Decorative film and its preparation method

Abstract

The present invention relates to a decorative film and a preparation method thereof. The decorative film includes a metal primer layer, a first transition layer, and a color layer. The first transition layer is disposed on the metal primer layer, and the material of the first transition layer is at least one of metal carbides, metal nitrides, and metal carbonitrides. The color layer is disposed on a side of the first transition layer away from the metal primer layer, and the material of the color layer is silicon oxide, and the molar content of oxygen atoms in the silicon oxide is 40% to 55%. The metal primer layer imparts good gloss and metallic texture to the decorative film. The first transition layer further contains at least one of C element and N element compared with the metal primer layer, which can increase the overall resistance of the decorative film. The material of the color layer is silicon oxide. By controlling the molar content of oxygen atoms in the silicon oxide to be 40% to 55%, the color L value of the decorative film is between 48 and 60, the a and b values are close to the neutral gray area, and the resistance is greater than 40 MΩ.

Description

Technical Field

[0001] The present invention relates to the field of coating, and particularly to a decorative film and a preparation method thereof. Background Art

[0002] Generally, a metal film is deposited on the surface of consumer electronic devices such as smart phones and smart wearables to play a role in protection and decoration. However, since the metal film is a conductive material, it will shield 5G communication signals and cannot achieve wireless charging of the device. Therefore, more and more consumer electronic devices require that the protective and decorative films on the surface have insulation properties, such as a resistance above 40 MΩ.

[0003] In magnetron sputtering technology, metals such as Cr, W, and Ti are commonly used materials for preparing light-colored decorative films. However, in the case of less reactive atmosphere, that is, the so-called metal sputtering mode, the coating is conductive. Only when the reactive atmosphere is increased to a state close to target poisoning, can it have a better insulation effect, that is, the so-called compound sputtering mode. After the above materials react with reactive gases such as C2H2 and N2, the resistance of the coating can increase, but the color will become darker. Generally, an L value less than 35 is required to meet the insulation requirements. That is to say, it is difficult to obtain a light-colored insulating coating using the above materials in traditional technology. Summary of the Invention

[0004] Based on this, it is necessary to provide a decorative film and a preparation method thereof to solve the problem that it is difficult to obtain a light-colored insulating coating in traditional technology.

[0005] A decorative film, comprising:

[0006] A metal primer layer;

[0007] A first transition layer disposed on the metal primer layer, the material of the first transition layer being at least one of metal carbides, metal nitrides, and metal carbonitrides; and

[0008] A color layer disposed on a side of the first transition layer away from the metal primer layer, the material of the color layer being silicon oxide, and the molar content of oxygen atoms in the silicon oxide being 40% - 55%.

[0009] In one embodiment, the material of the metal primer layer is one or two of Cr and Ti.

[0010] In one embodiment, in the first transition layer, the metal element is one or more of Cr, Ti, and W.

[0011] In one embodiment, in the first transition layer, the molar content of metal atoms is 85% - 97%.

[0012] In one embodiment, the oxygen content of the color layer gradually decreases from the side close to the first transition layer to the side of the first transition layer.

[0013] In one embodiment, the decorative film layer further includes a second transition layer, which is disposed between the first transition layer and the color layer, and the material of the second transition layer is at least one of metal silicon oxycarbide, metal silicon oxynitride, and metal silicon oxycarbonitride.

[0014] In one embodiment, in the second transition layer, the molar content of silicon atoms is 15% - 30%, the sum of the molar contents of carbon atoms and nitrogen atoms is 2% - 10%, and the molar content of oxygen atoms is 15% - 30%.

[0015] In one embodiment, the thickness of the metal primer layer is 0.1 μm - 0.5 μm. Further, the thickness of the metal primer layer is 0.2 μm.

[0016] In one embodiment, the thickness of the first transition layer is 0.5 μm - 2.0 μm. Further, the thickness of the first transition layer is 1.0 μm.

[0017] In one embodiment, the thickness of the second transition layer is 0.1 μm - 0.5 μm. Further, the thickness of the second transition layer is 0.3 μm.

[0018] In one embodiment, the thickness of the color layer is 0.2 μm - 1.0 μm. Further, the thickness of the color layer is 0.3 μm.

[0019] In one embodiment, the color parameters of the decorative film layer include: the L value is 48 - 60, the a value is +2 - -2, and the b value is +1 - -5.

[0020] In one embodiment, the resistance of the decorative film layer is above 40 MΩ.

[0021] A method for preparing a decorative thin film, comprising the following steps:

[0022] Forming a metal primer layer on a substrate;

[0023] Forming a first transition layer on the metal primer layer, and the material of the first transition layer is at least one of metal carbide, metal nitride, and metal carbonitride;

[0024] Forming a color layer on the side of the first transition layer away from the metal primer layer, and the material of the color layer is silicon oxide, and the molar content of oxygen atoms in the silicon oxide is 40% - 55%.

