CN109575554A - High finished product rate laser direct forming LDS composite material and preparation method - Google Patents
High finished product rate laser direct forming LDS composite material and preparation method Download PDFInfo
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- CN109575554A CN109575554A CN201811273770.8A CN201811273770A CN109575554A CN 109575554 A CN109575554 A CN 109575554A CN 201811273770 A CN201811273770 A CN 201811273770A CN 109575554 A CN109575554 A CN 109575554A
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
The present invention discloses a kind of high finished product rate laser direct forming LDS composite material, and the LDS composite material is grouped as by the group of following parts by weight: 52 ~ 86 parts of polycarbonate, ABS10 ~ 30 part, 10 ~ 30 parts of glass, 10 ~ 30 parts of fire retardant, 4 ~ 6 parts of toughener, 0.1 ~ 1 part of lubricant, 0.2 ~ 1 part of antioxidant, 10 ~ 30 parts of modified laser sensitive additives；The preparation step of the modified laser sensitive additives are as follows: with the mass ratio of 98.9:1:0.1 by B material, C material, A material be added high-speed mixer in, 70-80 DEG C, 450-550 turn/min revolving speed under obtain modified laser sensitive additives after mixing evenly.The present invention improves the yield rate of the LDS polymer composite of laser direct forming.LDS polymer composite has preferable LDS performance, can guarantee the yield rate of product surface electronic circuit after higher radium-shineization plating.
Description
Technical field
The present invention relates to LDS field of compound material more particularly to a kind of high finished product rate laser direct forming LDS composite materials
And preparation method thereof.
Background technique
LDS(Laser Direct Structuring) laser direct structuring technique is a kind of laser fabrication technology, industry
Also referred to as three-dimensional (3D) three-dimensional circuit printing technique, is the intelligence manufacture of the selectively formed metal wire pattern on plastic cement product
Technology, and the popular method of manufacture antenna for mobile phone recently.Traditional plastic cement product will have electric property, need to by with metal
Welding, the processes such as compound are completed, and product is not easily achieved microminiaturization, high precision int.And it is added to the plastic cement product of LDS auxiliary agent
After can be by processes such as laser engraving and electroless platings, directly has the function of electric interconnection.Obviously, it is no longer necessary to traditional
Circuit board, route design is also more flexible, while the assembling of part is also more convenient, it is most important that the volume of product can be made significant
It reduces.LDS laser Direct Three-dimensional circuit forming technique allows designer after completing molding, in the premise for not changing tool
Under its circuit design can be changed.It provides the ability that production has high-precision with more small silk-screen component.The development of LDS technology
So far more stable mature, relatively other traditional handicrafts, LDS makes with three-dimensional circuit, saves space, device is more
Small, lighter, function is more, and design freedom is bigger；Flexible manufacturing, as long as route modification modification CAD data, is not required to modification mould
Tool；Processing procedure is simplified, and only there are three steps, and research and development manufacturing time is short, and a process service prototype and mass production, processing procedure are stable；
Environmental protection, no chemical surface additive (anacidity), without photoresist, without etching；Accuracy is high, adds down to 150 microns of filaments
The technical advantages such as work ability.Intelligent mobile phone antenna, notebook electricity are had been widely used for using the LDS material of LDS technology at present
Brain antenna, in the products such as Medical Devices sensor, automobile equipment sensor, electric, vehicle electronics, computer, electromechanical equipment,
The industry fields such as medical instrument.
Realize LDS technique, it is important to one or more organometallic compounds (laser are added in high molecular material
Sensitive additives), after laser irradiation, restore organometallic compounds, and release metallic and be agglomerated into metal
Grain, metallic particles are anchored at the resin surface crossed by laser ablation and form metallic core, and this metallic core is in subsequent nothing
Electrochemical plating process plays the important function of nucleus and seed.Due to metallic core and plastic cement there are thermal expansion/contraction rate and
The difference of surface polarity causes metallic core to be easy to be detached from from the resin surface crossed by laser ablation, departing from metallic core
Position just lacked in next no electrochemical plating process and provide the nucleus and seed of implantation, plating metal for plating metal
Defect is occurred as soon as at the position, continuous electroplating line cannot be formed, eventually leads to that metal adhesion is poor, product defect, non-defective unit
Rate is low.
