CN109627712B - PBT composition and preparation method and application thereof - Google Patents
PBT composition and preparation method and application thereof Download PDFInfo
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- CN109627712B CN109627712B CN201811628500.4A CN201811628500A CN109627712B CN 109627712 B CN109627712 B CN 109627712B CN 201811628500 A CN201811628500 A CN 201811628500A CN 109627712 B CN109627712 B CN 109627712B
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- 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
- C08K2201/00—Specific properties of additives
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- C08K2201/003—Additives being defined by their diameter
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Abstract
The invention provides a PBT composition, a preparation method and application thereof. The PBT composition comprises PBT, glass fibers, and hollow metal oxide particles; the hollow metal oxide particles comprise hollow microspheres and metal oxide coated on the surfaces of the hollow microspheres, wherein the metal oxide can be activated by laser to form metal cores. The PBT composition is prepared by melt extruding PBT, glass fiber and hollow metal oxide particles by an extruder. Compared with the material directly taking metal oxide as the LDS additive, the PBT composition provided by the invention has the advantages that less LDS additive is added, the adhesion of a metal coating after laser etching is higher, the mechanical property is better, the cost is lower, and the PBT composition can be used as a material for preparing a three-dimensional molding interconnection device.
Description
Technical Field
The invention belongs to the technical field of laser direct forming materials, and relates to a PBT composition, and a preparation method and application thereof.
Background
The three-dimensional molding interconnection device (3D-MID), also called a three-dimensional circuit or a three-dimensional circuit, is a three-dimensional circuit carrier formed by integrating the electrical interconnection function, the function of supporting components, the functions of supporting and protecting the plastic shell and the like of a common circuit board into a whole by manufacturing wires and patterns with electrical functions on the plastic shell which is formed by injection molding. The three-dimensional molding interconnection device has the design advantages that the shape can be selected according to the design requirement, the function is new, and the three-dimensional molding interconnection device is suitable for smaller and lighter development trends; the method also has the advantages of reducing installation levels, reducing the number of components, improving reliability, reducing the investment of material quantity and variety, being beneficial to economic environment aspects such as environment-friendly treatment and the like. 3D-MID has already had a considerable number of applications in fields such as car, industry, computer, communication at present, will certainly become an important branch of circuit board trade in the future.
The forming process of the 3D-MID mainly comprises two types, namely 2Shot MID (two-mold injection molding) and Laser Direct Structure (Laser Direct Structure), and currently, the LDS is mainly used. The LDS is a method in which a computer controls the movement of a laser according to the trace of a conductive pattern, the laser is projected onto a three-dimensional plastic device molded by a special material, and a circuit pattern is activated within a few seconds.
The plastics for laser direct structuring disclosed in CN 101784607A, CN 102066473a and CN 102066122A are both added with a non-conductive organic metal compound (such as copper salt or copper chromium compound) with a spinel structure as an LDS additive, and the organic metal compound is expensive and has a large amount of addition, which is not favorable for popularization and use in laser direct structuring plastics.
CN 101654564A discloses a plastic composition and a surface selective metallization process thereof, the method adopts the steps that a photocatalyst is added into plastic, and the plastic composition containing the photocatalyst exposes part of the photocatalyst in the plastic composition under the condition of laser irradiation; then, putting the plastic composition subjected to laser etching into an aqueous solution containing metal ion salts and a cavity sacrificial agent, and under the condition of light source irradiation capable of exciting the photocatalyst, reducing the metal ions in the solution by the photocatalyst exposed on the surface of the plastic composition to obtain nano-scale metal particles; and finally, carrying out metal chemical plating. However, the process needs to use a special photocatalyst and also needs to be matched with a hole sacrificial agent to improve the photocatalytic efficiency, and the process is complex; the adopted photocatalyst has large addition amount and high price; and the mechanical properties of the obtained plastic are poor.
