CN100410325C - Resin composition and its use in bonding sheet and copper clad plate - Google Patents
Resin composition and its use in bonding sheet and copper clad plate Download PDFInfo
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- CN100410325C CN100410325C CNB2006100333397A CN200610033339A CN100410325C CN 100410325 C CN100410325 C CN 100410325C CN B2006100333397 A CNB2006100333397 A CN B2006100333397A CN 200610033339 A CN200610033339 A CN 200610033339A CN 100410325 C CN100410325 C CN 100410325C
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Abstract
The present invention relates to a resin composition. The resin composition is characterized in that the resin composition comprises the raw materials, in weight portions, 50 to 95 of cyanate resin, 3 to 50 of polyamine imide, 3 to 50 of epoxy resin and 0.05 to 0.5 of solidifying accelerator. The resin composition has the manufacturing technique that the raw materials of the cyanate resin, the polyamine imide, the epoxy resin, the solidifying accelerator and the like are stirred to obtain the resin composition after being mixed according to the weight portions. The glass temperature of the resin composition is improved to be above 350 DEG C, the thermal decomposition temperature is raised to more than 440 DEG C, the thermal delamination time T-300 is more than 60 minutes, and the combustion performance achieves the V-0 standard.
Description
Technical field
The present invention relates to wiring board material field, be specifically related to a kind of Halogen that requires corresponding to HDI and IC encapsulation, without phosphorus, high-performance refractory resin combination and in the application of preparation bonding sheet and copper-clad plate.
Background technology
In recent years, traditional FR-4 copper-clad plate is because thermotolerance is on the low side, second-order transition temperature generally has only 130～140 ℃, and heat decomposition temperature generally has only 300～310 ℃, though widespread use in general electronic products, but in high density interconnect and unicircuit encapsulation field, refused in application.Existing IC industry development is rapid, and along with the development of lightening, the multiple stratification and the semi-conductor field engineering of printed electronic circuit, requires substrate must have high Tg, and high heat resistance and low thermal coefficient of expansion performances such as (CTE) is to improve interconnected and the reliability of installing.Along with the raising of development of Communication Technique and computing speed, the dielectric properties of substrate also cause people's attention, require sheet material to have lower specific inductivity and lower dielectric loss simultaneously.
Summary of the invention
The objective of the invention is to overcome the problem that traditional FR-4 copper-clad plate exists, a kind of HDI of being suitable for and the IC Halogen that encapsulation requires, without phosphorus is provided, high-performance refractory resin combination and the application in producing bonding sheet and copper-clad plate thereof.
To achieve these goals, the present invention adopts following technical scheme:
Resin combination, its raw material that adopts are cyanate ester resin, polyamine imide and Resins, epoxy and curing catalyst.
The weight proportion of above-mentioned raw materials is
Cyanate ester resin 50～95,
Polyamine imide 3～50,
Resins, epoxy 3～50,
Curing catalyst 0.05～0.5.
Above-mentioned cyanate ester resin is bisphenol A cyanate ester resin or heterocyclic type cyanate ester resin or promise volt clarke type cyanate resin etc.
Above-mentioned Resins, epoxy is bisphenol A type epoxy resin or polyfunctional epoxy resin etc.
Above-mentioned curing catalyst is imidazoles or cobalt complex or naphthenate etc.
Its production technique is that raw materials such as above-mentioned cyanate ester resin, polyamine imide and Resins, epoxy and curing catalyst are mixed the back stirring and get resin compound by its proportioning.
The second-order transition temperature of resin compound of the present invention is brought up to more than 350 ℃, and heat decomposition temperature improves more than 440 ℃, and thermally stratified layer time T-300 is more than 60 minutes, and incendivity reaches the V-0 standard.
Description of drawings
Fig. 1 is the second-order transition temperature test curve;
Fig. 2 is the heat decomposition temperature test curve;
Fig. 3 is a thermally stratified layer time test curve;
Fig. 4 is the thermal expansivity test curve.
Embodiment
Embodiment 1, take by weighing 70 weight part cyanate ester resins, 15 parts of polyamine imides, 15 parts of Resins, epoxy and 0.05 part of acetylacetone cobalt, above-mentioned raw materials is mixed the back make thinner, be made into solids content and be 65% resin solution with butanone/dimethyl formamide mixed solvent.
Immerse in the above-mentioned resin solution with 8 7628E glass cloth, carry out gluing, baking is 5 minutes in 155 ℃ of baking ovens, makes the bonding sheet of semi-cured state.
