Use of tungsten-containing sensitization aids in the preparation of resin compositions that are laser activatable for selective metallization

Abstract

The application provides application of a tungsten-containing sensitization aid in preparation of a resin composition capable of being selectively metalized by laser activation, the tungsten-containing sensitization aid being selected from any one or two or more of tungsten oxide, tungsten sulfide, tungsten-containing acid and tungsten-containing salt, and belongs to the field of laser sensitization aids.The inventor of the application has unexpectedly found that after the resin composition to which the tungsten-containing sensitization aid is added is activated by a laser with a wavelength of 190-1064 nm, chemical copper plating can be well performed on the surface of the resin composition.On one hand, 190-1064 nm almost covers all laser wavelengths, and the resin composition activated under different laser wavelengths can exert the advantages of the laser wavelength itself;on the other hand, the tungsten-containing sensitization aid is more inexpensive than traditional copper-containing and tin-containing sensitization aids, and can significantly reduce production cost.The resin composition of the application can obtain excellent plating layer thickness and plating layer strength under the condition of a lower addition amount of the tungsten-containing sensitization aid, and has excellent industrial application value.

Description

Technical Field

[0001] This invention belongs to the field of laser sensitizing agents, specifically relating to the application of a tungsten-containing sensitizing agent in the preparation of a laser-activated selective metallization resin composition. Background Technology

[0002] Laser-activated selective metallization (LISM) uses a computer to control the movement of a laser along a conductive pattern, projecting the laser onto a molded three-dimensional plastic device. Within seconds, a circuit pattern is activated, and then chemically plated onto the activated surface, depositing metals such as copper, nickel, and gold into the activated area to form conductive lines. This process not only enables highly flexible production but also makes the fabrication and assembly of ultra-fine circuits possible.

[0003] Laser-activated selective metallization (LAM) technology offers advantages such as high production efficiency, low cost, small product size, flexible design, and high conductivity of the metal layer obtained through chemical plating. If the circuit pattern needs to be changed, it can be redesigned via computer without the need for additional masks. Compared to traditional selective metallization methods, LAM offers greater design flexibility, shorter production cycles, and suitability for large-scale production, making it widely used in fields such as communications, electronic equipment, and medical devices.

[0004] Laser-activated selective metallization (LAM) typically involves first activating the surface of the workpiece with a laser, followed by chemical plating to deposit a metal layer in the laser-activated area, thus obtaining the desired metal circuits and patterns. However, most polymers themselves have weak laser absorption, necessitating the addition of specific sensitizing agents to the polymer matrix. Currently, the types of traditional sensitizing agents are quite limited, mainly consisting of compounds containing copper and tin metals, such as copper salts and tin oxides. These are expensive, uneconomical, and produce resin compositions with a single base color. Chinese patent ZL201610154118.9 discloses a bismuth-containing sensitizing agent, primarily consisting of bismuth oxides, bismuth sulfides, bismuth hydroxides, bismuth chlorides, or bismuth salts. This agent is used in lower quantities and produces resin compositions with a lighter base color, partially solving the problem of the plastic's base color being affected. However, the bismuth-containing sensitizing agent can only be activated using a 1064nm near-infrared laser, failing to leverage the advantages of other laser wavelengths.

[0005] To overcome the shortcomings of existing sensitizing agents, it is necessary to develop a laser sensitizing agent that is low in cost, requires small dosage, comes in various colors, can be activated by various laser wavelengths, and has excellent laser activation effect, as well as a laser-activated resin product that has excellent chemical plating effect. Summary of the Invention

[0006] The purpose of this invention is to provide the application of tungsten-containing sensitizing agents in the preparation of laser-activated selective metallization resin compositions, as well as a laser-activated selective metallization resin composition and a laser-activated resin product with excellent further chemical plating effect.

[0007] This invention provides the application of a tungsten-containing sensitizing agent in the preparation of a laser-activated selective metallization resin composition. The tungsten-containing sensitizing agent is selected from any one or more of tungsten oxides, tungsten sulfides, tungsten-containing acids, and tungsten-containing salts. The laser activation is performed using a 190-1064 nm wavelength laser.

