CN113912976B - Application of molybdenum-containing sensitization auxiliary in laser activation selective metallization process of resin composition - Google Patents

Abstract

The invention provides an application of a molybdenum-containing sensitization auxiliary in preparing a resin composition capable of being selectively metallized by laser activation, wherein the molybdenum-containing sensitization auxiliary is selected from any one or more than two of molybdenum oxide, molybdenum sulfide, molybdenum hydroxide, molybdenum acid and molybdenum salt. The inventors of the present invention have unexpectedly found that electroless copper plating can be performed well on the surface of a resin composition containing a molybdenum-containing sensitizing assistant added thereto by activation with a laser having a wavelength of 190 to 1064 nm. On the one hand, 190-1064nm covers almost all laser wavelengths, and activating the resin composition at different laser wavelengths can exert the advantages of the laser wavelengths themselves; on the other hand, compared with the traditional sensitization auxiliary containing copper, tin and bismuth, the molybdenum-containing sensitization auxiliary has lower price, and can obviously reduce the production cost. The invention can obtain the resin composition with excellent coating thickness and coating strength under the condition of lower molybdenum-containing sensitization auxiliary addition amount, and has excellent industrial application value.

Description

Application of molybdenum-containing sensitizing agents in laser-activated selective metallization of resin compositions

Technical Field

The invention belongs to the field of laser sensitization aids, and in particular relates to application of a molybdenum-containing sensitization aid in preparing a laser-activated selectively metallized resin composition.

Background Art

Laser activated selective metallization (LISM) uses a computer to control the movement of the laser according to the trajectory of the conductive pattern, and projects the laser onto the molded three-dimensional plastic device. In a few seconds, the circuit pattern is activated, and then the activated surface is chemically plated so that metals such as copper, nickel, and gold are deposited in the activated area to form a conductive circuit. This process can not only achieve high-flexibility production, but also make ultra-fine circuit manufacturing and fine assembly possible.

Laser activated selective metallization technology has the advantages of high production efficiency, low cost, small product size, flexible design, and high conductivity of the metal layer obtained by chemical plating. If you want to change the circuit pattern, you only need to redesign the circuit pattern through a computer without the need for an additional mask. Compared with traditional selective metallization methods, laser-induced activated selective metallization has the characteristics of flexible design, short production cycle, and suitability for large-scale production. It is widely used in communications, electronic equipment, medical equipment and other fields. In particular, with the popularization of 5G communications, traditional FRPC antennas and PDS antennas can no longer meet the performance requirements of 5G mobile phones, and almost all smartphones are using LISM antennas.

The laser activated selective metallization process usually uses a laser to activate the surface of the workpiece first, and then uses chemical plating to deposit a metal layer in the laser activated area to obtain the required metal circuit and pattern. However, most polymers have weak laser absorption and need to add specific sensitizing agents, which can absorb laser energy and induce chemical plating. At present, the types of traditional sensitizing agents are quite limited, mainly compounds containing copper and tin metals, such as copper-containing salts and tin-containing oxides, which are expensive and have poor economic efficiency. Chinese patent ZL201610154118.9 discloses a bismuth-containing sensitizing agent, mainly bismuth oxide, bismuth sulfide, bismuth hydroxide, bismuth chloride oxide or bismuth salt, which has a low dosage and the prepared resin composition containing bismuth sensitizing agent has a lighter background color, which solves the problem of plastic background color being affected to a certain extent, but the price of bismuth-containing compounds is high, and the economic benefits need to be further improved. Moreover, the bismuth-containing sensitizing agent can only be activated by 1064nm near-infrared laser, and cannot play the advantages of lasers of other wavelengths.

In order to overcome the defects of existing sensitizing agents, it is necessary to develop a laser sensitizing agent with low cost, small addition amount, diverse activatable laser wavelengths, and excellent laser activation effect, as well as a laser-activatable resin product with excellent chemical plating effect.

Summary of the invention

The purpose of the present invention is to provide an application of a molybdenum-containing sensitizing agent in the preparation of a laser-activated selective metallized resin composition, a laser-activated selective metallized resin composition and a laser-activated resin product with excellent chemical plating effect.

