CN1610103A - Electric insulated resin pulp used for chip carrying and packaging - Google Patents
Electric insulated resin pulp used for chip carrying and packaging Download PDFInfo
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- CN1610103A CN1610103A CN 200310111843 CN200310111843A CN1610103A CN 1610103 A CN1610103 A CN 1610103A CN 200310111843 CN200310111843 CN 200310111843 CN 200310111843 A CN200310111843 A CN 200310111843A CN 1610103 A CN1610103 A CN 1610103A
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Abstract
The electrically insulating resin slurry for chip connection and packaging has the components including epoxy resin, liquid rubber toughening agent, imidazole derivative as curing agent, silicon powder stuffing and active diluent. The epoxy resin is the mixture of solid epoxy resin and liquid epoxy resin; the liquid rubber toughening agent is CTBN or HTBN in the amount of 10-20 % of the epoxy resin; the imidazole derivative as curing agent is imidazole derivative with substituted long chain; the silicon powder stuffing has the granularity of 0.1-1 micron and accounts for 20-30 %; and the active diluent is ethylene glycol diglycidol ether and accounts for 0-10 %. The electrically insulating resin slurry of the present invention, after being cured, has high toughness and proper inner stress and results in less cracking and damage of chip, element and device.
Description
Technical field
The present invention relates to the preparation of the gluey thing of polymer, relate in particular to the preparation that chip carries and the electric insulation resin of encapsulation usefulness is starched.
Background technology
Prior art relates to chip and carries and encapsulate material therefor, because current chip carries encapsulation many modes are arranged, as: COB (Chip On Board: encapsulation on the flat board), TAB (Tape On Board: encapsulate in the winding), COG (Chip On Glass: encapsulation on glass), all be to adopt Au/Sn welding or ACF (different direction conducting film) connection or ACP (conducting resinl) bonding, seal with plastic packaging material then, these technology all exist some defectives and deficiency, as: the Au/Sn welding can only guarantee the thick circuit pad; ACF connects the existence foaming, particle conductive is inhomogeneous; ACP is bonding when can not be implemented in directions X and Y direction and present insulation, vertical Z direction conduction.Along with carrying the encapsulation technology development, extension in TCP (winding carrier package technology), occur a kind of new system again and carried encapsulation COF (chip is installed on the flexible circuit) technology, it is by NCP (electric insulation resin slurry) the chip joint face upwards to be placed on the calandria of adsorbent equipment that chip directly carries the encapsulation circuit, to adhere to NCP from the top by camera and the automatic alignment system of camera temporarily, solidify fast, make COF chip module.Adopt the NCP technology to enhance productivity greatly, its key technology is that a kind of curing rate of configuration is fast, the thermal conductivity height, and thermal coefficient of expansion and dielectric constant are low, do not ftracture the one-component pasty state electric insulation resin slurry that electrical insulation capability is good.
Patent JP 62143P86 from the non-conductive paste packaged semiconductor devices of SUMITOMO CHEMICAL bakelite Co., Ltd. public use at first, Japanese afterwards Toshiba Chemical Corp., Hitachi Chemical Co., Ltd. discloses some patented technologies in succession, use therein epoxy resin kind is a lot, as: the bisphenol A epoxide resin among the JP 04332754, bisphenol F epoxy resin among the JP 2002226675, novolac epoxy resin among the JP 06096616, adjacent sylvan formaldehyde epoxy resin among the JP 0726235, cycloaliphatic epoxy resin among the WO02/15259, the dimeric dibasic acid epoxy resin of JP 11199850, JP 10120873 contains organosiloxane epoxy resin etc.The curing agent that uses in these patents is latent curing agent mostly, and as dicyandiamide imdazole derivatives: 2MI-Arine, 2E4MI-Arine adipoyl hydrazine and organo-aluminium compound are as praseodynium aluminium.The insulating packing that adds in these patents, using maximum is silicon dioxide powder, particle mean size 3 μ m, 5 μ m have, also useful nano level superfine silica flour, and boron nitride.
The Hyundai Institute Of Science And Technology discloses the manufacture method of a kind of NCA (electric insulation resin slurry adhesive) in world patent WO 02/15259, form adhesive by solid bisphenol A epoxy resin, liquid bisphenol F epoxy resin and the mixing of solid phenoxy resin, adopt liquid imidazole class curing agent, the titanium dioxide osmanthus of employing granularity 0.1-1 μ m and carborundum are as non-conductive filler.