Therefore, there is a need in the art to develop a laser direct structuring material with lower cost, simpler preparation process, and better mechanical properties to promote the development and application of 3D-MID.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a PBT composition, and a preparation method and application thereof. The PBT composition adopts hollow metal oxide particles as the LDS additive, can be directly formed by laser, and has the advantages of less LDS additive, higher adhesion of a metal coating after laser etching, better mechanical property and lower cost compared with a material directly taking metal oxide as the LDS additive.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a PBT composition comprising a PBT (polybutylene terephthalate), glass fibers, and hollow metal oxide particles;
the hollow metal oxide particles comprise hollow microspheres and metal oxide coated on the surfaces of the hollow microspheres, wherein the metal oxide can be activated by laser to form metal cores.
During the process of forming circuit patterns by irradiating the three-dimensional molding interconnection device with laser, only the LDS additive on the surface layer can be activated to form the metal core, and the LDS additive inside the plastic device does not participate in laser activation. The interior of the hollow metal oxide particles adopted by the invention is of a hollow structure and has lower density, and the PBT composition adopting the hollow metal oxide particles as the LDS additive can ensure that the surface of the material is activated to form a circuit pattern under laser irradiation, reduce the weight of the LDS additive in the material and reduce the cost, and the influence of a small addition amount on the mechanical property of the PBT base material is smaller.
As a preferred technical scheme of the invention, the PBT composition comprises the following components in percentage by weight:
PBT 30-89.5％；
10-50% of glass fiber;
0.5-20% of hollow metal oxide particles.
In the present invention, the weight percentage of the PBT may be 30%, 32%, 35%, 38%, 40%, 45%, 50%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 89.5%, or the like.
The weight percentage of the glass fiber may be 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, or the like.
The weight percentage of the hollow metal oxide particles can be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 7%, 8%, 9%, 10%, 12%, 13%, 15%, 16%, 18%, 20%, or the like.
Preferably, the PBT composition comprises the following components in percentage by weight:
PBT 61-74％；
25-35% of glass fiber;
1-4% of hollow metal oxide particles.
As a preferred embodiment of the present invention, the metal oxide is one or a combination of at least two selected from oxides of metal M, and the metal M is one or at least two selected from titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), niobium (Nb), rhodium (Rh), palladium (Pd), silver (Ag), cerium (Ce), iridium (Ir), platinum (Pt), or gold (Au).
Preferably, the metal oxide is copper chromium black.
Preferably, the metal oxide comprises 30-60% by mass of the hollow metal oxide particles; for example, it may be 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, etc.
Preferably, the hollow metal oxide particles have a particle size of 0.1 to 100. mu.m, and may be, for example, 0.1. mu.m, 0.5. mu.m, 1. mu.m, 2. mu.m, 5. mu.m, 8. mu.m, 10. mu.m, 15. mu.m, 20. mu.m, 25. mu.m, 30. mu.m, 35. mu.m, 40. mu.m, 45. mu.m, 50. mu.m, 60. mu.m, 70. mu.m, 80. mu.m, 90. mu.m, 100. mu.m, or the like; more preferably 1 to 50 μm.
Preferably, the density of the hollow metal oxide particles is from 1.5 to 3g/cm 3 (ii) a For example, it may be 1.5g/cm 3 、1.8g/cm 3 、2g/cm 3 、2.2g/cm 3 、2.5g/cm 3 、2.8g/cm 3 Or 3g/cm 3 And the like.
As a preferred embodiment of the present invention, the method for preparing the hollow metal oxide particles comprises the steps of:
(a) dissolving and dispersing the hollow microspheres and metal salts corresponding to the metal oxides in water to form a mixed solution;
(b) heating the mixed solution obtained in the step (a), adding a catalyst, adjusting the pH to 6-7, and heating until the water is evaporated to obtain a hollow metal oxide precursor;
(c) calcining the hollow metal oxide precursor obtained in step (b) to obtain hollow metal oxide particles;
in the step (a), the "metal salt corresponding to the metal oxide" refers to a salt of a metal element in the metal oxide, and may be a sulfate, a nitrate, an acetate, a chloride, or the like. The ratio of the hollow microspheres to the metal salt is not particularly limited, and can be calculated by a person skilled in the art according to the ratio of the hollow microspheres to the metal oxide in the hollow metal oxide particles by combining general technical knowledge.
