CN103923449B - The PC/ABS composite of laser direct forming and preparation method and application - Google Patents
The PC/ABS composite of laser direct forming and preparation method and application Download PDFInfo
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Abstract
The invention belongs to laser direct forming field of compound material, disclose one can laser direct forming, and there is the PC/ABS composite of superior thermal oxygen aging performance and its preparation method and application.This composite comprises the component of following mass fraction: PC/ABS base material 60～80%；Halogen-free flame retardants 5～15%；Laser activation particle 5～15%；Heat conduction inorganic filler 0～10%；Other additives 0～5%；Laser activation particle is obtained from following methods: drip copper nanoparticle, initiator, the alcoholic solution of silane coupler in the forward microemulsion that acrylic ester monomer/Dodecyl trimethyl ammonium chloride/water forms, reacting by heating, filter, be dried, obtain laser activation particle.Metallic copper is modified by the present invention by microemulsion polymerization method, it is thus achieved that both had good induced with laser plating performance, has again the PC/ABS composite of the laser direct forming of excellent thermo oxidative aging performance.
Description
Technical field
The invention belongs to laser direct forming technical field of composite materials, can be connected into by laser straight particularly to one
Type, and there is the PC/ABS composite of superior thermal oxygen aging performance and its preparation method and application.
Background technology
3D-molding interconnection element (Three-dimensional moulded interconnect device,
It is 3D-MID) a kind of making circuit pattern on the plastic basis material of injection mo(u)lding, thus by common
Electric interconnection function, supporting and the safeguard function of circuit board is implemented on a device, forms solid, collection
Dynamo-electric function is in the circuit carrier of one.Compared with traditional wiring board production technology, 3D-molds interconnector
Part production technology has speed of production faster, and flow process is simpler, and cost is more controlled, and application is broader
Feature.Such as, using the sensor that laser direct structuring technique (LDS) manufactures, minimum conductor width can
Reaching 100～200 μm, between minimum line, width is up to 100 μm, and this not only decreases the quantity of components and parts, also
Reach save space and alleviate the purpose of weight.At present, the antenna that laser direct structuring technique manufactures is used
It is widely used in automobile, on the mobile terminal such as smart mobile phone, notebook computer.
Laser direct structuring technique is to be irradiated to laser containing laser-sensitive additive under the control of the computer
Plastic part on, produce the circuit pattern of activation, this activating area can be by without the side of electrochemical plating
Method conductive metal deposition, thus realize producing the technical matters of conductive pattern on three-dimensional plastic product.Profit
The technique making molding interconnection element of laser direct forming mainly includes three below step: resin base material
Injection mo(u)lding, the Laser Processing of LDS element and circuit pattern metallization.This technical process can swash
The exploitation of the polymeric substrate of light straight forming is one of the most key part.Therefore, design and prepare tool
The polymer composites having laser direct forming performance has extremely important industrial value.
CN1198737C reports a kind of Merlon aliphatic radical material and has the Cupric chromate(III). of spinel structure
As laser activation agent can laser direct forming material.With iraser, base material is carried out Selective activation
After, by controlled circuit pattern can be formed at activating area without the method for electrochemical plating.
CN103450675A discloses a kind of resin combination with laser direct forming function: resin base
Body 15～60wt%；Heat filling 30～70wt%；Laser-sensitive additive 5～12wt%；And other
Additive 0～15wt%.Laser-sensitive additive therein be chemical general formula be XY2O4Copper-containing metal oxygen
Compound.
Above-mentioned document all it should be particularly mentioned and utilize the oxide of copper or copper organometallic complex as laser
Activating reagent.Under the corrasion of laser, polymeric substrate can occur melted or degraded depression, makes laser
The nano metal simple substance that activating reagent restores is deposited on etching surface.Using nano metal simple substance as nucleus,
Induction-chemical deposition conducting metal, can prepare the circuit pattern of μm level.But, on the one hand, due to this
A little metallic copper compounds are susceptible to decompose in the course of processing, and the elemental copper of generation is enriched in product surface,
Have a strong impact on the effect without electrochemical plating；Still further aspect, easily causes polymeric material due to copper compound
Thermo-oxidative ageing (Degradation and Stabilization of Polymer, Applied Science and
Publishers LTD London, 1975,90-92).In above-mentioned composite-material formula, metallic copper element with
There is directly contact between polymeric substrate, make polymeric substrate be easy in the catalysis of copper compound and issue heat
Oxygen aging reacts, and affects the service life of goods.Therefore, preparation one has good mechanics and resistance to ag(e)ing
Can the polymer composites of laser direct forming be a very important research topic.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, the primary and foremost purpose of the present invention is to provide one to swash
PC/ABS(polycarbonate/acrylonitrile-SB the alloy of light straight forming) composite wood
Material, this composite has good induced with laser plating performance and excellent thermo oxidative aging performance.
