Manufacturing method of a foldable and rollable flexible titanium metal component

Abstract

The present invention relates to the technical field of electronic devices, and particularly relates to a manufacturing method of a foldable and rollable flexible titanium metal component, including steps: pressing and shaping of a titanium metal plate, Ni and Au electroplating of a conductive contact part, and pattern etching. The manufacturing method provided by the present application can conveniently, quickly and efficiently manufacture titanium metal support fittings of various shapes, various forms and different thicknesses, as well as fittings made of other metal materials and non-metal materials and applied to a curling display device and related devices according to requirements, and there is no need to greatly change production equipment and production process flows; moreover, the main electroplating solution used in the gold electroplating process is a medium-alkaline cyanide-free electroplating system, and the titanium metal etching solution is also a weak acidic system. The electroplating and etching systems have simple pollution to the production environment and subsequent wastewater treatment processes, are convenient for recycling and reuse, and can achieve zero pollution discharge, are environmentally friendly, have good economic and environmental effects, and have broad application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of electronic devices, and particularly to a manufacturing method of a foldable and rollable flexible titanium metal component. Background Art

[0002] With the progress of the times and the rapid development of artificial intelligence technology in modern various electronic devices, higher requirements are also needed for the accessories of these devices. For example, various artificial intelligence devices, mobile devices, etc. are equipped with foldable and rollable display devices for display, such as mobile phones, laptops, in-vehicle stretch screens, roll screens, liquid crystal electronic clocks, military foldable and rollable clothing auxiliary displays, and so on.

[0003] Among them, the main materials for display support and conductive plates are metals or alloy materials. For example, titanium or alloys are applied in foldable and rollable display devices. However, such materials are prone to aging, corrosion, poor sealing, low hardness, and easy scratching. Whether they can achieve properties such as conductivity, thickness, hardness, repeated folding, and bending degree during application remains to be tested. Due to the advantages and disadvantages of these two cover plate materials, manufacturers generally use composite structural materials to improve the reliability of products.

[0004] Photochemical etching, the process principle of which is that after plate making, exposure, and development, the protective film in the etching area is removed, and the metal contacts the chemical solution during the etching process. Two positive patterns are used to achieve the effect of dissolution and corrosion through chemical etching from both sides, forming the effects of concavity, convexity, and hollowing. The etching process can etch almost all materials, and the products have advantages such as corrosion resistance, no stress deformation, and no burrs.

[0005] The prior art for manufacturing flexible display device support components using metal titanium or titanium alloy (hereinafter referred to as "titanium metal") usually goes through three main manufacturing process steps: First, pressing and processing of titanium metal thin plates; Second, local electroplating of titanium metal thin plates; Third, graphic etching of titanium metal thin plates, etc.

[0006] Ultra-thin titanium metal or titanium alloy thin plates are commonly used to manufacture support components of flexible display devices, etc. However, titanium metal and titanium alloy are relatively active and prone to forming a surface oxide layer, lacking conductivity and weldability. Therefore, the support backplane of flexible display components made of titanium metal and titanium alloy needs to be electroplated for conductivity, welded with electroplated layers of Ni and Au coatings, etc. However, the stress action of titanium metal thin plates manufactured by the prior art and the chemical properties of titanium metal determine that the adhesion of its Ni and Au coatings is poor, and the corresponding parts of the coatings undergo stress release deformation due to stress action, affecting the shape precision of titanium metal support components. Summary of the Invention

[0007] To solve the above problems, the present invention provides a manufacturing method for a foldable and rollable flexible titanium metal component, which has a simple process and effectively solves the stress release problem.

[0008] The technical solution adopted by the present invention is as follows:

[0009] A manufacturing method for a foldable and rollable flexible titanium metal component, comprising the following steps:

[0010] S1. Pressing and shaping of the titanium metal plate

[0011] Place the thick titanium metal plate in the NTS solution, soak for 3 - 10 seconds, and then wash;

[0012] Then place it in an N2 - Ar inert gas environment at a temperature of 550 - 750 °C, statically press it to the set thickness, and maintain for 30 - 120 seconds;

[0013] After that, cool it naturally, coat with a photocurable coating, fix the image, and develop the image;

[0014] S2. Ni and Au electroplating on the conductive contact part

[0015] The titanium metal plate in S1 is successively degreased, activated, electroplated with nickel, electroplated with gold in an AAB cyanide - free electroplating solution, washed, post - protected, the cured coating is removed, washed, and dried;

[0016] S3. Pattern etching

[0017] Coat the titanium metal plate in S2 with a photosensitive coating, laser - fix the image with a film, chemically develop the image, etch it in an LFGG etching solution, remove the photosensitive film, wash, dry, and trim the edges to obtain the finished product;

[0018] Among them, the NTS solution in step S1 is a dilute acid mixed solution of nickel salt and copper salt;

[0019] Among them, the LFGG etching solution in step S3 is composed of phosphate, fluoride, persulfate, and peroxide.