From the point of view of current domestic patent, it is described polycarbonate resin substrate LDS material preparation method, such as patent CN
106883577 A of 104497537A, CN is described glass fiber-reinforced polycarbonate resin LDS material preparation method, such as patent CN
107177180 107177181 A of A, CN, are described the preparation method of the LDS material of light color, such as patent CN 107236275
A, 106751389 A of CN is described the composite material and preparation method thereof suitable for NMT and LDS technique, such as patent CN
105368049 A,CN 105694447 B,CN 105623206 A,CN 105623206 B,.However, being related to preparing laser
The most crucial key of the LDS polymer composite of straight forming: after how ensuring laser irradiation by formula and preparation method
The metallic that LDS material restores can be fixed, and improve patent of the metal adhesion to improve yield rate and do not have substantially but
Have.
Summary of the invention
The object of the present invention is to provide a kind of high finished product rate laser direct forming LDS composite material, the high finished product rate laser
Straight forming LDS composite material can improve the yield rate of the LDS polymer composite of laser direct forming.The LDS composite wood
Material has preferable LDS performance, can guarantee higher qualification rate that is radium-shine, changing product surface electronic circuit after plating；Meanwhile it providing
A kind of preparation method of high finished product rate laser direct forming LDS composite material.
To reach foregoing invention composite material purpose, the present invention is compound using a kind of high finished product rate laser direct forming LDS
Material, the LDS composite material are grouped as by the group of following parts by weight:
52 ~ 86 parts of polycarbonate,
0 ~ 30 part of ABS,
0 ~ 30 part of glass,
10 ~ 30 parts of fire retardant,
4 ~ 6 parts of toughener,
0.1 ~ 1 part of lubricant,
0.2 ~ 1 part of antioxidant,
10 ~ 30 parts of modified laser sensitive additives；
The preparation step of the modified laser sensitive additives are as follows:
Be (1~3) by mass ratio: 3 weak acid and water obtains mixed solution A after mixing in proportion, and the weak acid is phosphorous
At least one of acid, phosphoric acid or two kinds of mixture；
Be (2~6) by mass ratio: 1 Cu-Cr spinelle and filler obtains B material after mixing, and the filler is titanium white
Powder, hydrotalcite, hollow glass micropearl, talcum powder, mica powder, it is a kind of in graphene or at least two mixture；
By metal cation salt ionomer broken up using super mixer or by mass ratio be 1:10 metal cation salt ionomer and
Acetone obtains modifying agent C material after mixing, and the metal cation salt ionomer is Zn2+、Al3+The acrylic acid of ion, sulfonic acid,
Phosphoric acid, acetic acid, stearic acid, maleate ionomer, it is preferable that the metal ion ionomer be sulfonated polysulfone zinc/aluminium salt from
Polymers, vinyl sulfonic acid zinc/aluminium salt ionomer, ethylene maleic acid zinc/aluminium salt ionomer, ethylene-acrylic acid copolymer zinc/aluminium salt are from poly-
One or two kinds of mixture in object, ethylene-vinyl acetate copolymerization zinc/aluminium salt ionomer；
With 100: (0.1~2): (1~20) mass ratio expects B, A material, C material sequentially add in high-speed mixer, every addition
After a kind of material, 5~30 minutes need to be stirred under 45~75 DEG C, 200~500rpm/min revolving speed, after mixing evenly again plus other one
Kind material obtains the modified laser sensitive additives until adding all material after mixing evenly.
The further improved technical solution of above-mentioned technical proposal is as follows:
1. in above scheme, the glass is plain cylindrical form section glass fibre and/or section glass fibre, preferably
Cross section is variable cross-section section glass fibre and/or cross-section section glass fibre, and more preferable cross-section abnormity is disconnected
Surface glass fiber, degree of profile are 1 .5~4:1；The diameter of fiber is 6~13mm, preferably 9~11mm.
2. in above scheme, the fire retardant is one or more compoundings of phosphorus flame retardant and nitrogenated flame retardant,
In the mixture, the weight percent content of the nitrogenated flame retardant is 0~70%, the weight hundred of the phosphorus flame retardant
Dividing than content is 10~100%.
