CN103450675A - Resin composition having laser direct-structuring function and its preparation method and use - Google Patents
Resin composition having laser direct-structuring function and its preparation method and use Download PDFInfo
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Abstract
The invention provides a resin composition having a laser direct-structuring function and its preparation method and use. The resin composition comprises 15-60wt% of a resin matrix, 30-70wt% of a heat-conduction filler, 5-12wt% of a laser-sensitive additive and 0-15wt% of other additives. The laser-sensitive additive has a general chemical formula of XY2O4, belongs to an isometric system and has axial length a=b=c and axial angle alpha=beta=gamma=90 degrees, wherein X and Y represent metal elements belonging to an IIIA group, an IB group, an IIB group, a VIB group, a VIIB group and a VIII group of the periodic table of elements. The resin composition has high temperature resistance and good thermal conductivity, realizes optional sedimentation of metals such as Cu, Ni and Au in a laser-scanned area and can be used for surface mounting technology (SMT) products.
Description
technical field
The present invention relates to a kind of resin combination, relate in particular to the heat-conductive resin composition of (the Laser Direct Structuring) function that there is laser direct forming, the application of its preparation method and this resin combination.
Background technology
Laser direct forming (LDS) technology refers to the zone that utilizes the computer control laser scanning, by laser radiation to the product that contains the laser-sensitive additive, activated circuit pattern, the zone be activated on this product can be without the metals such as metal refining copper, nickel, gold in electrochemistry plating, thereby realization produces conductive pattern on the three-dimensional plastic product.
Fast development along with laser direct forming (LDS) technology, the production rate of molding interconnection element (Moulded Interconnect Device) is more fast, flow process is more simplified, cost is more controlled, Application Areas is broader, its maximum advantage is, it can reduce the component number of electronic product and save space.Such as, adopt the antenna of LDS technology manufacture to be widely used on the mobile terminals such as smart mobile phone, notebook computer, the sensor that adopts the LDS technology to manufacture, minimum conductor width can reach 150 μ m, between minimum line, width can reach 150 μ m, this has not only reduced the quantity of components and parts, has also reached the purpose of saving space and loss of weight.
In addition, the advantage of LDS technology also is embodied in its handiness.If need to change conductive path on components and parts, only need the circuitous pattern design in change CAD to get final product, do not need to redesign mould.Because the LDS technology does not need mask, so its course of processing is easier, tooling cost is lower.The Materials science that is applied to the LDS technology has also obtained development fast.Resin matrix has covered general-purpose plastics, engineering plastics and special engineering plastics.Wherein relatively more typical application is the alloy of polycarbonate, polycarbonate and acrylonitrile/butadiene/styrene, and the LDS antenna of making of them has been widely used on smart mobile phone, panel computer and notebook computer.
Be applied to the product of surface mounting technology (SMT), resin matrix had to special requirement: high temperature resistant.Usually, the processing temperature of SMT processing procedure is up to 270 ℃, and at this temperature, resin matrix can not soften or melt, otherwise easily the bad phenomenon such as distortion, foaming occur.The material that can meet the SMT processing procedure has the polymkeric substance such as high-temperature nylon, liquid crystalline polymers and polyaryletherketone etc.
Electronic technology and the develop rapidly of material science and technology, electric components and parts, to the development of miniaturization densification, produce a large amount of heat in unicircuit, and heat are the important factors that affects equipment dependability.According to statistics, 2 ℃ of the every risings of electronic devices and components temperature, reliability decrease 10%; When the life-span that temperature rise is 50 ℃ only has 25 ℃ of temperature rises 1/6 of the life-span.This just requires material both to have good electrical insulating property and low thermal linear expansion coefficient, has again the excellent heat conductivity performance.Can say, the heat radiation and the heat conducting material that do not have new heat-conducting plastic to prepare, it is impossible that microelectronic device with better function is put into to less space.
, the simplification of plastic shaping can be combined with excellent heat conductivity as thermally conductive material with heat-conducting plastic, can realize some metal or the same thermal heat transfer capability of pottery by injection molding.The preferred aluminium of thermally conductive material commonly used, its thermal conductivity can reach 150W/mK.According to up-to-date research, find, if the speed that metal can fall apart heat to walk from surface higher than convection of air to the rate of heat transfer of product surface, its high thermal conduction just can not effectively realize, now thermophoresis is subject to flow restriction, relative metal, heat-conducting plastic is exactly suitable choosing.Heat-conducting plastic has than aluminium low thermal expansivity (CTE) also, has therefore reduced the stress that thermal expansion causes; Heat-conducting plastic is lighter by approximately 40% than aluminium, and the design freedom larger than aluminium is provided, and has also saved expensive post-treatment process, uses that heat-conducting plastic is more corrosion-resistant, more pliable and tougher, cost is lower.