Another object of the present invention is to provide the PC/ABS composite of a kind of above-mentioned laser direct forming
Preparation method.
Still a further object of the present invention is that the PC/ABS composite providing above-mentioned laser direct forming is at electronics
Application in the fields such as electrical equipment, Aero-Space, transportation, Industry Control.
The purpose of the present invention is realized by following proposal:
The PC/ABS composite of a kind of laser direct forming, comprises the component of following mass fraction:
Described laser activation particle is prepared by following methods:
Drip in the forward microemulsion of acrylic ester monomer/Dodecyl trimethyl ammonium chloride/water composition and receive
Rice copper powder, initiator, the alcoholic solution of silane coupler, reacting by heating, filters, is dried, obtain laser and live
Change particle.
Dodecyl trimethyl ammonium chloride, acrylic ester monomer, the mass ratio of water in described forward microemulsion
For 5:30:100.
Amount is acrylic ester monomer quality the 1～5% of copper nanoparticle used.
Amount is acrylic ester monomer quality the 1～2% of initiator used.
Amount is acrylic ester monomer quality the 1～5% of silane coupler used.
Described initiator is azo-initiator, preferably azo isobutyronitrile.
Described silane coupler is preferably isobutyl group triethoxy silicone couplet.
The solvent of described alcoholic solution is methanol, ethanol or isopropanol.
In described alcoholic solution, the concentration of copper nanoparticle is 10～30wt%.
Described reacting by heating refers to react 5h at 60～90 DEG C.
Described acrylic ester monomer is preferably acrylic acid methyl ester., methyl methacrylate, methacrylic acid
Propyl ester, butyl methacrylate, isobutyl methacrylate, sec-butyl acrylate, tert-butyl acrylate,
N-propyl, cyclohexyl acrylate, lauryl acrylate, 2-EHA, acrylic acid
At least one in 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester and methacrylic acid.More preferably acrylic acid
At least one in methyl ester and methyl methacrylate.
The present invention by micro-emulsion polymerization preparation obtain laser activation particle, on the one hand, utilize acrylate with
The compatibility of base material is good, improves laser activation particle in PC/ABS(polycarbonate/acrylonitrile-styrene-fourth
Diene copolymers alloy) dispersibility in base material；On the other hand, by surface modification can completely cut off metallic copper with
The directly contact of polymeric substrate, reduces the thermo-oxidative ageing reaction of the polymeric substrate of metallic copper catalysis, improves
The life-span of product.
In the PC/ABS composite of described laser direct forming, the addition of laser activation particle is preferably
7～10wt%.When laser activation particle addition is too low, need electroplating time long, circuit and base material
Adhesion is poor；When laser activation particle addition is too high, plating process easily causes the crackings such as excessive plating
Phenomenon, affects the electronic apparatus performance of goods.
In the PC/ABS composite of described laser direct forming, the poly-carbonic acid of PC(in PC/ABS base material
Ester) weight hundred parts be 50～90% than content, preferably 60～70%.
Described halogen-free flame retardants is preferably triphenylphosphine compound, three tertiary butyl phosphine compounds, tar acid phosphorus
Acid esters, alkyl diaryl phosphate, trialkyl phosphates, biphosphonate, carbon phosphate ester, chlorinated phosphate
With at least one in phosphoramidate, more preferably triphenylphosphine compound and three tertiary butyl phosphine compounds
At least one.
The heat conduction inorganic filler that the present invention uses is preferably glass fibre, titanium dioxide, Pulvis Talci, sericite
With at least one in Kaolin, more preferably glass fibre.
Other additives selected by the present invention include: at least one in releasing agent, antioxidant and compatilizer.
In order to the object of the invention is better achieved, releasing agent is preferably pentaerythritol stearate；Antioxidant is excellent
Elect three [2,4-di-t-butyl] phenyl phosphites as；Compatilizer is preferably ABS-g-MAH.
Present invention also offers the preparation method of the PC/ABS composite of above-mentioned laser direct forming, including
Following steps:
60～80wt%PC/ABS base materials, 5～15wt% halogen-free flame retardants, 5～15wt% laser activation grain
Son, 0～other additive mix homogeneously of 5wt%, add in screw extruder, and 0～10wt% heat conduction is inorganic fills out
Expect that, by entering the addition of glass mouth, through screw extruder extruding pelletization, the PC/ABS obtaining laser direct forming is combined
Material.
Described mix homogeneously preferably stirs in homogenizer.
Each section of temperature of described extruding pelletization is 230～260 DEG C.
Preferably, the main-machine screw rotating speed of described screw extruder is 250～330r/min, hopper feed spiral shell
The rotating speed of bar is 24～35r/min.