3. in above scheme, the nitrogenated flame retardant is melamine, dicyandiamide, melamine polyphosphate, trimerization
Cyanamide cyanurate, the phosphorus series non-halogen fire retardant are phosphate, phosphinate or hypophosphites, phenyl hypophosphites, two
Alkyl phosphinate, diphenyl phosphate.
4. in above scheme, the toughener is MBS, SEBS, SIS, POE, EBA, EMA, organosilicon core-shell polymer or
Silicon-containing compound or resin.
5. in above scheme, the lubricant is pentaerythritol stearate PETS.
6. in above scheme, the antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi
Alcohol ester (anti-1010), three [2,4- di-tert-butyl-phenyl] phosphite esters (anti-168), β-(3,5- di-tert-butyl-hydroxy phenyl)
Propionic acid n-octadecyl alcohol ester (anti-1076), N, N'- is bis--and (3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (resists
1098), one or more of four-(2,4- di-tert-butyl-phenyl) -4,4 '-xenyl bis-phosphites (anti-P-EPQ).
To reach above-mentioned preparation method goal of the invention, the present invention is compound using a kind of high finished product rate laser direct forming LDS
The preparation method of material, comprising the following steps:
Step 1: being (1~3) by mass ratio: 3 weak acid and water obtains mixed solution A, the weak acid after mixing in proportion
For at least one of phosphorous acid, phosphoric acid or two kinds of mixture；It is (2~6): 1 Cu-Cr spinelle and filling by mass ratio
Agent obtains B material after mixing, and the filler is titanium dioxide, hydrotalcite, hollow glass micropearl, talcum powder, mica powder, graphite
In alkene it is a kind of or at least two mixture；Metal cation salt ionomer is broken up using super mixer or is by mass ratio
The metal cation salt ionomer and acetone of 1:10 obtains modifying agent C material after mixing, and the metal cation salt ionomer is Zn2 +、Al3+Acrylic acid, sulfonic acid, phosphoric acid, acetic acid, stearic acid, the maleate ionomer of ion, it is preferable that the metal ion from
Polymers is sulfonated polysulfone zinc/aluminium salt ionomer, vinyl sulfonic acid zinc/aluminium salt ionomer, ethylene maleic acid zinc/aluminium salt ionomer, second
One or two kinds of mixing in alkene acrylic acid copolymer zinc/aluminium salt ionomer, ethylene-vinyl acetate copolymerization zinc/aluminium salt ionomer
Object；With 100: (0.1~2): (1~20) mass ratio expects B, A material, C material sequentially add in high-speed mixer, every to be added one
After kind material, it need to be stirred under 45~75 DEG C, 200~500rpm/min revolving speed 5~30 minutes, add another again after mixing evenly
Material obtains the modified laser sensitive additives until adding all material after mixing evenly；
Step 2: weighing 52 ~ 86 parts of polycarbonate, 0 ~ 30 part of ABS, 10 ~ 30 parts of fire retardant, toughener 4 ~ 6 according to parts by weight
After part, 0.1 ~ 1 part of lubricant, 0.2 ~ 1 part of antioxidant and 10 ~ 30 parts of modified laser sensitive additives, mixed
Material, adds mixture into the main feeding of double screw extruder, 0 ~ 30 part of glass is added in the side feed material of double screw extruder,
It is drawn after melting extrusion from the outlet of die head, pelletizing obtains high finished product rate laser direct forming LDS composite particles after water cooling.
The further improved technical solution of above-mentioned technical proposal is as follows:
In above scheme, the melting extrusion temperature of the double screw extruder is 250~350 DEG C, screw speed is 250~
450rpm/min。
Due to the application of the above technical scheme, compared with the prior art, the invention has the following advantages:
High finished product rate laser direct forming LDS composite material and preparation method of the present invention, uses the laser of modification quick
Sense additive can effectively improve the plating index of material and the yield rate of LDS product, this is because modification can effectively improve
Dispersibility of the laser-sensitive additive in resin, while it being formed by metallic core after capable of being effectively anchored laser irradiation, it prevents
It is detached from from the resin surface crossed by laser ablation, improves metal adhesion, so that product plating defect is significantly reduced,
Improve yields；In addition, modification can effectively eliminate adverse effect of the laser-sensitive additive to mechanical performance, improve
Tensile strength, notch impact strength mechanical strength, also improve the heat distortion temperature of material.