There are the not enough and bigger defective of internal stress of toughness in existing chip lift-launch and encapsulation with the electric insulation resin slurry, are prone to cracking and consequently cause chip and components and parts infringement.
Summary of the invention
The technical problem to be solved in the present invention is to avoid above-mentioned the deficiencies in the prior art part, and proposes a kind of well behaved chip lift-launch and encapsulate to starch with electric insulation resin.
The technical scheme that the present invention solve the technical problem employing is, prepare a kind of electric insulation resin slurry that chip carries and encapsulates that is used for, described electric insulation resin slurry is by annex solution body rubber flexibilizer in the epoxy resin, the imdazole derivatives curing agent, and silica flour filler and reactive diluent are formed.
Epoxy resin of the present invention adopts the mixture of liquid epoxies and solid epoxy; Wherein, liquid epoxies accounts for weight 70%, can be E-44 type epoxy tree, F-44 type epoxy resin or F-51 type epoxy resin, and described solid epoxy accounts for weight 30%, can be in E-20 type epoxy resin, E-12 type epoxy resin or the F-46 type epoxy resin one or more.For good toughness and suitable internal stress are arranged after solidifying, on the one hand, in epoxy resin, add an amount of liquid rubber flexibilizer, the epoxy radicals of its functional group and epoxy resin and curing agent reaction, form space network with epoxy resin, play effect toughness reinforcing and that strengthen.On the other hand, adopt the imdazole derivatives that has long fatty hydroxyl chain, increase flexibility, reduce internal stress as latent curing agent.
The present invention adopts and contains long-chain substituting group Imidazole Type Latent Curing Agent, as: 2,4-diaminourea-6-[-2-undecyl (1)]-ethyl one cis triazine, trade names are C11Z-AZINE, 1-cyanoethyl-2-undecyl one trimellitic acid imidazole salts, trade names are C11Z-AZINE, and consumption is the 15-25% of epoxy resin.
The flexibilizer that the present invention uses is end carboxyl liquid nitrile rubber (CTBN) or terminal hydroxy liquid nitrile rubber (HTBN), produces by Lanzhou Petroleum Chemical Engineering Institute, and molecular weight about 3000, degree of functionality is 2, consumption is the 10-20% of epoxy resin.
The inorganic filler that the present invention uses is super-fine silicon micro-powder, average grain diameter 2 μ m, and granularity 0.1-1 μ m, consumption are the 20-30% of total amount.
The present invention is according to using requirement to viscosity to add the technological requirement of a certain amount of reactive diluent when guaranteeing to use, and reactive diluent adopts ethylene glycol diglycidylether, and consumption is the 0-10% of total amount.
In sum, the basic recipe that electric insulation resin slurry of the present invention uses is by weight, and is as follows:
70 parts of liquid epoxiess;
30 parts of solid epoxies;
Liquid rubber flexibilizer 10-20 part;
Imdazole derivatives curing agent 15-25 part;
Silicon dioxide powder 40-60 part;
Reactive diluent 0-10 part.
The physical characteristic of described electric insulation resin slurry has:
Viscosity 100pas;
Adhesive strength＞6 (kg/tape);
Peel strength 1.5 (kg/tape);
Pin widths/spacing＜40 μ m.
Compare with prior art, the present invention is used for the electric insulation resin slurry of chip lift-launch and encapsulation, and good toughness and suitable internal stress are arranged after the curing, is not prone to cracking and consequently causes chip and components and parts infringement.
Embodiment
The electric insulation resin slurry that the present invention is used for chip lift-launch and encapsulation is described in detail by following examples.
Embodiment 1
Take by weighing E-44 epoxy resin 70g, add E-20 epoxy resin 30g stirring and dissolving, add the fine 15g of end carboxyl liquid fourth, ethylene glycol diglycidylether reactive diluent 8g, SILICA FUME 47g adds C11Z-AZINE imdazole derivatives curing agent 20g, and heating stirs, divide to install in the container, store at low temperatures.
This electric insulation resin slurry is tested, and the result is:
Viscosity: 120Pas; Adhesive strength:＞6kg/tape; Peel strength: 1.6kg/tape; Outside cracking number: 0/10; Pin widths/spacing:＜40 μ m.
