CN103694704B - A kind of heat conductive insulating resin of laser direct forming and preparation method thereof - Google Patents
A kind of heat conductive insulating resin of laser direct forming and preparation method thereof Download PDFInfo
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- CN103694704B CN103694704B CN201310698434.9A CN201310698434A CN103694704B CN 103694704 B CN103694704 B CN 103694704B CN 201310698434 A CN201310698434 A CN 201310698434A CN 103694704 B CN103694704 B CN 103694704B
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Abstract
Heat conductive insulating resin that the present invention relates to a kind of laser direct forming and preparation method thereof, adopts the raw material of following components and weight portion content to prepare: matrix resin 35-55, thermal conducting agent 40-60, laser additive 5-8, other component 0.1-0.9。Compared with prior art, the present invention adds thermal conducting agent in resin and realizes heat conduction and insulate, add laser additive to reach the purpose of laser direct forming simultaneously, it is mainly used in LED industry, both can mould Dai Gang, Simplified flowsheet reduces cost, can be designed in material by circuit again, design degree is freer and substantially increases firmness。
Description
Technical field
The present invention relates to the fluoropolymer resin being applied to LED field, heat conductive insulating resin especially relating to a kind of laser direct forming and preparation method thereof。
Background technology
Polyphenylene sulfide fusing point is higher than 280 DEG C, and heat distortion temperature is more than 260 DEG C, and life-time service temperature is 220-240 DEG C；
Self having anti-flammability, anti-flammability can reach UL94V-0 level, does not need to add any fire retardant when making flame retardant products, maintains the high-mechanical property of material itself；Rigidity is extremely strong, and case hardness is high, high-modulus, and has creep resistant and the fatigue durability of excellence；Chemical proofing is excellent, not yet finds to dissolve below 200 DEG C the solvent of PPS at present, can bear low temperature-70 DEG C and long-time salt mist environment condition, the repellence of mineral acid, alkali and salt very strong (except acid with strong oxidizing property)；Molding shrinkage is only small, and water absorption rate is low, and thermal linear expansion coefficient is little, still shows good dimensional stability electrical insulation capability good under high temperature or super-humid conditions, even if still having excellent electrical property when high temperature, high humidity, altofrequency；Melt viscosity is non-normally low, good fluidity, very easily with glass fibre wetting contact, simultaneously with the very easily moistening of various fillers。Owing to the filler addition of Heat Conduction Material is 40%-60%, therefore polyphenylene sulfide base material does Heat Conduction Material to be applied to LED shell is most suitable。
Heat filling, big more options are to add ceramic-like inorganic filler, because of itself insulation, use BN, MgO etc. such as what patent CN103183962A mentioned。But, ceramic packing heat conductivility is general, if wanting thermal conductivity at more than 5W/m.K, is then extremely difficult to。Carbons material, especially graphite, reinforced convenient, heat conductivility is excellent, controls adding proportion, can accomplish high heat conduction and insulate。
Laser direct forming, i.e. LaserDirectStructuring, it is called for short LDS, it is a kind of injection, laser machines 3D-MID (Three-dimensionalmoldedinterconnectdevice) production technology combined with electroplating technology, its principle is to give electric interconnection function by common plastic cement element, circuit board, make plastic casing, structural member except the functions such as support, protection, be combined with conducting channel and produce shielding, the function such as antenna。LDS material, mainly adds laser additive in matrix resin, and the particle after blended can form conducting wire after being injection molded into product chemical plating again, and advantage is that circuit design is freer and firm。
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and heat conductive insulating resin that a kind of laser direct forming is provided and preparation method thereof。
The purpose of the present invention can be achieved through the following technical solutions:
The heat conductive insulating resin of a kind of laser direct forming, adopts the raw material of following components and weight portion content to prepare:
Described matrix resin is polyphenylene sulfide or syndiotactic polystyrene resin。
Described matrix resin preferable weight-average molecular weight is more than 30000, and structure is straight chain type, polyphenylene sulfide without branching functional group
Described thermal conducting agent is the complex containing graphite Yu boron nitride。
The addition of described graphite is not more than the 20wt% of resin raw material gross weight, and boron nitride addition is the 20-40wt% of resin raw material gross weight。
Described laser additive is the cupric and chromic oxide with spinel structure。
Described laser additive includes alkali formula cupric phosphate, cupric phosphate or copper sulfate。
Other described component at least one in antioxidant, interior lubrication and releasing agent, antistatic additive, stabilizer, dyestuff or pigment。
The preparation method of the heat conductive insulating resin of laser direct forming adopts following steps:
(1) raw material is weighed by formula；
(2) matrix resin, thermal conducting agent, laser additive and other component are mixed 20min in moderate-speed mixers；
(3) raw material of mix homogeneously is thrown in double screw extruder, through melt extruding, pelletize, prepare the heat conductive insulating resin of laser direct forming。
Described double screw extruder includes ten temperature controlled region and two evacuation places,
Wherein, the temperature in temperature control 1-2 district is 200-290 DEG C, and the temperature in temperature control 3-4 district is 200-290 DEG C, and the temperature in temperature control 5-6 district is 200-290 DEG C, and the temperature in temperature control 7-8 district is 200-290 DEG C, and the temperature in temperature control 9-10 district is 200-290 DEG C。
Evacuation place lays respectively at the end of material conveying section, the starting end of melt zone and metering section。
Compared with prior art, the advantage that the present invention combines two kinds of dissimilar thermal conducting agents, graphite has the good advantage of heat conduction but has existence conduction risk, but the slightly worse effect with insulation of boron nitride heat conduction, bi-material is combined by the present invention, it is ensured that thermal conductivity is greatly improved under the premise of insulation, with the addition of laser additive simultaneously, can laser direct forming, thus circuit design freer and firm, a raw material achieves high heat conduction and laser direct forming both direction。
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail。
The selected PPS trade mark is PPS-HBDL, Sichuan Deyang Chemistry Co., Ltd.。
The selected graphite trade mark is C-Therm011, Te Migao graphite company limited。
Selected BN sintering temperature is 2000 DEG C, Weifang Bond's special material company limited。
The selected spinel compound trade mark is 1G, Xue Te pigment company of the U.S.。
Embodiment 1
By each component by weight: PPS52, C-Therm01120, BN20,1G8。Through the double screw extruder extrusion that melt temperature is 200-290 DEG C, pelletize。Wherein each district temperature is: the temperature in double screw extruder 1-2 district is 200-290 DEG C, and the temperature in 3-4 district is 200-290 DEG C, and the temperature in 5-6 district is 200-290 DEG C, and the temperature in temperature control 7-8 district is 200-290 DEG C, and the temperature in temperature control 9-10 district is 200-290 DEG C。
Embodiment 2
By each component by weight: PPS55, C-Therm01120, BN20,1G5。Through the double screw extruder extrusion that melt temperature is 200-290 DEG C, pelletize。Wherein each district temperature is: the temperature in double screw extruder 1-2 district is 200-290 DEG C, and the temperature in 3-4 district is 200-290 DEG C, and the temperature in 5-6 district is 200-290 DEG C, and the temperature in temperature control 7-8 district is 200-290 DEG C, and the temperature in temperature control 9-10 district is 200-290 DEG C。
Embodiment 3
By each component by weight: PPS35, C-Therm01120, BN40,1G5。Through the double screw extruder extrusion that melt temperature is 200-290 DEG C, pelletize。Wherein each district temperature is: the temperature in double screw extruder 1-2 district is 200-290 DEG C, and the temperature in 3-4 district is 200-290 DEG C, and the temperature in 5-6 district is 200-290 DEG C, and the temperature in temperature control 7-8 district is 200-290 DEG C, and the temperature in temperature control 9-10 district is 200-290 DEG C。
Embodiment 4