Specific embodiment
The present invention will be further described below with reference to examples:
Embodiment 1: a kind of high finished product rate laser direct forming LDS composite material, the LDS composite material is by following parts by weight
Group is grouped as:
86 parts of polycarbonate,
5 parts of melamine cyanurate,
4 parts of hypo-aluminum orthophosphate,
5 parts of MBS,
0.5 part of PETS,
0.2 part of antioxidant 1010,
0.1 part of irgasfos 168,
10 parts of modified laser sensitive additives；
The preparation methods of the modified laser sensitive additives the following steps are included:
Phosphoric acid and water that mass ratio is 2:3 are mixed to get mixed solution A；
Cu-Cr spinelle and hydrotalcite that mass ratio is 4:1 are obtained into B material after mixing；
Ethylene maleic acid aluminium salt ionomer and acetone that mass ratio is 1:10 are obtained into modifying agent C material after mixing；
B material, A material, C material are sequentially added in high-speed mixer with the mass ratio of 100:1:10,50 DEG C, 300rpm/min revolving speed
Lower stirring 15 minutes, adds another material again after mixing evenly, until adding all material, obtains described change after mixing evenly
Property laser-sensitive additive；
86 parts of polycarbonate, 5 parts of melamine polyphosphate, 4 parts of hypo-aluminum orthophosphate, MBS5 parts, PETS are weighed according to parts by weight
0.5 part, antioxidant 1010 be 0.2 part, irgasfos 168 is 0.1 part, after 10 parts of modified laser sensitive additives, be uniformly mixed
It to mixture, adds mixture into the main feeding of double screw extruder, is drawn after melting extrusion from the outlet of die head, after water cooling
Pelletizing obtains high finished product rate laser direct forming LDS composite particles.
The melting extrusion temperature of above-mentioned double screw extruder is 250~300 DEG C, screw speed 350rpm/min.
Embodiment 2: a kind of high finished product rate laser direct forming LDS composite material, the LDS composite material is by following weight
The group of part is grouped as:
60 parts of polycarbonate,
26 parts of ABS,
5 parts of melamine,
4 parts of diphenyl phosphate,
5 parts of SEBS,
0.3 part of PETS,
0.2 part of antioxidant 1076,
0.1 part of irgasfos 168,
15 parts of modified laser sensitive additives；
The preparation methods of the modified laser sensitive additives the following steps are included:
Hypophosphorous acid and water that mass ratio is 1:3 are mixed to get mixed solution A；
Cu-Cr spinelle and graphene and hollow glass micropearl mixture that mass ratio is 5:1 are obtained into B material after mixing,
This graphene is mixed with hollow glass micropearl according to 1:20 parts by weight；
Sulfonated polysulfone zinc salt ionomer/vinyl sulfonic acid aluminium salt ionomer and acetone that mass ratio is 1:1 are mixed with mass ratio 1:10
Modifying agent C material is obtained after closing uniformly；
B material, A material, C material are sequentially added in high-speed mixer with the mass ratio of 100:2:15,50 DEG C, 300rpm/min revolving speed
Lower stirring 15 minutes, adds another material again after mixing evenly, until adding all material, obtains described change after mixing evenly
Property laser-sensitive additive；
Weigh according to parts by weight 60 parts of polycarbonate, ABS26 parts, 5 parts of melamine, 4 parts of diphenyl phosphate, SEBS5 parts,
PETS0.3 parts, antioxidant 1076 be 0.2 part, irgasfos 168 is 0.1 part, after 15 parts of modified laser sensitive additives, mixing is equal
It is even to obtain mixture, it adds mixture into the main feeding of double screw extruder, is drawn after melting extrusion from the outlet of die head, water
Pelletizing obtains high finished product rate laser direct forming LDS composite particles after cold.
The melting extrusion temperature of above-mentioned double screw extruder is 250~280 DEG C, screw speed 400rpm/min.