Preferably, the temperature rise in the step (b) is to 40-100 ℃; for example, the temperature may be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃.
Preferably, the catalyst in step (b) is urea and/or sodium dodecylbenzenesulfonate.
Preferably, the method for adding the catalyst in the step (b) is dropwise.
Preferably, the temperature of the calcination in step (c) is 500-; further preferably 500 ℃ and 800 ℃.
Preferably, the calcination time is 1-5 h; for example, 1h, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h, 3.8h, 4h, 4.2h, 4.5h, 4.8h, or 5h, etc. may be mentioned.
As a preferable technical scheme of the invention, the hollow microspheres are hollow glass microspheres or hollow silicon dioxide microspheres.
Preferably, the glass fiber has a diameter of 10 to 13 μm and a diameter of 3 to 4 mm.
As a preferred embodiment of the invention, the PBT composition further comprises 0.02 to 2 wt.% (e.g., 0.02 wt.%, 0.05 wt.%, 0.08 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1 wt.%, 1.2 wt.%, 1.5 wt.%, 1.8 wt.%, or 2 wt.% of antioxidant).
Preferably, the antioxidant is a compound of a hindered phenol antioxidant and a phosphite antioxidant.
The mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is preferably 1: 1.
In a second aspect, the invention provides a method for preparing the PBT composition, which comprises the following steps:
(1) mixing PBT and optionally an antioxidant to form a premix;
(2) and (2) melt-extruding the premix obtained in the step (1), glass fibers and hollow metal oxide particles to obtain the PBT composition.
It is noted that the term "optionally" in step (1) above means either with or without the antioxidant, when added to the PBT composition, being mixed with the PBT; when the antioxidant is not added to the PBT composition, the PBT is directly melt-extruded with the glass fibers and the hollow metal oxide particles.
As a preferred embodiment of the present invention, the preparation method further comprises: the PBT is subjected to a drying treatment before the step (1).
The drying treatment method is preferably drying at 90-110 ℃ for 3-5 h.
Preferably, the mixing in step (1) is carried out in a mixer.
Preferably, the rotation speed of the mixer is 300-500r/min, such as 300r/min, 320r/min, 350r/min, 380r/min, 400r/min, 420r/min, 450r/min, 480r/min or 500 r/min; the mixing time is 10-20min, such as 10min, 12min, 13min, 15min, 16min, 18min or 20 min.
Preferably, the melt extrusion in step (2) is carried out in a parallel twin-screw extruder.
Preferably, the premix in step (2) is fed from a main feeding port of the parallel twin-screw extruder, and the hollow metal oxide particles are fed from a sixth zone of the parallel twin-screw extruder.