By each component by weight: PPS35, C-Therm01110, BN50,1G5。Through the double screw extruder extrusion that melt temperature is 200-290 DEG C, pelletize。Wherein each district temperature is: the temperature in double screw extruder 1-2 district is 200-290 DEG C, and the temperature in 3-4 district is 200-290 DEG C, and the temperature in 5-6 district is 200-290 DEG C, and the temperature in temperature control 7-8 district is 200-290 DEG C, and the temperature in temperature control 9-10 district is 200-290 DEG C。
By four formula by being extruded into plastic pellet, then being injection molded into ASTM batten, test its thermal conductivity and sheet resistance, last laser also carries out chemical plating, and final result is as follows:
From experimental result it can be seen that graphite is notable to thermal conductivity contribution, its addition is more high, and thermal conductivity is more high, it is contemplated that the composite effect of insulating properties requirement, graphite and BN is best；Copper picotite compound addition, at 5%-8%, can meet chemical plating requirement, and addition is too high, can affect mechanical performance。
Embodiment 5
The heat conductive insulating resin of a kind of laser direct forming, adopts the raw material of following components and content to prepare: matrix resin 35kg, thermal conducting agent 40kg, laser additive 5kg, other component 0.1kg。The matrix resin wherein used is weight average molecular weight is more than 30000, and structure is straight chain type, polyphenylene sulfide without branching functional group。Thermal conducting agent is the complex containing graphite Yu boron nitride。The addition of graphite is the 20wt% of resin raw material gross weight, and boron nitride addition is the 20wt% of resin raw material gross weight。Laser additive is the cupric and chromic oxide with spinel structure。Other component is selected as required, and this enforcement adopts antioxidant and antistatic additive。
The preparation method of the heat conductive insulating resin of laser direct forming adopts following steps:
(1) raw material is weighed by formula；
(2) matrix resin, thermal conducting agent, laser additive and other component are mixed 20min in moderate-speed mixers；
(3) raw material of mix homogeneously is thrown in double screw extruder, through melt extruding, pelletize, prepare the heat conductive insulating resin of laser direct forming。
The double screw extruder used includes ten temperature controlled region and two evacuation places, wherein, the temperature in temperature control 1-2 district is 200-290 DEG C, the temperature in temperature control 3-4 district is 200-290 DEG C, the temperature in temperature control 5-6 district is 200-290 DEG C, the temperature in temperature control 7-8 district is 200-290 DEG C, and the temperature in temperature control 9-10 district is 200-290 DEG C。Evacuation place lays respectively at the end of material conveying section, the starting end of melt zone and metering section。
Embodiment 7
A kind of heat conductive insulating resin of laser direct forming, the raw material adopting following components and content prepares: matrix resin 55kg, thermal conducting agent 60kg, laser additive 8kg, other component 0.9kg, wherein, the matrix resin used is syndiotactic polystyrene resin, and thermal conducting agent is the complex containing graphite Yu boron nitride。
Described graphite is 20kg, and boron nitride addition is 40kg, and laser additive is for adopting alkali formula cupric phosphate, and other component is selected as required, and this enforcement adopts antistatic additive, stabilizer, dyestuff。
The preparation method of the heat conductive insulating resin of laser direct forming adopts following steps:
(1) raw material is weighed by formula；
(2) matrix resin, thermal conducting agent, laser additive and other component are mixed 20min in moderate-speed mixers；
(3) raw material of mix homogeneously is thrown in double screw extruder, through melt extruding, pelletize, prepare the heat conductive insulating resin of laser direct forming。
The double screw extruder used includes ten temperature controlled region and two evacuation places, wherein, the temperature in temperature control 1-2 district is 200-290 DEG C, the temperature in temperature control 3-4 district is 200-290 DEG C, the temperature in temperature control 5-6 district is 200-290 DEG C, the temperature in temperature control 7-8 district is 200-290 DEG C, and the temperature in temperature control 9-10 district is 200-290 DEG C。Evacuation place lays respectively at the end of material conveying section, the starting end of melt zone and metering section。