Laser activation particle in the PC/ABS composite of laser direct forming of the present invention is multiple to PC/ABS
Condensation material plays an important role in laser processing procedure.The goods table that laser beam is made at composite
Face is inswept, material matrix is ablated off, and forms rough region, can increase electroless metal layer with
The adhesion strength of resin matrix；On the other hand, laser activation particle, under the effect of laser, restores metal
Granule is attached on rough matrices of composite material, follow-up without in electrochemical plating, and these metallic particles
Play the effect of active centre, promote the metal ion in chemical plating fluid to deposit selectively, formed
Metallic film.
The PC/ABS composite Laser Processing of the laser direct forming of the present invention is functional, and heat-resisting oxygen
Ageing properties is excellent, can be applicable in the fields such as electronic apparatus, Aero-Space, transportation, Industry Control.
It is particularly well-suited to the product of surface mounting technology, is mainly used in electric part field.Pass through laser
Then electric elements are directly sealed by straight forming Technology design and prepare the electric elements with difference in functionality
It is contained on circuit, this process simplification circuit production process of material, greatly improves the space profit of product
By rate.Such as the application on smart mobile phone, it is possible to realize circuit board of mobile phone system melting with sheathing material is one
Body, it is achieved product is more frivolous, dispels the heat more efficient, the effect in extending cell phone service life.
The mechanism of the present invention is:
The present invention utilizes acrylate be modified metallic copper by micro-emulsion polymerization and modify, it is thus achieved that at base
Dispersibility more preferable laser activation particle in material, and by the modification to metallic copper, completely cut off metallic copper and be polymerized
The directly contact of thing base material, reduces the thermo-oxidative ageing reaction of the polymeric substrate of metallic copper catalysis, improves product
Life-span, it is thus achieved that both there is good induced with laser plating performance, there is again excellent thermo oxidative aging performance
The PC/ABS composite of laser direct forming.
The present invention, relative to prior art, has such advantages as and beneficial effect:
(1) in the PC/ABS composite of the laser direct forming of the present invention laser activation particle due to warp
Acrylate modified, there is more preferable dispersibility in the substrate, improve the induced with laser plating of composite
Performance.
(2) in the PC/ABS composite of the laser direct forming of the present invention laser activation particle due to warp
Acrylate modified, reduce the thermo-oxidative ageing reaction of the polymeric substrate of metallic copper catalysis, improve heat resistanceheat resistant oxygen
Ageing properties, improves the life-span of product.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention do not limit
In this.
In following example, in the PC/ABS composite of laser direct forming, the content of PC is 70%, tool
The processing mode of body is: will be by the load weighted material of formula (except heat conduction inorganic filler) in following each embodiment
Join stirring 10min, the above-mentioned material (heat conduction inorganic filler that then will stir in homogenizer
It is directly added into by the glass mouth that adds of double screw extruder) to join draw ratio L/D be 38:1, screw diameter
For in the hopper of the parallel double-screw extruder of 30mm, set the extruder each section of temperature from hopper to die head
Degree is respectively (totally six district): 230 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 250 DEG C, 260 DEG C, main frame
Screw speed is 300r/min, and the rotating speed of hopper feed screw rod is 28r/min, and then by material blended melting
Extrusion；Above-mentioned grain bar cools down through tank, enters pelleter and carry out pelletizing after air-drying, and injection obtains swashing
The PC/ABS composite of light straight forming.
Embodiment 1: the preparation of the PC/ABS composite of laser direct forming
PC/ABS alloy 74wt%, halogen-free flame retardants selects Reofos TPP(triphenylphosphine compound) 10
Wt%, laser activation particle 5wt%；Glass fibre 10wt%；Antioxidant (three [2,4-di-t-butyl] benzene
Base phosphite ester) 0.5wt%, compatilizer (ABS-g-MAH) 0.5wt%.
The preparation of described laser activation particle: under nitrogen atmosphere, equipped with agitator, reflux condensing tube, perseverance
Press and the reactor of Dropping funnel, thermometer adds the acrylic ester monomer (methyl methacrylate configured
Ester) the forward microemulsion 1L of/Dodecyl trimethyl ammonium chloride/water composition, wherein acrylic ester monomer/
The mass ratio of Dodecyl trimethyl ammonium chloride/water is 30:5:100.Under conditions of room temperature is stirred vigorously, slowly
Dropping copper nanoparticle concentration is the 3% of 30wt%(acrylic ester monomer quality), (azo is different for initiator
Butyronitrile, the 1% of acrylic ester monomer quality), silane coupler (isobutyl group triethoxysilicane, propylene
The 1% of esters of gallic acid monomer mass) ethanol solution.After dropping, it is warming up to 80 DEG C of reaction 5h, cold
But, sucking filtration, it is dried to obtain laser activation particle.