Embodiment 3: a kind of high finished product rate laser direct forming LDS composite material, the LDS composite material is by following weight
The group of part is grouped as:
60 parts of polycarbonate,
26 parts of glass,
5 parts of melamine polyphosphate,
4 parts of dialkylphosphinic salts,
5 parts of POE,
0.8 part of PETS,
1,098 0.2 parts of antioxidant,
0.1 part of irgasfos 168,
20 parts of modified laser sensitive additives；
The preparation methods of the modified laser sensitive additives the following steps are included:
Phosphoric acid and water that mass ratio is 1:1 are mixed to get mixed solution A；
Cu-Cr spinelle and mica powder and titanium dioxide (1:1) mixture that mass ratio is 3:1 are obtained into B material after mixing；
Ethylene-vinyl acetate zinc salt ionomer and acetone that mass ratio is 1:10 are obtained into modifying agent C material after mixing；
B material, A material, C material are sequentially added in high-speed mixer with the mass ratio of 100:0.8:20,65 DEG C, 400rpm/min turns
The lower stirring of speed 30 minutes until adding all material, obtains described after mixing evenly after mixing evenly again plus another material
Modified laser sensitive additives；
60 parts of polycarbonate, 5 parts of melamine polyphosphate, 4 parts of dialkylphosphinic salts, POE5 are weighed according to parts by weight
Part, PETS0.8 part, antioxidant 1098 be 0.2 part, irgasfos 168 be 0.1 part, after 20 parts of modified laser sensitive additives, mix
Mixture uniformly is obtained, is added mixture into the main feeding of double screw extruder, by 26 parts of addition double screw extruders of glass
Side feed material in, drawn after melting extrusion from the outlet of die head, it is multiple to obtain high finished product rate laser direct forming LDS for pelletizing after water cooling
Condensation material particle.
The melting extrusion temperature of above-mentioned double screw extruder is 250~280 DEG C, screw speed 250rpm/min.
Embodiment 4: a kind of high finished product rate laser direct forming LDS composite material, the LDS composite material is by following weight
The group of part is grouped as:
45 parts of polycarbonate,
20 parts of ABS,
20 parts of glass,
5 parts of melamine cyanurate,
4 parts of diphenyl phosphate,
5 parts of SIS,
0.2 part of PETS,
0.2 part of antioxidant 1076,
0.1 part of irgasfos 168,
25 parts of modified laser sensitive additives；
The preparation methods of the modified laser sensitive additives the following steps are included:
Phosphoric acid and water that mass ratio is 2:3 are mixed to get mixed solution A；
Cu-Cr spinelle and talcum powder and graphene (20:1) mixture that mass ratio is 2:1 are obtained into B material after mixing；
Modifying agent C material is obtained after ethylene acrylic aluminium salt ionomer super mixer is broken up；
B material, A material, C material are sequentially added in high-speed mixer with the mass ratio of 100:0.2:2,50 DEG C, 200rpm/min revolving speed
Lower stirring 15 minutes, adds another material again after mixing evenly, until adding all material, obtains described change after mixing evenly
Property laser-sensitive additive；
45 parts of polycarbonate, ABS20 parts, 20 parts of glass, 5 parts of melamine cyanurate, di(2-ethylhexyl)phosphate are weighed according to parts by weight
4 parts of phenyl ester, SIS5 parts, PETS0.2 parts, antioxidant 1076 be 0.2 part, irgasfos 168 is 0.1 part, modified laser sensitivity addition
It after 25 parts of agent, is uniformly mixed and obtains mixture, add mixture into the main feeding of double screw extruder, 20 parts of glass are added
It in the side feed material of double screw extruder, is drawn after melting extrusion from the outlet of die head, pelletizing obtains high finished product rate laser after water cooling
Straight forming LDS composite particles.
The melting extrusion temperature of above-mentioned double screw extruder is 250~280 DEG C, screw speed 250rpm/min.
Embodiment 5: a kind of high finished product rate laser direct forming LDS composite material, the component and embodiment 1 of parts by weight
Except that: 86 parts of polycarbonate in 1 formula composition of alternative embodiment are 60 parts of polycarbonate, 26 parts of ABS, are formulated it
It is formed remains unchanged with dosage.Changing laser-sensitive additive in formula, the preparation method is the same as that of Example 1.The high finished product rate laser
The preparation method of straight forming LDS composite material is same as Example 1.