The present invention provides the use of a molybdenum-containing sensitizing agent in the preparation of a laser-activated selective metallized resin composition, wherein the molybdenum-containing sensitizing agent is selected from any one or more of molybdenum oxides, molybdenum sulfides, molybdenum hydroxides, molybdenum-containing acids, and molybdenum-containing salts; and the laser activation is performed using a laser with a wavelength of 190-1064 nm.

Further, the molybdenum oxide is selected from any one or more of molybdenum trioxide, molybdenum dioxide, iron-doped molybdenum oxide, molybdenum aluminum oxide, molybdenum copper oxide, molybdenum zinc oxide, and molybdenum titanium oxide;

And/or, the molybdenum sulfide is molybdenum disulfide;

And/or, the molybdenum hydroxide is molybdenum hydroxide;

And/or, the molybdenum-containing acid is any one or more of molybdic acid, phosphomolybdic acid, and silicomolybdic acid;

And/or, the molybdenum-containing salt is selected from any one or more of molybdenum phosphate, molybdenum sulfate, molybdenum nitrate, molybdenum silicate, molybdenum carbonate, molybdenum aluminate, molybdenum bismuthate, ammonium paramolybdate, ammonium metamolybdate, ammonium molybdate, sodium molybdate, potassium molybdate, cesium molybdate, calcium molybdate, bismuth molybdate, nickel molybdate, zinc molybdate, lithium molybdate, lead molybdate, sodium phosphomolybdate, sodium silicomolybdate, and niobium molybdate.

The present invention also provides a laser-activated selectively metallized resin composition, which is composed of the following components in weight percentage: 1.0% to 55% of a molybdenum-containing sensitizing agent and 45% to 99% of a polymer; wherein the molybdenum-containing sensitizing agent is selected from any one or more of molybdenum oxides, molybdenum sulfides, molybdenum-containing acids, and molybdenum-containing salts.

Furthermore, it is composed of the following components in weight percentage: 2% to 50% of a molybdenum-containing sensitizing agent and 50% to 98% of a polymer; preferably, it is composed of the following components in weight percentage: 10% to 50% of a molybdenum-containing sensitizing agent and 50% to 90% of a polymer.

Further, the molybdenum oxide is selected from any one or more of molybdenum trioxide, molybdenum dioxide, iron-doped molybdenum oxide, molybdenum aluminum oxide, molybdenum copper oxide, molybdenum zinc oxide, and molybdenum titanium oxide;

And/or, the molybdenum sulfide is molybdenum disulfide;

And/or, the molybdenum hydroxide is molybdenum hydroxide;

And/or, the molybdenum-containing acid is any one or more of molybdic acid, phosphomolybdic acid, and silicomolybdic acid;

And/or, the molybdenum-containing salt is selected from any one or more of molybdenum phosphate, molybdenum sulfate, molybdenum nitrate, molybdenum silicate, molybdenum carbonate, molybdenum aluminate, molybdenum bismuthate, ammonium paramolybdate, ammonium metamolybdate, ammonium molybdate, sodium molybdate, potassium molybdate, cesium molybdate, calcium molybdate, bismuth molybdate, nickel molybdate, zinc molybdate, lithium molybdate, lead molybdate, sodium phosphomolybdate, sodium silicomolybdate, and niobium molybdate.

Furthermore, the average particle size of the molybdenum-containing sensitizing agent is less than or equal to 150 μm; preferably, the average particle size of the molybdenum-containing sensitizing agent is 0.010 μm to 50 μm; more preferably, the average particle size of the molybdenum-containing sensitizing agent is 0.05 μm to 20 μm.

Furthermore, 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, polystyrene, K resin, styrene-acrylonitrile copolymer, PEN, polyphenylene ether, polyphenylene sulfide, polyetheretherketone, polyurethane, nylon elastomer, SEBS, SEPS, SEEPS, and polyester elastomer.

The present invention also provides a method for preparing the above-mentioned laser-activated selectively metallized resin composition, which comprises the following steps:

a. Take a molybdenum-containing sensitizing agent and a polymer, mix them evenly to obtain a mixture;

b. Melt-blending and granulating the mixture obtained in step a to obtain a laser-activated selectively metallized resin composition.