Preferably, the temperature of one zone of the parallel double-screw extruder is 200-;
the temperature of the second zone is 240 ℃ and 255 ℃, for example, 240 ℃, 242 ℃, 243 ℃, 245 ℃, 246 ℃, 248 ℃, 250 ℃, 252 ℃, 253 ℃, 255 ℃ and the like;
the temperature of the three zones is 240 ℃ and 255 ℃, for example, 240 ℃, 242 ℃, 243 ℃, 245 ℃, 246 ℃, 248 ℃, 250 ℃, 252 ℃, 253 ℃, 255 ℃ or the like;
the fourth zone is at a temperature of 240 ℃ and 255 ℃, and can be, for example, 240 ℃, 242 ℃, 243 ℃, 245 ℃, 246 ℃, 248 ℃, 250 ℃, 252 ℃, 253 ℃, 255 ℃ or the like;
the temperature of the fifth zone is 240 ℃ and 260 ℃, for example, 240 ℃, 242 ℃, 243 ℃, 245 ℃, 246 ℃, 248 ℃, 250 ℃, 252 ℃, 253 ℃, 255 ℃, 256 ℃, 258 ℃ or 260 ℃ and the like;
the temperature of the sixth zone is 240 ℃ and 260 ℃, for example, 240 ℃, 242 ℃, 243 ℃, 245 ℃, 246 ℃, 248 ℃, 250 ℃, 252 ℃, 253 ℃, 255 ℃, 256 ℃, 258 ℃ or 260 ℃ and the like;
the temperature of the seventh zone is 240 ℃ and 260 ℃, for example, 240 ℃, 242 ℃, 243 ℃, 245 ℃, 246 ℃, 248 ℃, 250 ℃, 252 ℃, 253 ℃, 255 ℃, 256 ℃, 258 ℃ or 260 ℃ and the like;
the temperature of the eight-zone is 240 ℃ and 260 ℃, for example, 240 ℃, 242 ℃, 243 ℃, 245 ℃, 246 ℃, 248 ℃, 250 ℃, 252 ℃, 253 ℃, 255 ℃, 256 ℃, 258 ℃ or 260 ℃ and the like;
the nine-zone temperature is 240 ℃ and 250 ℃, for example, 240 ℃, 241 ℃, 242 ℃, 243 ℃, 244 ℃, 245 ℃, 246 ℃, 247 ℃, 248 ℃, 249 ℃ or 250 ℃ and the like;
the die temperature is 240 ℃ to 250 ℃, and may be, for example, 240 ℃, 241 ℃, 242 ℃, 243 ℃, 244 ℃, 245 ℃, 246 ℃, 247 ℃, 248 ℃, 249 ℃, or 250 ℃.
Preferably, the residence time of the material in the parallel twin-screw extruder is 1-3 min; for example, the time period may be 1min, 1.2min, 1.5min, 1.8min, 2min, 2.2min, 2.5min, 2.8min or 3 min.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) drying the PBT, adding the PBT and an antioxidant into a mixer, and mixing for 10-20min at the rotating speed of 300-500r/min to form a premix;
(2) adding the premix obtained in the step (1) from a main feeding port of a parallel double-screw extruder, adding glass fiber from a side feeding port of the parallel double-screw extruder, adding hollow metal oxide particles from a sixth zone of the parallel double-screw extruder, controlling the temperature of a first zone of the parallel double-screw extruder to be 200-.
In a third aspect, the invention provides the use of a PBT composition as described above for a three-dimensional molded interconnect device.
Compared with the prior art, the invention has the following beneficial effects:
the PBT composition provided by the invention adopts the hollow metal oxide particles as the LDS additive, can be directly formed by laser, and has less LDS additive, higher adhesion of a metal coating after laser etching and 5B grade of adhesion of the metal coating when the addition of the hollow metal oxide particles reaches 3 wt% compared with a material directly taking the metal oxide as the LDS additive; better mechanical property and lower cost.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The sources of the raw materials adopted in the embodiment of the invention are as follows:
PBT: 1100A of blue Star (group) GmbH, China;
glass fiber: chongqing International composite materials GmbH, 3-4mm in length and 10-13 μm in diameter;
hollow metal oxide particles: the preparation method comprises the following steps:
preparation example 1
Preparing hollow copper-chromium black particles:
(a) adding 14g of hollow glass microspheres, 14g of copper nitrate trihydrate and 50g of chromium nitrate nonahydrate into 500mL of distilled water, and uniformly dissolving and dispersing to form a mixed solution;
(b) placing the mixed solution obtained in the step (a) on a constant-temperature magnetic stirrer, stirring and heating to 60 ℃, then dropwise adding urea, adjusting the pH of the mixed solution to 6-7 under the stirring condition, and continuously stirring and heating until the water evaporation is finished to obtain a hollow copper-chromium black precursor;
(c) placing the hollow copper-chromium black precursor obtained in the step (b) into an electric furnace, calcining for 2 hours at 550 ℃ to obtain hollow copper-chromium black particles, wherein the content of the copper-chromium black particles is 50 wt%, the particle size is 1-50 mu m, and the density is 1.8g/cm 3 。
Preparation example 2
(a) Adding 9g of hollow glass beads, 14g of copper nitrate trihydrate and 50g of chromium nitrate nonahydrate into 500mL of distilled water, and uniformly dissolving and dispersing to form a mixed solution;