[0008] Furthermore, the tungsten oxide is selected from WO3, WO4, and WO3. 2.8-2.97 WO 2.6-2.77 WO2, tungsten bronze, molybdenum-doped tungsten oxide, tantalum-doped tungsten oxide, cesium-doped tungsten oxide, sodium-doped tungsten oxide, potassium-doped tungsten oxide, titanium-doped tungsten oxide, and indium-doped tungsten oxide, preferably WO3 or WO4. 2.8-2.97 WO 2.6-2.77 WO2 or tungsten bronze;

[0009] And / or, the sulfide of said tungsten is tungsten disulfide;

[0010] And / or, the tungsten-containing acid is any one or more of tungstic acid, phosphotungstic acid, and silicotungstic acid;

[0011] And / or, the tungsten-containing salt is selected from any one or more of tungsten phosphate, tungsten sulfate, tungsten nitrate, tungsten silicate, tungsten carbonate, tungsten aluminate, tungsten bismuthate, ammonium paratungstate, ammonium metatungstate, sodium tungstate, potassium tungstate, cesium tungstate, calcium tungstate, bismuth tungstate, nickel tungstate, zinc tungstate, lithium tungstate, molybdenum tungstate, lead tungstate, sodium phosphotungstate, and niobium tungstate.

[0012] The present invention also provides a laser-activated selective metallization resin composition, which is composed of the following components in weight percentage: 0.5% to 55% tungsten-containing sensitizing agent and 45% to 99.5% polymer; wherein the tungsten-containing sensitizing agent is selected from any one or more of tungsten oxides, tungsten sulfides, tungsten-containing acids, and tungsten-containing salts.

[0013] Further, it is composed of the following components by weight percentage: 5% to 50% tungsten sensitizing agent and 50% to 95% polymer; preferably, it is composed of the following components by weight percentage: 10% to 20% tungsten sensitizing agent and 80% to 90% polymer.

[0014] Furthermore, the tungsten oxide is selected from WO3, WO4, and WO3. 2.8-2.97 WO 2.6-2.77WO2, tungsten bronze, molybdenum-doped tungsten oxide, tantalum-doped tungsten oxide, cesium-doped tungsten oxide, sodium-doped tungsten oxide, potassium-doped tungsten oxide, titanium-doped tungsten oxide, and indium-doped tungsten oxide, preferably WO3 or WO4. 2.8-2.97 WO 2.6-2.77 WO2 or tungsten bronze;

[0015] And / or, the sulfide of said tungsten is tungsten disulfide;

[0016] And / or, the tungsten-containing acid is any one or more of tungstic acid, phosphotungstic acid, and silicotungstic acid;

[0017] And / or, the tungsten-containing salt is selected from any one or more of tungsten phosphate, tungsten sulfate, tungsten nitrate, tungsten silicate, tungsten carbonate, tungsten aluminate, tungsten bismuthate, ammonium paratungstate, ammonium metatungstate, sodium tungstate, potassium tungstate, cesium tungstate, calcium tungstate, bismuth tungstate, nickel tungstate, zinc tungstate, lithium tungstate, molybdenum tungstate, lead tungstate, sodium phosphotungstate, and niobium tungstate.

[0018] Further, the average particle size of the tungsten-containing sensitizing agent is less than or equal to 150 μm; preferably, the average particle size of the tungsten-containing sensitizing agent is 0.005 μm to 50 μm; more preferably, the average particle size of the tungsten-containing sensitizing agent is 0.02 μm to 20 μm.

[0019] Further, the polymer is selected from any one or more of polycarbonate, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polypropylene, polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyurethane, polyester elastomer, polystyrene, K resin, styrene-acrylonitrile copolymer, PEN, polyphenylene ether, polyphenylene sulfide, polyetheretherketone, polyurethane, nylon elastomer, SEBS, SEPS, SEEPS, and polyester elastomer.

[0020] The present invention also provides a method for preparing the above-mentioned laser-activated selective metallization resin composition, which includes the following steps:

[0021] a. Take the tungsten-containing sensitizing agent and the polymer, mix them well to obtain a mixture;

[0022] b. Melt-blend the mixture obtained in step a, granulate it, and you will get a resin composition that can be selectively metallized by laser activation.

[0023] The present invention also provides the application of the above-described laser-activated selective metallizable resin composition in the preparation of microfabricated materials, including microcircuit materials.

[0024] The present invention also provides a microcircuit material, which is formed by selectively activating the above-mentioned resin composition under a laser with a wavelength of 190-1064nm, followed by chemical plating to deposit a conductive metal in the activated region; preferably, the conductive metal is copper, nickel or gold.

[0025] Experimental results show that the tungsten-containing sensitizing agent of the present invention requires a small amount of additive, which can significantly reduce the production cost of laser-activated selective metallization products. The tungsten-containing sensitizing agent of the present invention comes in various colors and, after processing with polymers, can be used to formulate laser-activated selective metallization resin compositions with different base colors, suitable for various application scenarios.

