CN103694704A - Laser direct structuring heat-conducting insulating resin and preparation method thereof - Google Patents
Laser direct structuring heat-conducting insulating resin and preparation method thereof Download PDFInfo
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- CN103694704A CN103694704A CN201310698434.9A CN201310698434A CN103694704A CN 103694704 A CN103694704 A CN 103694704A CN 201310698434 A CN201310698434 A CN 201310698434A CN 103694704 A CN103694704 A CN 103694704A
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Abstract
The invention relates to a laser direct structuring heat-conducting insulating resin and a preparation method thereof. The laser direct structuring heat-conducting insulating resin is prepared from the following raw materials in parts by weight: 35-55 parts of matrix resin, 40-60 parts of a heat-conducting agent, 5-8 parts of a laser additive, and 0.1-0.9 part of other ingredients. Compared with the prior art, the heat-conducting agent is added in the resin so as to realize heat conduction and insulation, meanwhile, the laser additive is also added so as to achieve the aim of laser direct structuring; the preparation method is mainly used in LED (Light-Emitting Diode) industry, can substitute steel with plastic, simplify process and reduce cost, and also can design circuits into the material, so that design can be more free and firmness is improved greatly.
Description
Technical field
The present invention relates to be applied to the fluoropolymer resin in LED field, especially relate to heat conductive insulating resin of a kind of laser direct forming and preparation method thereof.
Background technology
Polyphenylene sulfide fusing point is higher than 280 ℃, and heat-drawn wire surpasses 260 ℃, and life-time service temperature is 220-240 ℃;
Self has flame retardant resistance, and flame retardant resistance can reach UL94V-0 level, when making flame retardant products, does not need to add any fire retardant, has kept the high-mechanical property of material itself; Rigidity is extremely strong, and surface hardness is high, high-modulus, and there is excellent creep resistant and resistance to fatigue; Chemical proofing is excellent, and not yet finding at present can be at the solvent of 200 ℃ of following PPS of dissolving, can bear low temperature-70 ℃ and long-time salt mist environment condition, and the resistivity of mineral acid, alkali and salt is strong (except acid with strong oxidizing property) very; Molding shrinkage is very little, and water-intake 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 still have good electrical property under high temperature, high humidity, high frequency condition; Melt viscosity is very low, and good fluidity very easily contacts with glass fibre is wetting, simultaneously very easily wetting with various fillers.Because the filler addition of thermally conductive material is 40%-60%, so polyphenylene sulfide base material is done thermally conductive material, and to be applied to LED shell be most suitable.
Heat conductive filler, large more options are to add ceramic-like mineral filler, because of itself insulation, as patent CN103183962A mention with BN, MgO etc.Yet ceramic packing heat conductivility is general, if thermal conductivity more than 5W/m.K, is difficult to reach.Carbon class material, especially graphite, reinforced convenient, heat conductivility is excellent, controls adding proportion, can accomplish high heat conduction and insulation.
Laser direct forming, be Laser Direct Structuring, be called for short LDS, it is 3D-MID (the Three-dimensional molded interconnect device) production technology that a kind of ejaculation, laser processing combine with electroplating technology, its principle is to give electric interconnection function by common plastic cement element, circuit card, make plastic casing, structural part except the functions such as support, protection, be combined with conducting channel and the function such as the shielding that produces, antenna.LDS material, is mainly in matrix resin, to add laser additive, and the particle after blend is injection molded into product again after electroless plating, can form conducting wire, and advantage is that line design is freer and firm.
Summary of the invention
Object of the present invention is exactly to provide heat conductive insulating resin of a kind of laser direct forming and preparation method thereof in order to overcome the defect of above-mentioned prior art existence.
Object of the present invention can be achieved through the following technical solutions:
A heat conductive insulating resin for laser direct forming, adopts the raw material of following component and weight part 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, without the polyphenylene sulfide of branching functional group
Described thermal conducting agent is the mixture that contains graphite and 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 comprises alkali formula cupric phosphate, cupric phosphate or copper sulfate.