(b) placing the mixed solution obtained in the step (a) on a constant-temperature magnetic stirrer, stirring and heating to 60 ℃, then dropwise adding urea, adjusting the pH of the mixed solution to 6-7 under the stirring condition, and continuously stirring and heating until the water evaporation is finished to obtain a hollow copper-chromium black precursor;
(c) placing the hollow copper-chromium black precursor obtained in the step (b) into an electric furnace, and calcining for 2 hours at 550 ℃ to obtain hollow copper-chromium black particles with copper-chromium black content60 wt%, particle diameter of 1-50 μm, density of 2.0g/cm 3 。
Preparation example 3
(a) Adding 32g of hollow glass beads, 14g of copper nitrate trihydrate and 50g of chromium nitrate nonahydrate into 500mL of distilled water, and uniformly dissolving and dispersing to form a mixed solution;
(b) placing the mixed solution obtained in the step (a) on a constant-temperature magnetic stirrer, stirring and heating to 60 ℃, then dropwise adding urea, adjusting the pH of the mixed solution to 6-7 under the stirring condition, and continuously stirring and heating until the water evaporation is finished to obtain a hollow copper-chromium black precursor;
(c) placing the hollow copper-chromium black precursor obtained in the step (b) in an electric furnace, calcining for 2 hours at 550 ℃ to obtain hollow copper-chromium black particles, wherein the content of the copper-chromium black is 30 wt%, the particle size is 1-50 mu m, and the density is 1.6g/cm 3 。
Example 1
The embodiment provides a PBT composition, which comprises the following components in percentage by weight:
the preparation method of the PBT composition comprises the following steps:
(1) drying PBT at 100 ℃ for 4h, adding PBT together with hindered phenol antioxidant beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) octadecyl propionate (antioxidant 1076) and phosphite antioxidant tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168) into a mixer, and mixing at a rotation speed of 300r/min for 20min to form a premix;
(2) adding the premix obtained in the step (1) from a main feeding port of a parallel double-screw extruder, adding glass fibers from a side feeding port of the parallel double-screw extruder, adding the hollow copper-chromium black particles provided in the preparation example 1 from a sixth zone of the parallel double-screw extruder, controlling the temperature of a first zone of the parallel double-screw extruder to be 200 ℃, the temperature of a second zone to be 240 ℃, the temperature of a third zone to be 240 ℃, the temperature of a fourth zone to be 240 ℃, the temperature of a fifth zone to be 245 ℃, the temperature of the sixth zone to be 245 ℃, the temperature of a seventh zone to be 245 ℃, the temperature of an eighth zone to be 245 ℃, the temperature of a ninth zone to be 240 ℃, keeping time of materials in the parallel double-screw extruder to be 1min, and obtaining the PBT composition after melt extrusion.
Example 2
The embodiment provides a PBT composition, which comprises the following components in percentage by weight:
the preparation method of the PBT composition comprises the following steps:
(1) drying PBT at 90 ℃ for 5h, adding PBT together with hindered phenol antioxidant beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) octadecyl propionate (antioxidant 1076) and phosphite antioxidant tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168) into a mixer, and mixing at a rotation speed of 500r/min for 10min to form a premix;
(2) adding the premix obtained in the step (1) from a main feeding port of a parallel double-screw extruder, adding glass fibers from a side feeding port of the parallel double-screw extruder, adding the hollow copper-chromium black particles provided in the preparation example 1 from a sixth zone of the parallel double-screw extruder, controlling the temperature of a first zone of the parallel double-screw extruder to be 210 ℃, the temperature of a second zone to be 255 ℃, the temperature of a third zone to be 255 ℃, the temperature of a fourth zone to be 255 ℃, the temperature of a fifth zone to be 260 ℃, the temperature of the sixth zone to be 260 ℃, the temperature of a seventh zone to be 260 ℃, the temperature of an eighth zone to be 260 ℃, the temperature of a ninth zone to be 250 ℃, keeping time of materials in the parallel double-screw extruder to be 2min, and obtaining the PBT composition after melt extrusion.