[0026] The tungsten-containing sensitizing agent of this invention exhibits excellent laser activation ability under laser action in the wavelength range of 190-1064nm. The laser-activated selective metallizable resin obtained has good chemical plating effect after activation. With an addition amount as low as 0.5wt%, the coating thickness of the obtained resin composition reaches more than 2μm, and the coating strength reaches the highest level of 5B in cross-cut test (ASTM D3359). It has a very broad application prospect.

[0027] Obviously, based on the above description of the present invention, and according to common technical knowledge and conventional methods in the field, various other modifications, substitutions or alterations can be made without departing from the basic technical concept of the present invention.

[0028] The following detailed embodiments further illustrate the above-described content of the present invention. However, this should not be construed as limiting the scope of the present invention to the following examples. All technologies implemented based on the above-described content of the present invention fall within the scope of the present invention. Detailed Implementation

[0029] The raw materials and equipment used in the specific embodiments of the present invention are all known products, obtained by purchasing commercially available products.

[0030] (1) The equipment information used in this invention is as follows:

[0031] Twin-screw extruder, screw diameter 35mm, screw length-to-diameter ratio 36:1, manufactured by Nanjing J&T Electromechanical Co., Ltd.

[0032] Injection molding machine, model MA600, manufactured by Haitian Machinery Co., Ltd.

[0033] Laser marking machine, model MUV-ER, pulsed laser marking machine, maximum laser power 5W, laser wavelength 355nm;

[0034] Laser marking machine, model MV-U, pulsed laser marking machine, maximum laser power 3W, laser wavelength 190nm;

[0035] Laser marking machine, model DZ-Q, pulsed laser marking machine, maximum laser power 8W, laser wavelength 395nm;

[0036] Laser marking machine, model MF-EA, fiber pulse laser marking machine, maximum laser power 20W, laser wavelength 1064nm;

[0037] Laser marking machine, model YK-F20G, fiber pulse laser marking machine, maximum laser power 10W, laser wavelength 532nm.

[0038] (2) The specific information of the matrix polymer used in this invention to prepare the standard sample is as follows:

[0039] Polycarbonate: General Electric Company, USA, PC121R (density: 1.2 g / cm3; melt flow rate: 17.5 g / 10 min, 300℃, 1.2 kg; heat distortion temperature: 125℃).

[0040] Acrylonitrile-butadiene-styrene (ABS): Chi Mei Corporation, Taiwan, PA757 (density: 1.05 g / cm3; melt flow rate: 1.8 g / 10 min, 200℃, 5 kg).

[0041] Polystyrene: Dushan Petrochemical, GPPS-500 (density: 1.04 g / cm3; melt flow rate: 5 g / 10 min, 200℃, 5 kg; heat distortion temperature: 89℃).

[0042] Polyethylene terephthalate: Far Eastern Textile Industry, CB-602 (density: 1.40 g / cm3; melting temperature: 245℃).

[0043] Polybutylene terephthalate: BASF, Germany, PBTB4500 (density: 1.3 g / cm3; melt temperature: 230℃).

[0044] SEBS: Kuraray Japan, HYBRA7311F (Density: 0.89 g / cm3; Melting temperature: 200℃).

[0045] Polyamide 66: Lanxess, Germany, A30S (density: 1.14 g / cm3; melt temperature: 260℃).

[0046] Polypropylene: Daqing Petrochemical, T30S (density: 0.9 g / cm3; melting temperature: 189℃)

[0047] Polyethylene (PE): Maoming Petrochemical, TR144, a high-density polyethylene (density: 0.95 g / cm3; melt temperature: 142℃).

[0048] Polyurethane: Bayer, Germany, 9385 (density 1.005 g / cm3, melt temperature: 170℃)

[0049] Polyester elastomer: KP3355 (density 1.06 g / cm3, melt temperature: 170℃), from Kolon, South Korea.

[0050] Example 1

[0051] First, 99.5g of polypropylene resin and 0.5g of laser sensitizing agent WO3 powder (average particle size of 0.15μm) are thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material is placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature is 190℃ to obtain a resin composition that can be selectively metallized by laser activation.

[0052] Then, the prepared laser-activated selective metallizable resin composition is injection molded into plastic sheets using an injection molding machine at an injection temperature of 190°C.

[0053] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed near-infrared laser, laser wavelength of 1064nm, speed of 2000mm / s, laser energy of 16W, and laser frequency of 60kHz.

[0054] According to the well-known laser-activated selective metallization resin composition chemical plating method and process, the laser-activated plastic sheet is chemically plated with copper. Copper sulfate is used as the copper salt for chemical copper plating. The resin composition is placed in the chemical copper plating solution to react and plate copper. Air is continuously introduced and stirred in the middle to ensure the uniformity of the copper layer.

