CN103184024A - Reversible bonding-debonding epoxy resin adhesive and preparation method thereof - Google Patents
Reversible bonding-debonding epoxy resin adhesive and preparation method thereof Download PDFInfo
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- CN103184024A CN103184024A CN2011104454654A CN201110445465A CN103184024A CN 103184024 A CN103184024 A CN 103184024A CN 2011104454654 A CN2011104454654 A CN 2011104454654A CN 201110445465 A CN201110445465 A CN 201110445465A CN 103184024 A CN103184024 A CN 103184024A
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Abstract
The invention belongs to the field of new materials, and relates to a hot debond epoxy resin adhesive and a preparation method thereof. The adhesive is composed of the following materials: epoxy resin with epoxy equivalent less than 550 g/mol, an organic amine curing agent with the molecular weight less than 900 g/mol, thermoplastic resin with the molecular weight between 1000-100000 g/mol, and a solvent. Verified by the experiments, the prepared adhesive has good hot debonding property, can be easily peeled off by heating, can restore the high adhesive strength after composition, and achieves a reversible bonding-debonding capability. The adhesive has a good thermosetting property, and can wholly keep solid properties of the film in the case of heating. The adhesive can be used for various high-tech products requiring high bond strength and easy disassembling, such as recyclable high-performance radio frequency tags, electronic chips and removable electronic circuit boards.
Description
Technical field
The invention belongs to field of new, be specifically related to a kind of can hot unsticking epoxy resin binder and preparation method thereof.This tackiness agent has high strength and reversible adhesive-debinding ability, can be used for the bonding of functional materials and device, be particularly useful for needing high bond strength and can the high-tech product of easy dismounting in.
Technical background:
It is a kind of high-strength structureal adhesives with extensive use that prior art discloses epoxy resin binder.This tackiness agent is generally by the formulated engineering adhesive of Resins, epoxy base-material, solidifying agent, thinner, promotor and filler.Because characteristics such as it has that adhesiveproperties is good, good insulating, less expensive, technique for sticking are easy have obtained in household electrical appliances, automobile, water conservancy traffic, electronic apparatus and aerospace industry field using widely in recent decades.
Compare with the tackiness agent of other types, described epoxy adhesive has following advantage, as, epoxyn is bonding various material extremely widely: wherein during bonding object, under the situation of reasonable joint design, the stress distribution of its connecting portion is even; During bonding object, has more comprehensive favorable mechanical performance; Can also give multiple functions such as its sealing, leakproof, insulation, anticorrosion, heat conduction when having good strength.Yet, there is following defective on the described epoxy adhesive, as: crisp partially its cured article when not toughness reinforcing, cracking resistance and shock resistance are poor, and the material little to polarity (as polyethylene, polypropylene, fluoroplastics etc.) bonding force is little.
At the own characteristic of epoxyn, relevant researchist has carried out a large amount of research to Resins, epoxy toughness reinforcing, adopts different methods to improve Resins, epoxy gluing agent toughness, and has obtained significant achievement.Conclude and get up to mainly contain three kinds: 1. in epoxy matrix, add rubber elastomer or liquid crystalline polymers and wait next toughness reinforcing; 2. it is toughness reinforcing to form inierpeneirating network structure continuously in the epoxy networks with linear polyester; 3. solidify with the solidifying agent that contains " soft segment ", in cross-linked network, introduce soft segment, improve the kindliness of network, reach toughness reinforcing purpose.Commercial multiple high-strength high-toughness epoxy resin tackiness agent has at present, liquid rubber toughening modifying epoxy glue, polyurethane toughened epoxy glue, the toughness reinforcing epoxy glue of elastic microsphere, thermotropic liquid crystal polymer toughening modified epoxy and polymer blending toughening modifying epoxy glue etc.