Example 3
The embodiment provides a PBT composition, which comprises the following components in percentage by weight:
the preparation method of the PBT composition comprises the following steps:
(1) drying PBT at 110 ℃ for 3h, adding the PBT, hindered phenol antioxidant beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) octadecyl propionate (antioxidant 1076) and phosphite antioxidant tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168) into a mixer, and mixing at the rotating speed of 400r/min for 15min to form a premix;
(2) adding the premix obtained in the step (1) from a main feeding port of a parallel double-screw extruder, adding glass fibers from a side feeding port of the parallel double-screw extruder, adding the hollow copper-chromium black particles provided in the preparation example 1 from a sixth zone of the parallel double-screw extruder, controlling the temperature of a first zone of the parallel double-screw extruder to be 205 ℃, the temperature of a second zone to be 250 ℃, the temperature of a third zone to be 250 ℃, the temperature of a fourth zone to be 250 ℃, the temperature of a fifth zone to be 255 ℃, the temperature of a sixth zone to be 255 ℃, the temperature of a seventh zone to be 255 ℃, the temperature of an eighth zone to be 255 ℃, the temperature of a ninth zone to be 245 ℃, the temperature of a die head to be 245 ℃, keeping time of materials in the parallel double-screw extruder to be 3min, and obtaining the PBT composition after melt extrusion.
Example 4
The embodiment provides a PBT composition, which comprises the following components in percentage by weight:
the preparation method of the PBT composition comprises the following steps:
(1) drying PBT at 100 ℃ for 4h, adding the PBT, hindered phenol antioxidant beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) octadecyl propionate (antioxidant 1076) and phosphite antioxidant tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168) into a mixer, and mixing at the rotating speed of 300r/min for 20min to form a premix;
(2) adding the premix obtained in the step (1) from a main feeding port of a parallel double-screw extruder, adding glass fibers from a side feeding port of the parallel double-screw extruder, adding the hollow copper-chromium black particles provided in the preparation example 1 from a sixth zone of the parallel double-screw extruder, controlling the temperature of a first zone of the parallel double-screw extruder to be 200 ℃, the temperature of a second zone to be 240 ℃, the temperature of a third zone to be 240 ℃, the temperature of a fourth zone to be 240 ℃, the temperature of a fifth zone to be 250 ℃, the temperature of the sixth zone to be 250 ℃, the temperature of a seventh zone to be 250 ℃, the temperature of an eighth zone to be 250 ℃, the temperature of a ninth zone to be 250 ℃, and the residence time of materials in the parallel double-screw extruder to be 2min, and obtaining the PBT composition after melt extrusion.
Example 5
The difference from example 3 is that the weight percentage of PBT is 61.6%, and the weight percentage of the hollow copper-chromium black granules of preparation 1 is 8%.
Example 6
The difference from example 3 is that the weight percentage of PBT is 49.6%, and the weight percentage of the hollow copper-chromium black granules of preparation 1 is 20%.
Example 7
The difference from example 3 is that the hollow copper chromium black granules of preparation example 1 were replaced by the hollow copper chromium black granules of preparation example 2.
Example 8
The difference from example 3 is that the hollow copper chromium black granules of preparation example 1 were replaced with the hollow copper chromium black granules of preparation example 3.
Comparative example 1
The difference from example 3 is that the hollow copper chromium black particles were replaced with copper chromium black powder and the preparation procedure was the same as in example 3.
