CN101126003A - Moisture-heat-proof epoxy adhesive - Google Patents
Moisture-heat-proof epoxy adhesive Download PDFInfo
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- CN101126003A CN101126003A CNA2007100728004A CN200710072800A CN101126003A CN 101126003 A CN101126003 A CN 101126003A CN A2007100728004 A CNA2007100728004 A CN A2007100728004A CN 200710072800 A CN200710072800 A CN 200710072800A CN 101126003 A CN101126003 A CN 101126003A
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- fluorenes
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Abstract
The invention provides a heat and humidity resistance epoxy adhesive. The adhesive consists of a component A and a component B; the quality ratio of the component A is: 20 to 100 shares of fluoryl epoxy resin, 1 to 50 shares of bisphenol A epoxy resin, 1 to 100 shares of novolac epoxy resin or 1 to 50 shares of alicyclic glycidyl epoxy resin; the component B consists of 20 to 80 shares of aromatic diamine curing agents. The invention has the advantages of excellent high temperature resistance. Compared with a normal or a modified epoxide resin, the high temperature shearing strength is much higher and the water absorption rate is much lower. The invention is suitable for an occasion where strong high temperature shearing strength is required under hot and humid environment.
Description
(1) technical field
What the present invention relates to is a kind of tackiness agent.
(2) background technology
Along with electronic applications high-density installation technology rapid development, adopt the more and more of slimming encapsulation.But when this slim packaging is installed on the printed-wiring board (PWB), to be put into packaged piece integral body in the tin bath and flood, this weldprocedure will stand the high temperature more than 200 ℃, in addition, in high-tech areas such as space flight and aviation, national defence, because environment for use is abominable, requires packaged material must possess high heat resistance and high bonding strength.Resins, epoxy has good heat-resisting and dimensional stability, adhesiveproperties, electrical insulation capability and resistance to chemical corrosion, and the universal epoxy resin, as bisphenol A epoxide resin, novolac epoxy, the AG-80 of polyfunctionality (being TGDDM) Resins, epoxy, alicyclic glycidyl ester (as TDE-85) and modified resin thereof, after adopting general solidifying agent to solidify, resin crosslinks density height, internal stress is big, poor toughness, bigger because of hydroxyl concentration in the cross-linked network again, so exist moisture absorption big, hydrothermal stability is poor, shortcomings such as dimensional stability and dielectric properties are not good enough can not satisfy in recent years the service performance requirement to Resins, epoxy.Simultaneously, the solidifying agent kind also has very large related to thermotolerance and water-absorbent.For this reason, generally be in the structure of Resins, epoxy, to import many ring materials (as naphthalene nucleus, biphenyl etc.) such as aromatic nucleus to improve the thermotolerances of resin.The Resins, epoxy of polyfunctional group type is the degree of crosslinking that helps improving packaged material obviously.Along with the high performance of packaging, require Resins, epoxy not only will have high heat resistance, also must have low water absorption.If the wet fastness of used epoxy resin encapsulating material is bad, the then packaged piece metal wiring passivation that easily is corroded; On the other hand, if packaged piece is in the hot and humid environment, then moisture makes distribution structure produce bad defectives such as loosening easily from packaged material with draw wire frame interface or hole and immerse.
In order to reduce the water-intake rate of packaged material, in epoxy resin structural, reduce hydroxyl and the big radical concentration of ether isopolarity as far as possible, import bigger siliceous of little c h bond of polarity and hydrophobic nature and contain fluorine structure.Improving thermotolerance and reducing water-intake rate is a pair of contradiction.Because improve the thermotolerance of packaged material, generally be the degree of crosslinking that will improve packaged material.But the free volume of packaged material has also increased, and causes water-intake rate also to improve.This just need find the optimum balance value in the two, make packaged material both have high heat resistance, has low water absorption again.
(3) summary of the invention
The object of the present invention is to provide a kind of humidity resistance good, the moisture-heat-proof epoxy adhesive that high temperature bonding intensity is high.