Through the development of over half a century, the high-strength high-toughness epoxy resin tackiness agent is widely used, and in the behind of its excellent viscosifying power, also has a very challenging problem.That is exactly in a lot of fields, not only needs high cohesive strength, also to be convenient to when needed remove, and be to be difficult to remove and present epoxy resin binder exists with one of ging wrong.In the middle of the practical application of a lot of Industrial products, need selectivity to remove, reclaim or repair some parts, so preparation reversible adhesive type high-strength high-toughness epoxy resin tackiness agent meets great demand.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, carry arch a kind of novel reversible adhesive-debinding epoxy resin binder and preparation method thereof.This tackiness agent has high strength and reversible adhesive-debinding ability, can be used for the bonding of functional materials and device, be particularly useful for needing high bond strength and can the high-tech product of easy dismounting in.As being used for callable high-performance radio-frequency label, electronic chip and detachable electronic circuit board etc.
Particularly, reversible adhesive of the present invention-debinding epoxy resin binder is characterized in that, this tackiness agent can solidify under room temperature or heating condition, has reversible adhesive-debinding ability, and this tackiness agent is made by the following weight parts feed composition:
(a) 5～70 weight part Resins, epoxy, epoxy equivalent (weight) is less than 550g/mol;
(b) 3～50 weight part organic amine curing agent, molecular weight is less than 900g/mol;
(c) 0～50 weight part thermoplastic resin, molecular weight is between 1000-100000g/mol;
(d) 0～70 parts by weight solvent.
Wherein, (a) and (b), (c) and (d) be independent component or mix with other components in the described component, and described weight part is to be as the criterion with 100 parts of tackiness agents.
Among the present invention, Resins, epoxy is selected from following group: one or more in bisphenol A diglycidyl ether, Bisphenol F diglycidylether, epoxidization phenolic resin or the cycloaliphatic epoxy resin;
Contain plural epoxide group in each molecule of described Resins, epoxy.
Among the present invention, organic amine is selected from following group: one or more in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, diaminobenzene sulfone, benzidine, aminoethyl piperazine, polytrimethylene ether diamines or the polytrimethylene ether triamine.
Among the present invention, thermoplastic resin is selected from following group: one or more in thermoplastic acrylic resin, thermoplastic polyester or the polyvinyl alcohol;
Wherein, described thermoplastic acrylic resin mainly comprises polymethylmethacrylate, Jia Jibingxisuanyizhi, poly-n-butyl methacrylate or their multipolymer;
Wherein, described thermoplastic polyester mainly comprises polylactide, polycaprolactone, polybutyl terapthalate, and their mixture.
Thermoplastic resin of the present invention has linearity or branched structure.
Among the present invention, solvent is selected from following group: toluene, dimethylbenzene, vinyl acetic monomer, N-BUTYL ACETATE, acetone, butanone, pimelinketone, chloroform, chlorobenzene, methylene dichloride, ethylene dichloride and their mixture.
Tackiness agent of the present invention is through experimental verification, and the result shows, prepared adhesive has well can hot unsticking performance, and heating can easily be peeled off, and can recover high bond strength again after compound, realized reversible adhesive-unsticking ability.Its tool of this tackiness agent is good thermoset, and the characteristic of solid form that can intact its glued membrane of maintenance under the situation of being heated.Can be used for needing high bond strength and can all kinds of high-tech products of easy dismounting in, as being used for callable high-performance radio-frequency label, electronic chip and detachable electronic circuit board etc.
The invention provides the preparation method of reversible adhesive-debinding epoxy resin binder, it comprises step:
At first get an amount of Resins, epoxy (a component) and an amount of thermoplastic resin (c component), as mass ratio W
a/ W
c=1.5: 1, it is blended in the there-necked flask, at N
2Protection is heated and stirred down; Mixture adds an amount of organic amine curing agent (b component) after becoming clarification, compares W as amount of substance
a/ W
b==2: 1, stir 30min; Add an amount of solvent (d component), tackiness agent is transferred to suitable viscosity; Sizing agent liquid is spread upon on the aluminium sheet of preheating, after suitably sudden strain of a muscle is done, the aluminium sheet adhesive surface is compressed, be placed in the baking oven and solidify, make reversible adhesive-debinding epoxy resin binder; The gained batten is at room temperature placed the tensile test when carrying out normal temperature and 80 ℃ behind the 24h respectively.
