CN105754141B - Bismuth-containing be sensitized auxiliary agent preparation can application in the resin combination of laser direct forming - Google Patents

Abstract

The invention discloses the application of a bismuth-containing sensitizing assistant in the preparation of a resin composition capable of laser direct molding. The bismuth-containing sensitizing assistant is selected from bismuth oxide, bismuth sulfide, bismuth hydroxide, Any one or two or more of bismuth oxychlorides and bismuth salts. The inventors of the present application unexpectedly found that when the addition amount of the bismuth-containing sensitizing assistant is as low as 1 wt%, the thickness of the coating of the prepared resin composition reaches more than 10 μm, and the peeling strength of the coating is greater than 1.0 N/mm , and achieved technical effects that are completely unexpected by those skilled in the art; moreover, the bismuth-containing sensitizing assistant in the present invention does not contain copper elements, and the base color of the prepared resin composition is relatively light, which is especially suitable for light-colored and/or colored LDS resin products; at the same time, the present invention can also reduce the amount of sensitizing additives, reduce the production cost of laser direct structuring products, have very good economic benefits, and are very suitable for industrial applications.

Description

Application of bismuth-containing sensitizing assistant in the preparation of laser direct structurable resin composition

technical field

The invention belongs to the field of laser sensitization assistants, and in particular relates to the application of bismuth-containing sensitization assistants in the preparation of laser direct molding resin compositions.

Background technique

Laser Direct Structuring (LDS) is to control the scanning trajectory of the laser through the computer, irradiate the laser onto the workpiece (resin composition) containing the laser sensitization additive, activate the circuit pattern in a short time, and then activate it A layer of conductive metal is plated on the area, so that ordinary plastic components can be endowed with electrical interconnection functions, forming a three-dimensional molded interconnect device (Three-dimensional molded interconnect device, referred to as 3D-MID).

The advantage of this technology is that it can reduce the number of components of electronic products and save space, and the production flexibility is good: if you need to change the conductive circuit, you only need to adjust the trajectory of the laser scanning, without redesigning the mold, and it has higher production speed. With the advantages of quickness, simplified process, and more controllable cost, it is widely used in mobile phone antennas, aerospace, electronic medical, automotive dashboards, notebook computers, etc.

Among them, the sensitizing additive (also known as laser direct structuring additive) is one of the most important process conditions in laser direct structuring technology, which directly affects whether the activated area can be plated with metal.

At present, the types of reagents that can be used as sensitizing additives are quite limited, mainly compounds containing two or more specific metals, such as: copper-chromium compounds, copper-manganese compounds, etc., which are relatively expensive; moreover, such compounds are used as sensitizing additives. When adding an additive, it needs to be added up to 12wt% to obtain a coating thickness of more than 10 μm (see: paragraph [0072] of the CN 103450675A specification), which has high cost and poor economics in industrial application; meanwhile, These copper-containing sensitizing additives often bring "copper damage" to the polymer, which will accelerate the air aging of the polymer, thereby reducing the performance of the matrix of the composition and shortening its service life.

In order to overcome the defects of the existing sensitizing additives, it is necessary to develop or find a sensitizing additive with small addition, good effect, no copper element and can be used to prepare laser direct structuring products.

Contents of the invention

The object of the present invention is to provide the application of bismuth-containing sensitization assistant in the preparation of laser direct structurable resin composition.

The application of the bismuth-containing sensitizing auxiliary agent provided by the present invention in the preparation of laser direct structuring resin composition, the bismuth-containing sensitizing auxiliary agent is selected from bismuth oxide, bismuth sulfide, bismuth hydroxide, Any one or two or more of bismuth oxychlorides and bismuth salts.

Further, the bismuth oxide is selected from any one or more of Bi ₂ O ₃ , Bi ₂ O _2.33 , Bi ₂ O _2.75 , and Bi ₂ O ₄ ; preferably, the bismuth oxide is Bi ₂ O ₃ .

Further, the bismuth sulfide is bismuth sulfide.

Further, the bismuth hydroxide is selected from any one or both of bismuth hydroxide and bismuth partial hydroxide; preferably, the bismuth hydroxide is bismuth hydroxide.

Further, the bismuth oxychloride is bismuth oxychloride.

Further, the salt of bismuth is selected from any one or more of bismuth phosphate, bismuth sulfate, bismuth nitrate, bismuth hyponitrate, bismuth subcarbonate, and bismuth aluminate; preferably, the salt of bismuth is phosphoric acid Bismuth or bismuth subcarbonate.

Further, the average particle diameter of the bismuth-containing sensitization assistant is less than or equal to 150 μm; preferably, the average particle diameter of the bismuth-containing sensitization assistant is 0.1 μm˜50 μm.