With above-mentioned 8 bonding sheets stack alignment, respectively join 1 35 μ m electrolytic copper foil up and down again, in vacuum press, be 35Kgf/cm by 190 ℃ of temperature, pressure
2Condition, the double face copper that thickness is 1.6mm is made in hot pressing 90 minutes.
Embodiment 2, take by weighing 80 weight part cyanate ester resins, 10 parts of polyamine imides, 10 parts of Resins, epoxy and 0.05 part of acetylacetone cobalt, above-mentioned raw materials is mixed the back make thinner, be made into solids content and be 65% resin solution with butanone/dimethyl formamide mixed solvent.
The making of its bonding sheet and copper-clad plate is with embodiment 1.
Embodiment 3, take by weighing 40 weight part cyanate ester resins, 30 parts of polyamine imides, 30 parts of Resins, epoxy and 0.05 part of acetylacetone cobalt, above-mentioned raw materials is mixed the back make thinner, be made into solids content and be 65% resin solution with butanone/dimethyl formamide mixed solvent.
With reference to NEC circuit industry meeting standard, JPCA-CCL36-2000 " multilayer printed wiring board copper-clad plate-glass fiber fabric base bismaleimides/triazine/Resins, epoxy " detects copper-clad plate, and the result is as follows:
1, second-order transition temperature (Tg)
Second-order transition temperature (Tg), be meant sheet material under the situation of being heated by glassy transition be the pairing temperature of rubbery state (℃).
Detection method adopts dynamic mechanical analysis method (DMA).
Test result is seen figure-1.
The result shows that sheet material has very high second-order transition temperature, and Tg is 392.3 ℃.
2, heat decomposition temperature (Td)
Heat decomposition temperature (Td) is meant under the effect of heat, the temperature of sheet material generation pyrolysis (℃).
Detection method adopts thermogravimetry (TGA).Condition is: temperature rise rate is 10 ℃/minute, and thermal weight loss is 5%.
Detected result is seen figure-2.
The result shows that sheet material has quite high heat decomposition temperature, and Td is 467.33 ℃.
3, the thermally stratified layer time (T-300)
The T-300 thermally stratified layer time is meant under 300 ℃ design temperature and since heat effect, demixing phenomenon appears in sheet material, before this time that is continued (minute).
Detection method adopts thermomechanical analysis (TMA).
Detected result is seen figure-3.
The result shows that sheet material has very high thermally stratified layer temperature and very long thermally stratified layer time.T-300 is more than 60 minutes.
4, thermal stresses (288 ℃) limit
Thermal stresses (288 ℃), be meant sheet material on 288 ℃ fusion scolding tin, do not have time layering and foaming occur and to continue (minute).
The result shows that sheet material has outstanding thermal stresses.Under 288 ℃ of conditions, the time length is all more than 10 minutes.
5, thermal expansivity (CTE)
Thermal expansivity (CTE) is meant sheet material under heating condition, the dimensional change between its unit temperature rises.
The CTE and the temperature condition of sheet material have much relations.Particularly the CTE of thickness direction with when Tg is following, has very big-difference when temperature surpasses Tg.
The enforcement of pb-free solder will be because the rising of welding temperature will cause that the sheet material thermal deformation increases.In order to improve the thermal reliability of sheet material, require sheet material CTE under the situation of being heated as far as possible little.
Detection method adopts thermomechanical analysis (TMA).
Detected result is seen figure-4.
The result shows that sheet material has very outstanding dimensional stability under heat effect, and CTE is very little.
6, routine inspection sees Table-2
Table-2 routine inspections
7, this product belongs to the copper-clad plate of halogen-free phosphorus-free inflaming retarding type, and meets the requirement of the ROHS of European Union instruction.
Claims (5)
1. resin combination, it is characterized in that: its raw material that adopts is cyanate ester resin, polyamine imide and Resins, epoxy and curing catalyst;
The weight proportion of above-mentioned raw materials is
Cyanate ester resin 50～95
Polyamine imide 3～50
Resins, epoxy 3～50
Curing catalyst 0.05～0.5.
2. resin combination according to claim 1 is characterized in that: cyanate ester resin is bisphenol A cyanate ester resin or heterocyclic type cyanate ester resin or promise volt clarke type cyanate ester resin.
3. resin combination according to claim 1 is characterized in that: Resins, epoxy is bisphenol A type epoxy resin.
4. resin combination according to claim 1 is characterized in that: Resins, epoxy is polyfunctional epoxy resin.