The present invention also provides the use of the laser-activated selectively metallized resin composition in the preparation of micro-processing materials, wherein the micro-processing materials include micro-circuit materials.

The present invention also provides a fine circuit material, which is formed by selectively activating the above-mentioned resin composition under a laser with a wavelength of 190-1064nm, and then chemically plating it to deposit a conductive metal in the activated area; preferably, the conductive metal is copper, nickel or gold.

The experimental results show that the molybdenum-containing sensitizing agent of the present invention is low in price and small in addition amount, and can significantly reduce the production cost of laser-activated selective metallized products. The molybdenum-containing sensitizing agent of the present invention exhibits excellent laser activation ability under the action of lasers in the wavelength range of 190-1064nm. The prepared laser-activated selective metallized resin has a light color and good chemical plating effect after activation. When the addition amount is as low as 1wt%, the coating thickness of the obtained resin composition reaches more than 1.8μm, and the coating strength tested by a hundred-grid knife (ASTM D3359) reaches the highest level of 5B, and the application prospect is very broad.

Obviously, according to the above contents of the present invention, in accordance with common technical knowledge and customary means in the art, without departing from the above basic technical ideas of the present invention, other various forms of modification, replacement or change may be made.

The above contents of the present invention are further described in detail below through specific implementation methods in the form of embodiments. However, this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples. All technologies realized based on the above contents of the present invention belong to the scope of the present invention.

DETAILED DESCRIPTION

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

(1) The equipment information used in the present invention is as follows:

Twin-screw extruder, screw diameter 35 mm, screw length-diameter ratio 36:1, produced by Nanjing Jieente Electromechanical Co., Ltd.;

Injection molding machine, model MA600, produced by Haitian Machinery Co., Ltd.;

Laser marking machine, model MUV-E-R, pulse laser marking machine, maximum laser power 5W, laser wavelength 355nm;

Laser marking machine, model MV-U, pulse laser marking machine, maximum laser power 3W, laser wavelength 190nm;

Laser marking machine, model DZ-Q, pulse laser marking machine, maximum laser power 8W, laser wavelength 395nm;

Laser marking machine, model MF-E-A, fiber pulse laser marking machine, maximum laser power 20W, laser wavelength 1064nm;

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

(2) The specific information of the base polymer used to prepare the standard sample of the present invention is as follows:

Polycarbonate: General Electric Company, PC121R (density: 1.2 g/cm3; melt flow rate: 17.5 g/10 min, 300°C, 1.2 Kg; heat deformation temperature: 125°C).

Acrylonitrile butadiene styrene (ABS): Taiwan Chimei, PA757 (density: 1.05 g/cm3; melt flow rate: 1.8 g/10 min, 200°C, 5 kg).

Polystyrene: Duzishan Petrochemical, GPPS-500 (density: 1.04 g/cm3; melt flow rate: 5 g/10 min, 200°C, 5 Kg; heat deformation temperature: 89°C).

Polyethylene terephthalate: Yuanfang Industry, CB-602 (density: 1.40 g/cm3; melting temperature: 245°C).

Polybutylene terephthalate: BASF, Germany, PBTB4500 (density: 1.3 g/cm3; melting temperature: 230°C).

SEBS: Japan Kuraray, HYBRA7311F (density: 0.89 g/cm3; melting temperature: 200°C).

Polyamide 66: LANXESS, Germany, A30S (density: 1.14 g/cm3; melting temperature: 260°C).

Polypropylene: Daqing Petrochemical, T30S (density: 0.9 g/cm3; melting temperature: 189°C).

Polyethylene (PE): Maoming Petrochemical, TR144, a high-density polyethylene (density: 0.95 g/cm3; melting temperature: 142°C).

Example 1

First, 99 g of ABS resin and 1 g of laser sensitization aid molybdenum trioxide powder (average particle size of 2 μm) were fully mixed in a high-speed mixer for 2 minutes; then, the mixed material was placed in a twin-screw extruder for melt extrusion and granulation at an extrusion temperature of 220°C to obtain a laser-activated selectively metallized resin composition.

Then, the prepared laser-activated selectively metallized resin composition is injection molded into a plastic sheet by an injection molding machine at an injection molding temperature of 220°C.