[0020] Among them, the electroplating nickel process parameters are general commonly used electroplating nickel process parameters: voltage range, current density range;

[0021] Among them, the electroplating gold process parameters are general commonly used electroplating gold process parameters:

[0022] Voltage: 3.8 - 5.0 V;

[0023] Current density: 0.25 - 1.5 A / cm 2 .

[0024] Furthermore, the concentration of nickel salt in the NTS solution is 3-10 wt%; the concentration of copper salt is 0.01-0.03 wt%; the concentration of dilute acid is 5-25 wt%.

[0025] Furthermore, the nickel salt in the NTS solution is one or a mixture of more than one of nickel nitrate, nickel sulfate or nickel chloride;

[0026] The copper salt in the NTS solution is one or a mixture of more than one of copper sulfate, copper nitrate or copper chloride;

[0027] The dilute acid in the NTS solution is sulfuric acid and / or phosphoric acid solution.

[0028] Furthermore, in step S1, the N2-Ar inert gas environment is a mixture system of nitrogen and / or argon pure gas in any proportion, and the N2-Ar air pressure is maintained at greater than one atmospheric pressure.

[0029] Furthermore, in step S2, the AAB cyanide-free electroplating solution contains the following components:

[0030] Chloroaurate(III) 0.5-30 g / L, chloride 2-100 g / L, disodium iminosuccinate 3-60 g / L, n-butylhydantoin 3-30 g / L, diol or disulfonate of diacid 0.5-3 g / L, acetic acid 3-25 g / L, sodium acetate 4-30 g / L, sulfite 5-35 g / L and polyethylene glycol 1-15 g / L;

[0031] Furthermore, the chloroaurate(III) is one or a mixture of more than one of sodium chloroaurate(III), potassium chloroaurate(III) and ammonium chloroaurate(III);

[0032] The chloride salt is one or a mixture of more than one of sodium chloride, potassium chloride and ammonium chloride;

[0033] The diol or disulfonate of diacid is one or a mixture of more than one of ethylene glycol disodium salt, 1,4-butanediol-2-sulfonate sodium salt, sodium diethyl sulfosuccinate and sodium dioctyl sulfosuccinate;

[0034] The sulfite is one or a mixture of more than one of sodium sulfite, potassium sulfite and ammonium sulfite;

[0035] The average molecular weight of the polyethylene glycol is 800-4000.

[0036] Furthermore, the pH value of the AAB cyanide-free electroplating solution needs to be adjusted to 7.0-12.5 with hydrochloric acid and sodium hydroxide.

[0037] Furthermore, the LFGG etching solution in step S3 contains the following components:

[0038] 10 - 120 g / L of NaH2PO4, 25 - 85 g / L of NaF, 5 - 35 g / L of NH4F, 5 - 35 g / L of persulfate, 3 - 12 g / L of peroxide, 5 - 20 g / L of polyethylene glycol, 0.1 - 3 g / L of sodium alkyl sulfate, 0.1 - 2 g / L of sodium ethylenediaminetetraacetate, 1 - 15 g / L of NaNO2, 0.01 - 0.05 g / L of AgNO3.

[0039] Further, the persulfate is one or a mixture of more than one of K2S2O8, Na2S2O8, (NH4)2S2O8;

[0040] The peroxide is one or a mixture of more than one of Na2O2, BaO2, CaO2;

[0041] The sodium alkyl sulfonate is one or a mixture of more than one of sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate.

[0042] Further, the solutions in steps S1, S2 and S3 are all aqueous solutions.