Now, the LED industry is popular industry, and its heat radiation is more and more paid attention to by people, and this is directly relevant with its junction temperature because of the light decay of LED or its life-span.The bad junction temperature of dispelling the heat is just high, and the life-span is just short, can extend 2 times according to 10 ℃ of life-spans of the every reduction of A Leiniwusi equation temperature.And junction temperature not only affects the long-time life-span, yet directly affect the luminous efficiency of short period of time.In addition, the heating of LED also can make that its spectrum moves, colour temperature raises, forward current increases that (during the constant voltage power supply), reversible circulation also increase, the variety of problems such as thermal stresses increases, the aging acceleration of fluorescent material epoxy resin.So improving the radiating control junction temperature is an of paramount importance problem in the LED illumination Design.
The principal mode of at present LED encapsulation has discrete device, COB(Chip on board) encapsulate two large classes.Generally, the tube core of discrete device is sealed in package, and the effect of encapsulation is mainly the protection tube core and completes electric interconnection.The LED encapsulation has been output electrical signals, the normal operation of protection tube core, and the output visible ray, existing electrical parameter, have again design and the technical requirements of optical parameter.Discrete device, when application, needs plug-in unit or is welded on system substrate by surface mount process.A support is saved in COB encapsulation, directly by Chip Packaging to system circuit board, reduced the thermal resistance of interface and support itself.Yet heat dissipation technology develops into today, the thermal resistance that interface causes is more and more outstanding.Although COB has reduced interface, in application process, still need to be fixed on scatterer, intermediate interface is that hollow is close to or adds heat-conducting silicone grease.The existence of this interface resistance makes integral heat sink usefulness not good.
Summary of the invention
In view of the above, the present invention is necessary to provide the resin combination of a kind of LDS of having feature and heat conductivility excellence.
The technical solution adopted in the present invention is that a kind of resin combination consists of the following composition:
Resin matrix 15-60wt%;
Heat conductive filler 30-70wt%;
Laser-sensitive additive 5-12wt%; And
Other additives 0-15wt%;
Wherein, the chemical general formula of described laser-sensitive additive is XY
2o
4, tesseral system, referring to accompanying drawing 1, axial length a=b=c, shaft angle α=β=γ=90 °; X and Y are metallic element, from group IIIA, I B family, II B family, VI B family, VII B family or VIII family in the periodic table of elements.
Preferably, the selected resin matrix of the present invention comprises thermoplastics, thermosetting resin, rubber and elastomerics.Wherein, thermoplastic resin comprises: polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate with acrylonitrile-butadiene-styrene (ABS) arbitrarily than composition (PC/ABS), liquid crystalline polymers (LCP), polyamide (PA), polyphenylene sulfide (PPS), polyphenylene oxide (PPE), polysulfones, polyarylester, polyether-ether-ketone (PEEK), PEKK (PEKK), polyether ether ketone ketone (PEEKK), thermoplastic polyimide (TPI), polyacetal, polyethylene (PE), polypropylene (PP), polystyrene (PS), polytetrafluoroethylene (PTFE), polyacrylate(s), styrene-acrylonitrile copolymer (SA), polybutylene terephthalate (PBT) and polyethylene terephthalate (PET), poly terephthalic acid cyclohexanediol ester, the composition that perhaps comprises at least one above-mentioned polymkeric substance.
More preferably, selected polyamide resin comprises the blend composition of fatty polyamide, semiaromatic polyamide composition or semiaromatic polyamide composition and fatty polyamide.
More preferably, selected fatty polyamide carbochain is comprised of 4-36 carbon atom, typical fatty polyamide comprises PA6, PA66, PA610, PA612, the composition of one or more in PA1010, PA11, PA12, PA1012, but be not limited to these combinations.
More preferably, described semiaromatic polyamide composition is comprised of di-carboxylic acid unit and two amine units, wherein the di-carboxylic acid unit comprises the aromatic dicarboxylic acid unit of 45-100 molar percentage and the aliphatic dicarboxylic acid unit with 4-12 carbon atom of 0-55 molar percentage, and two amine units are 4-14 carbon atom straight chain aliphatic diamine, side chain aliphatic diamine or cycloalphatic diamine.
Still more preferably, the aromatic dicarboxylic acid unit comprises terephthalic acid, m-phthalic acid, 2-methyl terephthalic acid, 2,5-dichloroterephthalicacid acid, 2,6-dichloroterephthalicacid acid, 1,4-naphthalic acid, 4,4 '-biphenyl dicarboxylic acid or 2,2 '-biphenyl dicarboxylic acid.
Still more preferably, the aliphatic dicarboxylic acid unit comprises 1, 4-succinic acid, 1,6-hexanodioic acid, 1,8-suberic acid, 1,9-nonane diacid, 1,10-sebacic acid, 1,11-undecane diacid or 1,12-dodecanedioic acid.
Still more preferably, the straight chain aliphatic diamine comprises Putriscine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1，10-diaminodecane, 1,11-11 carbon diamines or 1,12-, 12 carbon diamines.
Still more preferably, the side chain aliphatic diamine comprises the 2-methyl isophthalic acid, 5-pentamethylene diamine, 3-methyl isophthalic acid, 5-pentamethylene diamine, 2,4-dimethyl-1,6-hexanediamine, 2,2,4-trimethylammonium-1,6-hexanediamine, 2,4,4-trimethylammonium-1,6-hexanediamine or 2-methyl isophthalic acid, 8-octamethylenediamine or 5-methyl isophthalic acid, 9-nonamethylene diamine.
