CN102002235B - Method for reducing thermal expansion coefficient of polybenzoxazine-based underfill - Google Patents
Method for reducing thermal expansion coefficient of polybenzoxazine-based underfill Download PDFInfo
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- CN102002235B CN102002235B CN 201010543815 CN201010543815A CN102002235B CN 102002235 B CN102002235 B CN 102002235B CN 201010543815 CN201010543815 CN 201010543815 CN 201010543815 A CN201010543815 A CN 201010543815A CN 102002235 B CN102002235 B CN 102002235B
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- benzoxazine
- expansion coefficient
- thermal expansivity
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Abstract
The invention relates to a method for reducing thermal expansion coefficient of a polybenzoxazine-based underfill. The method comprises the following steps of: preparing a resin mixture containing benzoxazine; adding 10 to 60 parts of negative thermal expansion coefficient filler into 25 to 60 parts of resin mixture containing benzoxazine, and mixing the filler and the resin mixture uniformly; adding 10 to 25 parts of curing agent, 0 to 2 parts of catalyst and 0.1 to 3 parts of coupling agent into the mixture of the resin mixture containing benzoxazine and the negative thermal expansion coefficient filler, and mixing the components uniformly; and putting the mixture into a reaction kettle, pumping air from the reaction kettle, and then curing the mixture. The method for reducing the thermal expansion coefficient of the polybenzoxazine-based underfill by adding the negative thermal expansion coefficient material reduces the thermal expansion coefficient of the polybenzoxazine-based underfill to approach the thermal expansion coefficient of an FR-4 substrate, and does not affect the fluidity of the system.
Description
Technical field
The present invention relates to a kind of method that reduces the thermal expansivity of underfill, relate in particular to a kind of method that reduces the thermal expansivity of polyphenyl and oxazines basis pontis filling glue.
Background technology
The bottom fill process is the additional process that produces along with high-density Electronic Packaging technology rapid development; Its objective is in order to solve the mismatch problems of the thermal expansivity between integrated circuit component, interconnection material and the substrate; To prolong the work-ing life of weld, improve the thermal reliability of electronic product.Therefore the thermal expansivity of underfill is had higher requirement.Underfill in the market is main with epoxies, has cure shrinkage big (3%～4%), and thermal expansivity shortcomings such as high (65ppm/ ℃～75ppm/ ℃) is difficult to satisfy the request for utilization of high-end electronic product encapsulation.Being directed to this situation, is at present the thermal expansivity that reduces cured article through the adding filler basically.Research report is arranged, and is that 75ppm/ ℃ polymeric system is reduced to 20ppm/ ℃ and needed to add 70% silicon powder with thermal expansivity, and the viscosity of system increases severely simultaneously, has influenced the flowability of glue, and this is very big to the filling effect influence of capillary flow bottom.Therefore can consider that employing itself has low-expansion polymkeric substance.But existing polyphenyl and oxazines basis pontis are filled the thermal expansivity of glue and the thermal expansivity of FR-4 substrate, and (18ppm/ ℃～25ppm/ ℃) still is that gap is bigger; The dicyclo benzoxazine adds SiO again after being heating and curing under the dicarboxylicacid catalyst action
2Can reduce thermal expansivity, make the thermal expansivity of itself and FR-4 substrate close, but filler content crosses conference and cause system viscosity too big, mobile not enough.
Summary of the invention
The present invention is directed to existing polyphenyl and oxazines basis pontis, to fill the thermal expansivity gap of thermal expansivity and substrate of glue bigger; And system viscosity is too big behind the filling filler; Mobile not enough deficiency provides a kind of method that reduces the thermal expansivity of polyphenyl and oxazines basis pontis filling glue.