[0043] The beneficial effects of the present invention are as follows:

[0044] 1. The manufacturing method provided by the present application passes through a nickel salt solution before titanium metal pressing. Due to the occurrence of a displacement reaction, a certain amount of nickel metal atoms penetrate into the titanium metal surface layer, forming a titanium-nickel alloy layer. The penetration depth of Ni is about in the range of 3 - 6 nm. Since a Ni-Ti alloy is formed on the titanium metal surface, there is no need for a pre-electroplating nickel step before electroplating nickel, which can save power consumption and greatly reduce the sewage discharge; at the same time, the formation of the Ni-Ti alloy greatly increases the adhesion between the Ni coating and the Ti metal substrate, and the adhesion level is higher;

[0045] 2. The manufacturing method provided by the present application significantly eliminates the corresponding back stress deformation through electroplating nickel and electroplating gold on titanium metal. The titanium metal thin plate pressing process undergoes a stress relief annealing treatment process. At the same time, under the dual action of forming a certain Ti-Ni alloy layer on the surface of the titanium metal substrate, the stress change of the titanium metal substrate during the subsequent electroplating of Ni and Au is minimal, and no further chemical etching treatment is required;

[0046] 3. The manufacturing method provided by this application, due to the adoption of a phosphate, NaF, persulfate and peroxide etching system, enables the etching reaction rate of titanium metal to be effectively controlled, can significantly improve the chemical etching rate of titanium metal, and can adjust the etching speed according to requirements. At the same time, due to the presence of nitrite ions, nitrate ions, sulfate ions, phosphate ions, etc., the selective chemical adsorption of these oxyacid root ions on the new surface of metal etching makes the etched pattern of titanium metal regular, with neat, regular and burr-free boundaries, and the etching effect is good. At the same time, it helps to improve the etching rate.

[0047] 4. The manufacturing method provided by this application, due to the use of auxiliary agents such as polyethylene glycol, alkyl sulfates and EDTA, these auxiliary agents change the contact effect between the surface of the etched metal and the etching solution, and at the same time make the etching reaction products Tin and ionic products and impurity metals Mn and ionic products leave the surface of titanium metal, enabling the etching chemical reaction to proceed smoothly and improving the etching effect.

[0048] 5. The manufacturing method provided by this application can conveniently, quickly and efficiently manufacture titanium metal support fittings of various shapes, multiple forms and different thicknesses, as well as fittings made of other metal materials and non-metal materials and applied to curling display devices and related devices according to requirements, and there is no need to greatly change the production equipment and production process.

[0049] 6. The manufacturing method provided by this application uses a medium-alkaline cyanide-free electroplating system as the main electroplating solution during the electroplating of gold, and the titanium metal etching solution is also a weakly acidic system. The electroplating and etching systems have simple pollution to the production environment and subsequent wastewater treatment processes, are convenient for recycling and reuse, and can achieve zero pollution discharge, are environmentally friendly, and have good economic and environmental effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 It is a schematic structural diagram of the circular fitting manufactured in Example 1 of this application;

[0051] Figure 2 It is a schematic structural diagram of the circular fitting manufactured in Example 2 of this application;

[0052] Figure 3 It is a schematic structural diagram of the square fitting manufactured in Example 3 of this application;

[0053] Figure 4 It is a schematic structural diagram of the square fitting manufactured in Example 4 of this application;

[0054] Figure 5 It is a schematic structural diagram of the oval fitting manufactured in Example 5 of this application;

[0055] Figure 6 It is a schematic structural diagram of the oval fitting manufactured in Example 6 of this application;

[0056] Figure 7 SEM image of Ni penetration depth of the fitting manufactured in Example 1 of this application;

[0057] Figure 8 SEM image of Ni penetration depth of the fitting manufactured in Example 3 of this application;

[0058] Figure 9 SEM image of Ni penetration depth of the fitting manufactured in Example 6 of this application;

[0059] Figure 10 Test diagram of Ni coating adhesion of the flexible folding and rolling fitting manufactured in Example 1 of this application;

[0060] Figure 11 Test diagram of Ni coating adhesion of the flexible folding and rolling fitting manufactured in the comparative example;

[0061] Reference signs in the drawings: such as 11, 21, 32 in the drawings, where the first digit 1 - 6 represents the sequence of the drawings in turn, and the second digits 1, 2, 3 represent the respective component parts of the component: 1 - represents the titanium metal substrate, 2 - represents the electroplated Ni and Au parts, 3 - represents the etched part. Detailed implementation manners

[0062] The following combines the accompanying drawings of the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the described embodiments are only part of the embodiments of this application, not all embodiments. The described embodiments are only the preferred embodiments of this application. Other similar embodiments obtained by those skilled in the art through improving individual or partial manufacturing steps, replacing a few similar chemical substances in the chemical compositions of NTS solution, AAB solution, LFGG solution, etc., and adjusting the chemical composition without creative labor all fall within the protection scope of this application.