Still more preferably, cycloalphatic diamine comprises cyclohexane diamine, methylcyclohexane diamines or 4,4 '-diamino-dicyclohexyl methane.
Preferably, thermosetting resin comprises: epoxy resin, resol, unsaturated polyester, polyimide, or comprise the composition of at least one aforementioned polymer.
Preferably, rubber comprises natural rubber and synthetic rubber, or comprises the composition of at least one aforementioned polymer.
Preferably, elastomerics comprises styrenic elastomerics, ethylene octane copolymer, polyester elastomer, polyamide elastomer and polyurethane elastomer, or comprises the composition of at least one aforementioned polymer.
Preferably, the selected heat conductive filler of the present invention comprises: aluminum oxide, aluminium nitride, silicon nitride, magnesium oxide, silicon carbide, boron nitride, carbon fiber, carbon nanotube, carbon black, graphite, aluminium hydroxide, zinc oxide, magnesium oxide, magnesium hydroxide, metallic stuffing or their composition.
More preferably, described heat conductive filler is boron nitride, and boron nitride can be cubic boron nitride, hexagonal boron nitride, amorphous boron nitride, rhombus boron nitride, and it can use with spherical, sheet or fibers form.
Wherein, the median size of ball-like structure heat conductive filler is at 10 μ m～200 μ m, preferably 15 μ m～150 μ m, more preferably 20 μ m～100 μ m, the radius-thickness ratio of sheet structure heat conductive filler is 10～100, preferably 10-80, more preferably 10-50, distribution of fiber diameters is at 3-25 μ m.
Resin combination of the present invention is insulating heat-conduction material, and the surface resistivity of resin combination is not less than 1013 Ω.The addition of the carbon nanotube used in heat conductive filler, carbon black, graphite is preferably 0.1wt%-10wt%.
Described laser-sensitive additive plays an important role in laser processing procedure to resin combination.The product surface that laser beam is made at resin combination is inswept, and resin matrix is ablated off, and forms rough zone, can increase the cohesive strength of chemical plating metal layer and resin matrix; On the other hand, the laser-sensitive additive is under the effect of laser, restoring metallic particles is attached on rough resin matrix, follow-up without in electrochemistry plating, these metallic particles play the effect of active center, impel the metal ion in chemical plating fluid to deposit selectively, form metallic film.
The selected laser-sensitive additive of the present invention is a kind of high temperature resistant inorganic additive, and the temperature that can bear is over 600 ℃.Refer to Fig. 1, the minimal structure unit comprised in the laser-sensitive additive is tetrahedral structure and octahedral structure.Wherein Sauerstoffatom occupies all center of areas position, forms close-packed, and two kinds of different metal ions are distributed to respectively tetrahedron central position and octahedra central position.The tetrahedron central position is the middle space of tetrahedron that four oxonium ions surround, and octahedra central position is the middle space of octahedron that six oxonium ions surround.Usually, contain eight tetrahedron atoms, 16 octahedra atoms and 32 Sauerstoffatoms in a kind of complete cell configuration, so, in its structural unit, the ratio of the simplest atom number of its correspondence is 1:2:4.
Preferably, selected its chemical general formula of laser-sensitive additive of the present invention is XY
2o
4, belong to tesseral system, axial length a=b=c, shaft angle α=β=γ=90 °; Wherein, X is metallic element, from the atoms metal of group IIIA, I B family, II B family, VI B family, VII B family, VIII family in the periodic table of elements, comprises any one in chromium metal, manganese, iron, cobalt, nickel, copper, zinc, palladium, aluminium; Y is metallic element, from the atoms metal of group IIIA, I B family, II B family, VI B family, VII B family, VIII family in the periodic table of elements, comprises any one of chromium metal, manganese, iron, cobalt, nickel, copper, zinc, palladium, aluminium; Illustrating can be with reference to teaching material " basic crystal theory ", and the author Qin is kind, and BJ University Press publishes.
Tetrahedron central atom wherein preferably comes from transition metal atoms, most preferably comes from the period 4.
Octahedra central atom wherein preferably comes from transition metal atoms, most preferably comes from the period 4.
The amount of the laser-sensitive additive that the present invention is selected is 5-12wt%, and preferred addition is 5-9wt%.When the addition of laser-sensitive additive is greater than 15wt%, product easily causes that in the process without the electrochemistry plating plating of overflowing waits degradation phenomena, affects the electric function of product.
Preferably, other selected additives of the present invention comprise halogen-free flame retardants, fire retarding synergist, solidifying agent, releasing agent, oxidation inhibitor, lubricant.
Usually, in product application, resin combination requires to meet UL 94 V-0 flame retardant ratings, but must not use red phosphorus simultaneously, the fire retardant of halogen fire retardant class is arranged.Have the material from flame-retarding characteristic for those, do not need the modification of carrying out flame-retarding characteristic to meet the demands, these materials comprise polyphenylene sulfide (PPS), liquid crystalline polymers (LCP), and polyaryletherketone (PAEK) etc.