[0025] In one embodiment, before forming the color layer, the preparation method further includes the following steps:

[0026] A second transition layer is formed on a side of the first transition layer away from the metal primer layer. The second transition layer is disposed between the first transition layer and the color layer, and the material of the second transition layer is at least one of metal silicon oxycarbide, metal silicon oxynitride, and metal silicon oxycarbonitride;

[0027] The color layer is formed on a side of the second transition layer away from the first transition layer.

[0028] In one embodiment, at least one of the metal primer layer, the first transition layer, the second transition layer, and the color layer is formed by a magnetron sputtering process.

[0029] In one embodiment, the color layer is formed by a magnetron sputtering process. A Si target is used, and O2 is introduced for reaction by a gas supply method with a gradually decreasing flow rate.

[0030] Compared with the existing solution, the above decorative film and its preparation method have the following beneficial effects:

[0031] The above decorative film includes a metal primer layer, a first transition layer, and a color layer. Among them, the metal primer layer imparts good gloss, metallic texture, and film-to-substrate adhesion to the decorative film. The first transition layer contains at least one of C element and N element compared with the metal primer layer, which can increase the overall resistance of the decorative film. The material of the color layer is silicon oxide. By controlling the molar content of oxygen atoms in the silicon oxide to be 40% - 55%, the color L value of the decorative film is between 48 and 60, the a and b values are close to the neutral gray area, and the resistance is greater than 40 MΩ. The insulation effect can be achieved without making the color too deep, while the traditional decorative film needs to make the L value about 30 to meet the resistance requirement. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 It is a schematic structural diagram of a decorative film according to an embodiment.

[0033] Description of the reference numerals:

[0034] 100, decorative film; 101, metal primer layer; 102, first transition layer; 103, second transition layer; 104, color layer; 200, substrate. DETAILED DESCRIPTION

[0035] To facilitate the understanding of the present invention, the present invention will be described more comprehensively below with reference to the relevant drawings. Preferred embodiments of the present invention are given in the drawings. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0036] It should be noted that when an element is referred to as being "disposed on" another element, it can be directly on the other element or there may also be an intermediate element. When an element is considered to be "connected" to another element, it can be directly connected to the other element or there may be an intermediate element at the same time.

[0037] In the description of the present invention, it should be understood that the terms "first" and "second" are only used for descriptive purposes and cannot be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include at least one of such features.

[0038] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs. The terms used in the description of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0039] Please refer to Figure 1 As shown, a decorative film 100 according to an embodiment of the present invention includes a metal primer layer 101, a first transition layer 102, and a color layer 104.

[0040] The metal primer layer 101 is used to be disposed on a substrate 200. The first transition layer 102 is disposed on the metal primer layer 101. The material of the first transition layer 102 is at least one of metal carbide, metal nitride, and metal carbonitride. The color layer 104 is disposed on a side of the first transition layer 102 away from the metal primer layer 101. The material of the color layer 104 is silicon oxide, and the molar content of oxygen atoms in the silicon oxide is 40% - 55%.

[0041] The above-mentioned decorative film 100 includes a metal primer layer 101, a first transition layer 102, and a color layer 104. Among them, the metal primer layer 101 endows the decorative film 100 with good gloss and metallic texture. The first transition layer 102 contains at least one of C element and N element compared with the metal primer layer 101, which can increase the overall resistance of the decorative film 100. The material of the color layer 104 is silicon oxide. By controlling the ratio of Si atoms and O atoms in the color layer 104, the color and resistance can be adjusted. By controlling the molar content of oxygen atoms in the silicon oxide to be 40% - 55%, the color L value of the decorative film 100 can be controlled between 48 and 60, the a and b values are close to the neutral gray area, and the resistance is greater than 40 MΩ. The insulation effect can be achieved without making the color very deep, while the traditional decorative film needs to make the L value about 30 to meet the resistance requirement.

[0042] In some examples, the material of the metal primer layer 101 is one or two of Cr and Ti. Selecting the above materials is beneficial to obtaining a lighter film color.

[0043] In some examples, the metal primer layer 101 is formed by magnetron sputtering process. The target is a corresponding metal target, such as one or two of Cr target and Ti target.

[0044] In some examples, the thickness of the metal primer layer 101 is 0.1 μm - 0.5 μm. In a specific example, the thickness of the metal primer layer 101 is 0.2 μm.

[0045] Compared with the metal primer layer 101, the first transition layer 102 also contains at least one of C element and N element, which can increase the overall resistance of the decorative film 100.

[0046] In some examples, in the first transition layer 102, the metal element is one or more of Cr, Ti, and W. Selecting the above materials is beneficial to obtaining a lighter film color.