[0055] After electroless copper plating, the following effect and / or performance tests are conducted:

[0056] (1) Chemical plating effect: visual inspection;

[0057] (2) Coating thickness of electroless copper plating: tested according to ASTM B568 (2009);

[0058] (3) Cross-cut adhesion test: According to ASTM D3359, a 1mm × 1mm square grid is drawn on the copper-plated area using a cross-cutting tool. Then, Scotch 3M 600-1PK test tape is applied to the grid area and quickly peeled off. The adhesion strength grade is determined based on the area of ​​copper plating detached. In the ASTM D3359 grading standard, a higher grade indicates stronger adhesion between the polymer substrate and the copper plating. Specifically:

[0059] The peeling area of ​​the 0B mesh is greater than 65%;

[0060] The peeling area of ​​1B grid is 35%-65%;

[0061] The peeling area of ​​2B grids is 15%-35%;

[0062] The peeling area of ​​3B mesh is 5%-15%;

[0063] The peeling area of ​​the 4B grid is 5%;

[0064] 5B has no mesh peeling.

[0065] The experimental results are shown in Table 1.

[0066] Example 2

[0067] A laser-activated selective metallizable resin composition and a laser-activated plastic sheet were prepared according to the method of Example 1, the only difference being the use of the matrix polymer and the laser sensitizing agent: 95g of polypropylene resin and 5g of laser sensitizing agent WO3 powder.

[0068] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0069] Example 3

[0070] A laser-activated selective metallizable resin composition and a laser-activated plastic sheet were prepared according to the method of Example 1, the only difference being the matrix polymer and the laser sensitizing agent used: 90g of polypropylene resin and 10g of laser sensitizing agent WO3 powder.

[0071] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0072] Example 4

[0073] A laser-activated selective metallizable resin composition and a laser-activated plastic sheet were prepared according to the method of Example 1, the only difference being the use of the matrix polymer and the laser sensitizing agent: 80g of polypropylene resin and 20g of laser sensitizing agent WO3 powder.

[0074] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0075] Example 5

[0076] 99.5g of polypropylene resin and laser sensitizing agent WO 2.8-2.97 0.5 g of powder (average particle size 0.2 μm) was thoroughly mixed in a high-speed mixer for 3 minutes; then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 195 °C to obtain a laser-activated selective metallization resin composition.

[0077] The prepared laser-activated selective metallization resin composition was injection molded into plastic sheets using an injection molding machine at an injection temperature of 190°C.

[0078] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed ultraviolet laser, laser wavelength of 355nm, speed of 2000mm / s, laser energy of 3W, and laser frequency of 60kHz.

[0079] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0080] Example 6

[0081] The laser-activated selective metallizable resin composition and laser-activated plastic sheet were prepared according to the method of Example 5, the only difference being the matrix polymer and the laser sensitizing agent used: 95g of polypropylene resin and WO2 laser sensitizing agent. 2.8-2.97 5g of powder.

[0082] The experimental method was the same as in Example 5, and the experimental results are shown in Table 1.

[0083] Example 7

[0084] The laser-activated selective metallizable resin composition and laser-activated plastic sheet were prepared according to the method of Example 5, the only difference being the matrix polymer and the laser sensitizing agent used: 90g of polypropylene resin and WO2 laser sensitizing agent. 2.8-2.97 10g of powder.

[0085] The experimental method was the same as in Example 5, and the experimental results are shown in Table 1.

[0086] Example 8

[0087] 98g of polyethylene resin and laser sensitizing agent WO 2.6-2.77 2g of powder (average particle size 0.65μm) was thoroughly mixed in a high-speed mixer for 3 minutes; then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 160℃ to obtain a laser-activated selective metallization resin composition.

[0088] The prepared laser-activated selective metallization resin composition was injection molded into plastic sheets using an injection molding machine at an injection temperature of 160°C.

[0089] The above-mentioned plastic sheet was laser activated under the following conditions: green laser, laser wavelength of 532nm, speed of 2000mm / s, laser energy of 6W, and laser frequency of 60kHz.

[0090] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0091] Example 9

[0092] A laser-activated selective metallizable resin composition and a laser-activated plastic sheet were prepared according to the method of Example 8, the only difference being the matrix polymer and the laser sensitizing agent used: 95g of polyethylene resin and WO3 laser sensitizing agent. 2.6-2.77 5g of powder.

[0093] The test method was the same as in Example 8, and the test results are shown in Table 1.