Yet most macromolecular materials itself are to have flammablely, it is carried out to flame-retardant modified common means is to add fire retardant.Due to the fire retardant mechanism difference of different fire retardants, different resin matrixes has very strong selectivity to fire retardant.As, the resin combination that is PC or PC/ABS for resin matrix, can improve its flame retardant properties by the one-tenth carbon ability that increases polycarbonate, and available fire retardant comprises the Sulfonates fire retardant, the phosphonic acid ester fire retardant, can also be used the organo-siloxane based flame retardant.
And the resin combination that is daiamid composition for resin matrix, the general formula of selected halogen-free flame retardants is:
(1)
Wherein, R1, R2 are identical or different, comprise alkyl and/or the aryl of 1-6 carbon atom of line style or branching.
R3 comprises the alkylidene group of 1-10 carbon atom of line style or branching, arylidene, alkyl arylene or the aryl alkylene of a 6-10 carbon atom.
M comprises the metal ion in the second and the 3rd main group in the periodic table of elements or subgroup.The preferred calcium ion of M metal ion or aluminum ion.
M is 2 or 3.
N is 1 or 3.
X is 1 or 2.
In described other additives, the halogen-free flame retardants used comprises dimethyl phosphinates, ethyl-methyl phosphinates, diethyl phosphinates, methyl-n-propylphosphinic acid salt, two (methyl-phosphinic acid) methane salt, 1,2-bis-(methyl-phosphinic acid) ethane salt, 1,6-bis-(methyl-phosphinic acid) hexane salt, Isosorbide-5-Nitrae-bis-(methyl-phosphinic acid) benzene salt, aminomethyl phenyl phosphinates, diphenyl phosphonic acid salt.
Other additives also comprise mineral filler, glass fibre for example, boron fibre, titanium dioxide, talcum powder, mica, barium titanate, glass microballon, CaCu 3 Ti 4 O, kaolin etc.
Resin combination of the present invention and to use the made product of this resin combination be electrical isolation, surface resistivity is not less than 10
13Ω.
In addition, the present invention is necessary to provide the preparation method of resin combination.
The preparation method of resin combination involved in the present invention is as follows:
Take material: according to following weight percent, take material: the thermoplastics of 15-60wt% or elastomer resin matrix; The heat conductive filler of 30-70wt%; The laser-sensitive additive of 5-12wt%; Other additives of 0-15wt%;
Mixture: resin matrix, part heat conductive filler, laser-sensitive additive, other additives are joined in high-speed mixer, mix;
Extrusion moulding: the material mixed charging from main feeding hopper, the charging from the side feeding hopper of the heat conductive filler of remainder, adopt the common double screw extrusion press to extrude, cooling, and pelletizing obtains the target product of resin combination.
Resin combination involved in the present invention also can obtain by following preparation method:
Take material: according to following weight percent, take material: the thermosetting resin of 15-60wt% or rubber resin matrix; The heat conductive filler of 30-70wt%; The laser-sensitive additive of 5-12wt%; Other additives of 0-15wt%;
Mixture: resin matrix, heat conductive filler, laser-sensitive additive, other additives are mixed;
Hot-forming: by the mould that it is suitable that resulting resin combination is packed into, heat treated, and employing shaping method to suppress moulding resin composition is the target product.
It is good that resin combination of the present invention has good high temperature resistant and thermal conductivity, can be in the zone of laser scanning metals such as deposited copper, nickel, gold selectively, the product that can be used for surface mounting technology (SMT), be mainly used in electric part field.By the resin combination of (LDS) feature that has laser direct forming is provided, by this resin combination by injection moulding, extrude or the moulding process molded article such as mold pressing, form circuit on product by laser direct structuring technique, then directly by electronic package on circuit, eliminate interface resistance fully, thereby realized high efficiency and heat radiation.As the application in the LED illumination, just can realize that LED chip, without the encapsulation of interface thermal resistance, combines system circuit board, scatterer together simultaneously, realize high efficiency and heat radiation, extend the LED illumination life-span.
The accompanying drawing explanation
Fig. 1 is laser-sensitive additive structural representation, and in figure, the figure A in the lower left corner is octahedra schematic diagram, and the figure B in the lower right corner is the tetrahedron schematic diagram.
embodiment
The present invention discloses a kind of resin combination with laser direct forming (Laser Direct Structuring) function, prepares the method for described resin combination and the application of this resin combination.
Described resin combination is composed of the following components:
Resin matrix 15-60wt%;
Heat conductive filler 30-70wt%;
Laser-sensitive additive 5-12wt%; And
Other additives 0-15wt%;
Wherein the chemical general formula of laser-sensitive additive is XY
2o
4, tesseral system, axial length a=b=c, shaft angle α=β=γ=90 °; Wherein X and Y are metallic element, from group IIIA, I B family, II B family, VI B family, VII B family, VIII family in the periodic table of elements.