Test result shows: notch impact strength is tested: 48KJ/m2；Flame retardant test: thick at 1.6mm
Degree meets fire-retardant UL94V-0 grade；Relative permitivity: 2.93；Dissipation factor: 0.007；Metallic film
Thickness 7.2 μm, hundred lattice test metallic films come off area < 5%；The thermo oxidative aging performance test of material:
Stretching strength retentivity 82%, impact strength conservation rate 84%.
Embodiment 2: the preparation of the PC/ABS composite of laser direct forming
PC/ABS alloy 69wt%, halogen-free flame retardants selects Reofos TPP(triphenylphosphine compound) 10
Wt%, laser activation particle 10wt%；Glass fibre 10wt%；Antioxidant (three [2,4-di-t-butyl] benzene
Base phosphite ester) 0.5wt%, compatilizer (ABS-g-MAH) 0.5wt%.
The preparation of described laser activation particle: under nitrogen atmosphere, equipped with agitator, reflux condensing tube, perseverance
Press and the reactor of Dropping funnel, thermometer adds the acrylic ester monomer (methyl methacrylate configured
Ester) the forward microemulsion 1L of/Dodecyl trimethyl ammonium chloride/water composition, wherein acrylic ester monomer/
The mass ratio of Dodecyl trimethyl ammonium chloride/water is 30:5:100.Under conditions of room temperature is stirred vigorously, slowly
Dropping copper nanoparticle concentration is the 1% of 20wt%(acrylic ester monomer quality), (azo is different for initiator
Butyronitrile, the 1% of acrylic ester monomer quality), silane coupler (isobutyl group triethoxysilicane, propylene
The 1% of esters of gallic acid monomer mass) methanol solution.After dropping, it is warming up to 80 DEG C of reaction 5h, cold
But, sucking filtration, it is dried to obtain laser activation particle.
Test result shows: notch impact strength is tested: 47KJ/m2；Flame retardant test: thick at 1.6mm
Degree meets fire-retardant UL94V-0 grade；Relative permitivity: 2.93；Dissipation factor: 0.007；Metallic film
Thickness 7.8 μm, hundred lattice test metallic films come off area < 5%；The thermo oxidative aging performance test of material:
Stretching strength retentivity 80%, impact strength conservation rate 82%.
Embodiment 3: the preparation of the PC/ABS composite of laser direct forming
PC/ABS alloy 64wt%, halogen-free flame retardants selects Reofos TPP(Great Lakes Chemical) 10wt%,
Laser activation particle 15wt%；Glass fibre 10wt%；Antioxidant (three [2,4-di-t-butyl] phenyl phosphorous
Acid esters) 0.5wt%, compatilizer (ABS-g-MAH) 0.5wt%.
The preparation of described laser activation particle: under nitrogen atmosphere, equipped with agitator, reflux condensing tube, perseverance
Press and the reactor of Dropping funnel, thermometer adds the acrylic ester monomer (methacrylic acid third configured
Ester) the forward microemulsion 1L of/Dodecyl trimethyl ammonium chloride/water composition, wherein acrylic ester monomer/
The mass ratio of Dodecyl trimethyl ammonium chloride/water is 30:5:100.Under conditions of room temperature is stirred vigorously, slowly
Dropping copper nanoparticle concentration is the 5% of 20wt%(acrylic ester monomer quality), (azo is different for initiator
Butyronitrile, the 2% of acrylic ester monomer quality), silane coupler (isobutyl group triethoxysilicane, propylene
The 5% of esters of gallic acid monomer mass) aqueous isopropanol.After dropping, it is warming up to 80 DEG C of reaction 5h,
Cooling, sucking filtration, it is dried to obtain laser activation particle.
Test result shows: notch impact strength is tested: 40KJ/m2；Flame retardant test: thick at 1.6mm
Degree meets fire-retardant UL94V-0 grade；Relative permitivity: 2.92；Dissipation factor: 0.007；Metallic film
Thickness 8.7 μm, hundred lattice test metallic films come off area < 5%；The thermo oxidative aging performance test of material:
Stretching strength retentivity 80%, impact strength conservation rate 85%.
Embodiment 4: the preparation of the PC/ABS composite of laser direct forming
PC/ABS alloy 69wt%, halogen-free flame retardants selects Reofos TPP(triphenylphosphine compound) 10
Wt%, laser activation particle 10wt%；Glass fibre 10wt%；Antioxidant (three [2,4-di-t-butyl] benzene
Base phosphite ester) 0.5wt%, compatilizer (ABS-g-MAH) 0.5wt%.
