CN102786771A - Resin liquid, metal substrate adopting the resin liquid, and manufacturing method of the metal substrate - Google Patents
Resin liquid, metal substrate adopting the resin liquid, and manufacturing method of the metal substrate Download PDFInfo
- Publication number
- CN102786771A CN102786771A CN2011101295938A CN201110129593A CN102786771A CN 102786771 A CN102786771 A CN 102786771A CN 2011101295938 A CN2011101295938 A CN 2011101295938A CN 201110129593 A CN201110129593 A CN 201110129593A CN 102786771 A CN102786771 A CN 102786771A
- Authority
- CN
- China
- Prior art keywords
- resin combination
- halogen
- combination according
- resin liquid
- compsn
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a halogen-free resin liquid, a copper foil-coated metal substrate adopting the halogen-free resin liquid, and a manufacturing method of the copper foil-coated metal substrate. The halogen-free resin liquid comprises: by weight, 20 to 70% of a halogen-free phosphorus-containing epoxy resin, 1 to 10% of one or more hardeners, 0.1 to 10% of one or more accelerators, 0 to 20% of inorganic powder, 5 to 85% of high-temperature conductive powder and 0 to 10% of one or more processing assistants. The halogen-free resin liquid has a high glass-transition temperature, excellent heat resistance, excellent flame resistance and good environmental protection functions, and can be used for a heat-conduction insulating layer of a printed circuit board so that the printed circuit board adopting the halogen-free resin liquid has high thermal conductivity.
Description
Technical field
The present invention relates to a kind of resin combination, refer to a kind of resin combination that has high glass-transition temperature and high thermal conduction characteristic concurrently and be applied to use as the heat conductive insulating layer on the printed substrate especially.
Background technology
Along with electronic product develops to light, thin, little, high-density, multifunction; Element packing density and integrated level are increasingly high in the printed board, and watt consumption is increasing, and be more and more urgent to the thermal diffusivity requirement of substrate; If the thermal diffusivity of substrate is bad; Will cause on the printed circuit board components and parts overheated, thereby whole aircraft reliability is descended, high heat radiating metal base copper-clad laminate has been born on this background.The beginning of the eighties, China's metal-based copper-clad laminate was mainly used in war products, and the complete dependence on import of metal substrate material cost an arm and a leg at that time.The middle and later periods eighties; Along with aluminium-based copper-clad laminate being widely used in automobile, motorcycle electric product reaches the expansion of consumption; The development that has promoted China's metal substrate research and manufacturing technology is especially high-power at some, in the high capacity electronic devices and components, require the aluminium-based copper-clad laminate under the 100-250C temperature, to have favorable mechanical, electric property.Heat-radiating substrate the earliest adopts ceramic substrate more; It all can not meet the demands aspect high thermal conductivity and the high security; Afterwards just to the development of metal-based-organic resin type heat-conducting substrate, metal-based-organic resin type heat-conducting substrate than ceramic mould heat-conducting substrate in the advantage that competition is all arranged aspect production cost and the safety.The intermediary insulation layer of existing metal-based copper-clad laminate mainly is the bonding sheet that adopts simple glass cloth impregnation made, in aspect of performance poor effect such as thermal conductivity, anti-water absorbability, anti-die-cut property; Another method is employed in coated with thermally conductive glue on the aluminium sheet, but this method is difficult to guarantee the heat conduction glue-line homogeneous thickness is arranged, and the metal-based copper-clad laminate thermal resistance stability of making is not high
Summary of the invention
Main purpose of the present invention provides a kind of Halogen insulation layer composition that is applicable to that high glass transition temperature of having of use in printed circuit board and high thermal conductivity are used, and said composition comprises halogen-free phosphorus-containing epoxy resin, accounts for the 30-70wt% of compsn; Stiffening agent accounts for the 1-10wt% of compsn; Promotor accounts for the 0.1-10wt% of compsn; Inorganic powder accounts for the 0-20wt% of compsn; High heat conduction powder accounts for the 5-85wt% of compsn; Processing aid accounts for the 0-10wt% of compsn.