Embodiment 2
Take by weighing E-51 epoxy resin 70g, add E-20 epoxy resin 15g, E-12 epoxy resin 15g, stirring and dissolving adds terminal hydroxy liquid nitrile rubber 12g, ethylene glycol diglycidylether reactive diluent 6g, SILICA FUME 47g adds C11Z-AZINE imdazole derivatives curing agent 16g, and heating stirs, divide to install in the container, store at low temperatures.
This electric insulation resin slurry is tested, and the result is:
Viscosity: 100pas; Adhesive strength:＞6kg/tape; Peel strength: 1.5kg/tape; Outside cracking number: 0/10; Pin widths/spacing:＜40 μ m.
Embodiment 3
Take by weighing E-44 epoxy resin 70g, add E-20 epoxy resin 30g stirring and dissolving, add the fine 18g of end carboxyl liquid fourth, ethylene glycol diglycidylether reactive diluent 1g, SILICA FUME 55g adds 1-cyanoethyl-2-undecyl one trimellitic acid miaow salt (C11-CNS) 20g, and heating stirs, divide to install in the container, store at low temperatures.
This electric insulation resin slurry is tested, and the result is:
Viscosity: 80Pas; Adhesive strength:＞6kg/tape; Peel strength: 0.8kg/tape; Outside cracking number: 5/10; Pin widths/spacing＜40 μ m.
Comparative example 4
Take by weighing E-44 epoxy resin 70g, add E-20 epoxy resin 30g stirring and dissolving, add the fine 15g of end carboxyl liquid fourth, SILICA FUME 47g adds C11Z-AZINE imdazole derivatives curing agent 20g, stirs, and divides to install in the container, stores at low temperatures.
This electric insulation resin slurry is tested, and the result is:
Viscosity: 90Pas; Adhesive strength:＞6kg/tape; Peel strength: 1.0kg/tape; Outside cracking number: 8/10; Pin widths/degree＜40 a μ m.
Embodiment 5
Take by weighing F-44 epoxy resin 70g, add F-12 epoxy resin 30g stirring and dissolving, add the fine 15g of end carboxyl liquid fourth, ethylene glycol diglycidylether reactive diluent 8g, SILICA FUME 47g adds C11Z-AZINE imdazole derivatives curing agent 20g, and heating stirs, divide to install in the container, store at low temperatures.
This electric insulation resin slurry is tested, and the result is:
Viscosity: 120Pas; Adhesive strength:＞6kg/tape; Peel strength: 1.6kg/tape; Outside cracking number: 0/10; Pin widths/spacing:＜40 μ m.
Embodiment 6
Take by weighing E-44 epoxy resin 70g, add F-46 epoxy resin 30g stirring and dissolving, add the fine 15g of end carboxyl liquid fourth, ethylene glycol diglycidylether reactive diluent 8g, SILICA FUME 47g adds C11Z-AZINE imdazole derivatives curing agent 20g, and heating stirs, divide to install in the container, store at low temperatures.
This electric insulation resin slurry is tested, and the result is:
Viscosity: 120Pas; Adhesive strength:＞6kg/tape; Peel strength: 1.6kg/tape; Outside cracking number: 0/10; Pin widths/spacing:＜40 μ m.
Embodiment 7
Take by weighing F-51 epoxy resin 70g, add EX-46 epoxy resin 30g stirring and dissolving, add the fine 15g of end carboxyl liquid fourth, ethylene glycol diglycidylether reactive diluent 8g, SILICA FUME 47g adds C11Z-AZINE imdazole derivatives curing agent 20g, and heating stirs, divide to install in the container, store at low temperatures.
This electric insulation resin slurry is tested, and the result is:
Viscosity: 120Pas; Adhesive strength:＞6kg/tape; Peel strength: 1.6kg/tape; Outside cracking number: 0/10; Pin widths/spacing:＜40 μ m.
Embodiment 8
Take by weighing E-44 epoxy resin 70g, add F-46 epoxy resin 30g stirring and dissolving, add the fine 15g of end carboxyl liquid fourth, ethylene glycol diglycidylether reactive diluent 8g, SILICA FUME 47g adds C11Z-AZINE imdazole derivatives curing agent 20g, and heating stirs, divide to install in the container, store at low temperatures.
This electric insulation resin slurry is tested, and the result is:
Viscosity: 120Pas; Adhesive strength:＞6kg/tape; Peel strength: 1.6kg/tape; Outside cracking number: 0/10; Pin widths/spacing:＜40 μ m.