[0047] In some examples, in the first transition layer 102, the molar content of metal atoms is 85% - 97%, specifically such as 85%, 87%, 89%, 91%, 93%, 95%, 97%, etc.

[0048] In some examples, the thickness of the first transition layer 102 is 0.5 μm - 2.0 μm. In a specific example, the thickness of the first transition layer 102 is 1.0 μm.

[0049] In some examples, the first transition layer 102 is formed by magnetron sputtering. The target material is a corresponding metal target material, such as one or more of a Cr target material, a Ti target material, and a W target material. At least one of the C element and the N element is introduced by introducing a reaction gas such as C2H2 and N2.

[0050] By controlling the ratio of Si atoms to O atoms, the color and resistance of the decoration film 100 can be adjusted. As the oxygen content of the color layer 104 increases, the color of the decoration film 100 becomes darker and the resistance increases.

[0051] In some examples, the oxygen content of the color layer 104 gradually decreases from the side close to the first transition layer 102 to the side of the first transition layer 102. As the oxygen content of the color layer 104 increases, although the resistance of the decorative film 100 increases, the problem of coloring will occur, affecting the decorative effect. The inventors found that by setting the oxygen content of the color layer 104 to gradually decrease from the side close to the first transition layer 102 to the side of the first transition layer 102, the problem of coloring of the decorative film 100 can be improved while maintaining a relatively large resistance of the decorative film 100, and the bonding strength of the film layer can be improved.

[0052] In some examples, the oxygen content of the color layer 104 gradually decreases from 35% to 40% on one side to 25% to 30% on the other side. In a specific example, the oxygen content of the color layer 104 gradually decreases from 35% on one side to 25% on the other side.

[0053] In some examples, the thickness of the color layer 104 is 0.2 μm to 1.0 μm. By controlling the thickness of the color layer 104 to 0.2 μm to 1.0 μm, the color layer 104 can be better matched with the inner film layer, so that the decorative film has a lighter color and a higher resistance. In a specific example, the thickness of the color layer 104 is 0.3 μm.

[0054] In some examples, the decoration film layer further includes a second transition layer 103, which is disposed between the first transition layer 102 and the color layer 104. The material of the second transition layer 103 is at least one of metal silicon oxycarbide, metal silicon oxynitride and metal silicon oxycarbonitride.

[0055] Compared with the first transition layer 102 , the second transition layer 103 also contains Si and O. Thus, compared with the first transition layer 102 , the composition of the second transition layer 103 is closer to that of the color layer 104 , which is beneficial to improving the interlayer bonding force.

[0056] In some of these examples, in the second transition layer 103, the molar content of silicon atoms is 15% to 30%, specifically such as 15%, 17%, 19%, 21%, 23%, 25%, 27%, 29%, etc.; the sum of the molar contents of carbon atoms and nitrogen atoms is 2% to 10%, specifically such as 2%, 4%, 6%, 8%, 10%, etc.; the molar content of oxygen atoms is 15% to 30%, specifically such as 15%, 17%, 19%, 21%, 23%, 25%, 27%, 29%, etc.

[0057] In some of these examples, the thickness of the second transition layer 103 is 0.1 μm to 0.5 μm. By controlling the thickness of the second transition layer 103 to be 0.1 μm to 0.5 μm, the second transition layer 103 can better cooperate with the color layer 104, so that the decorative film has a higher resistance while having a lighter color. In a specific example, the thickness of the second transition layer 103 is 0.3 μm.

[0058] In some of these examples, the color parameters of the decorative film layer include: the L value is 48 to 60, the a value is +2 to -2, and the b value is +1 to -5.

[0059] In some of these examples, the resistance of the decorative film layer is above 40 MΩ. In some of these examples, the resistance of the decorative film layer is 50 MΩ to 300 MΩ.

[0060] Furthermore, the present invention also provides a method for preparing the decorative film 100 according to any one of the above examples, including the following steps:

[0061] Form a metal primer layer 101 on the substrate 200;

[0062] Form a first transition layer 102 on the metal primer layer 101, and the material of the first transition layer 102 is at least one of metal carbide, metal nitride, and metal carbonitride;

[0063] Form a color layer 104 on the side of the first transition layer 102 away from the metal primer layer 101, and the material of the color layer 104 is silicon oxide, and the molar content of oxygen atoms in the silicon oxide is 40% to 55%.

[0064] The preparation method of the above decorative film 100 successively forms a metal primer layer 101, a first transition layer 102, and a color layer 104. Among them, the metal primer layer 101 endows the decorative film 100 with good gloss and metallic texture. The first transition layer 102 further contains at least one of C element and N element compared with the metal primer layer 101, which can increase the overall resistance of the decorative film 100. The material of the color layer 104 is silicon oxide. By controlling the ratio of Si atoms and O atoms in the color layer 104, the color and resistance can be adjusted. By controlling the molar content of oxygen atoms in the silicon oxide to be 40% - 55%, the color L value of the decorative film 100 can be controlled to be between 48 - 60, the a and b values are close to the neutral gray area, and the resistance is greater than 40 MΩ, so that the insulation effect can be achieved without making the color very deep.