The present invention also provides a resin composition capable of laser direct molding, which is composed of the following components in weight percent: 1%-60% of bismuth-containing sensitizing assistant, and 40%-99% of polymer; wherein, the The bismuth-containing sensitization assistant is selected from any one or two or more of bismuth oxides, bismuth sulfides, bismuth hydroxides, bismuth oxychlorides, and bismuth salts.

Further, 3% to 55% of bismuth-containing sensitization aids, 45% to 97% of polymers; preferably, it is composed of the following components in weight percentages: 5% to 55% of bismuth-containing sensitization aids, polymer Material 45% ~ 95%.

Further, it is composed of the following components by weight percentage: 1%-3% of bismuth-containing sensitization assistant, and 97%-99% of polymer.

Further, the bismuth oxide is selected from any one or more of Bi ₂ O ₃ , Bi ₂ O _2.33 , Bi ₂ O _2.75 , and Bi ₂ O ₄ ; preferably, the bismuth oxide is Bi ₂ O ₃ .

Further, the bismuth sulfide is bismuth sulfide.

Further, the bismuth hydroxide is selected from any one or both of bismuth hydroxide and bismuth partial hydroxide; preferably, the bismuth hydroxide is bismuth hydroxide.

Further, the bismuth oxychloride is bismuth oxychloride.

Further, the salt of bismuth is selected from any one or more of bismuth phosphate, bismuth sulfate, bismuth nitrate, bismuth hyponitrate, bismuth subcarbonate, and bismuth aluminate; preferably, the salt of bismuth is phosphoric acid Bismuth or bismuth subcarbonate.

Further, the average particle diameter of the bismuth-containing sensitization assistant is less than or equal to 150 μm; preferably, the average particle diameter of the bismuth-containing sensitization assistant is 0.1 μm˜50 μm.

Further, the polymer is selected from polycarbonate, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polypropylene, polyethylene terephthalate, polyethylene terephthalate Any one or two or more of butylene formate, polyamide, polystyrene, polyphenylene ether, and polyphenylene sulfide.

The present invention also provides the preparation method of above-mentioned resin composition, it comprises the following steps:

a. Take the bismuth-containing sensitizing assistant and the polymer, and mix them to obtain a mixture;

b. Melting and blending the mixture obtained in step a, and granulating to obtain a resin composition capable of laser direct molding.

The inventors of the present application unexpectedly found that when the addition amount of the bismuth-containing sensitizing assistant is as low as 1 wt%, the thickness of the coating of the prepared resin composition reaches more than 10 μm, and the peeling strength of the coating is greater than 1.0 N/mm , achieved technical effects completely unexpected by those skilled in the art; moreover, the bismuth-containing sensitizing assistant of the present invention has a lighter background color of the resin composition, and is especially suitable for light-colored and/or colored LDS resins products; at the same time, the present invention can also reduce the amount of sensitizing additives, reduce the production cost of laser direct structuring products, has very good economic benefits, and is very suitable for industrial applications.

Definition of terms used in the present invention: Unless otherwise stated, the initial definition provided by a group or term herein applies to the group or term throughout the specification; for terms that are not specifically defined herein, they should be based on the disclosure and context , giving the meanings a person skilled in the art can assign to them.

Apparently, according to the above content of the present invention, according to common technical knowledge and conventional means in this field, without departing from the above basic technical idea of the present invention, other various forms of modification, replacement or change can also be made.

The above-mentioned content of the present invention will be further described in detail below through specific implementation in the form of examples. However, this should not be construed as limiting the scope of the above-mentioned subject matter of the present invention to the following examples. All technologies realized based on the above contents of the present invention belong to the scope of the present invention.

Description of drawings

Fig. 1 is the electroless plating effect figure of the embodiment of the present invention and comparative example.

Detailed ways

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

Polycarbonate: American General Electric Company, PC 121R (density: 1.2g/cm3; melt flow rate: 17.5g/10min, 300°C, 1.2Kg; heat distortion temperature: 125°C).

Acrylonitrile-butadiene-styrene (ABS): Taiwan Chimei, PA747 (density: 1.03g/cm ³ ; melt flow rate: 1.2g/10min, 200°C, 5Kg).

Polystyrene: Duzishan Petrochemical, GPPS-500 (density: 1.04g/cm ³ ; melt flow rate: 5g/10min, 200°C, 5Kg; heat distortion temperature: 89°C).

Polyethylene terephthalate: Yuanbo Industrial Co., Ltd., CB-602 (density: 1.40 g/cm ³ ; melting temperature: 245° C.).

Polybutylene terephthalate: BASF, Germany, PBT B4500 (density: 1.3 g/cm ³ ; melting temperature: 230° C.).