Compare enforcement according to example case, contrast as follows:
Comparative examples A
Take by weighing E-44 epoxy resin 70g, add E-20 epoxy resin 30g stirring and dissolving, add ethylene glycol diglycidylether reactive diluent 8g, SILICA FUME 47g adds C11Z-AZINE imdazole derivatives curing agent 20g, and heating stirs, divide to install in the special container, store at low temperatures.
This electric insulation resin slurry is tested, and the result is: peel strength is crisp broken, local peel strength＜0.5kg/tape; Outside cracking several 10/10.
Comparative example 1 and Comparative examples A
Comparative examples A and embodiment 1 prescription are basic identical, just do not add end carboxyl liquid nitrile rubber in the Comparative examples A, and the result is; Toughness is obviously not enough, and outside cracking is very serious.
Comparative example B
Take by weighing E-44 epoxy resin 70g, add E-20 epoxy resin 30g stirring and dissolving and add ethylene glycol diglycidylether reactive diluent 8g, SILICA FUME 47g adds dicy-curing agent 20g, heats the branch that stirs and installs in the special container, stores at low temperatures.
The prescription of comparative example B and comparative example 1 is basic identical, and just latent curing agent is selected dicy-curing agent for use among the comparative example B, and the result is: find during use that curing rate is slow, reaction speed prolongs, solidfied material is flexible not enough, electric insulation resin pulp color blackout, flexural fatigue＜100 time.
Claims (10)
1. one kind is used for the electric insulation resin slurry that chip carries and encapsulates, and it is characterized in that: the component of described electric insulation resin slurry comprises epoxy resin, liquid rubber flexibilizer, imdazole derivatives curing agent, silica flour filler and reactive diluent.
2. electric insulation resin slurry as claimed in claim 1, it is characterized in that: described epoxy resin is the mixture of 70% weight liquid epoxies and 30% weight solid epoxy.
3. electric insulation resin slurry as claimed in claim 2, it is characterized in that: described liquid epoxies comprises E-44 type epoxy resin, E-51 type epoxy resin, F-44 type epoxy resin and F-51 type epoxy resin.
4. electric insulation resin slurry as claimed in claim 2, it is characterized in that: described solid epoxy comprises E-20 type epoxy resin, E-12 type epoxy resin, F-12 type epoxy resin, F-46 type epoxy resin and EX-46 type epoxy resin, can be wherein a kind of, also can be several mixing.
5. electric insulation resin slurry as claimed in claim 1 is characterized in that: described liquid rubber flexibilizer is end carboxyl nitrile rubber or end carboxyl nitrile rubber, and its consumption is the 10-20% weight of described content of epoxy resin.
6. electric insulation resin slurry as claimed in claim 1, it is characterized in that: described imdazole derivatives curing agent is for containing long-chain substituting group Imidazole Type Latent Curing Agent, and its consumption is the 15-25% weight of described content of epoxy resin.
7. electric insulation resin slurry as claimed in claim 6, it is characterized in that: the described long-chain substituting group Imidazole Type Latent Curing Agent that contains comprises 2,4-diaminourea-6-[-2-undecyl (1)]-ethyl-cis triazine (C11Z-AZINE) and 1-cyanoethyl-2-undecyl one trimellitic acid imidazole salts (C11Z-CNS).
8. electric insulation resin slurry as claimed in claim 1, it is characterized in that: the granularity 0.1-1 μ m of described silica flour filler, its consumption accounts for the 20-30% weight of total amount.
9. electric insulation resin slurry as claimed in claim 1, it is characterized in that: described reactive diluent is an ethylene glycol diglycidylether, its consumption accounts for the 0-10% weight of total amount.