[0065] In some of these examples, before forming the color layer 104, the preparation method further includes the following steps:

[0066] A second transition layer 103 is formed on the side of the first transition layer 102 away from the metal primer layer 101. The second transition layer 103 is disposed between the first transition layer 102 and the color layer 104. The material of the second transition layer 103 is at least one of metal silicon oxycarbide, metal silicon oxynitride, and metal silicon oxycarbonitride.

[0067] In this example, the color layer 104 is formed on the side of the second transition layer 103 away from the first transition layer 102.

[0068] In some of these examples, at least one of the metal primer layer 101, the first transition layer 102, the second transition layer 103, and the color layer 104 is formed by a magnetron sputtering process. In some of these examples, the metal primer layer 101, the first transition layer 102, the second transition layer 103, and the color layer 104 are all formed by a magnetron sputtering process.

[0069] Decorative films have high requirements for the appearance, mechanical and anti-corrosion properties presented by the films. In terms of appearance, not only is a uniform color required, but also high requirements are placed on surface gloss, metallic texture, etc.; in terms of mechanical properties, the film is required to have high hardness, good wear and scratch resistance; in terms of anti-corrosion properties, the film is required to have the ability to resist corrosion by various corrosive media.

[0070] Although traditional non-conductive vacuum metallization (NCVM) technology can achieve the purpose of coating insulation, its preparation process is not environmentally friendly. At the same time, its surface layer uses painting to protect the metallic texture layer, and its wear resistance and scratch resistance are poor, unable to meet the requirements of high-end products. The above example adopts the magnetron sputtering process. Due to the small particle size and high energy of magnetron sputtering particles, the deposited thin film has a smooth and flat appearance, the film layer is dense, has good gloss, uniform color, and also has excellent thin film properties, meeting the above requirements. Moreover, the entire deposition process is carried out in a vacuum, which is environmentally friendly and non-toxic.

[0071] In some of these examples, the metal underlayer 101 is formed by the magnetron sputtering process, and the process steps include:

[0072] Connect the corresponding metal target to the medium-frequency magnetron sputtering power supply, introduce a working gas, such as Ar, with a flow rate of 200 sccm to 800 sccm, apply a bias voltage of 50 to 400 V and a duty cycle of 20% to 80%, and the target power is 6 kW to 12 kW.

[0073] In some of these examples, the first transition layer 102 is formed by the magnetron sputtering process, and the process steps include:

[0074] Connect the corresponding metal target to the medium-frequency magnetron sputtering power supply, introduce a working gas, such as Ar, with a flow rate of 200 sccm to 800 sccm, introduce a reaction gas C2H2 with a flow rate of 30 sccm to 150 sccm, apply a bias voltage of 50 V to 400 V and a duty cycle of 20% to 80%, and the metal target power is 6 kW to 12 kW.

[0075] In some of these examples, the second transition layer 103 is formed by the magnetron sputtering process, and the process steps include:

[0076] Use a Cr target and a Si target, connect to the medium-frequency magnetron sputtering power supply, introduce a working gas, such as Ar, with a flow rate of 200 sccm to 800 sccm, introduce a reaction gas C2H2 with a flow rate of 30 sccm to 150 sccm, introduce a reaction gas O2 with a flow rate of 50 sccm to 150 sccm, apply a bias voltage of 50 V to 400 V and a duty cycle of 20% to 80% bias voltage, the Cr target power is 6 kW to 12 kW, and the Si target power is 5 kW to 10 kW.

[0077] In some of these examples, the color layer 104 is formed by the magnetron sputtering process, and the process steps include:

[0078] Use an Si target, connect it to a medium-frequency magnetron sputtering power supply, introduce working gas such as Ar with a flow rate of 200 sccm to 800 sccm, and introduce reaction gas O2 with a flow rate of 120 sccm to 200 sccm. Apply a bias voltage of 50 V to 400 V with a duty cycle of 20% to 80%, and the power of the Si target is 5 kW to 10 kW.

[0079] In some of these examples, the reaction gas O2 is supplied in a manner where the flow rate gradually decreases, such as a uniform linear decrease. The oxygen content of the formed color layer 104 gradually decreases from the side close to the first transition layer 102 to the side of the first transition layer 102. This gas supply method can improve the uniformity of different positions on the 3D surface of the product and the problem of color development of the decorative film 100 while maintaining a relatively large resistance of the decorative film 100, and also improve the film layer adhesion.