The plastic sheet was laser activated using the following conditions: pulsed ultraviolet laser, laser wavelength of 355 nm, speed of 2000 mm/s, laser energy of 2.5 W, and laser frequency of 60 kHz.

According to the laser-activated selective metallized resin composition chemical plating method and process known in the art, the plastic sheet after laser activation is chemically copper-plated. The chemical copper plating uses copper sulfate as the metal copper salt. The resin composition is placed in a chemical copper plating solution to react and plate copper. Air is continuously introduced for stirring in the middle to ensure the uniformity of the copper layer.

After chemical copper plating, the following effects and/or performance tests are performed:

(1) Chemical plating effect: visual inspection;

(2) Thickness of electroless copper plating: tested according to ASTM B568 (2009);

(3) Grid knife test: According to ASTM D3359, use a grid cutter to draw a small square grid of 1mm×1mm in the copper-plated layer area. Then, stick Scotch 3M600-1PK test tape to the grid area and quickly tear off the tape. The grade of adhesion strength is determined based on the area where the copper layer falls off. In the ASTM D3359 grading standard, the higher the grade, the higher the adhesion between the polymer substrate and the copper-plated layer. Among them:

The peeling area of 0B mesh is greater than 65%;

The peeling area of 1B grid is 35%-65%;

The peeling area of 2B mesh is 15%-35%;

The peeling area of 3B mesh is 5%-15%;

The spalling area of 4B mesh is 5%;

5B has no mesh peeling.

The test results are shown in Table 1.

Example 2

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 1, except that the matrix polymer and the laser sensitization aid were: 95 g of ABS resin and 5 g of molybdenum trioxide powder as the laser sensitization aid.

The test method is the same as that in Example 1. The test results are shown in Table 1.

Example 3

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 1, except that the matrix polymer and the laser sensitization aid were: 90 g of ABS resin and 10 g of molybdenum trioxide powder as the laser sensitization aid.

The test method is the same as that in Example 1. The test results are shown in Table 1.

Example 4

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 1, except that the matrix polymer and the laser sensitization aid were: 80 g of ABS resin and 20 g of molybdenum trioxide powder as the laser sensitization aid.

The test method is the same as that in Example 1. The test results are shown in Table 1.

Example 5

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 1, the only difference being that the matrix polymer and the laser sensitization aid used were: 50 g of ABS resin and 50 g of molybdenum trioxide powder as the laser sensitization aid.

The test method is the same as that in Example 1. The test results are shown in Table 1.

Example 6

99 g of ABS resin and 1 g of laser sensitization aid molybdenum dioxide powder (average particle size of 3 μm) were fully 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 215°C to obtain a laser-activated selectively metallized resin composition.

The prepared laser-activated selectively metallized resin composition is injection molded into a plastic sheet by an injection molding machine at an injection molding temperature of 210°C.

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

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Example 7

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 6, the only difference being that the matrix polymer and the laser sensitization aid used were: 95 g of ABS resin and 5 g of molybdenum dioxide powder as the laser sensitization aid.

The test method is the same as that of Example 6. The test results are shown in Table 1.

Example 8

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 6, the only difference being that the matrix polymer and the laser sensitization aid used were: 90 g of ABS resin and 10 g of laser sensitization aid molybdenum dioxide powder.

The test method is the same as that of Example 6. The test results are shown in Table 1.

Example 9

98 g of polybutylene terephthalate resin and 2 g of molybdenum aluminum oxide powder (average particle size of 6 μm), a laser sensitization aid, were fully 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 265°C to obtain a laser-activated selectively metallized resin composition.

The prepared laser-activated selectively metallized resin composition is injection molded into a plastic sheet by an injection molding machine at an injection molding temperature of 260°C.

The plastic sheet was laser activated using the following conditions: pulsed ultraviolet laser, laser wavelength of 395 nm, speed of 2000 mm/s, laser energy of 3 W, and laser frequency of 60 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Example 10

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 9, the only difference being that the matrix polymer and the laser sensitization aid used were: 95 g of polybutylene terephthalate resin and 5 g of the laser sensitization aid molybdenum aluminum oxide powder.