[0094] Example 10

[0095] A laser-activated selective metallizable resin composition and a laser-activated plastic sheet were prepared according to the method of Example 8, the only difference being the matrix polymer and the laser sensitizing agent used: 90g of polyethylene and WO3 laser sensitizing agent. 2.6-2.77 10g of powder.

[0096] The test method was the same as in Example 8, and the test results are shown in Table 1.

[0097] Example 11

[0098] 95g of SEBS resin and WO2 laser sensitizing agent powder (average particle size 0.8g).

[0099] 5g of (μm) was thoroughly mixed in a high-speed mixer for 3 minutes; then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature was 200℃, which yielded a resin composition that could be selectively metallized by laser activation.

[0100] The prepared laser-activated selective metallization resin composition was injection molded into plastic sheets using an injection molding machine at an injection temperature of 195°C.

[0101] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed ultraviolet laser, laser wavelength of 395nm, speed of 2000mm / s, laser energy of 5W, and laser frequency of 60kHz.

[0102] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0103] Example 12

[0104] A laser-activated selective metallizable resin composition and a laser-activated plastic sheet were prepared according to the method of Example 11, the only difference being the matrix polymer and the laser sensitizing agent used: 90g of SEBS resin and 10g of laser sensitizing agent WO2 powder.

[0105] The test method was the same as in Example 11, and the test results are shown in Table 1.

[0106] Example 13

[0107] 95g of polyethylene terephthalate resin and 5g of laser-sensitizing agent tungsten bronze powder (average particle size of 1μm) were thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature was 240℃ to obtain a resin composition that can be selectively metallized by laser activation.

[0108] The prepared laser-activated selective metallization resin composition was injection molded into plastic sheets using an injection molding machine at an injection temperature of 240℃.

[0109] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed ultraviolet laser, laser wavelength of 355nm, speed of 2000mm / s, laser energy of 3W, and laser frequency of 60kHz.

[0110] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0111] Example 14

[0112] A laser-activated selective metallizable resin composition and a laser-activated plastic sheet were prepared according to the method of Example 13, the only difference being the matrix polymer and the laser sensitizing agent used: 90g of polyethylene terephthalate resin and 10g of tungsten bronze powder as the laser sensitizing agent.

[0113] The test method was the same as in Example 13, and the test results are shown in Table 1.

[0114] Example 15

[0115] 95g of polystyrene resin and 5g of molybdenum-doped tungsten oxide powder (average particle size of 1μm) as a laser sensitizing agent were thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature was 160℃ to obtain a resin composition that can be selectively metallized by laser activation.

[0116] The prepared laser-activated selective metallization resin composition was injection molded into plastic sheets using an injection molding machine at an injection temperature of 160°C.

[0117] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed laser, laser wavelength of 190nm, speed of 2000mm / s, laser energy of 2W, and laser frequency of 60kHz.

[0118] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0119] Example 16

[0120] A laser-activated selective metallizable resin composition and a laser-activated plastic sheet were prepared according to the method of Example 15, the only difference being the use of the matrix polymer and the laser sensitizing agent: 90g of polystyrene resin and 10g of molybdenum-doped tungsten oxide powder as the laser sensitizing agent.

[0121] The test method was the same as in Example 15, and the test results are shown in Table 1.

[0122] Example 17

[0123] 90g of polybutylene terephthalate resin and 10g of tantalum-doped tungsten oxide powder (average particle size of 0.75μm) as a laser sensitizing agent were thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature was 265℃ to obtain a resin composition that can be selectively metallized by laser activation.

[0124] The prepared laser-activated selective metallization resin composition was injection molded into plastic sheets using an injection molding machine at an injection temperature of 260℃.

[0125] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed near-infrared laser, laser wavelength of 1064nm, speed of 2000mm / s, laser energy of 10W, and laser frequency of 60kHz.

[0126] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0127] Example 18

[0128] A laser-activated selective metallizable resin composition and a laser-activated plastic sheet were prepared according to the method of Example 17, the only difference being the matrix polymer and the laser sensitizing agent used: 80g of polybutylene terephthalate resin and 20g of tantalum-doped tungsten oxide powder as the laser sensitizing agent.

[0129] The test method was the same as in Example 17, and the test results are shown in Table 1.

[0130] Example 19

[0131] 90g of polycarbonate resin and 10g of cesium-doped tungsten oxide powder (average particle size of 1μm) as a laser sensitizing agent were thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature was 265℃ to obtain a resin composition that can be selectively metallized by laser activation.

[0132] The prepared laser-activated selective metallization resin composition was injection molded into plastic sheets using an injection molding machine at an injection temperature of 260℃.