[0080] In some of these examples, when depositing the color layer 104, the starting gas flow rate of the reaction gas O2 is 120 sccm to 200 sccm, and the ending gas flow rate is 80 sccm to 160 sccm. In a specific example, when depositing the color layer 104, the starting gas flow rate of the reaction gas O2 is 140 sccm, and the ending gas flow rate is 100 sccm.

[0081] In some of these examples, when depositing the color layer 104, the starting gas flow rate of the reaction gas O2 is 30 sccm to 60 sccm more than the ending gas flow rate. Further, in some of these examples, when depositing the color layer 104, the starting gas flow rate of the reaction gas O2 is 40 sccm more than the ending gas flow rate.

[0082] In some of these examples, before forming the metal underlayer 101, the preparation method further includes the following steps:

[0083] Clean the substrate 200.

[0084] Further, in some of these examples, the preparation method further includes the following steps:

[0085] Activate the substrate 200.

[0086] In some of these examples, the steps of the activation treatment include:

[0087] Place the substrate 200 in a vacuum chamber, evacuate and preheat, with the background vacuum pressure not higher than 8.0×10 -3 Pa, and the preheating temperature is 100 °C to 140 °C.

[0088] The substrate 200 is bombarded with an arc target, and a working gas is introduced with a flow rate of 200 sccm to 800 sccm. A bias voltage of 200 V to 500 V with a duty cycle of 20% to 80% is applied to the substrate 200, the arc current is 40 A to 100 A, and the time is 3 min to 10 min.

[0089] Through the above activation treatment, the surface of the substrate 200 can be activated, the bonding strength between the substrate 200 and the metal underlayer 101 can be improved, and at the same time, the residual foreign matters on the surface of the substrate 200 can be further removed.

[0090] The following is further described in conjunction with specific embodiments and comparative examples, but the present invention is not limited to the following specific embodiments.

[0091] Example 1

[0092] This example provides a decorative film and a preparation method thereof.

[0093] The decorative film includes:

[0094] A substrate;

[0095] A metal underlayer deposited on the substrate, the material is Cr, and the thickness is 0.2 μm;

[0096] A first transition layer deposited on the metal underlayer, the material is CrC, and the thickness is 1.0 μm;

[0097] A second transition layer deposited on the first transition layer, Si and O elements are added to this layer on the basis of the first transition layer, and the thickness is 0.2 μm;

[0098] A color layer deposited on the second transition layer, the material is SiO, and the thickness is 0.6 μm.

[0099] The preparation method of the decorative film in this example includes the following steps:

[0100] Step S1, the substrate is cleaned to remove dust, oil stains and other residual foreign matters on the surface of the substrate.

[0101] Step S2, the substrate that has passed the inspection and cleaning is placed in a vacuum chamber, and the vacuum is pumped to a background vacuum pressure not higher than 8.0×10 -3 Pa, and preheated, and the preheating temperature is 120 °C.

[0102] Step S3, the substrate is subjected to arc target bombardment treatment. The working gas Ar is introduced with a flow rate of 500 sccm, and a bias voltage of 500 V with a duty cycle of 50% is applied to the substrate, the arc current is 40 to 100 A, and the time is 3 to 10 min to activate the surface of the substrate, and at the same time, the residual foreign matters on the surface of the substrate can be further removed.

[0103] Step S4, deposit a metal primer layer on the above-mentioned substrate by using the medium-frequency magnetron sputtering process. Use a Cr target, connect it to the medium-frequency magnetron sputtering power supply, introduce the working gas Ar with a flow rate of 500 sccm, apply a bias voltage of 200 V and a duty cycle of 50%, and the power of the Cr target is 10 kW.

[0104] Step S5, deposit a first intermediate transition layer on the above-mentioned metal primer layer by using the medium-frequency magnetron sputtering process. Use a Cr target, connect it to the medium-frequency magnetron sputtering power supply, introduce the working gas Ar with a flow rate of 500 sccm, introduce the reactive gas C2H2 with a flow rate of 100 sccm, apply a bias voltage of 200 V and a duty cycle of 50%, and the power of the Cr target is 10 kW.

[0105] Step S6, deposit a second transition layer on the above-mentioned first transition layer by using the medium-frequency magnetron sputtering process. Use a Cr target and a Si target, connect them to the medium-frequency magnetron sputtering power supply, introduce the working gas Ar with a flow rate of 500 sccm, introduce the reactive gas C2H2 with a flow rate of 100 sccm, introduce the reactive gas O2 with a flow rate of 100 sccm, apply a bias voltage of 200 V and a duty cycle of 50%, the power of the Cr target is 9 kW, and the power of the Si target is 7 kW.