[0063] Example 1

[0064] The manufacturing method of the foldable flexible titanium metal component described in this embodiment includes the following steps:

[0065] The first step, the pressing and shaping process of the titanium metal plate:

[0066] Thick titanium metal plate → soaked in a mixed solution of nickel salt, copper salt and dilute acid (NTS solution, the same below) for 10 seconds → cleaned → pressed to the set thickness (0.065 - 0.15 mm) under the condition of N2 - Ar inert gas environment (atmospheric pressure ≥ 1 atmosphere) and at 550 °C for 120 seconds → cooled → coated with photocurable coating → fixed → developed;

[0067] The chemical composition of the NTS solution in this embodiment is:

[0068] Nickel sulfate 10 wt%

[0069] Copper sulfate 0.01 wt%

[0070] Sulfuric acid 5 wt%

[0071] Step 2: Electroplating Ni and Au on the conductive contact parts:

[0072] Degreasing → Activation → Nickel electroplating → Gold electroplating in AAB cyanide-free gold electroplating solution → Cleaning → Post-protection → Removal of cured coating (demoulding) → Cleaning → Drying;

[0073] The chemical composition of the AAB gold electroplating solution in this embodiment is:

[0074]

[0075] Among them, the process parameters of the gold electroplating are the commonly used gold electroplating process parameters:

[0076] Voltage: 3.8 - 5.0 V;

[0077] Current density: 0.25 - 1.5 A / cm2.

[0078] Step 3: Pattern etching:

[0079] Coating photosensitive coating → Laser fixing of film negative → Chemical development → Etching with LFGG etching solution → Removal of photosensitive film → Washing → Drying → Trimming → Finished product.

[0080] The composition of the LFGG etching solution is:

[0081]

[0082] Example 2

[0083] The manufacturing method of the foldable and rollable flexible titanium metal component described in this embodiment includes the following steps:

[0084] Step 1: Pressing and shaping process of titanium metal plate:

[0085] Thick titanium metal plate → Immersion in a mixed solution of nickel salt, silver nitrate and dilute acid (NTS solution, the same below) for 6 seconds → Cleaning → Pressing to the set thickness (0.065 - 0.15 mm) under the condition of N2-Ar inert gas environment (atmospheric pressure ≥ 1 atmosphere) at 650 °C and maintaining for 80 seconds → Cooling → Coating with photocurable coating → Fixing → Developing;

[0086] The chemical composition of the NTS solution in this embodiment is:

[0087] Nickel sulfate + nickel nitrate 3 + 3 wt%

[0088] Copper sulfate + copper nitrate 0.02 wt%

[0089] Phosphoric acid 15 wt%

[0090] Second step, electroplating Ni and Au on the conductive contact parts:

[0091] Degreasing → Activation → Nickel electroplating → Gold electroplating in AAB cyanide-free gold electroplating solution → Cleaning → Post-protection → Removal of cured coating (demoulding) → Cleaning → Drying;

[0092] The chemical composition of the AAB gold electroplating solution in this embodiment is:

[0093]

[0094] Among them, the gold electroplating process parameters are general commonly used gold electroplating process parameters:

[0095] Voltage: 3.8 - 5.0 V;

[0096] Current density: 0.25 - 1.5 A / cm 2 .

[0097] Third step, pattern etching:

[0098] Coating photosensitive coating → Laser fixing of film negative → Chemical development → PFSH etching solution → Removal of photosensitive film → Washing → Drying → Trimming → Finished product.

[0099] The composition of the LFGG etching solution is:

[0100]

[0101]

[0102] Example 3

[0103] The manufacturing method of the foldable flexible titanium metal component described in this embodiment includes the following steps:

[0104] First step, pressing and shaping process of titanium metal plate:

[0105] Thick titanium metal plate → Immersion in a mixed solution of nickel salt, silver nitrate and dilute acid (NTS solution, the same below) for 3 - 10 seconds → Cleaning → N2-Ar inert gas environment (atmospheric pressure ≥ 1 atmosphere), pressing to the set thickness (0.065 - 0.15 mm) at 750 °C and maintaining for 30 seconds → Cooling → Coating with photocurable coating → Fixing → Developing;

[0106] The chemical composition of the NTS solution in this embodiment is:

[0107] Nickel chloride 10 wt%

[0108] Copper chloride 0.03 wt%

[0109] Phosphoric acid 25 wt%

[0110] Second step, electroplating Ni and Au on the conductive contact parts:

[0111] Degreasing → Activation → Nickel electroplating → Gold electroplating in AAB cyanide-free gold electroplating solution → Cleaning → Post-protection → Removal of cured coating (demoulding) → Cleaning → Drying;

[0112] The chemical composition of the AAB gold electroplating solution in this embodiment is:

[0113]

[0114] Among them, the electroplating gold process parameters are general commonly used electroplating gold process parameters:

[0115] Voltage: 3.8 - 5.0 V;

[0116] Current density: 0.25 - 1.5 A / cm 2 .