The test method is the same as that of Example 9. The test results are shown in Table 1.

Embodiment 11

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 9, the only difference being that the matrix polymer and the laser sensitization aid used were: 90 g of polybutylene terephthalate resin and 10 g of the laser sensitization aid molybdenum aluminum oxide powder.

The test method is the same as that of Example 9. The test results are shown in Table 1.

Example 12

98 g of SEBS resin and 2 g of laser sensitization aid molybdenum copper oxide powder (average particle size of 3 μm) were fully 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 200°C to obtain a laser-activated selectively metallized resin composition.

The prepared laser-activated selectively metallized resin composition is injection molded into a plastic sheet by an injection molding machine at an injection molding temperature of 195°C.

The plastic sheet was laser activated using the following conditions: green laser, laser wavelength of 532 nm, speed of 2000 mm/s, laser energy of 5 W, and laser frequency of 50 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Example 13

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 12, the only difference being that the matrix polymer and the laser sensitization aid used were: 95 g of SEBS resin and 5 g of the laser sensitization aid molybdenum copper oxide powder.

The test method is the same as that of Example 12. The test results are shown in Table 1.

Embodiment 14

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 12, the only difference being that the matrix polymer and the laser sensitization aid used were: 90 g of SEBS resin and 10 g of the laser sensitization aid molybdenum copper oxide powder.

The test method is the same as that of Example 12. The test results are shown in Table 1.

Embodiment 15

98 g of polystyrene resin and 2 g of laser sensitization aid molybdenum zinc oxide powder (average particle size of 2 μm) were fully 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 215°C to obtain a laser-activated selectively metallized resin composition.

The prepared laser-activated selectively metallized resin composition is injection molded into a plastic sheet by an injection molding machine at an injection molding temperature of 210°C.

The plastic sheet was laser activated using the following conditions: pulsed laser, laser wavelength of 190 nm, speed of 2000 mm/s, laser energy of 1 W, and laser frequency of 60 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Example 16

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 15, the only difference being that the matrix polymer and the laser sensitization aid used were: 95 g of polystyrene resin and 5 g of laser sensitization aid molybdenum zinc oxide powder.

The test method is the same as that of Example 15. The test results are shown in Table 1.

Embodiment 17

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 15, the only difference being that the matrix polymer and the laser sensitization aid used were: 90 g of polystyrene resin and 10 g of laser sensitization aid molybdenum zinc oxide powder.

The test method is the same as that of Example 15. The test results are shown in Table 1.

Embodiment 18

98 g of polyethylene resin and 2 g of iron-doped molybdenum oxide powder (average particle size of 0.5 μm) as a laser sensitization aid are fully 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 160°C to obtain a laser-activated selectively metallized resin composition.

The prepared laser-activated selectively metallized resin composition is injection molded into a plastic sheet by an injection molding machine at an injection molding temperature of 160°C.

The plastic sheet was laser activated using the following conditions: pulsed near-infrared laser, laser wavelength of 1064 nm, speed of 2000 mm/s, laser energy of 12 W, and laser frequency of 50 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Embodiment 19

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 18, the only difference being that the matrix polymer and the laser sensitization aid used were: 95 g of polyethylene resin and 5 g of iron-doped molybdenum oxide powder as the laser sensitization aid.

The test method is the same as that of Example 18, and the test results are shown in Table 1.

Embodiment 20

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 18, the only difference being that the matrix polymer and the laser sensitization aid used were: 90 g of polyethylene resin and 10 g of iron-doped molybdenum oxide powder as the laser sensitization aid.

The test method is the same as that of Example 18, and the test results are shown in Table 1.

Embodiment 21

97 g of polypropylene resin and 3 g of molybdenum disulfide powder (average particle size of 4 μm), a laser sensitization aid, are fully 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 195°C to obtain a laser-activated selectively metallized resin composition.

The prepared laser-activated selectively metallized resin composition is injection molded into a plastic sheet by an injection molding machine at an injection molding temperature of 190°C.