Embodiment 6: a kind of high finished product rate laser direct forming LDS composite material, the component and embodiment 1 of parts by weight
Except that: 86 parts of polycarbonate in 1 formula composition of alternative embodiment are 60 parts of polycarbonate, 26 parts of glass, are formulated it
It is formed remains unchanged with dosage.Changing laser-sensitive additive in formula, the preparation method is the same as that of Example 1.The high finished product rate laser
The preparation method of straight forming LDS composite material is same as Example 1.
Embodiment 7: a kind of high finished product rate laser direct forming LDS composite material, the component and embodiment 1 of parts by weight
Except that: 86 parts of polycarbonate in 1 formula composition of alternative embodiment are 40 parts of polycarbonate, ABS20 parts, glass 26
Part, it is formulated other compositions and dosage remains unchanged.Changing laser-sensitive additive in formula, the preparation method is the same as that of Example 1.The height
The preparation method of yield rate laser direct forming LDS composite material is same as Example 1.
Comparative example 1:
With embodiment 1 except that without being expected using A material and C in the preparation step of modified laser sensitive additives.
Comparative example 2:
With embodiment 1 except that each component and the other components one of LDS composite-material formula in modified laser sensitive additives
It rises and is mixed directly rear double screw extruder extrusion processing.
Comparative example 3:
With embodiment 1 except that laser-sensitive addition of C u-Cr spinelle does not pass through modification and directly uses.
After tested, embodiment 1 ~ 7, the properties of comparative example 1 ~ 3 are as shown in table 1:
1 embodiment of table and comparative example the performance test results
| Tensile strength (MPa) | Extension at break (%) | Notch impact strength (J/M) | Heat distortion temperature (o) | Plating index | LDS finished product rate | |
| Embodiment 1 | 52 | 101 | 602 | 120 | 0.86 | 96% |
| Embodiment 2 | 41 | 110 | 512 | 110 | 0.86 | 96% |
| Embodiment 3 | 116 | 2 | 130 | 125 | 0.83 | 95.7% |
| Embodiment 4 | 104 | 4 | 121 | 115 | 0.82 | 95.3% |
| Embodiment 5 | 43 | 117 | 505 | 110 | 0.82 | 95.5% |
| Embodiment 6 | 118 | 2 | 128 | 1125 | 0.82 | 95.1% |
| Embodiment 7 | 103 | 4 | 120 | 116 | 0.81 | 94.8% |
| Comparative example 1 | 48 | 95 | 518 | 118 | 0.75 | 89% |
| Comparative example 2 | 50 | 100 | 590 | 118 | 0.79 | 92.2% |
| Comparative example 3 | 46 | 92 | 498 | 117 | 0.72 | 85% |
；
For mechanical strengths such as tensile strength, notch impact strengths, it is bright that comparative example and comparative example can be seen that embodiment 1
It is aobvious to be better than comparative example 3, show that modification can effectively eliminate adverse effect of the laser-sensitive additive to mechanical performance.Compare also
It was found that the heat distortion temperature of material can be improved using the laser-sensitive additive of modification.
Embodiment 1 is compared with embodiment 5-7, it can be seen that the modified laser sensitive additives of this patent introduction, it appears that
It is more suitable for PC resin system, PC/ABS resin system takes second place.Comparative example 2 and embodiment 5, embodiment 3 and embodiment 6, reality
Apply example 4 and embodiment 7, it has been found that in the preparation method of modified laser sensitive additives, when two kinds of fillers are used in combination the case where
Under, LDS performance is more preferable, and finished material rate is higher.
Embodiment 1 is compared with comparative example 1, it can be seen that in the preparation method of modified laser sensitive additives, component
Incomplete, final LDS deterioration in material properties obtained, yield rate reduces.
Comparing embodiment 1 and comparative example 2, discovery are prepared separately modified laser sensitive additives and are also necessary, finally
LDS material property obtained is good, high yield rate.
