CN110467811B - Bending-resistant laser direct forming material and preparation method thereof - Google Patents
Bending-resistant laser direct forming material and preparation method thereof Download PDFInfo
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- CN110467811B CN110467811B CN201910756729.4A CN201910756729A CN110467811B CN 110467811 B CN110467811 B CN 110467811B CN 201910756729 A CN201910756729 A CN 201910756729A CN 110467811 B CN110467811 B CN 110467811B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a bending-resistant laser direct structuring material which has good mechanical properties and bending resistance and has excellent LDS functionality. The composite material mainly comprises the following raw materials in percentage by weight: nylon 12: 75-90%, nylon 6: 3-10% of laser direct structuring additive, 3-15% of inorganic filler, 2-15% of toughening agent and 0.5-2% of other additives. The invention also discloses a method for preparing the laser direct structuring material. The compositions can be used in a variety of applications where both LDS functionality and flex resistance are required.
Description
Technical Field
The invention belongs to the field of functional polymer materials, and particularly relates to a bending-resistant laser direct forming material and a preparation method thereof.
Background
Nylon 12 is a long carbon chain polyamide, and its methylene chain is longer, and its amide density is low, and compared with nylon 6 and nylon 66, it has the good characteristics of small density, low melting point, good thermal stability, high decomposition temp., low-temp., flexibility resistance, oil resistance, corrosion resistance and friction loss resistance, etc., and has extensive application prospect.
LDS, the abbreviation of Laser Direct Structuring, is a 3D-MID production technology of professional Laser processing, injection and electroplating processes, and the principle thereof is that the common plastic component/circuit board is endowed with the functions of electrical interconnection, component supporting, supporting and protection of a plastic shell and the functions of shielding, antenna and the like generated by the combination of a mechanical entity and a conductive pattern are combined into a whole to form the 3D-MID, which is suitable for local fine line manufacturing.
LDS can avoid pollution and water consumption of the traditional plastic electroplating process to the environment to a great extent, simplifies the production flow, provides flexible and changeable design space and can realize rapid 3D forming through the flexibility of laser and the organic combination of precision and plasticity and functionality of engineering plastics, and simultaneously has high processing resolution. The technology can be applied to mobile phone antennas, notebook computer antennas, electronic circuits for automobiles, teller machine shells, medical hearing aids and the like. For example, the most common mobile phone antenna application at present, the LDS can directly laser the antenna on the mobile phone shell, the design is flexible, the degree of freedom is high, not only the internal mobile phone metal interference is avoided, but also the mobile phone volume is reduced, and the effects of saving space and reducing the product weight are achieved.
The LDS is manufactured by adding metal additives and auxiliaries into plastic, extruding the plastic into particles, then performing injection molding to obtain a blank, performing laser on the blank to form an etching area and activate metal, then performing chemical plating to form a conductive path in the etching area, and finally assembling.
In general, the evaluation of long-term service properties of laser direct structuring materials focuses on their stability, toughness, heat resistance, and functionality. With the rapid development of modern information industry, the requirements for the comprehensive performance of LDS materials are becoming more severe in some special application fields, such as communication, chip manufacturing, medical treatment, intelligent consumer electronics industry, bionic robot and other technical fields, and the materials are required to have better flexibility and product reliability while having functionality so as to meet some special requirements. Obviously, the polycarbonate substrate LDS materials commonly used in the industry at present have difficulty meeting this requirement.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a laser direct forming material with excellent bending resistance.
The invention also provides a preparation method of the laser direct forming material with excellent bending resistance.
In order to achieve the purpose, the invention adopts the technical scheme that: a bending-resistant laser direct forming material is mainly prepared from the following components in percentage by weight: nylon 12: 75-90%, nylon 6: 3-10%, laser direct structuring additive: 3-15%, inorganic filler: 1-8% of a toughening agent: 2-15%, and other additives: 0.5 to 2 percent.
Preferably, the bending-resistant laser direct structuring material is mainly prepared from the following components in percentage by weight: nylon 12: 75-85%, nylon 6: 5-10%, laser direct structuring additive: 3-10%, inorganic filler: 2-5% of a toughening agent: 3-5%, and other additives: 1 to 1.5 percent.
The melt index of the nylon 6 in the invention is 10-20g/10min under the condition of 230 ℃/2.16Kg, and the melt index of the nylon 12 is 5-10g/10min under the condition of 230 ℃/2.16 Kg.
The laser direct structuring additive comprises one or more of copper-iron spinel, copper-containing magnesium aluminum oxide, copper-chromium-manganese mixed oxide, copper-manganese-iron mixed oxide, basic copper phosphate, zinc stannate, tin pyrophosphate, tin phosphate, tin dioxide, stannous pyrophosphate and stannous oxide. As a further preference, the laser direct structuring additive comprises one or a mixture of two of basic copper phosphate and zinc stannate. When the two components are mixed for use, the weight ratio of the two components is 1 (2-5).