The plastic sheet was laser activated using the following conditions: pulsed ultraviolet laser, laser wavelength of 355 nm, speed of 2000 mm/s, laser energy of 3 W, and laser frequency of 50 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Example 22

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 21, the only difference being that the base polymer and the laser sensitization aid used were: 90 g of polypropylene resin and 10 g of laser sensitization aid molybdenum disulfide powder.

The test method is the same as that of Example 21, and the test results are shown in Table 1.

Embodiment 23

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 21, the only difference being that the base polymer and the laser sensitization aid used were: 80 g of polypropylene resin and 20 g of molybdenum disulfide powder, a laser sensitization aid.

The test method is the same as that of Example 21, and the test results are shown in Table 1.

Embodiment 24

97 g of polyethylene terephthalate resin and 3 g of molybdenum hydroxide powder (average particle size of 8 μm), a laser sensitization aid, are fully 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 240°C to obtain a laser-activated selectively metallized resin composition.

The prepared laser-activated selectively metallized resin composition is injection molded into a plastic sheet by an injection molding machine at an injection molding temperature of 240°C.

The plastic sheet was laser activated using the following conditions: pulsed laser, laser wavelength of 190 nm, speed of 2000 mm/s, laser energy of 1 W, and laser frequency of 50 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Embodiment 25

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 24, the only difference being that the matrix polymer and the laser sensitization aid used were: 90 g of polyethylene terephthalate resin and 10 g of laser sensitization aid molybdenum hydroxide powder.

The test method is the same as that of Example 24, and the test results are shown in Table 1.

Embodiment 26

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 24, the only difference being that the matrix polymer and the laser sensitization aid used were: 80 g of polyethylene terephthalate resin and 20 g of the laser sensitization aid molybdenum hydroxide powder.

The test method is the same as that of Example 24, and the test results are shown in Table 1.

Embodiment 27

97 g of polycarbonate resin and 3 g of molybdic acid powder (average particle size of 4 μm) as a laser sensitization aid are fully 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 265°C to obtain a laser-activated selectively metallized resin composition.

The prepared laser-activated selectively metallized resin composition is injection molded into a plastic sheet by an injection molding machine at an injection molding temperature of 260°C.

The plastic sheet was laser activated using the following conditions: pulsed ultraviolet laser, laser wavelength of 395 nm, speed of 2000 mm/s, laser energy of 4 W, and laser frequency of 60 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Embodiment 28

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 27, the only difference being that the base polymer and the laser sensitization aid used were: 90 g of polycarbonate resin and 10 g of molybdic acid powder as the laser sensitization aid.

The test method is the same as that of Example 27. The test results are shown in Table 1.

Embodiment 29

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 27, the only difference being that the base polymer and the laser sensitization aid used were: 80 g of polycarbonate resin and 20 g of molybdic acid powder as the laser sensitization aid.

The test method is the same as that of Example 27. The test results are shown in Table 1.

Embodiment 30

95 g of polyamide 66 resin and 5 g of molybdenum phosphate powder (average particle size of 2 μm) as a laser sensitization aid are fully 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 265°C to obtain a resin composition that can be laser-activated and selectively metallized.

The prepared laser-activated selectively metallized resin composition is injection molded into a plastic sheet by an injection molding machine at an injection molding temperature of 260°C.

The plastic sheet was laser activated using the following conditions: green laser, laser wavelength of 532 nm, speed of 2000 mm/s, laser energy of 6 W, and laser frequency of 80 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Embodiment 31

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 30, the only difference being that the base polymer and the laser sensitization aid used were: 90 g of polyamide 66 resin and 10 g of laser sensitization aid molybdenum phosphate powder.

The test method is the same as that of Example 30. The test results are shown in Table 1.

Embodiment 32

The laser-activated selectively metallized resin composition and the laser-activated plastic sheet were prepared by referring to the method of Example 30, with the only difference being that the base polymer and the laser sensitization aid used were: 80 g of polyamide 66 resin and 20 g of laser sensitization aid molybdenum phosphate powder.

The test method is the same as that of Example 30. The test results are shown in Table 1.

Comparative Example 1

The laser-activated selectively metallized resin composition and plastic sheet were prepared by referring to the method of Example 1, except that the matrix polymer and laser sensitization aid used were: 99.5 g of ABS resin and 0.5 g of molybdenum trioxide powder as the laser sensitization aid.