Other described component is selected from least one in oxidation inhibitor, interior lubricated and releasing agent, static inhibitor, stablizer, dyestuff or pigment.
The preparation method of the heat conductive insulating resin of laser direct forming adopts following steps:
(1) by formula, take raw material;
(2) matrix resin, thermal conducting agent, laser additive and other component are mixed to 20min in moderate-speed mixers;
(3) raw material mixing is thrown in twin screw extruder, through melt extruding, granulation, prepares the heat conductive insulating resin of laser direct forming.
Described twin screw extruder comprises that ten temperature controlled region and two vacuumize place,
Wherein, the temperature in temperature control 1-2 district is 200-290 ℃, and the temperature in temperature control 3-4 district is 200-290 ℃, and the temperature in temperature control 5-6 district is 200-290 ℃, and the temperature in temperature control 7-8 district is 200-290 ℃, and the temperature in temperature control 9-10 district is 200-290 ℃.
The place of vacuumizing lays respectively at the end of material conveying section, the starting end of melt zone and metering zone.
Compared with prior art, the present invention combines the advantage of two kinds of dissimilar thermal conducting agents, graphite has the advantage that heat conduction is good but has the conduction of existence risk, boron nitride heat conduction is slightly poor, but there is the effect of insulation, the present invention combines bi-material, can guarantee significantly to improve thermal conductivity under the prerequisite of insulation, added laser additive simultaneously, can laser direct forming, thus line design is freer and firm, and a raw material has been realized high heat conduction and laser direct forming both direction.
Embodiment
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 ℃, Weifang Bond's special material company limited.
The selected spinel compound trade mark is 1G, U.S. Xue Te pigment company.
Embodiment 1
By each component by weight: PPS52, C-Therm011 20, BN20,1G 8.The twin screw extruder that is 200-290 ℃ through melt temperature is extruded, granulation.Wherein each district's temperature is: the temperature in twin screw extruder 1-2 district is 200-290 ℃, and the temperature in 3-4 district is 200-290 ℃, and the temperature in 5-6 district is 200-290 ℃, and the temperature in temperature control 7-8 district is 200-290 ℃, and the temperature in temperature control 9-10 district is 200-290 ℃.
Embodiment 2
By each component by weight: PPS55, C-Therm011 20, BN20,1G 5.The twin screw extruder that is 200-290 ℃ through melt temperature is extruded, granulation.Wherein each district's temperature is: the temperature in twin screw extruder 1-2 district is 200-290 ℃, and the temperature in 3-4 district is 200-290 ℃, and the temperature in 5-6 district is 200-290 ℃, and the temperature in temperature control 7-8 district is 200-290 ℃, and the temperature in temperature control 9-10 district is 200-290 ℃.
Embodiment 3
By each component by weight: PPS35, C-Therm011 20, BN40,1G 5.The twin screw extruder that is 200-290 ℃ through melt temperature is extruded, granulation.Wherein each district's temperature is: the temperature in twin screw extruder 1-2 district is 200-290 ℃, and the temperature in 3-4 district is 200-290 ℃, and the temperature in 5-6 district is 200-290 ℃, and the temperature in temperature control 7-8 district is 200-290 ℃, and the temperature in temperature control 9-10 district is 200-290 ℃.
Embodiment 4
By each component by weight: PPS35, C-Therm01110, BN50,1G5.The twin screw extruder that is 200-290 ℃ through melt temperature is extruded, granulation.Wherein each district's temperature is: the temperature in twin screw extruder 1-2 district is 200-290 ℃, and the temperature in 3-4 district is 200-290 ℃, and the temperature in 5-6 district is 200-290 ℃, and the temperature in temperature control 7-8 district is 200-290 ℃, and the temperature in temperature control 9-10 district is 200-290 ℃.
Four formulas, by being extruded into plastic pellet, then are injection molded into ASTM batten, test its thermal conductivity and surface resistivity, last laser also carries out electroless plating, and net result is as follows:
From experimental result, can find out, to thermal conductivity contribution significantly, its addition is higher for graphite, and thermal conductivity is higher, considers insulating property requirement, and the composite effect of graphite and BN is best; Copper picotite compound addition, at 5%-8%, can meet electroless plating requirement, and addition is too high can affect mechanical property.