[0117] Third step, pattern etching:

[0118] Coating photosensitive coating → Laser fixing of film negative → Chemical development → PFSH etching solution → Removal of photosensitive film → Washing → Drying → Trimming → Finished product.

[0119] The composition of the LFGG etching solution is:

[0120]

[0121]

[0122] Example 4

[0123] The manufacturing method of the foldable flexible titanium metal part described in this embodiment includes the following steps:

[0124] First step, pressing and shaping process of titanium metal plate:

[0125] Thick titanium metal plate → Immersion in a mixed solution of nickel salt, silver nitrate and dilute acid (NTS solution, the same below) for 3 - 10 seconds → Cleaning → N2-Ar inert gas environment (atmospheric pressure ≥ 1 atmosphere), pressing to the set thickness (0.065 - 0.15 mm) at 550 °C and maintaining for 120 seconds → Cooling → Coating with photocurable coating → Fixing → Developing;

[0126] The chemical composition of the NTS solution in this embodiment is:

[0127] Nickel sulfate 3 wt%

[0128] Copper sulfate 0.01 wt%

[0129] Sulfuric acid 15 wt%

[0130] Step 2: Electroplating Ni and Au on the conductive contact parts:

[0131] Degreasing → Activation → Nickel electroplating → Gold electroplating in the AAB cyanide-free gold electroplating solution → Cleaning → Post-protection → Removal of the cured coating (demoulding) → Cleaning → Drying;

[0132] The chemical composition of the AAB gold electroplating solution in this example is:

[0133]

[0134] Among them, the process parameters for gold electroplating are the commonly used process parameters for gold electroplating:

[0135] Voltage: 3.8 - 5.0 V;

[0136] Current density: 0.25 - 1.5 A / cm 2 。

[0137] Step 3: Pattern etching:

[0138] Coating photosensitive coating → Laser fixing of the film negative → Chemical development → PFSH etching solution → Removal of the photosensitive film → Washing → Drying → Trimming → Finished product.

[0139] The composition of the LFGG etching solution is:

[0140]

[0141]

[0142] Example 5

[0143] The manufacturing method of the foldable flexible titanium metal part described in this example includes the following steps:

[0144] Step 1: Pressing and shaping process of the titanium metal plate:

[0145] Thick titanium metal plate → Immersion in a mixed solution of nickel salt, silver nitrate and dilute acid (NTS solution, the same below) for 3 - 10 seconds → Cleaning → Pressing to the set thickness (0.065 - 0.15 mm) under the condition of N2-Ar inert gas environment (atmospheric pressure ≥ 1 atmosphere) at 650 °C for 80 seconds → Cooling → Coating with photocurable coating → Fixing → Developing;

[0146] The chemical composition of the NTS solution in this example is:

[0147] Nickel sulfate 6 wt%

[0148] Copper sulfate 0.01 wt%

[0149] Sulfuric acid 15 wt%

[0150] Step 2: Electroplating Ni and Au on the conductive contact parts:

[0151] Degreasing → Activation → Nickel electroplating → Gold electroplating in AAB cyanide-free gold electroplating solution → Cleaning → Post-protection → Removal of cured coating (demoulding) → Cleaning → Drying;

[0152] The chemical composition of the AAB gold electroplating solution in this example is:

[0153]

[0154] Among them, the process parameters for gold electroplating are the commonly used process parameters for gold electroplating:

[0155] Voltage: 3.8 - 5.0 V;

[0156] Current density: 0.25 - 1.5 A / cm 2 .

[0157] Step 3: Pattern etching:

[0158] Coating photosensitive coating → Laser fixing of the film negative → Chemical development → PFSH etching solution → Removal of photosensitive film → Washing → Drying → Trimming → Finished product.