The plastic sheet was laser activated using the following conditions: pulsed ultraviolet laser, laser wavelength of 355 nm, speed of 2000 mm/s, laser energy of 2.5 W, and laser frequency of 60 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Comparative Example 2

The laser-activated selectively metallized resin composition and plastic sheet were prepared by referring to the method of Example 1, except that the matrix polymer and laser sensitization aid used were: 99.5 g of ABS resin and 0.5 g of laser sensitization aid molybdenum dioxide powder.

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

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Comparative Example 3

The plastic sheet was prepared by referring to the method of Example 1, except that no laser sensitizing agent was added, and the base polymer used was 100 g of ABS resin.

The plastic sheet was laser activated using the following conditions: pulsed ultraviolet laser, laser wavelength of 355 nm, speed of 2000 mm/s, laser energy of 2.5 W, and laser frequency of 60 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Comparative Example 4

The plastic sheet was prepared by referring to the method of Example 1, except that no laser sensitizing agent was added, and the base polymer used was 100 g of ABS resin.

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

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Comparative Example 5

The plastic sheet was prepared by referring to the method of Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100 g of polybutylene terephthalate resin.

The plastic sheet was laser activated using the following conditions: pulsed ultraviolet laser, laser wavelength of 395 nm, speed of 2000 mm/s, laser energy of 3 W, and laser frequency of 60 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Comparative Example 6

The plastic sheet was prepared by referring to the method of Example 1, except that no laser sensitizing agent was added, and the base polymer used was 100 g of SEBS resin.

The plastic sheet was laser activated using the following conditions: green laser, laser wavelength of 532 nm, speed of 2000 mm/s, laser energy of 5 W, and laser frequency of 50 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Comparative Example 7

The plastic sheet was prepared by referring to the method of Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100 g of polystyrene resin.

The plastic sheet was laser activated using the following conditions: pulsed laser, laser wavelength of 190 nm, speed of 2000 mm/s, laser energy of 1 W, and laser frequency of 60 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Comparative Example 8

The plastic sheet was prepared by referring to the method of Example 1, except that no laser sensitizing agent was added, and the base polymer used was 100 g of polyethylene resin.

The plastic sheet was laser activated using the following conditions: pulsed near-infrared laser, laser wavelength of 1064 nm, speed of 2000 mm/s, laser energy of 12 W, and laser frequency of 50 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Comparative Example 9

The plastic sheet was prepared by referring to the method of Example 1, except that no laser sensitizing agent was added, and the base polymer used was: 100 g of polypropylene resin.

The plastic sheet was laser activated using the following conditions: pulsed ultraviolet laser, laser wavelength of 355 nm, speed of 2000 mm/s, laser energy of 3 W, and laser frequency of 50 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Comparative Example 10

The plastic sheet was prepared by referring to the method of Example 1, except that no laser sensitizing agent was added, and the matrix polymer used was 100 g of polyethylene terephthalate resin.

The plastic sheet was laser activated using the following conditions: pulsed laser, laser wavelength of 190 nm, speed of 2000 mm/s, laser energy of 1 W, and laser frequency of 50 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Comparative Example 11

The plastic sheet was prepared by referring to the method of Example 1, except that no laser sensitizing agent was added, and the base polymer used was: 100 g of polycarbonate resin.

The plastic sheet was laser activated using the following conditions: pulsed ultraviolet laser, laser wavelength of 395 nm, speed of 2000 mm/s, laser energy of 4 W, and laser frequency of 60 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Comparative Example 12

The plastic sheet was prepared by referring to the method of Example 1, except that no laser sensitizing agent was added, and the base polymer used was 100 g of polyamide 66 resin.

The plastic sheet was laser activated using the following conditions: green laser, laser wavelength of 532 nm, speed of 2000 mm/s, laser energy of 6 W, and laser frequency of 80 kHz.

The effect and/or performance test method is the same as that in Example 1, and the test results are shown in Table 1.

Table 1. Important parameters and test results of Examples 1 to 32 and Comparative Examples 1 to 12

The results show that the activation effect of the resin composition containing the molybdenum sensitizer is good when the laser is activated in the wavelength range of 190-1064nm, and the chemical metal plating layer can be well performed on the surface thereof.