Comparative example 2
The difference from example 5 is that the hollow copper chromium black particles were replaced with copper chromium black powder and the preparation procedure was the same as in example 5.
The PBT compositions provided in examples 1-8 and comparative examples 1-2 above were injection molded into shaped plastic parts. According to the conventional method, the wavelength is 900-1080nm, and the energy is 150-300mJ/cm 2 The laser carries out laser etching on the preset area of the plastic part according to a set pattern at the scanning speed of 0.1-1mm/s, the plastic part after laser etching is plated with copper in a chemical way, and copper is formed in the laser etching area of the plastic partAnd (7) plating. The plastic parts and the electroless copper plated plastic parts were then tested for their performance according to the following criteria and methods:
tensile strength: the tensile rate is 50mm/min according to the test of ASTM-D638;
notched impact strength: the thickness of the sample strip is 3.2mm, the temperature is 23 ℃, and the RH is 50 percent according to the test of ASTM-D256 standard;
flexural strength and flexural modulus: the bending rate is 10mm/min according to the test of ASTM-D790;
and (3) adhesion of a copper plating layer: the test is carried out according to ASTM D3359 standard, which comprises the following steps:
under the conditions of room temperature of 23 +/-2 ℃ and relative humidity of 50 +/-5%, 10 multiplied by 10 small grids of 1 multiplied by 1mm are scribed on the surface of a test sample by a sharp blade (the angle of the blade is 15-30 ℃), and each scribing line is deep and a plating bottom layer is formed; brushing the test area by using a brush, firmly sticking the tested small grid by using a 3M 600 adhesive tape, and forcibly wiping the adhesive tape by using an eraser to increase the contact area and force between the adhesive tape and the tested area; grasping one end of the adhesive tape by hand, rapidly pulling off the adhesive tape at an angle of 60 degrees in the vertical direction, and carrying out 2 times of same tests at the same position;
and (4) judging a result: the adhesive force is qualified when the adhesive force is required to be more than or equal to 4B;
5B-the scribing edge is smooth, and no paint falls off at the scribing edge and the intersection;
4B-there are small pieces of paint falling off at the cross point of the line, and the total area of falling off is less than 5%;
3B-small pieces of paint fall off at the edges and the cross points of the drawn lines, and the total area of the fall off is between 5 and 15 percent;
2B-pieces of paint fall off at the edges and the cross points of the lines, and the total area of the fall off is 15-35%;
1B-pieces of paint fall off at the edges and intersections of the score lines, and the total area of the fall off is between 35 and 65 percent;
0B-there is a patch of paint falling off at the edge and intersection of the score line, and the total area of falling off is greater than 65%.
The results of the above performance tests are shown in tables 1 and 2 below:
TABLE 1
TABLE 2
As can be seen from the data in tables 1 and 2, the PBT compositions provided by the present invention can be laser direct molded. Comparing example 3 with comparative example 1, it can be seen that the PBT composition provided by the invention has higher metal plating adhesion, and the metal plating adhesion of the PBT composition added with 3 wt% of metal oxide powder does not meet the requirement; comparing example 3 with comparative example 2, it can be seen that when the adhesion of the metal plating layer is the same, the PBT composition provided by the invention requires fewer hollow metal oxide particles, and the mechanical properties of the obtained PBT composition are also better.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (24)
1. A PBT composition, comprising PBT, glass fibers and hollow metal oxide particles;
the PBT composition comprises the following components in percentage by weight:
PBT 61-74%；
25-35% of glass fiber;
1-4% of hollow metal oxide particles;
the hollow metal oxide particles comprise hollow microspheres and metal oxide coated on the surfaces of the hollow microspheres, and the metal oxide can be activated by laser to form metal cores;
the metal oxide is copper chromium black;
the metal oxide accounts for 30-60% of the mass of the hollow metal oxide particles;
the preparation method of the hollow metal oxide particles comprises the following steps:
(a) dissolving and dispersing the hollow microspheres and metal salts corresponding to metal oxides in water to form a mixed solution;
(b) heating the mixed solution obtained in the step (a), adding a catalyst, adjusting the pH to 6-7, and heating until the water is evaporated to obtain a hollow metal oxide precursor;
(c) calcining the hollow metal oxide precursor obtained in step (b) to obtain the hollow metal oxide particles.