[0133] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed laser, laser wavelength of 190nm, speed of 2000mm / s, laser energy of 2W, and laser frequency of 60kHz.

[0134] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0135] Example 20

[0136] A laser-activated selective metallizable resin composition and a laser-activated plastic sheet were prepared according to the method of Example 19, the only difference being the matrix polymer and the laser sensitizing agent used: 80g of polycarbonate resin and 20g of cesium-doped tungsten oxide powder as the laser sensitizing agent.

[0137] The test method was the same as in Example 19, and the test results are shown in Table 1.

[0138] Example 21

[0139] 90g of ABS resin and 10g of tungsten disulfide powder (average particle size of 0.5μm) as a laser sensitizing agent were thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature was 205℃ to obtain a resin composition that can be selectively metallized by laser activation.

[0140] The prepared laser-activated selective metallizable resin composition was injection molded into plastic sheets using an injection molding machine at an injection temperature of 210℃.

[0141] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed ultraviolet laser, laser wavelength of 395nm, speed of 2000mm / s, laser energy of 6W, and laser frequency of 60kHz.

[0142] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0143] Example 22

[0144] A laser-activated selective metallizable resin composition and a laser-activated plastic sheet were prepared according to the method of Example 21, the only difference being the matrix polymer and the laser sensitizing agent used: 80g of ABS resin and 20g of tungsten disulfide powder as the laser sensitizing agent.

[0145] The test method was the same as in Example 21, and the test results are shown in Table 1.

[0146] Example 23

[0147] 90g of polyamide 66 resin and 10g of laser-sensitizing tungstic acid powder (average particle size of 2μm) were thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature was 215℃ to obtain a resin composition that can be selectively metallized by laser activation.

[0148] The prepared laser-activated selective metallization resin composition was injection molded into plastic sheets using an injection molding machine at an injection temperature of 265°C.

[0149] The above-mentioned plastic sheet was laser activated under the following conditions: green laser, laser wavelength of 532nm, speed of 2000mm / s, laser energy of 6W, and laser frequency of 60kHz.

[0150] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0151] Example 24

[0152] A laser-activated selective metallizable resin composition and a laser-activated plastic sheet were prepared according to the method of Example 23, the only difference being the use of the matrix polymer and the laser sensitizing agent: 80g of polyamide 66 resin and 20g of tungstic acid powder as the laser sensitizing agent.

[0153] The test method was the same as in Example 23, and the test results are shown in Table 1.

[0154] Example 25

[0155] 90g of polyurethane resin and 10g of sodium tungstate powder (average particle size of 2μm), a laser sensitizing agent, are thoroughly mixed in a high-speed mixer for 3 minutes. Then, the mixed material is placed in a twin-screw extruder for melt extrusion and granulation. The extrusion temperature is 190℃ to obtain a resin composition that can be selectively metallized by laser activation.

[0156] The prepared laser-activated selective metallization resin composition was injection molded into plastic sheets using an injection molding machine at an injection temperature of 190°C.

[0157] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed near-infrared laser, laser wavelength of 1064nm, speed of 2000mm / s, laser energy of 10W, and laser frequency of 60kHz.

[0158] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0159] Example 26

[0160] A laser-activated selective metallizable resin composition and a laser-activated plastic sheet were prepared according to the method of Example 25, the only difference being the matrix polymer and the laser sensitizing agent used: 80g of polyurethane resin and 20g of sodium tungstate powder as the laser sensitizing agent.

[0161] The test method was the same as in Example 25, and the test results are shown in Table 1.

[0162] Example 27

[0163] 90g of polyester elastomer resin and 10g of laser sensitizing agent calcium tungstate powder (average particle size of 2μm) are thoroughly mixed in a high-speed mixer for 3 minutes; then, the mixed material is placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 190℃ to obtain a resin composition that can be selectively metallized by laser activation.

[0164] The prepared laser-activated selective metallization resin composition was injection molded into plastic sheets using an injection molding machine at an injection temperature of 185°C.

[0165] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed ultraviolet laser, laser wavelength of 355nm, speed of 2000mm / s, laser energy of 2.5W, and laser frequency of 60kHz.

[0166] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0167] Example 28

[0168] A laser-activated selective metallizable resin composition and a laser-activated plastic sheet were prepared according to the method of Example 27, the only difference being the matrix polymer and the laser sensitizing agent used: 80g of polyester elastomer resin and 20g of calcium tungstate powder as laser sensitizing agent.

[0169] The test method was the same as in Example 27, and the test results are shown in Table 1.