Embodiment 5
A heat conductive insulating resin for laser direct forming, adopts the raw material of following component and content to prepare: matrix resin 35kg, thermal conducting agent 40kg, laser additive 5kg, other component 0.1kg.Use therein matrix resin is that weight-average molecular weight is more than 30000, and structure is straight chain type, without the polyphenylene sulfide of branching functional group.Thermal conducting agent is the mixture that contains graphite and 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 oxidation inhibitor and static inhibitor.
The preparation method of the heat conductive insulating resin of laser direct forming adopts following steps:
(1) by formula, take raw material;
(2) matrix resin, thermal conducting agent, laser additive and other component are mixed to 20min in moderate-speed mixers;
(3) raw material mixing is thrown in twin screw extruder, through melt extruding, granulation, prepares the heat conductive insulating resin of laser direct forming.
The twin screw extruder using comprises that ten temperature controlled region and two vacuumize place, wherein, the temperature in temperature control 1-2 district is 200-290 ℃, the temperature in temperature control 3-4 district is 200-290 ℃, the temperature in temperature control 5-6 district is 200-290 ℃, the temperature in temperature control 7-8 district is 200-290 ℃, and the temperature in temperature control 9-10 district is 200-290 ℃.The place of vacuumizing lays respectively at the end of material conveying section, the starting end of melt zone and metering zone.
Embodiment 7
A kind of heat conductive insulating resin of laser direct forming, adopt the raw material of following component and content to prepare: matrix resin 55kg, thermal conducting agent 60kg, laser additive 8kg, other component 0.9kg, wherein, the matrix resin using is syndiotactic polystyrene resin, and thermal conducting agent is the mixture that contains graphite and boron nitride.
Described graphite be 20kg, boron nitride addition is 40kg, laser additive is for adopting alkali formula cupric phosphate, other component is selected as required, this enforcements employing static inhibitor, stablizer, dyestuff.
The preparation method of the heat conductive insulating resin of laser direct forming adopts following steps:
(1) by formula, take raw material;
(2) matrix resin, thermal conducting agent, laser additive and other component are mixed to 20min in moderate-speed mixers;
(3) raw material mixing is thrown in twin screw extruder, through melt extruding, granulation, prepares the heat conductive insulating resin of laser direct forming.
The twin screw extruder using comprises that ten temperature controlled region and two vacuumize place, wherein, the temperature in temperature control 1-2 district is 200-290 ℃, the temperature in temperature control 3-4 district is 200-290 ℃, the temperature in temperature control 5-6 district is 200-290 ℃, the temperature in temperature control 7-8 district is 200-290 ℃, and the temperature in temperature control 9-10 district is 200-290 ℃.The place of vacuumizing lays respectively at the end of material conveying section, the starting end of melt zone and metering zone.
Claims (10)
1. a heat conductive insulating resin for laser direct forming, is characterized in that, adopts the raw material of following component and weight part content to prepare:
2. the heat conductive insulating resin of a kind of laser direct forming according to claim 1, is characterized 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, is characterized in that, described matrix resin preferable weight-average molecular weight is more than 30000, and structure is straight chain type, without the polyphenylene sulfide of branching functional group.
4. the heat conductive insulating resin of a kind of laser direct forming according to claim 1, is characterized in that, described thermal conducting agent is the mixture that contains graphite and boron nitride.
5. the heat conductive insulating resin of a kind of laser direct forming according to claim 4, is characterized in that, 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.
6. the heat conductive insulating resin of a kind of laser direct forming according to claim 1, is characterized in that, described laser additive is the cupric and chromic oxide with spinel structure.
7. the heat conductive insulating resin of a kind of laser direct forming according to claim 1, is characterized in that, described laser additive comprises alkali formula cupric phosphate, cupric phosphate or copper sulfate.