[0106] Step S7, deposit a color layer on the above-mentioned second transition layer by using the medium-frequency magnetron sputtering process. Use a Si target, connect it to the medium-frequency magnetron sputtering power supply, introduce the working gas Ar with a flow rate of 500 sccm, introduce the reactive gas O2 with a flow rate of 160 sccm. Among them, the feeding mode of the reactive gas O2 is uniform linear decreasing feeding, and the starting gas volume is 40 sccm more than the ending gas volume. Apply a bias voltage of 200 V and a duty cycle of 50%, and the power of the Si target is 8 kW.

[0107] The decorative film prepared in this embodiment has good adhesion, has a very high resistance, the typical color values are L: 53.5, a: 0.53, b: -2.5, and there is no problem of color bleeding on the goods. The resistance value is 250 - 260 MΩ, and there will be slight fluctuations in the resistance measured at different positions of the sample.

[0108] Example 2

[0109] This embodiment provides a decorative film and a preparation method thereof.

[0110] The decorative film includes:

[0111] A substrate;

[0112] A metal primer layer deposited on the substrate, the material is Ti, and the thickness is 0.2 μm;

[0113] A first transition layer deposited on the metal primer layer, the material is TiC, and the thickness is 1.0 μm;

[0114] A second transition layer deposited on the first transition layer, which adds Si and O elements on the basis of the first transition layer and has a thickness of 0.2 μm;

[0115] A color layer deposited on the second transition layer, made of SiO and having a thickness of 0.6 μm.

[0116] The preparation method of the decorative film in this embodiment includes the following steps:

[0117] Steps S1 to S3 are the same as those in Embodiment 1.

[0118] Step S4: Deposit a metal underlayer on the above-mentioned substrate by using a medium-frequency magnetron sputtering process. Use a Ti target, connect it to a medium-frequency magnetron sputtering power supply, introduce working gas Ar with a flow rate of 500 sccm, apply a bias voltage of 200 V and a duty cycle of 50%, and the power of the Ti target is 10 kW.

[0119] Step S5: Deposit a medium-frequency first transition layer on the above-mentioned metal underlayer by using a medium-frequency magnetron sputtering process. Use a Ti target, connect it to a medium-frequency magnetron sputtering power supply, introduce working gas Ar with a flow rate of 500 sccm, introduce reaction gas C2H2 with a flow rate of 100 sccm, apply a bias voltage of 200 V and a duty cycle of 50%, and the power of the Ti target is 10 kW.

[0120] Step S6: Deposit a second transition layer on the above-mentioned first transition layer by using a medium-frequency magnetron sputtering process. Use a Ti target and a Si target, connect them to a medium-frequency magnetron sputtering power supply, introduce working gas Ar with a flow rate of 500 sccm, introduce reaction gas C2H2 with a flow rate of 100 sccm, introduce reaction gas O2 with a flow rate of 100 sccm, apply a bias voltage of 200 V and a duty cycle of 50% bias voltage, the power of the Ti target is 9 kW, and the power of the Si target is 7 kW.

[0121] Step S7 is the same as that in Embodiment 1.

[0122] The decorative film prepared in this embodiment has good adhesion, a very high resistance, a typical color value of L: 53.5, a: 0.53, b: -2.5, and a resistance value of 250 - 260 MΩ.

[0123] Compared with Embodiment 1, after changing the metal element from Cr to Ti in this embodiment, the above changes have almost no effect on the color and resistance of the film. The obtained decorative film has good adhesion, a very high resistance, a typical color value of L: 53.2, a: 0.51, b: -2.65, and there is no problem of color bleeding in the goods. The resistance value is 210 - 220 MΩ, and there will be slight fluctuations in the resistance measured at different positions of the sample.

[0124] Embodiment 3

[0125] This embodiment provides a decorative film and a preparation method thereof.

[0126] The decorative film includes:

[0127] A substrate;

[0128] A metal underlayer deposited on the substrate, made of TiCr, with a thickness of 0.2 μm;

[0129] A first transition layer deposited on the metal underlayer, made of TiCrCN, with a thickness of 1.0 μm;

[0130] A second transition layer deposited on the first transition layer, with Si and O elements added on the basis of the first transition layer, and a thickness of 0.2 μm;

[0131] A color layer deposited on the second transition layer, made of SiO, with a thickness of 0.6 μm.

[0132] The preparation method of the decorative film in this embodiment includes the following steps:

[0133] Steps S1 to S3 are the same as those in Embodiment 1.

[0134] In step S4, a metal underlayer is deposited on the above-mentioned substrate by means of medium-frequency magnetron sputtering. Ti target and Cr target are used, connected to a medium-frequency magnetron sputtering power supply, working gas Ar is introduced, with a flow rate of 500 sccm, a bias voltage of 200 V and a duty cycle of 50% is applied, the power of the Ti target is 7 kW, and the power of the Cr target is 9 kW.