Claims (8)
1. the heat conductive insulating resin of a laser direct forming, it is characterised in that adopt the raw material of following components and weight portion content to prepare:
Described thermal conducting agent is the complex containing graphite Yu boron nitride, and the addition of graphite is not more than the 20wt% of resin raw material gross weight, and boron nitride addition is the 20-40wt% of resin raw material gross weight。
2. the heat conductive insulating resin of a kind of laser direct forming according to claim 1, it is characterised in that described matrix resin is polyphenylene sulfide or syndiotactic polystyrene resin。
3. the heat conductive insulating resin of a kind of laser direct forming according to claim 2, it is characterised in that described matrix resin is weight average molecular weight is more than 30000, structure is straight chain type, polyphenylene sulfide without branching functional group。
4. the heat conductive insulating resin of a kind of laser direct forming according to claim 1, it is characterised in that described laser additive is the cupric and chromic oxide with spinel structure。
5. the heat conductive insulating resin of a kind of laser direct forming according to claim 1, it is characterised in that described laser additive includes alkali formula cupric phosphate, cupric phosphate or copper sulfate。
6. the heat conductive insulating resin of a kind of laser direct forming according to claim 1, it is characterised in that other described component at least one in antioxidant, interior lubrication and releasing agent, antistatic additive, stabilizer, dyestuff or pigment。
7. the preparation method of the heat conductive insulating resin of the laser direct forming as according to any one of claim 1-6, it is characterised in that the method adopts following steps:
(1) raw material is weighed by formula；
(2) matrix resin, thermal conducting agent, laser additive and other component are mixed 20min in moderate-speed mixers；
(3) raw material of mix homogeneously is thrown in double screw extruder, through melt extruding, pelletize, prepare the heat conductive insulating resin of laser direct forming。
8. the preparation method of the heat conductive insulating resin of a kind of laser direct forming according to claim 7, it is characterised in that described double screw extruder includes ten temperature controlled region and two evacuation places,
Wherein, the temperature in temperature control 1-2 district is 200-290 DEG C, the temperature in temperature control 3-4 district is 200-290 DEG C, the temperature in temperature control 5-6 district is 200-290 DEG C, the temperature in temperature control 7-8 district is 200-290 DEG C, the temperature in temperature control 9-10 district is 200-290 DEG C, and evacuation place lays respectively at the end of material conveying section, the starting end of melt zone and metering section。
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| EP3108033B1 (en) * | 2014-01-27 | 2019-10-16 | BYD Company Limited | Method for metalizing polymer substrate |
| KR101806597B1 (en) | 2014-12-24 | 2018-01-11 | 롯데첨단소재(주) | Thermoplastic resin composition for laser direct structuring and molded article using thereof |
| CN106675020B (en) * | 2016-12-05 | 2019-02-12 | 广东中塑新材料有限公司 | Laser direct forming polyamide 6 T composite material and preparation method |
| CN106675012B (en) * | 2016-12-05 | 2019-02-12 | 广东中塑新材料有限公司 | Laser direct forming polyamide compoiste material and preparation method thereof |
| CN106751800B (en) * | 2016-12-05 | 2019-02-12 | 广东中塑新材料有限公司 | Laser direct forming copolyamide 6T composite material and preparation method |
| CN107312303B (en) * | 2017-06-29 | 2019-09-17 | 上海锦湖日丽塑料有限公司 | A kind of PC/ABS alloy and preparation method thereof for laser welding |
| WO2019098701A1 (en) * | 2017-11-15 | 2019-05-23 | 주식회사 아모그린텍 | Composition for producing graphite-polymer composite and graphite-polymer composite produced therethrough |
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| US8309640B2 (en) * | 2008-05-23 | 2012-11-13 | Sabic Innovative Plastics Ip B.V. | High dielectric constant laser direct structuring materials |
| CN103450675A (en) * | 2012-05-31 | 2013-12-18 | 金发科技股份有限公司 | Resin composition having laser direct-structuring function and its preparation method and use |
| CN102796372B (en) * | 2012-08-01 | 2014-06-11 | 东莞市信诺橡塑工业有限公司 | Laser-direct-structuring high-thermal-conductivity insulated polyamide 66 composition used for LED (Light Emitting Diode) light source substrate and preparation method of composition |
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