The molybdenum-containing sensitizing agent of the present invention is low in price and can significantly reduce the production cost of laser-activated selective metallized products; and when the amount of the molybdenum-containing sensitizing agent added is as low as 1wt%, the coating thickness of the obtained resin composition reaches more than 1.8μm, and the coating strength tested by a grid knife (ASTMD3359) reaches the highest level of 5B, which is very suitable for industrial production and application.

In summary, the present invention provides the use of a molybdenum-containing sensitizing agent in the preparation of a laser-activated selective metallized resin composition, as well as a laser-activated selectively metallized resin composition and a laser-activated resin product with excellent chemical plating effect. The inventors of the present invention unexpectedly discovered that after using a laser with a wavelength of 190-1064nm to activate the resin composition to which a molybdenum-containing sensitizing agent is added, chemical copper plating can be performed well on its surface. On the one hand, 190-1064nm covers almost all laser wavelengths, and activating the resin composition under different laser wavelengths can give play to the advantages of the laser wavelength itself; on the other hand, the molybdenum-containing sensitizing agent is cheaper than traditional copper, tin, and bismuth-containing sensitizing agents, which can significantly reduce production costs. The present invention can obtain a resin composition with excellent coating thickness and coating strength under the condition of a relatively low addition amount of the molybdenum-containing sensitizing agent, and has excellent industrial application value.

Claims (10)

1. The application of the molybdenum-containing sensitization auxiliary in the laser activation selective metallization process of the resin composition is characterized in that: the molybdenum-containing sensitization auxiliary agent is selected from any one or more than two of molybdenum oxides, molybdenum sulfides, molybdenum hydroxides and molybdenum-containing acids, wherein the molybdenum oxides are selected from any one or more than two of molybdenum trioxide, molybdenum dioxide, iron-doped molybdenum oxide, molybdenum aluminum oxide and molybdenum zinc oxide, the molybdenum sulfides are molybdenum disulfide, the molybdenum hydroxides are molybdenum hydroxides, and the molybdenum-containing acids are any one or two of molybdic acid and phosphomolybdic acid; the laser activation is carried out by utilizing 190-1064nm wavelength laser;

the molybdenum-containing sensitization auxiliary agent and the polymer form a resin composition according to the following weight percentage: 1.0 to 55 percent of molybdenum-containing sensitization auxiliary agent and 45 to 99 percent of polymer.

2. The use according to claim 1, wherein: the resin composition comprises the following components in percentage by weight: 2-50% of molybdenum-containing sensitization auxiliary agent and 50-98% of polymer.

3. The use according to claim 2, wherein: the resin composition comprises the following components in percentage by weight: 10-50% of molybdenum-containing sensitization auxiliary agent and 50-90% of polymer.

4. The use according to claim 1, wherein: the average particle size of the molybdenum-containing sensitization auxiliary is less than or equal to 150 mu m.

5. The use according to claim 4, wherein: the average grain diameter of the molybdenum-containing sensitization auxiliary is 0.010 mu m-50 mu m.

6. The use according to claim 5, wherein: the average particle diameter of the molybdenum-containing sensitization auxiliary is 0.05-20 mu m.

7. The use according to claim 1, wherein: the polymer is selected from any one or more than two of polycarbonate, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyamide, polystyrene, K resin, PEN, polyphenyl ether, polyphenylene sulfide, polyether ether ketone, polyurethane, nylon elastomer, SEBS, SEPS, SEEPS and polyester elastomer.

8. The use according to claim 1, wherein: the preparation method of the resin composition comprises the following steps:

a. taking a molybdenum-containing sensitization auxiliary agent and a polymer, and uniformly mixing to obtain a mixture;

b. and d, carrying out melt blending and granulation on the mixture obtained in the step a to obtain the resin composition.

9. A method of preparing a microcircuit material, characterized by: the method is characterized in that the resin composition in any one of claims 1-8 is selectively activated under the laser with the wavelength of 190-1064nm, and then is subjected to electroless plating, so that the conductive metal is deposited in an activated area.

10. The method of claim 9, wherein: the conductive metal is copper, nickel or gold.