For LDS performance, it can be seen that the plating of material can be effectively improved using the laser-sensitive additive of modification
The yield rate of index and LDS product, this is because modification can effectively improve dispersion of the laser-sensitive additive in resin
Property, while it being formed by metallic core after capable of being effectively anchored laser irradiation, prevent it from taking off from the resin surface crossed by laser ablation
From improving metal adhesion, to significantly reduce product plating defect, improve yields.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of high finished product rate laser direct forming LDS composite material, it is characterised in that: the LDS composite material is by following heavy
The group of amount part is grouped as:
52 ~ 86 parts of polycarbonate,
0 ~ 30 part of ABS,
0 ~ 30 part of glass,
10 ~ 30 parts of fire retardant,
4 ~ 6 parts of toughener,
0.1 ~ 1 part of lubricant,
0.2 ~ 1 part of antioxidant,
10 ~ 30 parts of modified laser sensitive additives；
The preparation step of the modified laser sensitive additives are as follows:
Be (1~3) by mass ratio: 3 weak acid and water obtains mixed solution A after mixing in proportion, and the weak acid is phosphorous
At least one of acid, phosphoric acid or two kinds of mixture；
Be (2~6) by mass ratio: 1 Cu-Cr spinelle and filler obtains B material after mixing, and the filler is titanium white
Powder, hydrotalcite, hollow glass micropearl, talcum powder, mica powder, it is a kind of in graphene or at least two mixture；
By metal cation salt ionomer broken up using super mixer or by mass ratio be 1:10 metal cation salt ionomer and
Acetone obtains modifying agent C material after mixing, and the metal cation salt ionomer is Zn2+、Al3+The acrylic acid of ion, sulfonic acid,
Phosphoric acid, acetic acid, stearic acid, maleate ionomer, it is preferable that the metal ion ionomer be sulfonated polysulfone zinc/aluminium salt from
Polymers, vinyl sulfonic acid zinc/aluminium salt ionomer, ethylene maleic acid zinc/aluminium salt ionomer, ethylene-acrylic acid copolymer zinc/aluminium salt are from poly-
One or two kinds of mixture in object, ethylene-vinyl acetate copolymerization zinc/aluminium salt ionomer；
With 100: (0.1~2): (1~20) mass ratio expects B, A material, C material sequentially add in high-speed mixer, every addition
After a kind of material, 5~30 minutes need to be stirred under 45~75 DEG C, 200~500rpm/min revolving speed, after mixing evenly again plus other one
Kind material obtains the modified laser sensitive additives until adding all material after mixing evenly.
2. high finished product rate laser direct forming LDS composite material according to claim 1, it is characterised in that: the glass
For plain cylindrical form section glass fibre and/or section glass fibre, advantageous cross sections are variable cross-section section glass
Fiber and/or cross-section section glass fibre, more preferable cross-section section glass fibre, degree of profile are 1 .5~4:
1；The diameter of fiber is 6~13mm, preferably 9~11mm.
3. high finished product rate laser direct forming LDS composite material according to claim 1, it is characterised in that: the resistance
Fire one or more compoundings that agent is phosphorus flame retardant and nitrogenated flame retardant, in the mixture, the nitrogenated flame retardant
Weight percent content is 0~70%, and the weight percent content of the phosphorus flame retardant is 10~100%.
4. high finished product rate laser direct forming LDS composite material according to claim 1, it is characterised in that: the nitrogen
Flame retardant is melamine, dicyandiamide, melamine polyphosphate, melamine cyanurate, the phosphorus series non-halogen resistance
Combustion agent is phosphate, phosphinate or hypophosphites, phenyl hypophosphites, dialkylphosphinic salts, diphenyl phosphate.
5. high finished product rate laser direct forming LDS composite material according to claim 1, it is characterised in that: the toughening
Agent is MBS, SEBS, SIS, POE, EBA, EMA, organosilicon core-shell polymer or silicon-containing compound or resin.
6. high finished product rate laser direct forming LDS composite material according to claim 1, it is characterised in that: the lubrication
Agent is pentaerythritol stearate PETS.
7. high finished product rate laser direct forming LDS composite material according to claim 1, it is characterised in that: the antioxygen
Agent is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (anti-1010), three [2,4- di-tert-butyls
Base] phosphite ester (anti-168), β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester (anti-1076), N, N'-
Double-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine (anti-1098), four-(2,4- di-tert-butyl-phenyls) -4,
One or more of 4 '-xenyl bis-phosphites (anti-P-EPQ).