The phosphorous epoxy resin that the present invention is used particularly has the halogen-free phosphorus-containing epoxy resin of following structural formula:
Described stiffening agent be selected from amine, anhydrides, resol class, poly-thiol compound, isocyanate compound or Synolac wherein one or more, be preferably amine, resol or anhydrides or its multiple mixture.
Described promotor is selected from imidazoles (for example: 2-ethyl-4-methylimidazole, 2-phenylimidazole, glyoxal ethyline, 1-cyano ethyl-glyoxal ethyline), list or polyphenolic substance or its mixture.
Described inorganic powder be selected from ball-type or irregular silicon-dioxide, titanium oxide, white lake, Marinco H, lime carbonate wherein one or more.The particle diameter of inorganic powder is good between the 0.01-20 micron, is convenient to process operation.
Described high heat conduction powder for be selected from metal nitride, MOX, carbide or adamantine wherein one or more.Wherein, described metal nitride can be selected from aluminium nitride AlN, SP 1 or silicon nitride; Described MOX can be selected from aluminum oxide, Natural manganese dioxide or zinc oxide; Described carbide can be selected from silit or norbide.But be preferably aluminum oxide, Natural manganese dioxide, zinc oxide, SP 1, aluminium nitride AlN, silicon nitride, more preferably have the aluminum oxide or a SP 1 of low-k or soft.That its shape can be is Powdered, ball-type shape, fibrous, sheet or stratiform, but difform high heat conduction powder can use in blending.
Described processing aid be selected from coupler, softening agent, dispersion agent one or more, preferred coupler and softening agent.This resin combination preferably adds the affinity that silicane coupler and plasticizer phthalic acid dibutyl ester improve inorganic powder, high heat conduction powder and interlaminar resin, uses softening agent can effectively reduce the fragility of product, is convenient to downstream client's processing.Silicane coupler structural formula is following:
The present invention compared with prior art; Be applied to wiring board and have following advantage: except that possessing excellent anti-water absorbability, shock-resistance, also have high thermal conductivity; Help the quick loss of heat that produced when the electronic component on the printed substrate operated, to promote the work-ing life and the stability of electronic component.
The present invention also will provide the metal copper-clad plate that above-mentioned resin combination makes of a kind of usefulness, and this metal copper-clad plate has excellent anti-water absorbability, high thermal conductivity, high glass transition temperature and firing resistance.This substrate is the Halogen substrate simultaneously, and environment is not polluted.
The present invention also will provide a kind of making method of above-mentioned metal-based copper-clad plate.Its making method is following:
(1), preparation glue: by above-mentioned prescription, in the glue groove, add halogen-free phosphorus-containing epoxy resin successively, stiffening agent, promotor and processing aid are opened high-speed stirring simultaneously; Slowly add inorganic powder, high heat conduction powder and processing aid then, finish, continue high-speed stirring.
(2), gluing: with the glasscloth is base cloth, makes the evenly gluing of base cloth surface through the dipping gum-solution method, in baking box, about 200 ℃, toasts then and makes prepreg;
(3), hot-forming: prepreg that will cut and electrolytic copper foil and the metal aluminum foil of handling combine, and put into the vacuum hotpressing machine then, and about 200 ℃ of temperature of heat plate, pressure 40Kg/cm2 pressed obtains the metal copper-clad plate.
Embodiment
Below in conjunction with specific embodiment the present invention is done further detailed explanation, but the present invention is not limited to following examples.
Embodiment 1
Present embodiment provides the glue that a kind of metal-based copper-clad plate uses and the making method of metal copper-clad plate.Said glue is made up of following component by weight: 30 parts of phosphorous epoxy resins (92547, DOW Chemical); 0.67 part of dihydro-amine; 0.05 part of glyoxal ethyline; 13.5 parts in white lake (CL 303, the fringe friend); 35 parts of aluminum oxide heat conduction powders (AM-21, fringe friend); 0.3 part of coupling agent (6040, DOW CORNING); 2 parts in softening agent (DOP, Puyang hundred million is rich).
The making method of metal-based copper-clad plate comprises the steps:
(1), preparation glue: by above-mentioned prescription, in the glue groove, add halogen-free phosphorus-containing epoxy resin successively, stiffening agent, promotor are opened high-speed stirring simultaneously; Slowly add inorganic powder, high heat conduction powder and processing aid then, finish, continue high-speed stirring.