The object of the present invention is achieved like this:
Sizing agent of the present invention is made up of first, second two-pack, and the mass ratio of first component is formed and comprised 20～100 parts of fluorenyl Resins, epoxy, 1～50 part of bisphenol A epoxide resin, 1～100 part of novolac epoxy or 1～50 part of alicyclic ethylene oxidic ester epoxy resin; The second group is 20～80 parts of aromatic amine curing agents.
The present invention can also comprise:
1, described fluorenyl Resins, epoxy is a kind of in bisphenol fluorene Resins, epoxy, two ortho-cresol fluorenes Resins, epoxy or two (2,6-dimethyl-4-hydroxyphenyl) fluorenes Resins, epoxy.
2, described aromatic amine curing agent is a kind of in DDS, diamine fluorenes, two adjacent methylamine fluorenes or two (4-methylamine phenyl) fluorenes.
Before sizing agent uses, first, second component is mixed under 100～120 ℃, and solidified 2～8 hours down at 150～200 ℃, its condition of cure is 150 ℃/0.5～2 hour+180 ℃/1～4 hour+200 ℃/0.5～2 hour.
One of characteristics of the present invention are to be matrix resin with fluorenyl Resins, epoxy, therefore, in cross-linked network, introduce the wet-hot aging performance that macromole fluorenes ring skeleton improves resin, by carrying out blend with conventional bisphenol A epoxide resin, novolac epoxy or alicyclic ethylene oxidic ester epoxy resin, when satisfying product performance, both improved the processing characteristics of resin, also can reduce cost simultaneously.
Another characteristics of the present invention are exactly to adopt to have the diamine phenyl fluorenes of high heat-resisting skeleton as solidifying agent, solved the aliphatics amine, as quadrol, hexanediamine, diethylenetriamine, triethylene tetramine etc., aromatic diamine, as (to) phenylenediamine, diaminodiphenylsulfone(DDS) (DDS), diaminodiphenylmethane (DDM), and the high shortcoming of water-intake rate of acid anhydride type curing agent existence, simultaneously, can increase the range of choice and the use of ordinary epoxy resin.
With sizing agent of the present invention, the shearing resistance under 200 ℃ of hot conditionss reaches more than the 10MPa, and boils experiment through 48 hours boiling water, and its water-intake rate can be used for occasion higher to the shear at high temperature requirement of strength under the hygrothermal environment less than 2.1%.
Sizing agent of the present invention has good resistance to elevated temperatures, its shear at high temperature strength ratio routine or modified epoxy sizing agent are high, and water-intake rate is significantly less than conventional Resins, epoxy, can be used in occasion higher to the shear at high temperature requirement of strength under the hygrothermal environment.
(4) embodiment
For example the present invention is done in more detail below and describes:
The brand of the part material among the present invention is chosen as: bisphenol A epoxide resin is E-44, E-51 or E-54 (homemade trade names), novolac epoxy is F-44, F-48 or F-51 (homemade trade names), and alicyclic ethylene oxidic ester epoxy resin is TDE-85 (homemade trade names).
Embodiment 1:
First component: 65 parts of F-44 Resins, epoxy, 35 parts of bisphenol fluorene Resins, epoxy (oxirane value is 0.40);
Component B: 35 parts of diamine fluorenes.
The first component mixes at 120 ℃ in advance, adds the second component, and 120 ℃ were stirred 10 minutes, made the liquid sizing agent, and this sizing agent solidified by 150 ℃/1 hour+180 ℃/3 hours+200 ℃/1 hour.By national standard test shearing resistance, water absorption test is the test piece of cured resin being made 20mm * 5mm * 2mm specification, boils in boiling water 48 hours, and test-results is: room temperature shearing resistance 11.54MPa, 200 ℃ of shearing resistance 12.91MPa, water-intake rate are 1.6%.