The technical scheme that the present invention solves the problems of the technologies described above is following: a kind of method that reduces the thermal expansivity of polyphenyl and oxazines basis pontis filling glue may further comprise the steps: at first, preparation comprises the resin compound of benzoxazine; Then, in 25 parts～60 parts the resin compound that comprises benzoxazine, add the filler of 10 parts～60 parts negative expansion coefficient, and mix; Then, in the mixture of the filler of resin compound that comprises benzoxazine and negative expansion coefficient, add 10 parts～25 parts solidifying agent, 0 part～2 parts catalyzer and 0.1 part～3 parts coupling agent, and after mixing; At last, mixture being put into reaction kettle vacuumizes to be cured again and gets final product.
The resin compound that said preparation comprises benzoxazine is about to benzoxazine and other resin Compositions except that benzoxazine mix; The blended temperature is 50 ℃～80 ℃; The blended time is 30 minutes, and said 50 ℃～80 ℃ temperature is the fusing point of benzoxazine.
Said mixture is put into reaction kettle, and the pressure-0.1Mpa that in reaction kettle, vacuumizes, the time that vacuumizes is 45 minutes, saidly vacuumizes 45 minutes in order to drain the bubble in the mixture only, and its each component is mixed.
The temperature that is cured again after said the vacuumizing is 150 ℃～175 ℃, and the solidified time is 3 hours～4 hours, and the curing that can progressively heat up also can be solidified under a temperature.The said curing that progressively heats up can reduce thermal stresses.
The invention has the beneficial effects as follows: the method that the present invention reduces the thermal expansivity of polyphenyl and oxazines basis pontis filling glue has the method for minus thermal-expansion coefficient through adding; Reduce polyphenyl and oxazines basis pontis and fill the thermal expansivity of glue the thermal expansivity of itself and FR-4 substrate is close to reach, do not influence the system flowability simultaneously; Adopt the thermal expansivity of the resulting underfill of this method low, mate with the FR-4 substrate; Adopt the Cl of the resulting underfill of this method
-, K
+, Na
+Concentration is below 5ppm; Adopt the water absorbability of the resulting underfill of this method low, normal low-temperature storage property is good; Adopt the second-order transition temperature of the resulting underfill of this method high, mechanical property is good; Also can be used for preparing the electronic package material of other low thermal coefficient of expansion, like joint sealant, die bonding glue, (non-) conductive resin etc.
On the basis of technique scheme, the present invention can also do following improvement.
Further, said benzoxazine is one or both a mixture in monocycle benzoxazine and the dicyclo benzoxazine.
The general structure of said benzoxazine is:
Wherein: R1 and R2 can be Wasserstoffatoms, fatty alkyl or aromatic base, also can be the benzoxazine structures, and R1 and R2 can be identical, also can be different.
Further, the said resin compound that comprises benzoxazine also comprises one or more the mixture in epoxy resin, resol, cyanate ester resin, bimaleimide resin and the acrylate resin.
Further, the quality of said benzoxazine accounts for 80%～90% of the mixed with resin amount that comprises benzoxazine.
Further, the filler of said negative expansion coefficient is one or both the mixture in zirconium thing and the tungsten thing.
The fineness of said zirconium thing and tungsten thing is 5 μ m～10 μ m.
Further, said zirconium thing is ZrO (NO
3)
2, Zr (NO
3)
4, Zr (OH)
4, Zr (SO
4)
2, Zr (O (CH
2)
3CH
3)
4, Zr (OC (CH
3)
3)
4, Zr (OC
2H
5)
4, Zr (CF
3COCHCOCF
3)
4, Zr (CH
3COCHCOCH
3)
4, Zr (OCH (CH
3)
2)
4, Zr (O (CH
2)
2CH
3)
4And Zr
3(C
6H
5O
7)
4In one or more mixture.
Further, said tungsten thing is H
2WO
12, H
2W
4O
12, W (OC
2H
5)
6, W (OCH (CH
3)
2)
6, ZrWO
4And ZrW
2O
8In one or more mixture.
Preferably, said tungsten thing is ZrWO
4Perhaps ZrW
2O
8
Further, said solidifying agent is one or more the mixture in modified amine, acid anhydrides and the resol.