5. resin combination according to claim 1 is characterized in that: curing catalyst is imidazoles or cobalt complex or naphthenate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100333397A CN100410325C (en) | 2006-01-26 | 2006-01-26 | Resin composition and its use in bonding sheet and copper clad plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100333397A CN100410325C (en) | 2006-01-26 | 2006-01-26 | Resin composition and its use in bonding sheet and copper clad plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1844244A CN1844244A (en) | 2006-10-11 |
| CN100410325C true CN100410325C (en) | 2008-08-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2006100333397A Active CN100410325C (en) | 2006-01-26 | 2006-01-26 | Resin composition and its use in bonding sheet and copper clad plate |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585955B (en) * | 2008-12-31 | 2012-02-22 | 广东生益科技股份有限公司 | Resin composition, resin-coated copper foil produced by same and copper-clad plate produced by utilizing resin-coated copper foil |
| CN102029746A (en) * | 2010-09-21 | 2011-04-27 | 广东生益科技股份有限公司 | Copper-clad board and production method thereof |
| CN102382302A (en) * | 2011-06-17 | 2012-03-21 | 北京化工大学常州先进材料研究院 | Asymmetric cyanate resin and curing system thereof |
| CN108314991A (en) * | 2018-02-12 | 2018-07-24 | 成都理工大学 | Resistance to 180 DEG C of high temperature adhesives of one kind and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0357006A1 (en) * | 1988-08-29 | 1990-03-07 | Cytec Technology Corp. | Structures exhibitting improved transmission of ultrahigh frequency electromagnetic radiation and structural materials which allow their construction |
| JPH03263462A (en) * | 1990-03-13 | 1991-11-22 | Fujikura Ltd | Cover coating composition for printed circuit |
| US5350635A (en) * | 1992-12-22 | 1994-09-27 | Minnesota Mining And Manufacturing Company | Cyanate resin adhesive for polyimide film |
| JP3263462B2 (en) * | 1993-02-22 | 2002-03-04 | ローム株式会社 | Wire holding device for wire bonding |
| US20020131247A1 (en) * | 2001-01-12 | 2002-09-19 | Fujitsu Limited | Dielectric resin composition and multilayer circuit board comprising dielectric layers formed therefrom |
| JP2003347358A (en) * | 2002-05-28 | 2003-12-05 | Sumitomo Bakelite Co Ltd | Semiconductor adhesion film, semiconductor device and manufacturing method of semiconductor device |
| CN1509317A (en) * | 2002-03-08 | 2004-06-30 | ��Ԩ��ѧ��ҵ��ʽ���� | Thermosetting resin composition and laminates and circuit board substrates made by using same |
| EP1507448A1 (en) * | 2003-08-12 | 2005-02-16 | Elmicron AG | Base material, substrate and connection module |
| CN1231539C (en) * | 2000-09-28 | 2005-12-14 | 住友电木株式会社 | Low temperature bonding adhesive composition |
-
2006
- 2006-01-26 CN CNB2006100333397A patent/CN100410325C/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0357006A1 (en) * | 1988-08-29 | 1990-03-07 | Cytec Technology Corp. | Structures exhibitting improved transmission of ultrahigh frequency electromagnetic radiation and structural materials which allow their construction |
| JPH03263462A (en) * | 1990-03-13 | 1991-11-22 | Fujikura Ltd | Cover coating composition for printed circuit |
| US5350635A (en) * | 1992-12-22 | 1994-09-27 | Minnesota Mining And Manufacturing Company | Cyanate resin adhesive for polyimide film |
| JP3263462B2 (en) * | 1993-02-22 | 2002-03-04 | ローム株式会社 | Wire holding device for wire bonding |
| CN1231539C (en) * | 2000-09-28 | 2005-12-14 | 住友电木株式会社 | Low temperature bonding adhesive composition |
| US20020131247A1 (en) * | 2001-01-12 | 2002-09-19 | Fujitsu Limited | Dielectric resin composition and multilayer circuit board comprising dielectric layers formed therefrom |
| CN1509317A (en) * | 2002-03-08 | 2004-06-30 | ��Ԩ��ѧ��ҵ��ʽ���� | Thermosetting resin composition and laminates and circuit board substrates made by using same |
| JP2003347358A (en) * | 2002-05-28 | 2003-12-05 | Sumitomo Bakelite Co Ltd | Semiconductor adhesion film, semiconductor device and manufacturing method of semiconductor device |
| EP1507448A1 (en) * | 2003-08-12 | 2005-02-16 | Elmicron AG | Base material, substrate and connection module |
Non-Patent Citations (2)
| Title |
|---|
| 改性聚酰亚胺覆铜板. 辜信实.铜箔与板材，第5期. 1996 |
| 改性聚酰亚胺覆铜板. 辜信实.铜箔与板材，第5期. 1996 * |
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| CN1844244A (en) | 2006-10-11 |
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