The inorganic filler in the invention comprises one or more of kaolin, talcum powder, wollastonite, silica and mica. Preferably, the inorganic fillers used are kaolin and talc, the particle size of which is 6000-10000 mesh.
The toughening agent in the invention is selected from one or a mixture of two of MBS (methyl methacrylate-butadiene-styrene copolymer), SBS (styrene-butadiene-styrene block copolymer), SEBS (styrene-ethylene-butylene-styrene copolymer), EVA (ethylene-vinyl acetate copolymer), EMA (ethylene-methyl acrylate copolymer), EEA (ethylene-ethyl acrylate copolymer), EBA (ethylene-butyl acrylate copolymer), POE (ethylene-octene copolymer). Preferably, the toughening agent is one or more of POE, EBA and EMA.
Other additives in the present invention include heat stabilizers, mold release agents, and the like. For example, composition mold release agents include, but are not limited to, pentaerythritol esters of tetracarboxylic acids, glycerol monocarboxylates, polyolefins, silicone oils, alkyl waxes, and amides. Other additives can include antioxidant stabilizers, such as hindered phenol stabilizers, thioether ester stabilizers, amine stabilizers, phosphite stabilizers, phosphonite stabilizers, or a combination comprising at least one of the foregoing types of stabilizers.
The invention comprises a method for preparing a laser direct structuring material with excellent bending resistance, wherein nylon 12, nylon 6, a laser direct structuring additive, an inorganic filler, a toughening agent and other additives are uniformly premixed according to a metering ratio, and are extruded by a double-screw extruder to be melted, blended, extruded and granulated, so that the plastic molding compound material for laser direct structuring is obtained.
Preferably, the blending temperature is 220-240 ℃, the torque value is kept at 50-60%, and the rotating speed is 200-400 r/min. The premixing may be carried out in a high speed mixer at a speed of 1000 rpm to 3000 rpm.
According to the invention, by utilizing the synergistic and crystal form regulation and control effects between nylon 12 and nylon 6, and simultaneously adding a certain proportion of laser direct forming additive, inorganic filler, toughening agent, other additives and the like into nylon 12, through the interaction of different components, the polymer material LDS is endowed with functionality, and simultaneously, the good forming processability and mechanical properties of the base material, especially the bending resistance, are well maintained, so that the application range of the LDS material is widened.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples. The following examples are intended to provide those of ordinary skill in the art with a complete disclosure and description of how the methods disclosed and claimed herein are made and evaluated, and are purely exemplary and are not intended to limit the disclosure.
The raw materials used in the examples of the present invention were all commercially available products.
The formulation compositions and corresponding performance of examples 1-5 and comparative examples 1-2 are shown in Table 1.
TABLE 1
| Examples | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 |
| Polycarbonate resin | 87.9 | ||||||
| Nylon 12 | 84.4 | 84.4 | 76.9 | 76.9 | 76.9 | 80.9 | |
| Nylon 6 | 5 | 5 | 10 | 10 | 10 | 10 | |
| Basic copper phosphate | 1 | 1 | 1 | 1 | 1 | 3 | |
| Zinc stannate | 3 | 3 | 3 | 3 | 3 | ||
| POE | 3 | 5 | 2.5 | 5 | |||
| MBS | 3 | 5 | 2.5 | ||||
| PTW | 2.5 | 2.5 | |||||
| Talcum powder | 2.5 | 2.5 | 3 | ||||
| Kaolin clay | 3 | 3 | 3 | 3 | |||
| Notched impact strength, J/m | 76 | 62 | 78 | 70 | 83 | 140 | 300 |
| Unnotched impact strength, J/m | NB | NB | NB | NB | NB | NB | NB |
| Tensile strength, MPa | 61 | 63 | 61 | 59 | 57 | 59 | 52 |
| Elongation at break,% | 87 | 81 | 89 | 70 | 91 | 93 | 50 |
| Plating index | 9 | 10 | 9 | 10 | 10 | / | 10 |
| Bending property test | PASS | PASS | PASS | PASS | PASS | PASS | FAIL |
In embodiments 1-5, the LDS additive includes copper hydroxide phosphate and zinc stannate, and the weight percentage of the copper hydroxide phosphate and the zinc stannate in the total raw materials is 4 wt%.
The tougheners in examples 1-5 and comparative examples were POE (Dow 8150), MBS (Dow EXL-2690) and ethylene-butyl acrylate-glycidyl methacrylate copolymer (Dow PTW).
In examples 1 to 5 and comparative examples, the inorganic filler was ultrafine talc powder and kaolin.
Other additives in the examples and comparative examples included antioxidant 1010, antioxidant 168 and silicone oil in amounts of 0.15 wt%, 0.15 wt% and 0.8 wt%, respectively.
