the surface.

[0082] 2) After drying the PC material obtained above, it was placed in the chamber of the PECVD coating device and 1×10 -2The chamber was evacuated to a pressure of 100 Pa or less, and Ar was introduced at a flow rate of 100 sccm, the degree of vacuum was maintained at 0.5 Pa, a bias of 500 V was applied to the turntable, the ICP power was set to 300 W, and plasma impact activation was performed for 10 minutes.Furthermore, activation gas (O2 or H2) was introduced at a flow rate of 100 sccm, the degree of vacuum was maintained at 0.5 Pa, a bias of 200 V was applied to the turntable, the ICP power was set to 500 W, and plasma impact activation was performed for 10 minutes to increase surface activity.

[0083] 3) Tetramethyltetrasiloxane monomer vapor was introduced at a monomer flow rate of 600 μL / min. Simultaneously, Ar and O were introduced at flow rates of 100 sccm and 300 sccm, respectively. The butterfly valve was adjusted to maintain a vacuum pressure of 12 Pa. A bias of 500 V was applied to the turntable, and the ICP power was set to 600 W. Film deposition was performed for 1800 s.

[0084] The film prepared according to Example 4 had a thickness of 350 nm and was not damaged after 10,000 rubs with a dust-free cloth.

[0085] Those skilled in the art should understand that the embodiments of the present invention shown in the above description are merely examples and do not limit the present invention. The objects of the present invention have been fully and effectively achieved. The functions and structural principles of the present invention are also shown in the examples, and any changes or modifications can be made to the embodiments of the present invention without departing from the above principles.

Claims

1. 1. A method for modifying the surface of plastics, comprising the steps of introducing a siloxane monomer as a reactive raw material into a chamber of a PECVD coating apparatus and forming a transparent abrasion-resistant film layer on the surface of at least one plastic substrate by plasma-enhanced chemical vapor deposition, and further comprising the step of activating the plastic substrate by bombarding the plastic substrate with plasma before the step of forming the transparent abrasion-resistant film layer, wherein the step of activating the plastic substrate by bombarding the plastic substrate with plasma includes introducing an activation gas and initiating plasma discharge, and the activation gas includes one selected from the group consisting of oxygen gas and hydrogen gas.

2. The modification method described in claim 1, wherein in the step of forming the transparent wear-resistant film layer, an auxiliary gas is introduced while introducing the siloxane monomer, and the auxiliary gas is one or more selected from the group consisting of an inert gas and an oxygen gas.

3. 2. The modification method according to claim 1, wherein in the step of activating the plastic substrate by bombarding the plastic substrate with plasma, an inert gas is introduced to start plasma discharge before introducing the activation gas, and the inert gas includes one or more selected from the group consisting of He, Ar, and Kr.

4. A modification method as described in claim 1, wherein in the step of forming the transparent wear-resistant film layer, a siloxane monomer, an inert gas and oxygen gas are introduced as reaction raw materials, or a siloxane monomer and oxygen gas are introduced as reaction raw materials.

5. 2. The plastic surface modification method according to claim 1, wherein the PECVD coating apparatus uses an ICP source as a plasma source.

6. 6. The method for modifying a plastic surface according to claim 5, wherein the plastic substrate is placed on a carrier, and a bias voltage is applied to the carrier in the chamber of the PECVD coating apparatus.

7. The method for modifying a plastic surface according to claim 1 , wherein the plastic substrate is placed on a turntable and coated while moving.

8. The method for modifying a plastic substrate according to claim 1 , wherein the plastic substrate is cleaned with a cleaning agent before the step of activating the plastic substrate by bombarding the plastic substrate with plasma.

9. The step of activating the plastic substrate by bombarding the plastic substrate with plasma includes: The vacuum level of the chamber is 1×10 -1 a step of evacuating the chamber to a pressure of 0.05 Pa or less; Injecting an inert gas to apply a bias of 10 to 1000 V to the carrier in the chamber, on which the plastic substrate is placed, controlling the ICP source power to 50 to 1000 W, and controlling the vacuum level to 0.1 to 50 Pa to perform plasma impact activation; The modification method according to claim 1, further comprising the steps of: introducing an activation gas to apply a bias of 10 to 1000 V to the carrier in the chamber; controlling the ICP source power to 100 to 1000 W; and controlling the degree of vacuum to 0.1 to 50 Pa to perform plasma impact activation.

10. The step of forming the transparent wear-resistant film layer comprises: The method for modifying a substrate according to any one of claims 1 to 9, wherein a siloxane monomer vapor is introduced to apply a bias of 100 to 1000 V to the carrier in the chamber, the ICP source power is controlled to 100 to 1000 W, and the degree of vacuum is controlled to 0.5 to 80 Pa to grow a vapor-deposited film.

11. The method for modifying a substrate according to claim 10, wherein the siloxane monomer vapor enters the chamber through a vacuum liquid-phase evaporator, and the liquid-phase siloxane monomer passes through a diaphragm valve in a quantitatively controlled manner into an evaporation chamber of the vacuum liquid-phase evaporator, and then evaporates into vapor and enters the chamber.

12. The siloxane monomer is one or more selected from the group consisting of octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, trimethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, decamethylcyclopentasiloxane, dimethylsiloxane, tetraethoxysilane, tetramethoxysilane, hexamethyldisiloxane, tetramethyldisiloxane, and hexaethyldisiloxane. The modification method according to any one of claims 1 to 9.

13. The modification method according to any one of claims 1 to 9, wherein the plastic substrate is one or more selected from the group consisting of plastic substrates and substrates having a plastic surface.

14. The modification method according to any one of claims 1 to 9, wherein the siloxane monomer has the following structure: (However, R 1 ~R 6 are each independently 1 ~C 6 Alkyl group, C 2 ~C 6 is one selected from the group consisting of an alkenyl group and hydrogen, where R 1 ~R 6 At least one of these does not represent hydrogen.

15. The modification method according to any one of claims 1 to 9, wherein the siloxane monomer has the following structure: (However, R 7 ~R 10 are each independently 1 ~C 6 Alkyl group, C 1 ~C 6 Alkyloxy group, C 2 ~C 6 alkenyl group, hydrogen, wherein R 7 ~R 10 At least one of does not represent hydrogen, and R 7 ~R 10 At least one of the groups has oxygen to form a silicon-oxygen bond.

16. The modification method according to any one of claims 1 to 9, wherein the siloxane monomer has the following structure: (where n represents 3 or 4, and R 11 and R 12 are each independently 1 ~C 6 Alkyl group, C 2 ~C 6 alkenyl group, and hydrogen, with the proviso that R 11 and R 12 At least one of these does not represent hydrogen.

17. A product having a transparent abrasion-resistant film layer provided on at least one surface, the surface of the product being a plastic material, and the transparent abrasion-resistant film layer being formed on the surface of the product by the plastic surface modification method described in any one of claims 1 to 16.

18. 18. The article of manufacture of claim 17, wherein the article is one or more selected from the group consisting of a plastic article, a printed circuit board, an electronic article, an electronic assembly workpiece, and an electrical component.

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