When using resol to make solidifying agent, other resins in the aforementioned resin mixture are general has just no longer selected resol for use.
Said modified amine can be the PN23 of Japanese aginomoto, and said acid anhydrides can be the methyl carbic anhydride, and said resol can be the HRJ1166 of Schenectady International.
Further, said catalyzer is modified imidazole and verivate thereof.
Said catalyzer can be selected 1-phenmethyl-glyoxal ethyline of Aldrich for use; The 1-1-cyanoethyl-2-methylimidazole, 1-cyanic acid-ethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole; The PN-H of the 2PHZ of Shikoku chemistry, 2E4MZ-CN, Japanese aginomoto, wherein PN-H is preferred.
Further, said coupling agent is one or more the mixture in tetrabutyl titanate, aminopropyl triethoxysilane (KH-550), γ-glycidoxypropyl trimethoxysilane (KH-560) and the γ-methacryloxypropyl trimethoxy silane (KH-570).
Embodiment
Below principle of the present invention and characteristic are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
Embodiment 1
Take by weighing 40 parts in the mixture of monocycle benzoxazine and epoxy resin (828EL), mixed weight is than being 9:1, adds ZrWO at 50 ℃ after mixing half a hour down
447 parts; Fineness 10 μ m add solidifying agent resol (HRJ1166) 10 parts, 0.5 part of catalyst modification imidazoles (PN-H) after three-roller mixes; 0.5 part of coupling agent tetrabutyl titanate; 0.5 part of γ-glycidoxypropyl trimethoxysilane (KH-560) joins behind the mixing in the reaction kettle, vacuumizes 45 minutes under-the 0.1MPa at pressure.Materials and solidify according to the temperature-rise period classification of 150 ℃/1 h → 160 ℃/1h → 170 ℃/2 h, the thermal expansivity of gained cured article (Coefficient of thermal expansion is called for short CTE) is 18.3 ppm/ ℃.
Embodiment 2
Take by weighing 35 parts in the mixture of dicyclo benzoxazine and resol (HRJ1166), mixed weight is than being 9:1, adds ZrWO at 80 ℃ after mixing half a hour down
437 parts, fineness 10 μ m., three-roller adds 25 parts of curing agent dicyandiamides after mixing; 0.5 part of coupling agent tetrabutyl titanate; 2 parts of γ-methacryloxypropyl trimethoxy silane (KH-570) join behind the mixing in the reaction kettle, vacuumize 45 minutes under-the 0.1MPa at pressure.Materials and solidified 4 hours down at 150 ℃, the CTE of gained cured article is 20.2 ppm/ ℃.
Embodiment 3
Take by weighing 55 parts in the mixture of dicyclo benzoxazine and epoxy resin (EPON825), mixed weight is than being 9:1, adds ZrW at 70 ℃ after mixing half a hour down
2O
827 parts, fineness 5 μ m., three-roller adds 15 parts of solidifying agent methyl carbic anhydrides after mixing, 1 part of catalyst modification imidazoles (2PHZ), 0.5 part of coupling agent tetrabutyl titanate, 1.5 parts of aminopropyl triethoxysilanes (KH-550).Join behind the mixing in the reaction kettle, vacuumized 45 minutes under-the 0.1MPa at pressure.Materials and solidified 4 hours down at 170 ℃, the CTE of gained cured article is 22.7 ppm/ ℃.
Embodiment 4
Take by weighing 25 parts in the mixture of monocycle benzoxazine, dicyclo benzoxazine and epoxy resin (830LVP), mixed weight is than being 6:3:1, adds ZrWO at 75 ℃ after mixing half a hour down
4And ZrW
2O
860 parts in mixture, fineness 5 μ m., three-roller adds modified amine curing agent (PN23) 10 parts, 2 parts of catalyst modification imidazoles (PN-H), 0.5 part of coupling agent tetrabutyl titanate, 2.5 parts of γ-glycidoxypropyl trimethoxysilane (KH-560) after mixing.Join behind the mixing in the reaction kettle, vacuumized 45 minutes under-the 0.1MPa at pressure.Materials and solidified 3 hours down at 160 ℃, the CTE of gained cured article is 12.5 ppm/ ℃.