The preparation method comprises the following steps: according to the metering ratio, the nylon 12, the nylon 6, the laser direct forming additive, the inorganic filler, the toughening agent and other additives are premixed uniformly, and are melted, blended, extruded and granulated by a double-screw extruder to obtain the plastic molding compound material for laser direct forming. The specific process is as follows: the desired raw materials are weighed and pre-mixed in a high speed mixer at a speed of about 1000 to 3000 rpm. The premix was fed into a twin screw extruder, all samples were prepared by melt extrusion, using a temperature of about 220 ℃ to about 240 ℃, screw speed was maintained at about 300 revolutions per minute and torque values were maintained at about 50% to about 60%, and operated under standard processing conditions well known to those skilled in the art, post-blending extruded, cooled, pelletized. After the pellets were extruded, the pellets were dried at about 80 ℃ before molding the test samples. The molding process is performed with a temperature interval of 220 to 240 c and a mold temperature maintained at 80 c.
The polycarbonate system of comparative example 2 was prepared as above, but the temperature range for melt extrusion and molding of the test specimens was 250 ℃ to 260 ℃.
The overall properties of the material are characterized by notched and unnotched impact performance testing, tensile testing, bending testing, and plating performance testing. The test criteria are as follows:
impact test ASTM D256 and ASTM D4812
Tensile Property test ASTM D638;
bending performance test, namely enterprise standard, taking 3000 times as a limit;
and (3) testing the plating performance: the enterprise standard, data set point is between 1-10, where 10 corresponds to the best plating performance. It is generally considered that the index is greater than or equal to 9 to satisfy the practical requirement.
As can be seen from table 1, in examples 1 to 5, nylon 12 and nylon 6 interact with a certain proportion of laser direct structuring additive, inorganic filler, toughening agent, etc., so that while the nylon base material is endowed with good LDS functionality, the strength and toughness, especially the bending resistance, of the material are well maintained, which is significantly better than that of the polycarbonate base material LDS material (comparative example 2), and is at the same level as that of comparative example 1 which does not contain the laser direct structuring additive.
Claims (6)
1. The bending-resistant laser direct forming material is characterized by mainly comprising the following components in percentage by weight: nylon 12: 75-85%, nylon 6: 5-10%, laser direct structuring additive: 3-10%, inorganic filler: 2-5% of a toughening agent: 3-5%, and other additives: 1 to 1.5 percent
The melt index of the nylon 6 is 10-20g/10min under the condition of 230 ℃/2.16Kg, and the melt index of the nylon 12 is 5-10g/10min under the condition of 230 ℃/2.16 Kg;
the laser direct forming additive is a mixture of basic copper phosphate and zinc stannate, and the weight ratio of the basic copper phosphate to the zinc stannate is 1 (2-5).
2. The bend-resistant laser direct structuring material of claim 1, wherein the inorganic filler comprises one or more of kaolin, talc, wollastonite, silica, mica.
3. The bend-resistant laser direct structuring material according to claim 1, wherein the toughening agent is selected from one or a mixture of two of MBS, SBS, SEBS, EVA, EMA, EEA, EBA, POE.
4. The bend-resistant laser direct structuring material of claim 1, wherein the other additives comprise one or more of a thermal stabilizer and a mold release agent.
5. A method for preparing the bending-resistant laser direct structuring material according to any one of claims 1 to 4, comprising: according to the metering ratio, the nylon 12, the nylon 6, the laser direct forming additive, the inorganic filler, the toughening agent and other additives are premixed uniformly, and are melted, blended, extruded and granulated by a double-screw extruder to obtain the plastic molding compound material for laser direct forming.
6. The method for preparing the bending-resistant laser direct structuring material as claimed in claim 5, wherein the blending temperature is 220 ℃ to 240 ℃, the torque value is maintained at 50% to 60%, and the rotation speed is 200 to 400 rpm.
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| CN104619783A (en) * | 2012-09-14 | 2015-05-13 | 三菱工程塑料株式会社 | Thermoplastic resin composition, resin molded article, and method for producing resin molded article having plated layer attached thereto |
| CN104672890A (en) * | 2014-12-22 | 2015-06-03 | 杭州杭复新材料科技有限公司 | Polymer matrix composite with laser-induced metallization characteristic |
| CN105531309A (en) * | 2013-06-04 | 2016-04-27 | 沙特基础全球技术有限公司 | Thermally conductive polymer compositions with laser direct structuring function |
| CN106928682A (en) * | 2017-03-01 | 2017-07-07 | 无锡赢同新材料科技有限公司 | A kind of laser direct forming material with good combination property and preparation method thereof |
| CN107646047A (en) * | 2015-05-28 | 2018-01-30 | 帝斯曼知识产权资产管理有限公司 | Thermoplastic polymer composition, the product being made from it and preparation method thereof |
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- 2019-08-16 CN CN201910756729.4A patent/CN110467811B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103665831A (en) * | 2012-08-28 | 2014-03-26 | Ems专利股份公司 | Polyamide moulding material and its application |
| CN104619783A (en) * | 2012-09-14 | 2015-05-13 | 三菱工程塑料株式会社 | Thermoplastic resin composition, resin molded article, and method for producing resin molded article having plated layer attached thereto |
| CN105531309A (en) * | 2013-06-04 | 2016-04-27 | 沙特基础全球技术有限公司 | Thermally conductive polymer compositions with laser direct structuring function |
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