The preparation of described laser activation particle: under nitrogen atmosphere, equipped with agitator, reflux condensing tube, perseverance
Press and the reactor of Dropping funnel, thermometer adds acrylic ester monomer (the methacrylic acid fourth configured
Ester) the forward microemulsion 1L of/Dodecyl trimethyl ammonium chloride/water composition, wherein acrylic ester monomer/
The mass ratio of Dodecyl trimethyl ammonium chloride/water is 30:5:100.Under conditions of room temperature is stirred vigorously, slowly
Dropping copper nanoparticle concentration is the 3% of 30wt%(acrylic ester monomer quality), (azo is different for initiator
Butyronitrile, the 1% of acrylic ester monomer quality), silane coupler (isobutyl group triethoxysilicane, propylene
The 1% of esters of gallic acid monomer mass) ethanol solution.After dropping, it is warming up to 80 DEG C of reaction 5h, cold
But, sucking filtration, it is dried to obtain laser activation particle.
Test result shows: notch impact strength is tested: 35KJ/m2；Flame retardant test: thick at 1.6mm
Degree meets fire-retardant UL94V-0 grade；Relative permitivity: 2.92；Dissipation factor: 0.007；Metallic film
Thickness 8.4 μm, hundred lattice test metallic films come off area < 5%；The thermo oxidative aging performance test of material:
Stretching strength retentivity 79%, impact strength conservation rate 85%.
Embodiment 5: the preparation of the PC/ABS composite of laser direct forming
PC/ABS alloy 69wt%, halogen-free flame retardants selects Reofos TPP(triphenylphosphine compound) 10
Wt%, laser activation particle 10wt%；Glass fibre 10wt%；Antioxidant (three [2,4-di-t-butyl] benzene
Base phosphite ester) 0.5wt%, compatilizer (ABS-g-MAH) 0.5wt%.
The preparation of described laser activation particle: under nitrogen atmosphere, equipped with agitator, reflux condensing tube, perseverance
(methacrylic acid is different to press the acrylic ester monomer that in the reactor of Dropping funnel, thermometer, addition has configured
Butyl ester) the forward microemulsion 1 of/Dodecyl trimethyl ammonium chloride/water composition, wherein acrylic ester monomer/
The mass ratio of Dodecyl trimethyl ammonium chloride/water is 30:5:100.Under conditions of room temperature is stirred vigorously, slowly
Dropping copper nanoparticle concentration is the 1.5% of 30wt%(acrylic ester monomer quality), initiator (azo
Isopropyl cyanide, the 1% of acrylic ester monomer quality), silane coupler (isobutyl group triethoxysilicane, third
The 1% of olefin(e) acid esters monomer quality) ethanol solution.After dropping, it is warming up to 80 DEG C of reaction 5h,
Cooling, sucking filtration, it is dried to obtain laser activation particle.
Test result shows: notch impact strength is tested: 32KJ/m2；Flame retardant test: thick at 1.6mm
Degree meets fire-retardant UL94V-0 grade；Relative permitivity: 2.92；Dissipation factor: 0.007；Metallic film
Thickness 8.6 μm, hundred lattice test metallic films come off area < 5%；The thermo oxidative aging performance test of material:
Stretching strength retentivity 79%, impact strength conservation rate 83%.
Embodiment 6: the preparation of the PC/ABS composite of laser direct forming
PC/ABS alloy 69wt%, halogen-free flame retardants selects Reofos TPP(triphenylphosphine compound) 10
Wt%, laser activation particle 10wt%；Glass fibre 10wt%；Antioxidant (three [2,4-di-t-butyl] benzene
Base phosphite ester) 0.5wt%, compatilizer (ABS-g-MAH) 0.5wt%.
The preparation of described laser activation particle: under nitrogen atmosphere, equipped with agitator, reflux condensing tube, perseverance
Press and the reactor of Dropping funnel, thermometer adds the acrylic ester monomer (tert-butyl acrylate) configured
The forward microemulsion 1L of/Dodecyl trimethyl ammonium chloride/water composition, wherein acrylic ester monomer/12
The mass ratio of alkyl trimethyl ammonium bromide/water is 30:5:100.Under conditions of room temperature is stirred vigorously, it is slowly added dropwise
Copper nanoparticle concentration is the 1.5% of 20wt%(acrylic ester monomer quality), initiator (azo isobutyl
Nitrile, the 2% of acrylic ester monomer quality), silane coupler (isobutyl group triethoxysilicane, acrylic acid
The 1% of esters monomer quality) ethanol solution.After dropping, it is warming up to 80 DEG C of reaction 5h, cools down,
Sucking filtration, is dried to obtain laser activation particle.
Test result shows: notch impact strength is tested: 37KJ/m2；Flame retardant test: thick at 1.6mm
Degree meets fire-retardant UL94V-0 grade；Relative permitivity: 2.97；Dissipation factor: 0.007；Metallic film
Thickness 7.8 μm, hundred lattice test metallic films come off area < 5%；The thermo oxidative aging performance test of material:
Stretching strength retentivity 76%, impact strength conservation rate 78%.