The selected laser-sensitive additive of the present invention is hot good conductor.The laser-sensitive additive is a kind of heavy metal oxide, wherein can comprise one or more metal oxide of copper, manganese, iron, zinc, nickel, aluminium, titanium, cobalt, magnesium, antimony, tin.On the one hand, for resin matrix, they are all hot good conductors, and the heat diffusion that can rapidly electronic component, electronic package and LED lamp be produced, in the middle of environment, has synergistic effect to the capacity of heat transmission that improves composition.On the other hand, the particle dia of the laser-sensitive additive that the present invention is selected is little, is distributed in 1.5 μ m-2.1 μ m, and specific surface area is greater than 35000cm
2/ cm
3.It is evenly distributed in the gap of macrobead heat conductive filler, can effectively increase the contact area of heat conduction network skeleton, forms numerous heat conduction networks, thereby improves the heat transfer efficiency of composition.
The preparation method of resin combination of the present invention is as follows:
Take material: the thermoplastics of 15-60wt%, or thermosetting resin, or rubber, or elastomer resin matrix; The heat conductive filler of 30-70wt%; The laser-sensitive additive of 5-12wt%; Other additives of 0-15wt%;
Mixture: resin matrix, heat conductive filler, laser-sensitive additive, other additives are joined in high-speed mixer, mix;
Resulting mixture is utilized to twin screw extruder is extruded, cooling, pelletizing obtains target product; Or resulting mixture is packed in mould, heating compression moulding obtains the target product.
Resin combination of the present invention is mainly used to make electric component, comprises the circuit base material, as the timbering material of electronic component, electronic package, base or the circuit card of high-powered LED lamp.
In application, electronic unit can be welded on the circuit base material after the LDS technological forming by the SMT mode.No matter adopt which kind of mode, all can the Presence of an interface thermal resistance between electronic unit and base material.Because the thermal conductivity of traditional base material (such as pcb board) is low, the heat that electronic unit produces can't be diffused in environment and go, can seriously have influence on the work-ing life of the product after assembling, particularly thermo-responsive electronic unit is worked in lasting hot environment, and the performance damage is more obvious.If the Presence of an interface thermal resistance, the radiating effect of electronic unit can be poorer, and can seriously shorten work-ing life.
Resin combination provided by the present invention has high thermal conductivity, and electronic unit is directly installed on the circuit formed by LDS technique, can improve significantly radiating effect.This is to be convenient to heat radiation because electronic component directly is encapsulated on the base material of high thermal conductivity coefficient; On the other hand, this conducting wire is by being deposited on base material without the electrochemistry depositing process, and conducting wire and base material have formed perfect integral body, Presence of an interface resistance not, and heat-conducting effect can be better.
The resin combination, preparation method, effect and the purposes that the present invention are had to the laser direct forming function below in conjunction with embodiment and Comparative Examples are described in further detail, but embodiments of the present invention are not limited to this.
The laser-sensitive additive of selecting in following examples has copper chromium type laser-sensitive additive, copper manganese type laser-sensitive additive, and its structure as shown in Figure 1.The cited copper manganese type additive of the present invention is one of optimal selection, at the laser processing procedure and in without electrochemistry plating process, without the toxic metal ion, produce, under the effect of laser, the lattice of laser-sensitive additive is destroyed, the metallic element of the inside can discharge, and is attended by redox reaction.Such as, the chromium in copper chromium type laser-sensitive additive can become high valence state by lower valency, generates Cr
6+, be poisonous ion.Manganese in copper manganese type laser-sensitive additive becomes high valence state by lower valency equally, is but nontoxic, and this is conducive to environmental friendliness.
Embodiment 1
Resin matrix is selected poly-paraphenylene terephthalamide's decamethylene diamine (PA10T, from JinFa Science Co., Ltd) 35wt%, heat conductive filler is selected boron nitride 30wt% and magnesium oxide 20wt%, copper manganese type laser-sensitive additive (from huge Fa Science Co., Ltd) 5wt%, other additives are selected nano aluminium oxide 2wt%, glass fibre (from Jushi Group Co., Ltd.) 8wt%.
Embodiment 2
Resin matrix is selected poly-paraphenylene terephthalamide's decamethylene diamine, 28wt%, and heat conductive filler is selected boron nitride 30wt% and magnesium oxide 20wt%, copper manganese type laser-sensitive additive 12wt%, other additives are selected nano aluminium oxide 2wt%, glass fibre 8wt%.
Comparative Examples 3
Resin matrix is selected poly-paraphenylene terephthalamide's decamethylene diamine 40wt%, and heat conductive filler is selected boron nitride 30wt% and magnesium oxide 20wt%, copper manganese type laser-sensitive additive 0wt%, and other additives are selected nano aluminium oxide 2wt%, glass fibre 8wt%.
Comparative Examples 4
Resin matrix is selected poly-paraphenylene terephthalamide's decamethylene diamine 37wt%, and heat conductive filler is selected boron nitride 30wt% and magnesium oxide 20wt%, copper manganese type laser-sensitive additive 3wt%, and other additives are selected nano aluminium oxide 2wt%, glass fibre 8wt%.