Embodiment 5
Take by weighing 55 parts in the mixture of dicyclo benzoxazine, epoxy resin (830LVP) and resol (HRJ1166), mixed weight is than being 8:1:1, adds ZrWO at 65 ℃ after mixing half a hour down
4And ZrW
2O
823 parts in mixture, fineness 5 μ m., three-roller adds modified amine curing agent (PN23) 20 parts after mixing; 0.5 part of catalyst modification imidazoles (2E4MZ-CN); 0.5 part of γ-methacryloxypropyl trimethoxy silane (KH-570), 2.0 parts of γ-glycidoxypropyl trimethoxysilane (KH-560).Join behind the mixing in the reaction kettle, vacuumized 45 minutes under-the 0.1MPa at pressure.Materials and solidified 4 hours down at 170 ℃, the CTE of gained cured article is 23.6 ppm/ ℃.
Embodiment 6
Take by weighing 60 parts in the mixture of monocycle benzoxazine, epoxy resin (828EL) and resol (HRJ1166), mixed weight is than being 8:1:1, adds ZrWO at 60 ℃ after mixing half a hour down
4And ZrW
2O
810 parts in mixture, fineness 5 μ m., three-roller adds 25 parts of curing agent dicyandiamides after mixing; 2 parts of catalyst modification imidazoles (PN-H); 1 part of aminopropyl triethoxysilane (KH-550); 2.0 parts of γ-glycidoxypropyl trimethoxysilane (KH-560) join behind the mixing in the reaction kettle, vacuumize 45 minutes under-the 0.1MPa at pressure.Materials and solidified 4 hours down at 175 ℃, the CTE of gained cured article is 27.3 ppm/ ℃.
The above is merely preferred embodiment of the present invention, and is in order to restriction the present invention, not all within spirit of the present invention and principle, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. one kind is reduced the method that polyphenyl and oxazines basis pontis are filled the thermal expansivity of glue; It is characterized in that; Said method comprising the steps of: at first; Preparation comprises the resin compound of benzoxazine, and wherein, the quality of said benzoxazine accounts for 80%～90% of the mixed with resin amount that comprises benzoxazine; Then; In 25 parts～60 parts the resin compound that comprises benzoxazine, add the filler of 10 parts～60 parts negative expansion coefficient, and mix, wherein; The filler of said negative expansion coefficient is one or both the mixture in zirconium thing and the tungsten thing, and said zirconium thing is ZrO (NO
3)
2, Zr (NO
3)
4, Zr (OH)
4, Zr (SO
4)
2, Zr (O (CH
2)
3CH
3)
4, Zr (OC (CH
3)
3)
4, Zr (OC
2H
5)
4, Zr (CF
3COCHCOCF
3)
4, Zr (CH
3COCHCOCH
3)
4, Zr (OCH (CH
3)
2)
4, Zr (O (CH
2)
2CH
3)
4And Zr
3(C
6H
5O
7)
4In one or more mixture, said tungsten thing is H
2WO
12, H
2W
4O
12, W (OC
2H
5)
6, W (OCH (CH
3)
2)
6, ZrWO
4And ZrW
2O
8In one or more mixture; Then, in the mixture of the filler of resin compound that comprises benzoxazine and negative expansion coefficient, add 10 parts～25 parts solidifying agent, 0 part～2 parts catalyzer and 0.1 part～3 parts coupling agent, and after mixing; At last, mixture being put into reaction kettle vacuumizes to be cured again and gets final product.