Embodiment 7: the preparation of the PC/ABS composite of laser direct forming
PC/ABS alloy 69wt%, halogen-free flame retardants selects Reofos TPP(triphenylphosphine compound) 10
Wt%, laser activation particle 10wt%；Glass fibre 10wt%；Antioxidant (three [2,4-di-t-butyl] benzene
Base phosphite ester) 0.5wt%, compatilizer (ABS-g-MAH) 0.5wt%.
The preparation of described laser activation particle: under nitrogen atmosphere, equipped with agitator, reflux condensing tube, perseverance
Press and the reactor of Dropping funnel, thermometer adds the acrylic ester monomer (methyl methacrylate configured
Ester) the forward microemulsion 1L of/Dodecyl trimethyl ammonium chloride/water composition, wherein acrylic ester monomer/
The mass ratio of Dodecyl trimethyl ammonium chloride/water is 30:5:100.Under conditions of room temperature is stirred vigorously, slowly
Dropping copper nanoparticle concentration is the 1.5% of 10wt%(acrylic ester monomer quality), initiator (azo
Isopropyl cyanide, the 1% of acrylic ester monomer quality), silane coupler (isobutyl group triethoxysilicane, third
The 3% of olefin(e) acid esters monomer quality) ethanol solution.After dropping, it is warming up to 80 DEG C of reaction 5h,
Cooling, sucking filtration, it is dried to obtain laser activation particle.
Test result shows: notch impact strength is tested: 38KJ/m2；Flame retardant test: thick at 1.6mm
Degree meets fire-retardant UL94V-0 grade；Relative permitivity: 2.92；Dissipation factor: 0.007；Metallic film
Thickness 7.4 μm, hundred lattice test metallic films come off area < 5%；The thermo oxidative aging performance test of material:
Stretching strength retentivity 78%, impact strength conservation rate 81%.
Embodiment 8: the preparation of the PC/ABS composite of laser direct forming
PC/ABS alloy 69wt%, halogen-free flame retardants selects Reofos TPP(triphenylphosphine compound) 10
Wt%, laser activation particle 10wt%；Glass fibre 10wt%；Antioxidant (three [2,4-di-t-butyl] benzene
Base phosphite ester) 0.5wt%, compatilizer (ABS-g-MAH) 0.5wt%.
The preparation of described laser activation particle: under nitrogen atmosphere, equipped with agitator, reflux condensing tube, perseverance
Press and the reactor of Dropping funnel, thermometer adds the acrylic ester monomer (methyl methacrylate configured
Ester) the forward microemulsion 1L of/Dodecyl trimethyl ammonium chloride/water composition, wherein acrylic ester monomer/
The mass ratio of Dodecyl trimethyl ammonium chloride/water is 30:5:100.Under conditions of room temperature is stirred vigorously, slowly
Dropping copper nanoparticle concentration is the 5% of 30wt%(acrylic ester monomer quality), (azo is different for initiator
Butyronitrile, the 1% of acrylic ester monomer quality), silane coupler (isobutyl group triethoxysilicane, propylene
The 5% of esters of gallic acid monomer mass) ethanol solution.After dropping, it is warming up to 80 DEG C of reaction 5h, cold
But, sucking filtration, it is dried to obtain laser activation particle.
Test result shows: notch impact strength is tested: 36KJ/m2；Flame retardant test: thick at 1.6mm
Degree meets fire-retardant UL94V-0 grade；Relative permitivity: 2.92；Dissipation factor: 0.007；Metallic film
Thickness 7.6 μm, hundred lattice test metallic films come off area < 5%；The thermo oxidative aging performance test of material:
Stretching strength retentivity 77%, impact strength conservation rate 80%.
Embodiment 9: the preparation of the PC/ABS composite of laser direct forming
PC/ABS alloy 69wt%, halogen-free flame retardants selects Reofos TPP(triphenylphosphine compound) 10
Wt%, laser activation particle 10wt%；Glass fibre 10wt%；Antioxidant (three [2,4-di-t-butyl] benzene
Base phosphite ester) 0.5wt%, compatilizer (ABS-g-MAH) 0.5wt%.