In embodiment 1 and 2, in Comparative Examples 3 and 4, selected boron nitride is the microcosmic sheet structure, and median size is about 150 μ m, and diameter and Thickness Ratio are about 20; Magnesium nitride is the microcosmic ball-like structure, and median size is about 20 μ m; Nano aluminium oxide is the microcosmic ball-like structure, and median size is about 20 μ m; The average particle diameter of copper manganese type laser-sensitive additive is 1.8 ± 0.3 μ m, and specific surface area is greater than 35000cm
2/ cm
3.Boron nitride belongs to the thermally conductive material of large particle diameter sheet structure, the main heat conduction network skeleton function that rises in resin matrix, the oxidized aluminium of the magnesium oxide of small particle size ball-like structure coats, and is evenly distributed in resin matrix, and tend to be distributed between the sheet structure of boron nitride, form the heat conduction network.
Magnesium oxide in the various embodiments described above is joined in high-speed mixer, add again nano aluminium oxide to continue to mix, make nano aluminium oxide evenly adhere to magnesian superficies, then with copper manganese type laser-sensitive additive, poly-paraphenylene terephthalamide's decamethylene diamine mixed with resin evenly after, from the main feeding hopper charging of twin screw extruder.Glass fibre is from the first side spout charging, and boron nitride is from the second side spout charging, and extruding pelletization, obtain a kind of LDS resin material with heat conduction function.
LDS resin material with heat conduction function need to be tested thermal conductivity, thickness test, hundred lattice tests (Cross-Cut Test).The testing standard of thermal conductivity is ISO 8301.Thickness test, be the thickness of metal film of test LDS material deposition in without the electrochemistry plating, and it is qualified in industry, to require film thickness to be distributed in to be in 7-12 μ m.Hundred lattice tests are cut the grid of 100 1mm*1mm with cutter on metallic film, and with vertical pull-up after the about 2min of placement after 3M 610 adhesive tape stickings, it is qualified that the area that comes off of metallic film<5% is.The testing standard of surface resistivity is ASTM D257.
Test result is as shown in table 1.When the amount of laser-sensitive additive is less than 5wt%, under the effect of laser, the metallic particles discharged very little, can't be realized copper facing, nickel, gold in without electrochemistry plating process.During at 5-12%, discharge enough metallic particles when addition under lasing, and play the effect of active center in the process without the electrochemistry plating, and successfully copper facing, nickel, gold.By the test thermal conductivity, can find that the laser-sensitive additive also has synergistic effect to hot conduction.
Table 1 test result
Known in table 1, along with the increase of the weight percent of laser-sensitive additive, in weight percent content and the proportioning of heat conductive filler, do not have in vicissitudinous situation, thermal conductivity progressively increases.Visible, the laser-sensitive additive has improved the thermal conduction capability of LDS resin material effectively.In addition, when the consumption of laser-sensitive additive LDS feature not obvious during lower than 5wt%, hundred lattice test failures.
Embodiment 5
Polyphenylene sulfide (purchased from Sichuan Deyang Chemistry Co., Ltd.) 17wt%, boron nitride 40wt%, magnesium oxide 30wt%, copper chromium type laser-sensitive additive 5wt%, nano aluminium oxide 3wt%, carbon fiber 5wt%.
Processing mode and testing standard reference example 1.
Test result shows, the thermal conductivity of this material is 3.36 W/mK, and thickness of metal film is 7.68um, hundred lattice test metallic films area<5% that comes off.
Embodiment 6
TLCP (from JinFa Science Co., Ltd) 58wt%, aluminium nitride 10wt%, zinc oxide 10wt%, copper chromium type laser-sensitive additive 12wt%, carbon fiber 10wt%.
The fusing point of described liquid crystalline polymers is 325 ℃, and processing temperature is not higher than 350 ℃, and aluminium nitride is the microcosmic sheet structure, and median size is about 100 μ m, and diameter and Thickness Ratio are about 25; Described zinc oxide is the microcosmic ball-like structure, median size 15 μ m.The average particle diameter of copper chromium type laser-sensitive additive is 1.8 ± 0.3 μ m, and specific surface area is greater than 35000cm
2/ cm
3.
Processing mode and testing standard are with reference to embodiment 1.
Test result shows, the thermal conductivity of this material is 1.10 W/mK, and thickness of metal film is 10.55um, hundred lattice test metallic films area<5% that comes off.
Embodiment 7
Resin matrix is selected polymeric amide PA6 18wt% and acrylic resin PP 3wt%, and heat conductive filler is boron nitride 50wt% and graphite 20wt%, copper manganese type laser-sensitive additive 9wt%.After adding boron nitride, the mobility variation of melt.Graphite has played lubricated effect in resin matrix, has reduced the viscosity of melt, is conducive to processing, has also improved the capacity of heat transmission of composition simultaneously.
Selected PA6 density is about 1.13g/cm
3, 215 ℃ of fusing points, processing temperature is not higher than 250 ℃; Selected PP is isotatic polypropylene, and density is about 1.04 g/cm
3, processing temperature is not higher than 250 ℃; The average particle diameter of copper manganese type laser-sensitive additive is 1.8 ± 0.3 μ m, and specific surface area is greater than 35000cm
2/ cm
3.