(2), gluing: with the glasscloth is base cloth, makes the evenly gluing of base cloth surface through the dipping gum-solution method, in baking box, about 200 ℃, toasts then and makes prepreg;
(3), hot-forming: prepreg that will cut and electrolytic copper foil and the metal aluminum foil of handling combine, and put into the vacuum hotpressing machine then, and about 200 ℃ of temperature of heat plate, pressure 40Kg/cm2 pressed obtains the metal copper-clad plate.
Embodiment 2
Basically with embodiment 1, but adopt glue according to the making method of the copper-clad plate of present embodiment: 35 parts of phosphorous epoxy resins (92547, DOW Chemical) with following composition; 0.78 part of dihydro-amine; 0.05 part of glyoxal ethyline; 17 parts in white lake (CL303, fringe friend); 45 parts of SP 1 heat conduction powders (PTX120, Momentive); 0.6 part of coupling agent (6040, DOW CORNING); 2.5 parts in softening agent (DOP, Puyang hundred million is rich).
Embodiment 3
Basically with embodiment 1, but adopt glue according to the making method of the copper-clad plate of present embodiment: 65 parts of phosphorous epoxy resins (92547, DOW Chemical) with following composition; 1.5 parts of dihydro-amines; 0.05 part of glyoxal ethyline; 21 parts in white lake (CL303, fringe friend); 70 parts of SP 1 heat conduction powders (PTX120, Momentive); 0.08 part of coupling agent (6040, DOW CORNING); 3 parts in softening agent (DOP, Puyang hundred million is rich).
Embodiment 4
Basically with embodiment 1, but adopt glue according to the making method of the copper-clad plate of present embodiment: 53 parts of phosphorous epoxy resins (92547, DOW Chemical) with following composition; 1.4 parts of dihydro-amines; 0.05 part of glyoxal ethyline; 14 parts in white lake (CL303, fringe friend); 50 parts of aluminum oxide heat conduction powders (PTX120, Momentive); 0.06 part of coupling agent (6040, DOW CORNING); 2 parts in softening agent (DOP, Puyang hundred million is rich).
Comparative Examples 1
Basically with embodiment 1, but adopt glue according to the making method of the copper-clad plate of present embodiment: 65 parts of phosphorous epoxy resins (92547, DOW Chemical) with following composition; 1.5 parts of dihydro-amines; 0.05 part of glyoxal ethyline; 10 parts in white lake (CL 303, the fringe friend); 20 parts of SP 1 heat conduction powders (PTX120, Momentive); 0.02 part of coupling agent (6040, DOW CORNING); 1 part in softening agent (DOP, Puyang hundred million is rich).
Comparative Examples 2
Basically with embodiment 1, but adopt glue according to the making method of the copper-clad plate of present embodiment: 20 parts of phosphorous epoxy resins (92547, DOW Chemical) with following composition; 0.5 part of dihydro-amine; 0.05 part of glyoxal ethyline; 16.5 parts in white lake (CL303, fringe friend); 60 parts of aluminum oxide heat conduction powders (PTX120, Momentive); 0.05 part of coupling agent (6040, DOW CORNING); 2 parts in softening agent (DOP, Puyang hundred million is rich).
The performance test of the metal copper-clad plate of embodiment 1 to 4 and Comparative Examples 1 to 2,According to the testing method of IPC-TM650 the mechanical property of copper-clad plate and dielectric properties etc. are tested, the result sees table 1.
The performance data of the copper-clad plate of table 1 embodiment 1 to 4 and Comparative Examples 1 to 2
Visible from table 1, the metal copper-clad plate of making according to the inventive method has higher thermal conductivity, excellent thermotolerance, anti-water absorbability and anti-die-cut property.Can be known by embodiment 3,4 and comparison array 1, reduce inorganic powder and the high heat conduction powder weight ratio at whole prescription, after the weight ratio of increase resin, heat conductivility and mechanical property have all reduced a lot.Can know that by embodiment 1,2,3,4 and comparative example 2 after the weight ratio of reduction resin, the resistance toheat of product has reduced a lot.