The preparation of described laser activation particle: under nitrogen atmosphere, equipped with agitator, reflux condensing tube, perseverance
Press and the reactor of Dropping funnel, thermometer adds the acrylic ester monomer (acrylic acid methyl ester .) configured
The forward microemulsion 1L of/Dodecyl trimethyl ammonium chloride/water composition, wherein acrylic ester monomer/12
The mass ratio of alkyl trimethyl ammonium bromide/water is 30:5:100.Under conditions of room temperature is stirred vigorously, it is slowly added dropwise
Copper nanoparticle concentration is the 1.5% of 30wt%(acrylic ester monomer quality), initiator (azo isobutyl
Nitrile, the 1% of acrylic ester monomer quality), silane coupler (isobutyl group triethoxysilicane, acrylic acid
The 1% of esters monomer quality) ethanol solution.After dropping, it is warming up to 60 DEG C of reaction 5h, cools down,
Sucking filtration, is dried to obtain laser activation particle.
Test result shows: notch impact strength is tested: 35KJ/m2；Flame retardant test: thick at 1.6mm
Degree meets fire-retardant UL94V-0 grade；Relative permitivity: 2.92；Dissipation factor: 0.007；Metallic film
Thickness 7.9 μm, hundred lattice test metallic films come off area < 5%；The thermo oxidative aging performance test of material:
Stretching strength retentivity 81%, impact strength conservation rate 85%.
Embodiment 10: the preparation of the PC/ABS composite of laser direct forming
PC/ABS alloy 69wt%, halogen-free flame retardants selects Reofos TPP(triphenylphosphine compound) 10
Wt%, laser activation particle 10wt%；Glass fibre 10wt%；Antioxidant (three [2,4-di-t-butyl] benzene
Base phosphite ester) 0.5wt%, compatilizer (ABS-g-MAH) 0.5wt%.
The preparation of described laser activation particle: under nitrogen atmosphere, equipped with agitator, reflux condensing tube, perseverance
Press and the reactor of Dropping funnel, thermometer adds acrylic ester monomer (the methacrylic acid fourth configured
Ester) the forward microemulsion 1L of/Dodecyl trimethyl ammonium chloride/water composition, wherein acrylic ester monomer/
The mass ratio of Dodecyl trimethyl ammonium chloride/water is 30:5:100.Under conditions of room temperature is stirred vigorously, slowly
Dropping copper nanoparticle concentration is the 1.5% of 30wt%(acrylic ester monomer quality), initiator (azo
Isopropyl cyanide, the 1% of acrylic ester monomer quality), silane coupler (isobutyl group triethoxysilicane, third
The 1% of olefin(e) acid esters monomer quality) ethanol solution.After dropping, it is warming up to 80 DEG C of reaction 3h,
Cooling, sucking filtration, it is dried to obtain laser activation particle.
Test result shows: notch impact strength is tested: 36KJ/m2；Flame retardant test: thick at 1.6mm
Degree meets fire-retardant UL94V-0 grade；Relative permitivity: 2.92；Dissipation factor: 0.007；Metallic film
Thickness 7.4 μm, hundred lattice test metallic films come off area < 5%；The thermo oxidative aging performance test of material:
Stretching strength retentivity 78%, impact strength conservation rate 83%.
Comparative example
PC/ABS alloy 79wt%, halogen-free flame retardants selects Reofos TPP(triphenylphosphine compound) 10
Wt%, laser activation particle addition 0wt%；Glass fibre 10wt%；Antioxidant (three [the tertiary fourths of 2,4-bis-
Base] phenyl phosphites) 0.5wt%, compatilizer (ABS-g-MAH) 0.5wt%.
Test result shows: notch impact strength is tested: 46KJ/m2；Flame retardant test: thick at 1.6mm
Degree meets fire-retardant UL94V-0 grade；Relative permitivity: 2.95；Dissipation factor: 0.007；Resisting of material
Thermal-oxidative aging property is tested: stretching strength retentivity 83%, impact strength conservation rate 85%；Laser ablation
After can not carry out without electrochemical plating.
In above-described embodiment, the method for test is: the simple beam impact strength of material is carried out by ISO179, examination
Sample ruler cun 80 × 6 × 4mm, notch depth is 1/3rd of sample thickness；The fire resistance test of material
Standard is that GB2409-84 uses vertical combustion；Relative permitivity and dissipation factor testing standard are ASTM
D150.The test of thickness without electrochemical plating of material, i.e. test LDS material deposit in without electrochemical plating
Thickness of metal film, requires in industry that film thickness is in being distributed in 7～12 μm qualified.Hundred lattice tests,
On metallic film, i.e. cut the grid of 100 1mm × 1mm with cutter, stick with 3M610 adhesive tape
Place vertical pull-up after about 2min after patch, the area that comes off of metallic film < 5% be qualified；Material
Thermo oxidative aging performance is tested according to GB/T7141-2008, prepared plastics carries out artificial accelerated aging real
Test (90 DEG C, 500h), and measure the hot strength before and after this plastic artificial's accelerated ageing, cantilever beam respectively
Notch impact strength.