[0159] The composition of the LFGG etching solution is:

[0160]

[0161]

[0162] Example 6

[0163] The manufacturing method of the foldable flexible titanium metal component described in this example includes the following steps:

[0164] Step 1: Pressing and shaping process of the titanium metal plate:

[0165] Thick titanium metal plate → Immersion in a mixed solution of nickel salt, silver nitrate and dilute acid (NTS solution, the same below) for 3 - 10 seconds → Cleaning → Pressing to the set thickness (0.065 - 0.15 mm) under the condition of N2-Ar inert gas environment (atmospheric pressure ≥ 1 atm) at 750 °C and maintaining for 30 seconds → Cooling → Coating with photocurable coating → Fixing → Developing;

[0166] The chemical composition of the NTS solution in this example is:

[0167] Nickel nitrate + nickel sulfate + nickel chloride 4 + 3 + 3 wt%

[0168] Copper sulfate + copper nitrate + copper chloride 0.01 + 0.01 + 0.01 wt%

[0169] Sulfuric acid + phosphoric acid 10 + 15 wt%

[0170] Step 2, electroplating Ni and Au on the conductive contact part:

[0171] Degreasing → Activation → Nickel electroplating → Gold electroplating in AAB cyanide-free gold electroplating solution → Cleaning → Post-protection → Removal of cured coating (demoulding) → Cleaning → Drying;

[0172] The chemical composition of the AAB gold electroplating solution in this example is:

[0173]

[0174]

[0175] Among them, the electroplating gold process parameters are general commonly used electroplating gold process parameters:

[0176] Voltage: 3.8 - 5.0 V;

[0177] Current density: 0.25 - 1.5 A / cm 2 .

[0178] Step 3, pattern etching:

[0179] Coating photosensitive coating → Laser fixing of film negative → Chemical development → PFSH etching solution → Removal of photosensitive film → Washing → Drying → Trimming → Finished product.

[0180] The composition of the LFGG etching solution is:

[0181]

[0182]

[0183] Comparative example

[0184] The flexible titanium metal component in this comparative example is manufactured according to the following main process steps:

[0185] Step 1, commercially available 0.15 mm thick titanium metal plate → Degreasing → Water washing → Drying → Coating photocurable coating → Fixing → Developing;

[0186] Step 2, electroplating Ni and Au on the conductive contact part: Degreasing → Activation → Pre-nickel plating → Nickel electroplating → Gold electroplating in cyanide-free gold electroplating solution (using the cyanide-free gold plating solution formula in the literature: Chinese Patent Application No. CN202210467430.9) → Cleaning → Post-protection → Removal of cured coating (demoulding) → Cleaning → Drying;

[0187] The chemical composition of the cyanide-free gold electroplating solution in the comparative example (see: Paragraph

[0051] of Example 1 of Chinese Patent Application No. CN202210467430.9) is as follows:

[0188]

[0189] Sodium gold sulfite with a gold element content of 15 g

[0190] Sodium arsenite with an arsenic content of 10 mg

[0191] Cerium sulfate with a cerium content of 1 mg

[0192] Adjust the pH value to 8.

[0193] Among them, the electroplating gold process parameters are the commonly used electroplating gold process parameters:

[0194] Voltage: 3.8 - 5.0 V;

[0195] Current density: 0.25 - 1.5 A / cm 2 .

[0196] The third step, pattern etching: Coating photosensitive coating → Laser fixing of the film negative → Chemical development → Etching solution (using the etching solution in the document: Chinese Patent Application No. CN202210209699.7) → Removing the photosensitive film → Washing → Drying → Trimming → Finished product.

[0197] The composition and process parameters of the described etching solution (see: Paragraphs

[0028] -

[0033] of the specification of Chinese Patent Application No. CN202210209699.7) are as follows:

[0198]

[0199] See Figures 1-6 As shown, they are titanium metal components manufactured in Examples 1 - 6 respectively. Among Examples 1 - 2, circular fittings are manufactured; among Examples 2 - 4, square fittings are manufactured; among Examples 5 - 6, oval fittings are manufactured. It can be seen that the manufacturing method provided in this application is applicable to the manufacturing of flexible titanium metal fittings of various shapes, and the manufactured titanium metal components have regular shapes, neat and flush etched parts.

[0200] See Appendix Figures 7-9 As described, they are SEM diagrams of the Ni penetration depth of the titanium metal components manufactured in Examples 1, 3, and 6. It can be seen from the figures that the Ni penetration depth is approximately in the range of 3 - 6 nm (see the arrow in Appendix Figures 7-9 ), and the bonding force between the Ni coating and the titanium matrix at the electroplated part is good.