[0170] Comparative Example 1

[0171] A laser-activated selective metallization resin composition and plastic sheet were prepared according to the method of Example 1, the difference being that the matrix polymer and laser sensitizing agent used were: 99.75g of polypropylene resin and 0.25g of laser sensitizing agent WO3 powder.

[0172] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed near-infrared laser, laser wavelength of 1064nm, speed of 2000mm / s, laser energy of 16W, and laser frequency of 60kHz.

[0173] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0174] Comparative Example 2

[0175] A laser-activated selective metallization resin composition and plastic sheet were prepared according to the method of Example 1, the difference being that the matrix polymer and laser sensitizing agent used were: 99.75g of polypropylene resin and WO3 laser sensitizing agent. 2.8-2.97 0.25g of powder.

[0176] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed ultraviolet laser, laser wavelength of 355nm, speed of 2000mm / s, laser energy of 3W, and laser frequency of 60kHz.

[0177] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0178] Comparative Example 3

[0179] Plastic sheets were prepared according to the method in Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100g of polypropylene resin.

[0180] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed near-infrared laser, laser wavelength of 1064m, velocity of 2000mm / s, laser energy of 16W, and laser frequency of 60kHz.

[0181] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0182] Comparative Example 4

[0183] Plastic sheets were prepared according to the method in Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100g of polypropylene resin.

[0184] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed ultraviolet laser, laser wavelength of 355nm, speed of 2000mm / s, laser energy of 3W, and laser frequency of 60kHz.

[0185] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0186] Comparative Example 5

[0187] Plastic sheets were prepared according to the method in Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100g of polyethylene resin.

[0188] The above-mentioned plastic sheet was laser activated under the following conditions: green laser, laser wavelength of 532nm, speed of 2000mm / s, laser energy of 6W, and laser frequency of 60kHz.

[0189] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0190] Comparative Example 6

[0191] Plastic sheets were prepared according to the method in Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100g of SEBS resin.

[0192] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed ultraviolet laser, laser wavelength of 395nm, speed of 2000mm / s, laser energy of 5W, and laser frequency of 60kHz.

[0193] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0194] Comparative Example 7

[0195] Plastic sheets were prepared according to the method of Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100g of polyethylene terephthalate resin.

[0196] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed ultraviolet laser, laser wavelength of 355nm, speed of 2000mm / s, laser energy of 3W, and laser frequency of 60kHz.

[0197] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0198] Comparative Example 8

[0199] Plastic sheets were prepared according to the method in Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100g of polystyrene resin.

[0200] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed laser, laser wavelength of 190nm, speed of 2000mm / s, laser energy of 2W, and laser frequency of 60kHz.

[0201] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0202] Comparative Example 9

[0203] Plastic sheets were prepared according to the method of Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100g of polybutylene terephthalate resin.

[0204] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed near-infrared laser, laser wavelength of 1064nm, speed of 2000mm / s, laser energy of 10W, and laser frequency of 60kHz.

[0205] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0206] Comparative Example 10

[0207] Plastic sheets were prepared according to the method in Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100g of polycarbonate resin.

[0208] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed laser, laser wavelength of 190nm, speed of 2000mm / s, laser energy of 2W, and laser frequency of 60kHz.

[0209] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0210] Comparative Example 11

[0211] Plastic sheets were prepared according to the method in Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100g of ABS resin.

[0212] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed ultraviolet laser, laser wavelength of 395nm, speed of 2000mm / s, laser energy of 6W, and laser frequency of 60kHz.

[0213] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0214] Comparative Example 12

[0215] Plastic sheets were prepared according to the method in Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100g of polyamide 66 resin.

[0216] The above-mentioned plastic sheet was laser activated under the following conditions: green laser, laser wavelength of 532nm, speed of 2000mm / s, laser energy of 6W, and laser frequency of 60kHz.

[0217] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0218] Comparative Example 13

[0219] Plastic sheets were prepared according to the method in Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100g of polyurethane resin.

[0220] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed near-infrared laser, laser wavelength of 1064nm, speed of 2000mm / s, laser energy of 10W, and laser frequency of 60kHz.

[0221] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0222] Comparative Example 14

[0223] Plastic sheets were prepared according to the method in Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100g of polyester elastomer resin.

[0224] The above-mentioned plastic sheet was laser activated under the following conditions: pulsed ultraviolet laser, laser wavelength of 355nm, speed of 2000mm / s, laser energy of 2.5W, and laser frequency of 60kHz.

[0225] The test methods for effects and / or performance are the same as those in Example 1, and the test results are shown in Table 1.