8. a kind of preparation method for high finished product rate laser direct forming LDS composite material described in claim 1, feature
It is: the following steps are included:
Step 1: being (1~3) by mass ratio: 3 weak acid and water obtains mixed solution A, the weak acid after mixing in proportion
For at least one of phosphorous acid, phosphoric acid or two kinds of mixture；It is (2~6): 1 Cu-Cr spinelle and filling by mass ratio
Agent obtains B material after mixing, and the filler is titanium dioxide, hydrotalcite, hollow glass micropearl, talcum powder, mica powder, graphite
In alkene it is a kind of or at least two mixture；Metal cation salt ionomer is broken up using super mixer or is by mass ratio
The metal cation salt ionomer and acetone of 1:10 obtains modifying agent C material after mixing, and the metal cation salt ionomer is Zn2 +、Al3+Acrylic acid, sulfonic acid, phosphoric acid, acetic acid, stearic acid, the maleate ionomer of ion, it is preferable that the metal ion from
Polymers is sulfonated polysulfone zinc/aluminium salt ionomer, vinyl sulfonic acid zinc/aluminium salt ionomer, ethylene maleic acid zinc/aluminium salt ionomer, second
One or two kinds of mixing in alkene acrylic acid copolymer zinc/aluminium salt ionomer, ethylene-vinyl acetate copolymerization zinc/aluminium salt ionomer
Object；With 100: (0.1~2): (1~20) mass ratio expects B, A material, C material sequentially add in high-speed mixer, every to be added one
After kind material, it need to be stirred under 45~75 DEG C, 200~500rpm/min revolving speed 5~30 minutes, add another again after mixing evenly
Material obtains the modified laser sensitive additives until adding all material after mixing evenly；
Step 2: weighing 52 ~ 86 parts of polycarbonate, 0 ~ 30 part of ABS, 10 ~ 30 parts of fire retardant, toughener 4 ~ 6 according to parts by weight
After part, 0.1 ~ 1 part of lubricant, 0.2 ~ 1 part of antioxidant and 10 ~ 30 parts of modified laser sensitive additives, mixed
Material, adds mixture into the main feeding of double screw extruder, 0 ~ 30 part of glass is added in the side feed material of double screw extruder,
It is drawn after melting extrusion from the outlet of die head, pelletizing obtains high finished product rate laser direct forming LDS composite particles after water cooling.
9. the preparation method of high finished product rate laser direct forming LDS composite material according to claim 8, feature exist
In: the melting extrusion temperature of the double screw extruder is 250~350 DEG C, and screw speed is 250~450rpm/min.
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| CN110655792A (en) * | 2019-10-29 | 2020-01-07 | 中广核高新核材科技（苏州）有限公司 | Low-dielectric-laser direct-forming composite material suitable for 5G communication and preparation method thereof |
| CN111961339A (en) * | 2020-07-31 | 2020-11-20 | 山东大学 | Laser direct forming thermoplastic composite material and preparation method and application thereof |
| CN112225944A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | LDS (laser direct structuring) additive with good dispersibility, LDS material containing additive and application |
| CN112341666A (en) * | 2020-11-09 | 2021-02-09 | 中广核高新核材科技（苏州）有限公司 | Preparation method of modified LDS laser etching auxiliary agent and LDS composite material |
| CN112662159A (en) * | 2020-12-19 | 2021-04-16 | 杭州本松新材料技术股份有限公司 | Polycarbonate laser direct forming material with good plating property and degradation resistance, preparation method and product |
| CN112812532A (en) * | 2020-12-28 | 2021-05-18 | 广东格瑞新材料股份有限公司 | Material for laser etching and preparation method thereof |
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| CN112225944A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | LDS (laser direct structuring) additive with good dispersibility, LDS material containing additive and application |
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| CN112662159A (en) * | 2020-12-19 | 2021-04-16 | 杭州本松新材料技术股份有限公司 | Polycarbonate laser direct forming material with good plating property and degradation resistance, preparation method and product |
| CN112662159B (en) * | 2020-12-19 | 2022-10-14 | 杭州本松新材料技术股份有限公司 | Polycarbonate laser direct forming material with good plating property and degradation resistance, preparation method and product |
| CN112812532A (en) * | 2020-12-28 | 2021-05-18 | 广东格瑞新材料股份有限公司 | Material for laser etching and preparation method thereof |
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Application publication date: 20190405 |