More than the present invention has been done detailed description; Its purpose is to let the personage that is familiar with this art can understand content of the present invention and implements; Can not limit protection scope of the present invention with this; All equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (13)
1. the resin combination of a high heat conduction, high glass tansition temperatures is characterized in that: comprise following component: halogen-free phosphorus-containing epoxy resin accounts for the 30-70wt% of compsn; Stiffening agent accounts for the 1-10wt% of compsn; Promotor accounts for the 0.1-10wt% of compsn; Inorganic powder accounts for the 0-20wt% of compsn; High heat conduction powder accounts for the 5-85wt% of compsn; Processing aid accounts for the 0-10wt% of compsn.
2. resin combination according to claim 1 is characterized in that: described stiffening agent be selected from amine, anhydrides, resol class, poly-thiol compound, isocyanate compound or Synolac wherein one or more.
3. resin combination according to claim 1 is characterized in that: described promotor is selected from 2-ethyl-4-methylimidazole, 2-phenylimidazole, glyoxal ethyline, 1-cyano ethyl-glyoxal ethyline, list or polyphenolic substance or its mixture.
4. resin combination according to claim 1 is characterized in that: the structural formula of described halogen-free phosphorus-containing epoxy resin is:
5. resin combination according to claim 1 is characterized in that: described inorganic powder be selected from ball-type or irregular silicon-dioxide, titanium oxide, white lake, Marinco H, lime carbonate wherein one or more.
6. resin combination according to claim 1 is characterized in that: described high heat conduction powder be selected from metal nitride, MOX, carbide or adamantine wherein one or more.
7. resin combination according to claim 1 is characterized in that: described processing aid be selected from coupler, softening agent, dispersion agent one or more.
8. resin combination according to claim 6 is characterized in that: described metal nitride comprises aluminium nitride AlN, SP 1 or silicon nitride.
9. resin combination according to claim 6 is characterized in that: described MOX comprises aluminum oxide, Natural manganese dioxide or zinc oxide.
10. resin combination according to claim 7 is characterized in that: described coupler is the silicane coupler, and its structural formula is:
11. resin combination according to claim 7 is characterized in that: described softening agent is an o-phthalic acid dibutyl ester.
12. a metal copper clad foil substrate is characterized in that: its coat contains any described Halogen glue in the claim 1～11.
13. the making method of the described metal copper clad foil substrate of claim 12 is characterized in that: this method comprises the steps:
(1), preparation glue: by above-mentioned prescription, in the glue groove, add halogen-free phosphorus-containing epoxy resin successively, stiffening agent, promotor and processing aid are opened high-speed stirring simultaneously; Slowly add inorganic powder, high heat conduction powder and processing aid then, finish, continue high-speed stirring.
(2), gluing: with the glasscloth is base cloth, makes the evenly gluing of base cloth surface through the dipping gum-solution method, in baking box, about 200 ℃, toasts then and makes prepreg;
(3), hot-forming: prepreg that will cut and electrolytic copper foil and the metal aluminum foil of handling combine, and put into the vacuum hotpressing machine then, and about 200 ℃ of temperature of heat plate, pressure 40Kg/cm2 pressed obtains the metal copper-clad plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101295938A CN102786771A (en) | 2011-05-19 | 2011-05-19 | Resin liquid, metal substrate adopting the resin liquid, and manufacturing method of the metal substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101295938A CN102786771A (en) | 2011-05-19 | 2011-05-19 | Resin liquid, metal substrate adopting the resin liquid, and manufacturing method of the metal substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102786771A true CN102786771A (en) | 2012-11-21 |
Family
ID=47152370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101295938A Pending CN102786771A (en) | 2011-05-19 | 2011-05-19 | Resin liquid, metal substrate adopting the resin liquid, and manufacturing method of the metal substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102786771A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103192577A (en) * | 2013-04-26 | 2013-07-10 | 铜陵浩荣电子科技有限公司 | High-thermal-conductivity copper-clad plate manufacturing method |