Embodiment 2:
First component: 50 parts of E-44 Resins, epoxy, 50 parts of two ortho-cresol fluorenes Resins, epoxy (oxirane value is 0.38)
Component B: 37 parts of diamine fluorenes
Other condition is with embodiment 1, and the shear strength test result is: room temperature shearing resistance 14.54MPa, 200 ℃ of shearing resistance 12.34MPa, water-intake rate are 1.4%.
Embodiment 3:
First component: 25 parts of TDE-85 Resins, epoxy, 25 parts of E-44,50 parts of bisphenol fluorene Resins, epoxy (oxirane value is 0.40)
Component B: 46 parts of diamine fluorenes
Other condition is with embodiment 1, and the shear strength test result is: room temperature shearing resistance 13.26MPa, 200 ℃ of shearing resistance 11.72MPa, water-intake rate are 2.1%.
Embodiment 4:
First component: 100 parts of bisphenol fluorene Resins, epoxy (oxirane value is 0.40)
Component B: 35 parts of diamine fluorenes
This sizing agent solidified under the condition at 150 ℃/2 hours+180 ℃/3 hours+200 ℃/2 hours, and other condition is with embodiment 1, and the shear strength test result is: room temperature shearing resistance 10.45MPa, 200 ℃ of shearing resistance 13.10MPa, water-intake rate are 1.6%.
Embodiment 5:
First component: 65 parts of F-44 Resins, epoxy, 35 parts of two ortho-cresol fluorenes Resins, epoxy (oxirane value is 0.38);
Component B: 25 parts of DDS
Other condition is with embodiment 1, and the shear strength test result is: room temperature shearing resistance 13.38MPa, 200 ℃ of shearing resistance 10.52MPa, water-intake rate are 1.7%.
Embodiment 6:
First component: 50 parts of E-44 Resins, epoxy, 50 parts of bisphenol fluorene Resins, epoxy (oxirane value is 0.40)
Component B: 26 parts of DDS
Other condition is with embodiment 1, and the shear strength test result is: room temperature shearing resistance 12.84MPa, 200 ℃ of shearing resistance 13.67MPa, water-intake rate are 1.9%.
Comparing embodiment 1:
First component: 100 parts of E-44 Resins, epoxy
Component B: 27.5 parts of DDS
Other condition is with embodiment 1, and the shear strength test result is: room temperature shearing resistance 20.22MPa, 200 ℃ of shearing resistance 0.57MPa, water-intake rate are 3.6%.
Comparing embodiment 2:
First component: 100 parts of F-44 Resins, epoxy
Component B: 25 parts of DDS
Other condition is with embodiment 1, and the shear strength test result is: room temperature shearing resistance 14.49MPa, 200 ℃ of shearing resistance 5.32MPa, water-intake rate are 3.4%.
Comparing embodiment 3:
First component: 100 parts of TDE-85 Resins, epoxy
Component B: 53 parts of DDS
Other condition is with embodiment 1, and the shear strength test result is: room temperature shearing resistance 18.77MPa, and water-intake rate is 18.6%.
Claims (3)
1. moisture-heat-proof epoxy adhesive, it is characterized in that: be made up of first, second two-pack, the mass ratio of first component is formed and is comprised 20～100 parts of fluorenyl Resins, epoxy, 1～50 part of bisphenol A epoxide resin, 1～100 part of novolac epoxy or 1～50 part of alicyclic ethylene oxidic ester epoxy resin; The second group is 20～80 parts of aromatic amine curing agents.
2. moisture-heat-proof epoxy adhesive according to claim 1 is characterized in that: described fluorenyl Resins, epoxy is a kind of in bisphenol fluorene Resins, epoxy, two ortho-cresol fluorenes Resins, epoxy or two (2,6-dimethyl-4-hydroxyphenyl) fluorenes Resins, epoxy.