2. The PBT composition of claim 1, wherein the hollow metal oxide particles have a particle size of 0.1 to 100 μm.
3. The PBT composition of claim 1, wherein the hollow metal oxide particles have a particle size of 1-50 μm.
4. PBT composition according to claim 1, wherein the density of the hollow metal oxide particles is between 1.5 and 3g/cm 3 。
5. PBT composition according to claim 1, wherein the temperature increase in step (b) of the process for the preparation of the hollow metal oxide particles is to 40-100 ℃.
6. The PBT composition of claim 1, wherein the catalyst in step (b) of the process for preparing the hollow metal oxide particles is urea and/or sodium dodecylbenzenesulfonate.
7. The PBT composition of claim 1, wherein the catalyst is added in step (b) of the process for preparing the hollow metal oxide particles by dropwise addition.
8. The PBT composition of claim 1, wherein the temperature of the calcination in step (c) in the process for preparing the hollow metal oxide particles is 500-1200 ℃.
9. The PBT composition of claim 1, wherein the temperature of the calcination in step (c) in the process for preparing the hollow metal oxide particles is 500-800 ℃.
10. PBT composition according to claim 1, wherein the time of calcination in step (C) in the process for the preparation of hollow metal oxide particles is between 1 and 5 h.
11. The PBT composition of claim 1, wherein the cenospheres are cenospheres of hollow glass or hollow silica.
12. PBT composition according to claim 1, wherein the glass fibres have a length of 3-4mm and a diameter of 10-13 μm.
13. The PBT composition of claim 1, further comprising 0.02 to 2 wt.% of an antioxidant.
14. The PBT composition of claim 13, wherein the antioxidant is a combination of a hindered phenolic antioxidant and a phosphite antioxidant.
15. A process for the preparation of a PBT composition according to any of claims 1-14, comprising the steps of:
(1) mixing the PBT and optionally an antioxidant to form a premix;
(2) and (2) melt-extruding the premix obtained in the step (1), glass fibers and hollow metal oxide particles to obtain the PBT composition.
16. The method of manufacturing according to claim 15, further comprising: the PBT is subjected to a drying treatment before the step (1).
17. The method of claim 15, wherein the mixing in step (1) is performed in a mixer.
18. The method as claimed in claim 17, wherein the rotation speed of the mixer is 300-500r/min, and the mixing time is 10-20 min.
19. The production method according to claim 15, wherein the melt extrusion in step (2) is carried out in a parallel twin-screw extruder.
20. The method of claim 19, wherein said premix in step (2) is fed from a main feeding port of said parallel twin-screw extruder, and said hollow metal oxide particles are fed from a sixth zone of said parallel twin-screw extruder.
21. The method as claimed in claim 19, wherein the temperature of the first zone of the parallel twin-screw extruder is 200-.
22. The method of claim 19, wherein the residence time of the material in the parallel twin screw extruder is 1-3 min.
23. The method of manufacturing according to claim 15, comprising the steps of:
(1) drying the PBT, adding the PBT and an antioxidant into a mixer, and mixing for 10-20min at the rotating speed of 300-500r/min to form a premix;
(2) adding the premix obtained in the step (1) from a main feeding port of a parallel double-screw extruder, adding glass fiber from a side feeding port of the parallel double-screw extruder, adding hollow metal oxide particles from a sixth zone of the parallel double-screw extruder, controlling the temperature of a first zone of the parallel double-screw extruder to be 200-.
24. Use of the PBT composition of any of claims 1-14, wherein the PBT composition is used in a three-dimensional molded interconnect device.
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