From above-mentioned test result, the PC/ABS composite wood of the laser direct forming that the present invention prepares
Material can realize laser direct forming, and has good heatproof air aging performance and physical property, meets industry
The needs produced.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-mentioned reality
Execute the restriction of example, the change made under other any spirit without departing from the present invention and principle, modification,
Substitute, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. the PC/ABS composite of a laser direct forming, it is characterised in that comprise following quality and divide
The component of number:
Described laser activation particle is prepared by following methods:
Drip in the forward microemulsion of acrylic ester monomer/Dodecyl trimethyl ammonium chloride/water composition and receive
Rice copper powder, initiator, the alcoholic solution of silane coupler, reacting by heating, filters, is dried, obtain laser and live
Change particle.
The PC/ABS composite of laser direct forming the most according to claim 1, its feature exists
In: Dodecyl trimethyl ammonium chloride, acrylic ester monomer, the mass ratio of water in described forward microemulsion
For 5:30:100.
The PC/ABS composite of laser direct forming the most according to claim 1, its feature exists
In: the amount of copper nanoparticle used is the 1～5% of acrylic ester monomer quality；The amount of initiator used is third
The 1～2% of olefin(e) acid esters monomer quality；The amount of silane coupler used is acrylic ester monomer quality
1～5%.
The PC/ABS composite of laser direct forming the most according to claim 1, its feature exists
In: in described alcoholic solution, the concentration of copper nanoparticle is 10～30wt%；Described reacting by heating refers at 60～90 DEG C
Reaction 5h.
The PC/ABS composite of laser direct forming the most according to claim 1, its feature exists
In: described acrylic ester monomer be acrylic acid methyl ester., methyl methacrylate, propyl methacrylate,
Butyl methacrylate, isobutyl methacrylate, sec-butyl acrylate, tert-butyl acrylate, acrylic acid
N-propyl, cyclohexyl acrylate, lauryl acrylate, 2-EHA, acrylic acid 2-hydroxyl
At least one in ethyl ester and acrylic acid 2-hydroxy propyl ester.
The PC/ABS composite of laser direct forming the most according to claim 1, its feature exists
In: described halogen-free flame retardants be triphenylphosphine compound, three tertiary butyl phosphine compounds, tar acid phosphate ester,
Alkyl diaryl phosphate, trialkyl phosphates, biphosphonate, carbon phosphate ester, chlorinated phosphate and amino
At least one in phosphate ester；Described heat conduction inorganic filler be glass fibre, titanium dioxide, Pulvis Talci,
At least one in sericite and Kaolin；Described initiator is azo-initiator；Described other add
Adding agent is at least one in releasing agent, antioxidant and compatilizer.
The PC/ABS composite of laser direct forming the most according to claim 1, its feature exists
In: described acrylic ester monomer is at least one in acrylic acid methyl ester. and methyl methacrylate；Institute
The halogen-free flame retardants stated is at least one in triphenylphosphine compound and three tertiary butyl phosphine compounds；Described
Initiator is azo isobutyronitrile；Described silane coupler is isobutyl group triethoxy silicone couplet；Described
Heat conduction inorganic filler is glass fibre.
8. the PC/ABS composite wood according to the laser direct forming described in any one of claim 1～7
The preparation method of material, it is characterised in that comprise the following steps:
60～80wt%PC/ABS base materials, 5～15wt% halogen-free flame retardants, 5～15wt% laser activation grain
Son, 0～other additive mix homogeneously of 5wt%, add in screw extruder, and 0～10wt% heat conduction is inorganic fills out
Expect that, by entering the addition of glass mouth, through screw extruder extruding pelletization, the PC/ABS obtaining laser direct forming is combined
Material.
The preparation method of the PC/ABS composite of laser direct forming the most according to claim 8,
It is characterized in that: each section of temperature of described extruding pelletization is 230～260 DEG C.
10. exist according to the PC/ABS composite of the laser direct forming described in any one of claim 1～7
Application in electronic apparatus, Aero-Space, transportation, Industry Control.
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| CN104387738B (en) * | 2014-11-19 | 2016-08-17 | 东莞市三条化成实业有限公司 | A kind of preparation method of the laser powder of white laser straight forming material |
| TWI507459B (en) * | 2015-02-12 | 2015-11-11 | Taiflex Scient Co Ltd | Resin composition capable of forming metal circuit |
| CN105504745B (en) * | 2015-12-25 | 2018-07-27 | 金发科技股份有限公司 | A kind of polycarbonate composite material |
| CN105514601A (en) * | 2015-12-31 | 2016-04-20 | 昆山骅盛电子有限公司 | Fin-style vehicular antenna and method for producing same |
| CN106883580A (en) * | 2017-04-07 | 2017-06-23 | 深圳市华盈新材料有限公司 | Laser direct forming PC composites and its preparation technology |
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