[0135] In step S5, a medium-frequency first transition layer is deposited on the above-mentioned metal underlayer by means of medium-frequency magnetron sputtering. Ti target and Cr target are used, connected to a medium-frequency magnetron sputtering power supply, working gas Ar is introduced, with a flow rate of 500 sccm, reaction gas C2H2 is introduced, with a flow rate of 100 sccm, reaction gas N2 is introduced, with a flow rate of 70 sccm, a bias voltage of 200 V and a duty cycle of 50% is applied, the power of the Ti target is 7 kW, and the power of the Cr target is 9 kW.

[0136] In step S6, a second transition layer is deposited on the above-mentioned first transition layer by means of medium-frequency magnetron sputtering. Ti target, Cr target and Si target are used, connected to a medium-frequency magnetron sputtering power supply, working gas Ar is introduced, with a flow rate of 500 sccm, reaction gas C2H2 is introduced, with a flow rate of 100 sccm, reaction gas O2 is introduced, with a flow rate of 100 sccm, reaction gas N2 is introduced, with a flow rate of 70 sccm, a bias voltage of 200 V and a duty cycle of 50% is applied, the power of the Ti target is 7 kW, the power of the Cr target is 9 kW, and the power of the Si target is 7 kW.

[0137] Step S7 is the same as that in Embodiment 1.

[0138] Compared with Example 1, in this example, the metal element is changed from Cr to a mixture of Ti and Cr, and the reactive element is changed from C to a mixture of C and N. The above changes have little effect on the color and resistance of the thin film. The obtained decorative thin film has good adhesion and high resistance. The typical color values are L: 52.8, a: 0.48, b: -3.0, and there is no problem of color bleeding on the goods. The resistance value is 220 - 230 MΩ, and there will be slight fluctuations in the resistance measured at different positions of the sample.

[0139] Example 4

[0140] This example provides a decorative thin film and a preparation method thereof.

[0141] The decorative thin film includes:

[0142] A substrate;

[0143] A metal primer layer deposited on the substrate, made of Cr, with a thickness of 0.2 μm;

[0144] A first transition layer deposited on the metal primer layer, made of CrC, with a thickness of 1.0 μm;

[0145] A second transition layer deposited on the first transition layer, with Si and O elements added on the basis of the first transition layer, and a thickness of 0.2 μm;

[0146] A color layer deposited on the second transition layer, made of SiO, with a thickness of 0.6 μm.

[0147] The preparation method of the decorative thin film in this example includes the following steps:

[0148] Steps S1 - S6 are the same as those in Example 1.

[0149] Step S7: Deposit the color layer on the above - mentioned second transition layer by using the medium - frequency magnetron sputtering process. Use a Si target, connect it to the medium - frequency magnetron sputtering power supply, introduce the working gas Ar with a flow rate of 500 sccm, and introduce the reactive gas O2 with a flow rate of 160 sccm. Different from Example 1, the gas volume is in place in one step and remains fixed throughout the process instead of decreasing. Apply a bias voltage of 200 V and a duty cycle of 50%, and the power of the Si target is 8 kW.

[0150] In this example, the resistance value of the obtained thin film is greater than 100 MΩ, but after the sample is bent at 90°, the film layer peels and cracks, and the adhesion of the film layer is poor. Moreover, there is a problem of color bleeding on the goods. Not only are the colors of the goods at different positions inconsistent, but even the front and side, angles, holes, etc. of the same good have color bleeding.

[0151] Example 5

[0152] This example provides a decorative thin film and a preparation method thereof.

[0153] The decorative film includes:

[0154] A substrate;

[0155] A metal primer layer deposited on the substrate, made of Cr, with a thickness of 0.2 μm;

[0156] A first transition layer deposited on the metal primer layer, made of CrC, with a thickness of 1.0 μm;

[0157] A color layer deposited on the first transition layer, made of SiO, with a thickness of 0.6 μm.

[0158] The preparation method of the decorative film in this embodiment includes the following steps:

[0159] Steps S1 to S5 are the same as those in Embodiment 1.

[0160] In step S6, a color layer is deposited on the first transition layer by using a medium-frequency magnetron sputtering process. A Si target is used, connected to a medium-frequency magnetron sputtering power supply, and working gas Ar is introduced with a flow rate of 500 sccm, and reactive gas O2 is introduced with a flow rate of 160 sccm. Among them, the feeding mode of the reactive gas O2 is a uniform linear decreasing mode, and the starting gas volume is 40 sccm more than the ending gas volume. A bias voltage of 200 V and a duty cycle of 50% are applied, and the power of the Si target is 8 kW.

[0161] In this embodiment, the obtained film has a resistance value greater than 100 MΩ, and there is no problem of color development on the goods. However, after the sample is bent at 90°, the film layer peels off and cracks, and the film layer adhesion is poor.