[0201] See the appendix Figure 10 As shown, it is the coating adhesion test diagram of the titanium metal component manufactured in Example 1. This test is carried out according to the cross-cut method (GB / T9286-88). The test results show that the coating adhesion of the titanium metal component manufactured in this example is of grade 5B. Using the same test conditions and test methods to test the coating adhesion of the titanium metal component manufactured in the comparative example, the test results only reach grade 3B. See the appendix Figure 11 , it can be seen that for the flexible titanium metal fittings manufactured by the manufacturing method of the present application, the coating adhesion is significantly improved.

[0202] Based on the above performance tests, it can be concluded that for the flexible titanium metal fittings manufactured by the manufacturing method of the present application, the gold coating Au on its surface is smooth, bright, and closely combined with the nickel coating and the substrate. There are no visible stress deformation marks on the corresponding parts of the titanium substrate. For the square titanium metal component manufactured in the comparative example, its etched shape is relatively irregular, the serrated structure and burr structure are obvious in the etched part, and in some cases, complete etching cannot be completed (the folded part is engraved through). The binding force between the Ni coating and the titanium substrate in the electroplated part is poor, only reaching grade 3B. The surface brightness of the gold coating Au is poor, and it is not closely combined with the nickel coating and the substrate. Obvious visible stress deformation marks can be seen on the corresponding parts of the titanium substrate.

[0203] In summary, for the manufacturing method provided in this application, before titanium metal pressing, it passes through a nickel salt solution. Due to the occurrence of displacement reaction, a certain amount of nickel metal atoms penetrate into the surface layer of titanium metal, forming a titanium-nickel alloy layer. The penetration depth of Ni is about in the range of 3 - 6 nm. Since a Ni-Ti alloy is formed on the surface of titanium metal, there is no need for a pre-electroplating nickel step before electroplating nickel, which can save power consumption and significantly reduce the sewage discharge; at the same time, the formation of the Ni-Ti alloy greatly increases the adhesion between the Ni coating and the Ti metal substrate, and the adhesion level is higher; through electroplating nickel and gold on titanium metal, the corresponding back stress deformation is significantly eliminated. The titanium metal thin plate pressing process undergoes a stress relief annealing treatment process. At the same time, under the dual action of forming a certain Ti-Ni alloy layer on the surface of the titanium metal substrate, the stress change of the titanium metal substrate during the subsequent electroplating of Ni and Au is negligible, and no further chemical etching treatment is required; and due to the use of a phosphate, NaF, persulfate and peroxide etching system, the etching reaction rate of titanium metal can be effectively controlled, which can significantly improve the chemical etching rate of titanium metal and can adjust the etching speed according to requirements; at the same time, due to the presence of nitrite ions, nitrate ions, sulfate ions, phosphate ions, etc., the selective chemical adsorption of these oxyacid root ions on the new surface of metal etching makes the titanium metal etching pattern regular, the boundary neat, regular, without burrs, the etching effect is good, and at the same time, the etching rate is assisted to increase; and by using auxiliary agents such as polyethylene glycol, alkyl sulfate and EDTA, these auxiliary agents change the contact effect between the etched metal surface and the etching solution, and at the same time make the etching reaction products Tin and ionic products and impurity metals Mn and ionic products leave the titanium metal surface, enabling the etching chemical reaction to proceed smoothly and improving the etching effect.

[0204] The manufacturing method provided in this application can conveniently, quickly and efficiently manufacture titanium metal support fittings of various shapes, multiple forms and different thicknesses, as well as fittings made of other metal materials and non-metal materials and applied to flexible display devices and related devices according to requirements, and there is no need to greatly change the production equipment and production process; and the main electroplating solution used in the electroplating gold process is a medium-alkaline cyanide-free electroplating system, and the titanium metal etching solution is also a weak acidic system. The electroplating and etching systems have less pollution to the production environment and the subsequent wastewater treatment process is simple, convenient for recycling and reuse, and can achieve zero pollution discharge, are environmentally friendly, have good economic and environmental effects, and have broad application prospects.

[0205] The above-described embodiments merely represent several implementation manners of the present invention. The description thereof is relatively specific and detailed, but it should not be construed as a limitation to the scope of the patent for the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention shall be subject to the appended claims.