8. the heat conductive insulating resin of a kind of laser direct forming according to claim 1, is characterized in that, other described component is selected from least one in oxidation inhibitor, interior lubricated and releasing agent, static inhibitor, stablizer, dyestuff or pigment.
9. the preparation method of the heat conductive insulating resin of the laser direct forming as described in any one in claim 1-8, is characterized in that, the method adopts following steps:
(1) by formula, take raw material;
(2) matrix resin, thermal conducting agent, laser additive and other component are mixed to 20min in moderate-speed mixers;
(3) raw material mixing is thrown in twin screw extruder, through melt extruding, granulation, prepares the heat conductive insulating resin of laser direct forming.
10. the preparation method of the heat conductive insulating resin of a kind of laser direct forming according to claim 9, is characterized in that, described twin screw extruder comprises that ten temperature controlled region and two vacuumize place,
Wherein, the temperature in temperature control 1-2 district is 200-290 ℃, and the temperature in temperature control 3-4 district is 200-290 ℃, and the temperature in temperature control 5-6 district is 200-290 ℃, and the temperature in temperature control 7-8 district is 200-290 ℃, and the temperature in temperature control 9-10 district is 200-290 ℃.
The place of vacuumizing lays respectively at the end of material conveying section, the starting end of melt zone and metering zone.
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Cited By (7)
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| WO2015110089A1 (en) * | 2014-01-27 | 2015-07-30 | Byd Company Limited | Method for metalizing polymer substrate and polymer article prepared thereof |
| CN105733234A (en) * | 2014-12-24 | 2016-07-06 | 三星Sdi株式会社 | Thermoplastic Resin Composition for Laser Direct Structuring, Molded Article Comprising the Same and method for manufacturing molded article |
| CN106675012A (en) * | 2016-12-05 | 2017-05-17 | 广东中塑新材料有限公司 | LDS polyamide composite material and preparation method thereof |
| CN106675020A (en) * | 2016-12-05 | 2017-05-17 | 广东中塑新材料有限公司 | Laser direct forming polyamide 6T composite material and preparation method thereof |
| CN106751800A (en) * | 2016-12-05 | 2017-05-31 | 广东中塑新材料有限公司 | Laser direct forming copolyamide 6T composites and preparation method thereof |
| CN107312303A (en) * | 2017-06-29 | 2017-11-03 | 上海锦湖日丽塑料有限公司 | It is a kind of for PC/ABS alloys of laser welding and preparation method thereof |
| CN111328337A (en) * | 2017-11-15 | 2020-06-23 | 阿莫绿色技术有限公司 | Composition for producing graphite-polymer composite material and graphite-polymer composite material produced by using same |
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| CN102796372A (en) * | 2012-08-01 | 2012-11-28 | 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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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US10179949B2 (en) | 2014-01-27 | 2019-01-15 | Byd Company Limited | Method for metalizing polymer substrate and polymer article prepared thereof |
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| CN106675020A (en) * | 2016-12-05 | 2017-05-17 | 广东中塑新材料有限公司 | Laser direct forming polyamide 6T composite material and preparation method thereof |
| CN106751800A (en) * | 2016-12-05 | 2017-05-31 | 广东中塑新材料有限公司 | Laser direct forming copolyamide 6T composites and preparation method thereof |
| CN106675012A (en) * | 2016-12-05 | 2017-05-17 | 广东中塑新材料有限公司 | LDS polyamide composite material and preparation method thereof |
| 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 |
| 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 |
| 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 |
| CN107312303A (en) * | 2017-06-29 | 2017-11-03 | 上海锦湖日丽塑料有限公司 | It is a kind of for PC/ABS alloys of laser welding and preparation method thereof |
| 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 |
| CN111328337A (en) * | 2017-11-15 | 2020-06-23 | 阿莫绿色技术有限公司 | Composition for producing graphite-polymer composite material and graphite-polymer composite material produced by using same |
| CN111328337B (en) * | 2017-11-15 | 2022-01-25 | 阿莫绿色技术有限公司 | Composition for producing graphite-polymer composite material and graphite-polymer composite material produced by using same |
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