Polyamide 66: Germany LANXESS, A30S (density: 1.14 g/cm ³ ; melting temperature: 260° C.).

Example 1

First, 99g of ABS resin and 1g of laser sensitization additive bismuth trioxide powder (average particle size is 0.5 μm) were fully mixed in a high-speed mixer for 2 minutes; then, the mixed material was placed in a twin-screw extruder Melt extrusion, granulation, the extrusion temperature is 230 ° C, and the resin composition that can be directly formed by laser is obtained.

Next, the prepared laser direct structuring resin composition was injected into a plastic sheet through an injection molding machine, and the injection molding temperature was 240°C.

The following conditions were used for laser activation of the above plastic sheet: a pulsed near-infrared laser with a laser wavelength of 1064nm, a marking speed of 2000mm/s, a laser energy of 8W, and a laser frequency of 60KHz.

According to the LDS plastic electroless plating method and process known in the art, electroless copper plating is performed on the plastic plate after laser activation.

After electroless copper plating, conduct the following effects and/or performance tests:

(1) Electroless plating effect: visual inspection;

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

(3) Peel strength of the coating: according to IPC-TM-650 2.4.28, it is measured with an electroless copper plating peel tester.

The test results are shown in Table 1.

Example 2

ABS resin 95g and laser sensitization auxiliary agent bismuth trioxide powder 5g.

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

Example 3

ABS resin 93g and laser sensitization auxiliary agent bismuth trioxide powder 7g.

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

Example 4

ABS resin 90g and laser sensitization auxiliary agent bismuth trioxide powder 10g.

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

Example 5

ABS resin 70g and laser sensitization auxiliary agent bismuth trioxide powder 30g.

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

Example 6

ABS resin 45g and laser sensitization auxiliary agent bismuth trioxide powder 55g.

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

Example 7

Polycarbonate 97g and laser sensitization auxiliary agent bismuth sulfide powder (average particle diameter is 10 μ m) 3g, fully mix 2 minutes in high-speed mixer; Then, the material after mixing is placed in twin-screw extruder and melted and extruded, Pelletize and extrude at a temperature of 260°C to obtain a resin composition that can be directly molded by laser.

The prepared laser direct structuring resin composition was injected into a plastic plate through an injection molding machine, and the injection molding temperature was 265°C.

The following conditions were used for laser activation of the above plastic sheet: a pulsed near-infrared laser with a laser wavelength of 1064nm, a marking speed of 2000mm/s, a laser energy of 8W, and a laser frequency of 60KHz.

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

Example 8

95g of polycarbonate and 5g of laser sensitization auxiliary bismuth sulfide powder.

The test method is the same as in Example 7, and the test results are shown in Table 1.

Example 9

90g of polycarbonate and 10g of laser sensitization auxiliary bismuth sulfide powder.

The test method is the same as in Example 7, and the test results are shown in Table 1.

Example 10

First, 95g of polyethylene terephthalate and 5g of laser sensitization additive bismuth oxychloride powder (average particle size is 35 μm) were fully mixed in a high-speed mixer for 2 minutes; then, the mixed material was placed in a double Melting extrusion in a screw extruder, granulation, the extrusion temperature is 245° C., to obtain a resin composition capable of laser direct molding.

Next, the prepared laser direct structuring resin composition was injected into a plastic sheet through an injection molding machine, and the injection molding temperature was 245°C.

The following conditions were used for laser activation of the above plastic sheet: a pulsed near-infrared laser with a laser wavelength of 1064nm, a marking speed of 2000mm/s, a laser energy of 8W, and a laser frequency of 60KHz.

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

Example 11

First, 95 g of polybutylene terephthalate and 5 g of bismuth phosphate powder (average particle size of 30 μm) of laser sensitization auxiliary agent were fully mixed in a high-speed mixer for 2 minutes; then, the mixed material was placed in a twin-screw Melting and extruding in an extruder, granulating, and extruding at a temperature of 230° C., the resin composition capable of laser direct shaping is obtained.

Next, the prepared laser direct structuring resin composition was injected into a plastic plate through an injection molding machine, and the injection molding temperature was 235°C.

The following conditions were used for laser activation of the above plastic sheet: a pulsed near-infrared laser with a laser wavelength of 1064nm, a marking speed of 2000mm/s, a laser energy of 8W, and a laser frequency of 60KHz.

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

Example 12

First, 60g of polyamide 66 and 40g of laser sensitization additive bismuth hydroxide powder (average particle size 20 μm) were fully mixed in a high-speed mixer for 2 minutes; then, the mixed material was melt-extruded in a twin-screw extruder. out, granulated, and extruded at a temperature of 265°C to obtain a resin composition capable of laser direct molding.

Next, the prepared laser direct structuring resin composition was injected into a plastic sheet through an injection molding machine, and the injection molding temperature was 265°C.