10. as electric insulation resin slurry as described in arbitrary in the claim 1 to 9, it is characterized in that: the basic recipe of described electric insulation resin slurry is by weight:
70 parts of liquid epoxiess;
30 parts of solid epoxies;
Liquid rubber flexibilizer 10-20 part;
Imdazole derivatives curing agent 15-25 part;
Silicon dioxide powder 40-60 part;
Reactive diluent 0-10 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101118430A CN100422235C (en) | 2003-10-17 | 2003-10-17 | Electric insulated resin pulp used for chip carrying and packaging |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101118430A CN100422235C (en) | 2003-10-17 | 2003-10-17 | Electric insulated resin pulp used for chip carrying and packaging |
Publications (2)
| Publication Number | Publication Date |
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| CN1610103A true CN1610103A (en) | 2005-04-27 |
| CN100422235C CN100422235C (en) | 2008-10-01 |
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| CN101812217A (en) * | 2010-04-15 | 2010-08-25 | 河南许绝电工绝缘材料有限公司 | Partial discharge resistant epoxy casting resin |
| CN101974302A (en) * | 2010-10-19 | 2011-02-16 | 烟台德邦电子材料有限公司 | Low-viscosity and high-heat conduction epoxy resin electronic potting adhesive |
| CN102061060A (en) * | 2010-11-26 | 2011-05-18 | 烟台德邦电子材料有限公司 | High-reliability intelligent-card encapsulating glue and preparation method thereof |
| CN101497774B (en) * | 2009-03-04 | 2011-08-31 | 三友（天津）高分子技术有限公司 | Semiconductor chip liquid encapsulation material |
| CN102660211A (en) * | 2012-05-29 | 2012-09-12 | 四川力通复合材料科技有限公司 | Modified epoxy adhesive for aramid paper honeycomb |
| CN103436210A (en) * | 2013-08-08 | 2013-12-11 | 深圳丹邦科技股份有限公司 | Electric-insulation resin grout used for packaging chips and preparation method of electric-insulation resin grout |
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| CN85100135A (en) * | 1985-04-01 | 1986-08-13 | 清华大学 | The intermediate temperature setting high strength epoxy adhesive |
| US6632893B2 (en) * | 1999-05-28 | 2003-10-14 | Henkel Loctite Corporation | Composition of epoxy resin, cyanate ester, imidazole and polysulfide tougheners |
| JP2002009091A (en) * | 2000-06-19 | 2002-01-11 | Sumitomo Bakelite Co Ltd | Resin paste for semiconductor and semiconductor device using the same |
| KR100315158B1 (en) * | 2000-08-02 | 2001-11-26 | 윤덕용 | High reliability non-conductive adhesives for non-solder flip chip bondings and flip chip bonding method using the same |
| TWI281478B (en) * | 2000-10-11 | 2007-05-21 | Sumitomo Bakelite Co | Die-attaching paste and semiconductor device |
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| CN101812217A (en) * | 2010-04-15 | 2010-08-25 | 河南许绝电工绝缘材料有限公司 | Partial discharge resistant epoxy casting resin |
| CN101974302A (en) * | 2010-10-19 | 2011-02-16 | 烟台德邦电子材料有限公司 | Low-viscosity and high-heat conduction epoxy resin electronic potting adhesive |
| CN102061060A (en) * | 2010-11-26 | 2011-05-18 | 烟台德邦电子材料有限公司 | High-reliability intelligent-card encapsulating glue and preparation method thereof |
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| CN103436210A (en) * | 2013-08-08 | 2013-12-11 | 深圳丹邦科技股份有限公司 | Electric-insulation resin grout used for packaging chips and preparation method of electric-insulation resin grout |
| CN103627360A (en) * | 2013-11-28 | 2014-03-12 | 蓝星（成都）新材料有限公司 | Latent epoxy resin composite suitable for insulative impregnation of conformal felt and binding rope of motor and preparation method of composite |
| CN103937432A (en) * | 2014-02-14 | 2014-07-23 | 上海禧合应用材料有限公司 | Sealant |
| CN104845040A (en) * | 2015-01-14 | 2015-08-19 | 无锡龙舜实业有限公司 | Preparation process of G-20 type epoxy casting agent |
| CN104845041A (en) * | 2015-01-14 | 2015-08-19 | 无锡龙舜实业有限公司 | G-20 type epoxy casting agent |
| CN105331049A (en) * | 2015-11-24 | 2016-02-17 | 苏州盖德精细材料有限公司 | High-elasticity epoxy resin encapsulating material and preparation method thereof |
| US10653009B1 (en) | 2018-11-21 | 2020-05-12 | At&S (China) Co., Ltd. | Component carrier with improved toughness factor |
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| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: Guangdong province Shenzhen city Nanshan District high tech Industrial Park North Long Hill Road danbang Technology Building Patentee after: SHENZHEN DANBOND TECHNOLOGY Co.,Ltd. Address before: Guangdong province Shenzhen city Nanshan District high tech park, Long Hill Road Patentee before: Shenzhen Danbang Science & Technology Co.,Ltd. |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081001 Termination date: 20211017 |