After being mixed in high-speed mixer with copper manganese type laser-sensitive additive, resin matrix adds from twin-screw extrusion owner spout, boron nitride adds from the first side feeding hopper, and graphite adds from the second side feeding hopper, extrudes, cooling, pelletizing obtains resin combination.
Testing standard is with reference to embodiment 1.
Test result shows, thermal conductivity is 3.47W/mK, and thickness of metal film is 9.58um, hundred lattice test metallic films area<5% that comes off.
Embodiment 8
Bisphenol A epoxide resin (Epoxy 828) 25wt%, boron nitride 45wt%, carbon fiber 20wt%, copper manganese type laser-sensitive additive 5wt%, anhydride curing agent (MT-500TZ) 4.95wt%, 2-ethyl-4-methylimidazole (2E4MZ) 0.05wt%.Pour mould into after said components is mixed, in hot-air oven, 100 ℃ solidify 2 hours, then 130 ℃ of curing resin combinations that are prepared in 3 hours.
Testing standard is with reference to embodiment 1.
Test result shows, thermal conductivity is 2.10W/mK, and thickness of metal film is 7.11um, hundred lattice test metallic films area<5% that comes off.
Comparative Examples 9
Polycarbonate (PC) 60.2wt%, silicon carbide 15wt%, ball-type graphite 10wt%, copper manganese type laser-sensitive additive 4wt%, sulfonate fire retardant 0.3wt%, talcum powder 0.5wt%, carbon fiber 10wt%.
Selected PC processing temperature is at 240 ℃-280 ℃, and under 260 ℃/5KG, the test melting index is 10-28g/10min, and the average particle diameter of copper manganese type laser-sensitive additive is 1.8 ± 0.3 μ m, and specific surface area is greater than 35000cm
2/ cm
3.
Processing mode and testing standard are with reference to embodiment 1.
Test result shows, the thermal conductivity of this material is 0.78 W/mK, and thickness of metal film is 5.73um, the hundred lattice test metallic films area that comes off > 5%, combustionproperty meets UL 94 V-0 standards, and batten thickness is 1.0mm.
The test result of embodiment 5-8, Comparative Examples 9 is as shown in table 2.
Table 2 test result
By the comparison of embodiment 5-8 and Comparative Examples 9, the better proportion span of known laser-sensitive additive is 5-12 wt%, and the better proportion span of heat conductive filler is 30-70 wt%.
Embodiment 10
Resin matrix is selected the composition of heat resistant polyamide PA10T and fatty polyamide PA66, wherein PA10T is 10wt%, PA66 is 20wt%, heat conductive filler is boron nitride 30wt% and magnesium oxide 20wt%, copper manganese laser-sensitive additive 10wt%, it is dimethyl phospho acid aluminium (purchased from Clariant company) 8wt% that other additives are selected halogen-free flame retardants, boehmite 2wt%.
The processing temperature of twin screw is distributed in 290 ℃-330 ℃.Resin matrix, boehmite copper manganese type laser-sensitive additive are added from twin-screw extrusion owner spout after mixing in high-speed mixer, boron nitride adds from the first side feeding hopper, and halogen-free flame retardants adds from the second side feeding hopper, extrudes, cooling, pelletizing obtains resin combination.
Testing standard reference example 1.
Test result shows, thermal conductivity is 1.96W/mK, and thickness of metal film is 8.39um, and hundred lattice test metallic films area<5% that comes off, meet fire-retardant UL 94 V-0 grades at 1.0mm-3.0mm thickness.
From the various embodiments described above, at resin matrix 15-60wt%; Heat conductive filler 30-70wt%; Laser-sensitive additive 5-12wt%; And during other additives 0-15wt% scope, can test and the test of hundred lattice by thickness, and heat conductivility is good.
To sum up, it is good that resin combination of the present invention has good high temperature resistant and thermal conductivity, can be in the zone of laser scanning metals such as deposited copper, nickel, gold selectively, the product that can be used for surface mounting technology (SMT), be mainly used in electric part field, as LED lamp scatterer.
The foregoing is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or conversion of equivalent flow process that utilizes description of the present invention to do; or directly or indirectly be used in other relevant technical fields, all in like manner be included in scope of patent protection of the present invention.
Claims (21)
1. the resin combination with laser direct forming function, composed of the following components:
Resin matrix 15-60wt%;
Heat conductive filler 30-70wt%;
Laser-sensitive additive 5-12wt%; And
Other additives 0-15wt%;
Wherein the chemical general formula of laser-sensitive additive is XY
2o
4, tesseral system, axial length is equal, and shaft angle is identical is 90 °; Wherein X and Y are metallic element, from group IIIA, I B family, II B family, VI B family, VII B family, VIII family in the periodic table of elements.
2. resin combination according to claim 1, it is characterized in that: described X metallic element and described Y metallic element comprise one or more in chromium, manganese, iron, cobalt, nickel, copper, zinc, palladium, aluminium.
3. resin combination according to claim 1, it is characterized in that: described X metallic element and described Y metallic element are selected from the period 4 in the periodic table of elements.