[0226] Table 1. Key parameters and test results of Examples 1-28 and Comparative Examples 1-15

[0227]

[0228]

[0229]

[0230] The results show that using lasers with wavelengths in the range of 190-1064 nm to activate resin compositions containing tungsten sensitizing agents has a good activation effect and allows for excellent chemical plating of metal layers on their surfaces.

[0231] The tungsten-containing sensitizing agent of this invention, even at an addition amount as low as 0.5 wt%, produces a coating thickness of over 2 μm in the resulting resin composition, and the coating strength reaches the highest level of 5B in cross-cut adhesion testing (ASTM D3359), making it highly suitable for industrial production applications. Furthermore, the resin compositions prepared using the tungsten-containing sensitizing agent of this invention offer a variety of base color options, making them suitable for use in diverse applications.

[0232] In summary, this invention provides the application of tungsten-containing sensitizing agents in the preparation of laser-activated selective metallization resin compositions, as well as a laser-activated selective metallization resin composition and a laser-activated resin product with excellent further electroless plating performance. The inventors unexpectedly discovered that using a laser with a wavelength of 190-1064 nm to activate a resin composition containing a tungsten-containing sensitizing agent allows for excellent electroless copper plating on its surface. On one hand, 190-1064 nm covers almost all laser wavelengths, allowing the resin composition to leverage the inherent advantages of different laser wavelengths. On the other hand, tungsten-containing sensitizing agents come in various colors, and after processing with polymers, they can be used to create laser-activated selective metallization resin compositions with different base colors, suitable for various applications. Furthermore, tungsten-containing sensitizing agents are significantly cheaper than traditional copper- and tin-containing sensitizing agents, thus reducing production costs. This invention achieves resin compositions with excellent plating thickness and strength even with relatively low tungsten-containing sensitizing agent addition, demonstrating excellent industrial application value.

Claims

1. The application of a tungsten-containing sensitizing agent in the preparation of resin compositions for laser-activated selective metallization processes, characterized in that: The tungsten-containing sensitizing agent is selected from any one or more of tungsten oxides, tungsten sulfides, tungsten-containing acids, and tungsten-containing salts; the laser activation is performed using a 190-1064nm wavelength laser. The laser-activated selective metallization resin composition comprises the following components by weight percentage: 0.5%–55% tungsten sensitizing agent and 45%–99.5% polymer; The tungsten oxide is selected from any one or more of tungsten bronze, molybdenum-doped tungsten oxide, tantalum-doped tungsten oxide, and cesium-doped tungsten oxide. The tungsten sulfide is tungsten disulfide; The tungsten-containing acid is tungstic acid; The tungsten-containing salt is selected from any one or two of sodium tungstate and calcium tungstate.

2. The application as described in claim 1, characterized in that: The tungsten oxide is tungsten bronze.

3. The application as described in claim 1, characterized in that: The laser-activated selective metallization resin composition comprises the following components by weight percentage: 5%–50% tungsten sensitizing agent and 50%–95% polymer.

4. The application as described in claim 3, characterized in that: The laser-activated selective metallization resin composition comprises the following components by weight percentage: 10%–20% tungsten-containing sensitizing agent and 80%–90% polymer.

5. The application according to claim 1, characterized in that: The average particle size of the tungsten-containing sensitizing agent is less than or equal to 150 μm.

6. The application according to claim 5, characterized in that: The average particle size of the tungsten-containing sensitizing agent is 0.005 μm to 50 μm.

7. The application according to claim 6, characterized in that: The average particle size of the tungsten-containing sensitizing agent is 0.02 μm to 20 μm.

8. The application according to claim 1, characterized in that: The polymer is selected from any one or more of polycarbonate, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polypropylene, polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyurethane, polyester elastomer, polystyrene, K resin, PEN, polyphenylene ether, polyphenylene sulfide, polyether ether ketone, SEBS, SEPS, SEEPS.

9. The application according to claim 8, characterized in that: The polyamide is a nylon elastomer.

10. The application according to claim 1, characterized in that: The method for preparing the laser-activated selective metallization resin composition includes the following steps: a. Take the tungsten-containing sensitizing agent and the polymer, mix them well to obtain a mixture; b. Melt-blend the mixture obtained in step a, granulate it, and you will get a resin composition that can be selectively metallized by laser activation.

11. A method for preparing microcircuit materials, characterized in that: The method involves selectively activating the resin composition according to any one of claims 1-10 under a laser with a wavelength of 190-1064 nm, followed by chemical plating to deposit conductive metal in the activated area.

12. The method according to claim 11, characterized in that: The conductive metal is copper, nickel, or gold.

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