| CN103694644A (en) * | 2013-12-30 | 2014-04-02 | 景旺电子科技(龙川)有限公司 | Epoxy resin composition, metal-based copper-clad plate and manufacturing method thereof |
| CN107502253A (en) * | 2017-07-26 | 2017-12-22 | 江苏诺德新材料股份有限公司 | A kind of glue for high heat conduction type copper-clad plate aluminium base and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580630A (en) * | 2009-06-23 | 2009-11-18 | 腾辉电子（苏州）有限公司 | Halogen-free flame retarding epoxy resin composition |
| CN101580626A (en) * | 2009-01-24 | 2009-11-18 | 南亚塑胶工业股份有限公司 | Resin composition with high thermal conductivity, no halogen and difficult fire retardance and pre-impregnated body and coating material thereof |
-
2011
- 2011-05-19 CN CN2011101295938A patent/CN102786771A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580626A (en) * | 2009-01-24 | 2009-11-18 | 南亚塑胶工业股份有限公司 | Resin composition with high thermal conductivity, no halogen and difficult fire retardance and pre-impregnated body and coating material thereof |
| CN101580630A (en) * | 2009-06-23 | 2009-11-18 | 腾辉电子（苏州）有限公司 | Halogen-free flame retarding epoxy resin composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103192577A (en) * | 2013-04-26 | 2013-07-10 | 铜陵浩荣电子科技有限公司 | High-thermal-conductivity copper-clad plate manufacturing method |
| CN103694644A (en) * | 2013-12-30 | 2014-04-02 | 景旺电子科技(龙川)有限公司 | Epoxy resin composition, metal-based copper-clad plate and manufacturing method thereof |
| CN103694644B (en) * | 2013-12-30 | 2015-11-04 | 景旺电子科技(龙川)有限公司 | A kind of composition epoxy resin, metal-based copper-clad plate and preparation method thereof |
| CN107502253A (en) * | 2017-07-26 | 2017-12-22 | 江苏诺德新材料股份有限公司 | A kind of glue for high heat conduction type copper-clad plate aluminium base and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104228186B (en) | A kind of high heat conduction high-performance aluminum matrix copper-clad laminate and preparation method thereof | |
| CN102516718B (en) | Resin composition and metal-based copper-clad plate using resin composition as heat conducting insulation layer | |
| CN104647868B (en) | A kind of preparation method of Copper Clad Laminates Based On Polytetrafluoroethylene | |
| CN102051023B (en) | Halogen-free resin composition and resin-coated copper foil and copper-clad plate prepared from same | |
| CN100539803C (en) | Lead-free compatible high frequency copper clad laminate and preparation method thereof | |
| CN102660210A (en) | Halogen-free high heat-resistant and heat-conducting resin film and manufacturing method thereof | |
| CN103722807A (en) | High-thermal-conductivity and high-pressure-resistance aluminum-based copper-clad plate and preparation method thereof | |
| CN1938358A (en) | Resin composition, metal foil with resin, insulating sheet with base material and multilayer printed wiring board | |
| CN109504038A (en) | A kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate | |
| CN101550264A (en) | Resin matching fluid used for metal foil laminated board | |
| CN102838962A (en) | Epoxy resin adhesive and preparation method thereof | |
| CN102504332A (en) | Inorganic filler and electric material containing same | |
| CN104002524A (en) | Making method for high thermal conductive, high heat resistant and high CTI FR-4 copper-clad plate | |
| CN102548199A (en) | Circuit board and manufacturing method thereof | |
| TWI321517B (en) | Opaque polyimide coverlay | |
| CN101955678B (en) | Flame retardant thermosetting resin composition and copper-clad plate | |
| CN112048155A (en) | Glue solution for halogen-free medium-Tg loss copper-clad plate and preparation method and application thereof | |
| CN102786771A (en) | Resin liquid, metal substrate adopting the resin liquid, and manufacturing method of the metal substrate | |
| CN114148048A (en) | High-heat-dissipation aluminum-based copper-clad plate and preparation method thereof | |
| CN102746798A (en) | High-heat-conductivity semi-cured glue film and preparation method of high-heat-conductivity semi-cured glue film | |
| CN103702511A (en) | High thermal conductivity metal substrate and manufacturing method thereof | |
| CN102775734A (en) | Halogen-free resin composition and prepreg prepared by using same | |
| CN103554437B (en) | A kind of IC encapsulation halogen-free epoxy resin composition | |
| CN102504333A (en) | Inorganic filler, resin composition and application thereof | |
| CN103554833A (en) | Halogen-free low expansion epoxy resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121121 |