3. moisture-heat-proof epoxy adhesive according to claim 1 and 2 is characterized in that: described aromatic amine curing agent is a kind of in DDS, diamine fluorenes, two adjacent methylamine fluorenes or two (4-methylamine phenyl) fluorenes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100728004A CN100569885C (en) | 2007-09-12 | 2007-09-12 | Moisture-heat-proof epoxy adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100728004A CN100569885C (en) | 2007-09-12 | 2007-09-12 | Moisture-heat-proof epoxy adhesive |
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| Publication Number | Publication Date |
|---|---|
| CN101126003A true CN101126003A (en) | 2008-02-20 |
| CN100569885C CN100569885C (en) | 2009-12-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2007100728004A Expired - Fee Related CN100569885C (en) | 2007-09-12 | 2007-09-12 | Moisture-heat-proof epoxy adhesive |
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| CN (1) | CN100569885C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477275A (en) * | 2010-11-26 | 2012-05-30 | 上海恩意材料科技有限公司 | Preparation method of epoxy adhesive with high bonding strength |
| CN102477276A (en) * | 2010-11-26 | 2012-05-30 | 上海恩意材料科技有限公司 | Epoxy adhesive with high bonding strength |
| CN102676093A (en) * | 2011-03-11 | 2012-09-19 | 日东电工株式会社 | Die-bonding film and use thereof |
| CN106252441A (en) * | 2016-08-31 | 2016-12-21 | 江苏裕康复合材料有限公司 | A kind of photovoltaic component back plate |
| CN107400492A (en) * | 2017-09-26 | 2017-11-28 | 安徽大松树脂有限公司 | A kind of heat-proof combustion-resistant epoxy resin adhesive |
| CN107459957A (en) * | 2017-09-26 | 2017-12-12 | 安徽大松树脂有限公司 | A kind of high fire-retardance epoxy resin adhesive |
| CN111187393A (en) * | 2020-02-19 | 2020-05-22 | 中科院广州化灌工程有限公司 | Hyperbranched epoxy resin, hyperbranched epoxy resin-based building structure adhesive, preparation and application |
| CN112680083A (en) * | 2020-12-28 | 2021-04-20 | 四川赛尔科美新材料科技有限公司 | Heat-preservation sound-insulation composite material containing micro-nano particles and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4707534A (en) * | 1986-12-09 | 1987-11-17 | Minnesota Mining And Manufacturing Company | Glycidylethers of fluorene-containing bisphenols |
| CN100506938C (en) * | 2006-12-20 | 2009-07-01 | 哈尔滨工程大学 | Thermostable epoxy resin adhesive and its preparation method |
-
2007
- 2007-09-12 CN CNB2007100728004A patent/CN100569885C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477275A (en) * | 2010-11-26 | 2012-05-30 | 上海恩意材料科技有限公司 | Preparation method of epoxy adhesive with high bonding strength |
| CN102477276A (en) * | 2010-11-26 | 2012-05-30 | 上海恩意材料科技有限公司 | Epoxy adhesive with high bonding strength |
| CN102676093A (en) * | 2011-03-11 | 2012-09-19 | 日东电工株式会社 | Die-bonding film and use thereof |
| CN102676093B (en) * | 2011-03-11 | 2015-11-25 | 日东电工株式会社 | Die bonding film and uses thereof |
| CN106252441A (en) * | 2016-08-31 | 2016-12-21 | 江苏裕康复合材料有限公司 | A kind of photovoltaic component back plate |
| CN107400492A (en) * | 2017-09-26 | 2017-11-28 | 安徽大松树脂有限公司 | A kind of heat-proof combustion-resistant epoxy resin adhesive |
| CN107459957A (en) * | 2017-09-26 | 2017-12-12 | 安徽大松树脂有限公司 | A kind of high fire-retardance epoxy resin adhesive |
| CN111187393A (en) * | 2020-02-19 | 2020-05-22 | 中科院广州化灌工程有限公司 | Hyperbranched epoxy resin, hyperbranched epoxy resin-based building structure adhesive, preparation and application |
| CN112680083A (en) * | 2020-12-28 | 2021-04-20 | 四川赛尔科美新材料科技有限公司 | Heat-preservation sound-insulation composite material containing micro-nano particles and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100569885C (en) | 2009-12-16 |
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Granted publication date: 20091216 Termination date: 20120912 |