The following conditions were used for laser activation of the above plastic sheet: a pulsed near-infrared laser with a laser wavelength of 1064nm, a marking speed of 2000mm/s, a laser energy of 8W, and a laser frequency of 60KHz.

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

Example 13

First, 95 g of polystyrene and 5 g of laser sensitization additive bismuth subcarbonate powder (average particle size 1 μm) were fully mixed in a high-speed mixer for 2 minutes; then, the mixed material was placed in a twin-screw extruder for melting Extrude, granulate, and extrude at a temperature of 220°C to obtain a resin composition that can be directly molded by laser.

Next, the prepared laser direct structuring resin composition was injected into a plastic plate through an injection molding machine, and the injection molding temperature was 210°C.

The following conditions were used for laser activation of the above plastic sheet: a pulsed near-infrared laser with a laser wavelength of 1064nm, a marking speed of 2000mm/s, a laser energy of 8W, and a laser frequency of 60KHz.

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

Comparative example 1

ABS resin 99.5g and laser sensitization auxiliary agent bismuth trioxide powder 0.5g.

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

Comparative example 2～7

According to the same method as above, pure ABS resin, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide 66, and polystyrene are made into plastic sheets, and then Laser activation, effect and/or performance tests were carried out, and the test results are shown in Table 1.

The test result of table 1, embodiment 1～13 and comparative example 1～7

The results show that the bismuth-containing sensitizing assistant of the present invention, when the addition amount is as low as 1wt%, the coating thickness of the prepared resin composition has just reached more than 10 μm, and the coating peeling strength is greater than 1.0N/mm, which has achieved this achievement. A technical effect completely unexpected by those skilled in the art; moreover, the present invention contains bismuth-containing sensitizing assistant, and the background color of the prepared resin composition is relatively light, and is particularly suitable for light-colored and/or colored LDS resin products; at the same time, The invention can also reduce the dosage of sensitizing additives, reduce the production cost of laser direct molding products, has very good economic benefits, and is very suitable for industrial application.

Claims (11)

1. A resin composition capable of laser direct molding, characterized in that: it is composed of the following components by weight percentage: 1% to 60% of a bismuth-containing sensitizing assistant, and 40% to 99% of a polymer; wherein, The bismuth-containing sensitizer is selected from any one or more than two of bismuth oxides, bismuth sulfides, bismuth hydroxides, bismuth oxychlorides, and bismuth salts; The bismuth oxide is selected from Bi ₂ O ₃ , Bi ₂ O _2.33 , Bi ₂ O _2.75 , Bi ₂ O ₄ ; the bismuth sulfide is bismuth sulfide; the bismuth hydroxide is selected from bismuth hydroxide , bismuth partial hydroxide; the oxychloride of bismuth is bismuth oxychloride; the salt of bismuth is selected from bismuth phosphate, bismuth sulfate, bismuth nitrate, bismuth subnitrate, bismuth subcarbonate, bismuth aluminate. 2. The resin composition according to claim 1, characterized in that it is composed of the following components in weight percentage: 3%-55% of bismuth-containing sensitizing assistant, and 45%-97% of polymer. 3. The resin composition according to claim 2, characterized in that it is composed of the following components in weight percent: 5%-55% of bismuth-containing sensitizing assistant, and 45%-95% of polymer. 4. The resin composition according to claim 1, characterized in that it is composed of the following components in weight percentage: 1%-3% of bismuth-containing sensitizing assistant, and 97%-99% of polymer. 5 . The resin composition according to claim 1 , wherein the bismuth oxide is Bi ₂ O ₃ . 6. The resin composition according to claim 1, characterized in that: the bismuth hydroxide is bismuth hydroxide. 7. The resin composition according to claim 1, characterized in that: the bismuth salt is bismuth phosphate or bismuth subcarbonate. 8. The resin composition according to claim 1, characterized in that: the average particle size of the bismuth-containing sensitization assistant is less than or equal to 150 μm. 9. The resin composition according to claim 8, characterized in that: the average particle diameter of the bismuth-containing sensitization assistant is 0.1 μm˜50 μm. 10. The resin composition according to claim 1, characterized in that: said polymer is selected from the group consisting of polycarbonate, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polypropylene, Any one or two or more of polyethylene terephthalate, polybutylene terephthalate, polyamide, polystyrene, polyphenylene ether, and polyphenylene sulfide. 11. The method for preparing the resin composition according to any one of claims 1 to 10, characterized in that it comprises the following steps: a. Take the bismuth-containing sensitizing assistant and the polymer, and mix them to obtain a mixture; b. Melting and blending the mixture obtained in step a, and granulating to obtain a resin composition capable of laser direct molding.