Claims

1. A manufacturing method of a foldable and rollable flexible titanium metal component, characterized in that, It includes the following steps: S1. Pressing and shaping of titanium metal plate Place the thick titanium metal plate in the NTS solution, soak for 3 - 10 seconds, and then wash; Then place it in an N2 - Ar inert gas environment at a temperature of 550 - 750 °C, statically press to the set thickness, and maintain for 30 - 120 seconds; After that, cool naturally, coat with a photocurable coating, fix the image, and develop; S2. Ni and Au electroplating on the conductive contact parts The titanium metal plate in S1 is successively degreased, activated, electroplated with nickel, electroplated with gold in the AAB non - cyanide electroplating solution, washed, post - protected, the cured coating is removed, washed, and dried; S3. Pattern etching Coat the titanium metal plate in S2 with a photosensitive coating, laser - fix the image with a film, chemically develop, etch in the LFGG etching solution, remove the photosensitive film, wash, dry, and trim the edges to obtain the finished product; Among them, the NTS solution in step S1 is a dilute acid mixed solution of nickel salt and copper salt; Among them, the LFGG etching solution in step S3 is composed of phosphate, fluoride, persulfate, and peroxide; Among them, the concentration of nickel salt in the NTS solution is 3 - 10 wt%; the concentration of copper salt is 0.01 - 0.03 wt%; the concentration of dilute acid is 5 - 25 wt%; Among them, the nickel salt in the NTS solution is one or a mixture of nickel nitrate, nickel sulfate, or nickel chloride; the copper salt in the NTS solution is one or a mixture of copper sulfate, copper nitrate, or copper chloride; the dilute acid in the NTS solution is sulfuric acid and / or phosphoric acid solution; The LFGG etching solution in step S3 contains the following components: NaH2PO4 10 - 120 g / L, NaF 25 - 85 g / L, NH4F 5 - 35 g / L, persulfate 5 - 35 g / L, peroxide 3 - 12 g / L, polyethylene glycol 5 - 20 g / L, sodium alkyl sulfate 0.1 - 3 g / L, sodium ethylenediaminetetraacetate 0.1 - 2 g / L, NaNO2 1 - 15 g / L, AgNO3 0.01 - 0.05 g / L.

2. The manufacturing method of the foldable and rollable flexible titanium metal component according to claim 1, characterized in that, In step S1, the N2 - Ar inert gas environment is a mixture system of nitrogen and / or argon pure gas in any proportion, and the N2 - Ar gas pressure is maintained at greater than one atmosphere.

3. The manufacturing method of the foldable and rollable flexible titanium metal component according to claim 1, characterized in that, In step S2, the AAB non - cyanide electroplating solution contains the following components: Tetrachloroaurate(III) 0.5 - 30 g / L, chloride 2 - 100 g / L, disodium iminosuccinate 3 - 60 g / L, n - butylhydantoin 3 - 30 g / L, diol or disulfonate of diacid 0.5 - 3 g / L, acetic acid 3 - 25 g / L, sodium acetate 4 - 30 g / L, sulfite 5 - 35 g / L, and polyethylene glycol 1 - 15 g / L.

4. The manufacturing method of the foldable and rollable flexible titanium metal component according to claim 3, characterized in that, The tetrachloroaurate(III) is a mixture of one or more of sodium tetrachloroaurate(III), potassium tetrachloroaurate(III), and ammonium tetrachloroaurate(III); The chloride salt is a mixture of one or more of sodium chloride, potassium chloride, and ammonium chloride; The diol or disulfonate of diacid is one or a mixture of more than one of sodium ethylene glycol, sodium 1,4-butanediol-2-sulfonate, sodium diethyl sulfosuccinate, and sodium dioctyl sulfosuccinate; The sulfite is one or a mixture of more than one of sodium sulfite, potassium sulfite, and ammonium sulfite; The average molecular weight of the polyethylene glycol is 800 to 4000.

5. The manufacturing method of the foldable and rollable flexible titanium metal component according to claim 3, characterized in that, The pH value of the AAB cyanide-free electroplating solution needs to be adjusted to 7.0 to 12.5 with hydrochloric acid and sodium hydroxide.

6. The manufacturing method of the foldable and rollable flexible titanium metal component according to claim 1, characterized in that, The persulfate is one or a mixture of more than one of K2S2O8, Na2S2O8, and (NH4)2S2O8; The peroxide is one or a mixture of more than one of Na2O2, BaO2, and CaO2; The sodium alkyl sulfate is one or a mixture of more than one of sodium dodecyl sulfate, sodium hexadecyl sulfate, and sodium octadecyl sulfate.

7. The manufacturing method of the foldable and rollable flexible titanium metal component according to claim 1, characterized in that, The solutions described in steps S1, S2, and S3 are all aqueous solutions.

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