2. reduction polyphenyl according to claim 1 and oxazines basis pontis are filled the method for the thermal expansivity of glue, it is characterized in that, said benzoxazine is one or both a mixture in monocycle benzoxazine and the dicyclo benzoxazine.
3. reduction polyphenyl according to claim 1 and oxazines basis pontis are filled the method for the thermal expansivity of glue; It is characterized in that the said resin compound that comprises benzoxazine also comprises one or more the mixture in epoxy resin, resol, cyanate ester resin, bimaleimide resin and the acrylate resin.
4. reduction polyphenyl according to claim 1 and oxazines basis pontis are filled the method for the thermal expansivity of glue, it is characterized in that, said solidifying agent is one or more the mixture in modified amine, acid anhydrides and the resol.
5. reduction polyphenyl according to claim 1 and oxazines basis pontis are filled the method for the thermal expansivity of glue, it is characterized in that said catalyzer is modified imidazole and verivate thereof.
6. reduction polyphenyl according to claim 1 and oxazines basis pontis are filled the method for the thermal expansivity of glue; It is characterized in that said coupling agent is one or more the mixture in tetrabutyl titanate, aminopropyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane and the γ-methacryloxypropyl trimethoxy silane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010543815 CN102002235B (en) | 2010-11-15 | 2010-11-15 | Method for reducing thermal expansion coefficient of polybenzoxazine-based underfill |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010543815 CN102002235B (en) | 2010-11-15 | 2010-11-15 | Method for reducing thermal expansion coefficient of polybenzoxazine-based underfill |
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| Publication Number | Publication Date |
|---|---|
| CN102002235A CN102002235A (en) | 2011-04-06 |
| CN102002235B true CN102002235B (en) | 2012-07-25 |
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|---|---|---|---|
| CN 201010543815 Expired - Fee Related CN102002235B (en) | 2010-11-15 | 2010-11-15 | Method for reducing thermal expansion coefficient of polybenzoxazine-based underfill |
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|---|---|---|---|---|
| CN110734722A (en) * | 2019-10-21 | 2020-01-31 | 李小忠 | weather-resistant pouring sealant and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000027921A1 (en) * | 1998-11-10 | 2000-05-18 | Edison Polymer Innovation Corporation | Ternary systems of benzoxazine, epoxy, and phenolic resins |
| CN101302327A (en) * | 2007-05-10 | 2008-11-12 | 广科工业股份有限公司 | Halogen-free fire-resistant epoxy resin composition, film and copper clad laminate |
| CN101613530A (en) * | 2008-06-23 | 2009-12-30 | 联茂电子股份有限公司 | Resin combination and application thereof |
-
2010
- 2010-11-15 CN CN 201010543815 patent/CN102002235B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000027921A1 (en) * | 1998-11-10 | 2000-05-18 | Edison Polymer Innovation Corporation | Ternary systems of benzoxazine, epoxy, and phenolic resins |
| CN101302327A (en) * | 2007-05-10 | 2008-11-12 | 广科工业股份有限公司 | Halogen-free fire-resistant epoxy resin composition, film and copper clad laminate |
| CN101613530A (en) * | 2008-06-23 | 2009-12-30 | 联茂电子股份有限公司 | Resin combination and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 叶朝阳 等.苯并口恶嗪树脂插层蛭石纳米复合材料的制备与表征.《四川大学学报(工程科学版)》.2002,第34卷(第4期), * |
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Owner name: DARBOND TECHNOLOGY CO., LTD., YANTAI Free format text: FORMER OWNER: YANTAI DARBOND ELECTRONICS MATERIALS CO., LTD. Effective date: 20120815 |
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Effective date of registration: 20120815 Address after: 264006 Jinsha River Road, Yantai Development Zone, Shandong, No. 98 Patentee after: Yantai Darbond Technology Co., Ltd. Address before: 264006, No. 98, Jinsha River Road, Yantai Development Zone, Shandong, Yantai Patentee before: Yantai Darbond Electronic Materials Co., Ltd. |
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