4. resin combination according to claim 1, it is characterized in that: described resin matrix comprises thermoplastics, thermosetting resin, rubber and elastomerics.
5. resin combination according to claim 4, it is characterized in that: described thermoplastics comprises: polycarbonate, acrylonitrile-butadiene-styrene copolymer, liquid crystalline polymers, polymeric amide, polyphenylene sulfide, polyphenylene oxide, polysulfones, polyarylester, polyether-ether-ketone, PEKK, polyether ether ketone ketone, thermoplastic polyimide, polyacetal, polyethylene, polypropylene, polystyrene, tetrafluoroethylene, polyacrylate(s), styrene-acrylonitrile copolymer, polybutylene terephthalate, polyethylene terephthalate, the composition of one or more in poly terephthalic acid cyclohexanediol ester.
6. resin combination according to claim 4, it is characterized in that: described thermosetting resin comprises: the composition of one or more in epoxy resin, resol, unsaturated polyester, polyimide.
7. resin combination according to claim 4 is characterized in that: described rubber comprises one or more the composition in natural rubber and synthetic rubber.
8. resin combination according to claim 4 is characterized in that: described elastomerics comprises one or more the composition in styrenic elastomerics, ethylene octane copolymer, polyester elastomer, polyamide elastomer and polyurethane elastomer.
9. resin combination according to claim 1, it is characterized in that: described resin combination surface resistivity is not less than 10
13Ω.
10. resin combination according to claim 1, it is characterized in that: the addition of described laser-sensitive additive is 5-9wt%.
11., according to the described resin combination of claim 1-10 any one, it is characterized in that: described heat conductive filler comprises: one or more in aluminum oxide, aluminium nitride, silicon nitride, magnesium oxide, silicon carbide, boron nitride, carbon fiber, carbon nanotube, carbon black, graphite, aluminium hydroxide, zinc oxide, magnesium oxide, magnesium hydroxide and metallic stuffing.
12. resin combination according to claim 11 is characterized in that: described heat conductive filler boron nitride is spherical, sheet or fibers form, comprises cube boron nitride, hexagonal boron nitride, rhombus boron nitride and amorphous boron nitride.
13. resin combination according to claim 11 is characterized in that: the median size of described ball-like structure heat conductive filler is at 10 μ m-200 μ m, and the radius-thickness ratio of sheet heat conductive filler is at 10-100, and distribution of fiber diameters is at 3-25 μ m.
14. according to the described resin combination of claim 1-10 any one, it is characterized in that: described other additives comprise mineral filler, halogen-free flame retardants, fire retarding synergist, solidifying agent, releasing agent, oxidation inhibitor, one or more of lubricant.
15. resin combination according to claim 14 is characterized in that: described resin matrix is daiamid composition, and other additives comprise halogen-free flame retardants, and the general formula of halogen-free flame retardants is:
Wherein, R1, R2 represent alkyl and/or the aryl of 1-6 carbon atom of line style or branching;
R3 represents the alkylidene group of 1-10 carbon atom of line style or branching, arylidene, alkyl arylene or the aryl alkylene of a 6-10 carbon atom;
Metal ion in M representative element periodictable in the second and the 3rd main group or subgroup;
M is 2 or 3; N is 1 or 3; X is 1 or 2.
16. resin combination according to claim 14 is characterized in that: described mineral filler comprises glass fibre, boron fibre, titanium dioxide, talcum powder, mica, barium titanate, glass microballon, CaCu 3 Ti 4 O, one or more in kaolin.
17. the preparation method according to the described resin combination of claim 1-16 any one comprises the following steps:
Take material: the thermoplastics of 15-60wt% or elastomer matrix; The heat conductive filler of 30-70wt%; The laser-sensitive additive of 5-12wt%; Other additives of 0-15wt%;
Mixture: thermoplastics or elastomer matrix, part heat conductive filler, laser-sensitive additive, other additives are joined in high-speed mixer, mix;
Utilize that twin screw extruder is extruded, cooling, pelletizing makes resin combination.
18. the preparation method of resin combination according to claim 17, it is characterized in that: in described extrusion moulding step, by the material charging from the main feeding hopper of forcing machine mixed, the charging from the side feeding hopper of the heat conductive filler of remainder, the employing twin screw extruder is extruded, cooling, pelletizing, make resin combination.
19. the preparation method according to the described resin combination of claim 1-16 any one comprises the following steps:
Take material: the thermosetting resin of 15-60wt% or rubber matrix; The heat conductive filler of 30-70wt%; The laser-sensitive additive of 5-12wt%; Other additives of 0-15wt%;
Mixture: thermosetting resin or rubber matrix, heat conductive filler, laser-sensitive additive, other additives are mixed;
The material mixed is poured in suitable mould into to heating, compression moulding.
20. the purposes of the described resin combination of claim 1-16 any one for making electric component.
21. resin combination according to claim 20 is characterized in that: for making LED lamp scatterer.
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| PCT/CN2012/078643 WO2013177850A1 (en) | 2012-05-31 | 2012-07-13 | Resin composition with laser direct structuring function, preparation method thereof, and application of resin composition |
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