[0162] Comparative Example 1

[0163] The decorative film in this comparative example includes:

[0164] A substrate;

[0165] A metal primer layer deposited on the substrate, made of Cr, with a thickness of 0.2 μm;

[0166] A first transition layer deposited on the metal primer layer, made of CrC, with a thickness of 1.0 μm;

[0167] A second transition layer deposited on the first transition layer, with Si and O elements added on the basis of the first transition layer, with a thickness of 0.2 μm;

[0168] A color layer deposited on the second transition layer, made of CrC, with a thickness of 0.6 μm.

[0169] The preparation method of the decorative film in this embodiment includes the following steps:

[0170] Steps S1 to S6 are the same as those in Embodiment 1.

[0171] In step S7, a color layer is deposited on the above-mentioned second transition layer by means of medium-frequency magnetron sputtering. A Cr target is used, connected to a medium-frequency magnetron sputtering power supply. Working gas Ar is introduced with a flow rate of 500 sccm, and reaction gas C2H2 is introduced with a flow rate of 500 sccm. The gas is added in an increasing manner. A bias voltage of 200 V and a duty cycle of 50% are applied, and the power of the Cr target is 8 kW.

[0172] In this comparative example, although a film with a resistance value greater than 100 MΩ can be obtained, the color values in this embodiment are L: 31.2, a: -0.15, b: -1.8, the color is very deep, and the L value is close to 30.

[0173] The color measuring instrument used in the above Embodiments 1 to 4 and Comparative Example 1 is a CM-3700A-U spectrocolorimeter, and the light source angle is F2 / 10°. The resistance measurement is carried out with a standard model multimeter. The measurement method is to place the cathode probe on the surface of the sample and place the anode probe at a position 10 mm away from the cathode probe to measure the resistance. The adhesion test method is to observe whether the film layer peels off or cracks after the sample is bent by 90°. If there is no peeling or cracking, the adhesion of the film layer is good; if peeling or cracking occurs, it indicates that the adhesion of the film layer is poor.

[0174] The technical features of the above-mentioned embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0175] The above-mentioned embodiments only represent several implementation manners of the present invention. The description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several deformations and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent should be subject to the appended claims, and the specification can be used to explain the content of the claims.

Claims

1. A decorative film, characterized in that, Comprising: A metal bottom layer; A first transition layer disposed on the metal bottom layer, the material of the first transition layer being at least one of metal carbide, metal nitride, and metal carbonitride; and A color layer disposed on a side of the first transition layer away from the metal bottom layer, the material of the color layer being silicon oxide, and the molar content of oxygen atoms in the silicon oxide being 40% - 55%; The oxygen content of the color layer gradually decreases from a side close to the first transition layer to a side away from the first transition layer.

2. The decorative film according to claim 1, wherein In the first transition layer, the molar content of metal atoms is 85% - 97%.

3. The decorative film according to any one of claims 1 to 2, characterized in that, The decorative film layer further includes a second transition layer disposed between the first transition layer and the color layer, the material of the second transition layer being at least one of metal silicon oxycarbide, metal silicon oxynitride, and metal silicon oxycarbonitride.

4. The decorative film according to claim 3, wherein In the second transition layer, the molar content of silicon atoms is 15% - 30%, the sum of the molar contents of carbon atoms and nitrogen atoms is 2% - 10%, and the molar content of oxygen atoms is 15% - 30%.

5. The decorative film according to claim 3, characterized in that, The decorative thin film satisfies at least one of the following characteristics: The thickness of the second transition layer is 0.1 μm - 0.5 μm; The thickness of the color layer is 0.2 μm - 1.0 μm.

6. The decorative film according to any one of claims 1 to 2, 4, and 5, characterized in that The color parameters of the decorative film layer include: the L value is 48 - 60, the a value is +2 - -2, and the b value is +1 - -5; The resistance of the decorative film layer is above 40 MΩ.

7. A method for preparing a decorative film, characterized in that, Including the following steps: Forming a metal bottom layer on a substrate; Forming a first transition layer on the metal bottom layer, the material of the first transition layer being at least one of metal carbide, metal nitride, and metal carbonitride; Forming a color layer on a side of the first transition layer away from the metal bottom layer, the material of the color layer being silicon oxide, and the molar content of oxygen atoms in the silicon oxide being 40% - 55%; The color layer is formed by a magnetron sputtering process, using a Si target and introducing O2 for reaction in a gas supply manner with a gradually decreasing flow rate.

8. The preparation method according to claim 7, characterized in that, Before forming the color layer, the preparation method further includes the following steps: Forming a second transition layer on a side of the first transition layer away from the metal bottom layer, the second transition layer being disposed between the first transition layer and the color layer, the material of the second transition layer being at least one of metal silicon oxycarbide, metal silicon oxynitride, and metal silicon oxycarbonitride; The color layer is formed on a side of the second transition layer away from the first transition layer.

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