Among the described preparation method, Resins, epoxy is selected from following group: one or more of the diglycidylether of dihydroxyphenyl propane, Bisphenol F diglycidylether, epoxidization phenolic resin, cycloaliphatic epoxy resin.
Among the described preparation method, organic amine is selected from following group: one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, diaminobenzene sulfone, benzidine, aminoethyl piperazine, polytrimethylene ether diamines, polytrimethylene ether triamine and their affixture.
Among the described preparation method, thermoplastic resin is selected from following group: one or more of thermoplastic acrylic resin, thermoplastic polyester, polyvinyl alcohol.
Description of drawings
Fig. 1: the pulling force under the room temperature and the relation curve of displacement (for the first time bonding).
Fig. 2: the pulling force under 80 ℃ and the relation curve of displacement.
Fig. 3: the pulling force under the room temperature and the relation curve of displacement (for the second time bonding).
Fig. 4: the pulling force under the room temperature and the relation curve of displacement (for the first time bonding).
Fig. 5: the pulling force under 80 ℃ and the relation curve of displacement.
Fig. 6: the pulling force under the room temperature and the relation curve of displacement (for the second time bonding).
Embodiment
Embodiment 1:
Get the poly-own lactones (Mn=40000g/mol) of 1.5g bisphenol A epoxide resin (epoxy equivalent (weight) 172-176) and 1.0g, it is blended in the there-necked flask, at N
2Protection is heated and stirred to 120 ℃ down.Mixture becomes clarification post-heating to 140 ℃, adds 0.53g diaminobenzene sulfone, stirs 30min and dissolves fully to the diaminobenzene sulfone.Temperature is down to 120 ℃, stirs 10min, sizing agent liquid is spread upon on the aluminium sheet of preheating, and the aluminium sheet adhesive surface is compressed, and is placed in 180 ℃ the baking oven to solidify 3h, and the gained batten is at room temperature placed the tensile test when carrying out normal temperature and 80 ℃ behind the 24h respectively.
Used aluminium sheet specification is 35mm*20mm*5mm, and bond area is 20mm*5mm.As can be seen, the maximum of tackiness agent is born pulling force and is respectively 1.27KN in the curve of pulling force and the displacement at room temperature of tackiness agent as shown in Figure 1; And when being heated to 80 ℃, the maximum of sample is born pulling force and sharply is reduced to 21.9N (as shown in Figure 2); With the sample that draws back bonding and cool to room temperature again under 150 ℃, carry out tensile test behind the 24h again, maximum is born pulling force and is respectively 1.18KN (as shown in Figure 3).Above-mentioned experimental result shows, prepared adhesive has well can hot unsticking performance, i.e. heating can easily be peeled off, and can recover high bond strength again after compound, realized reversible adhesive-unsticking ability.
Embodiment 2:
Experimental technique is close with embodiment 1, and different is that bisphenol A epoxide resin (epoxy equivalent (weight) 172-176) is different with the proportioning of poly-own lactones (Mn=45000g/mol), mass ratio W
a/ W
c=1.8: 1.Behind the gluing, the aluminium sheet adhesive surface is compressed, be placed in 180 ℃ the baking oven and solidify 3h, the gained batten is at room temperature placed the tensile test when carrying out normal temperature and 80 ℃ behind the 24h respectively.The curve of pulling force and the displacement at room temperature of tackiness agent as shown in Figure 4 as can be seen, it is 1.47KN that the maximum of tackiness agent is born pulling force; And when being heated to 80 ℃, it is 41.4N (as shown in Figure 5) that the maximum of sample is born pulling force; The sample that draws back is being carried out tensile test behind the bonding and cool to room temperature 24h under 150 ℃ again again, and maximum is born pulling force and is respectively 1.45KN (as shown in Figure 6).
Embodiment 3:
Resins, epoxy 619 is mixed by the mass ratio in the table 1 with poly-own lactones, add a certain amount of chlorobenzene and make system become the solution of 65% solid content, stirring and evenly mixing.Then, be that 4: 1 ratio adds solidifying agent in above-mentioned mixture in Resins, epoxy 619 and solidifying agent 593 mass ratioes, be made into three groups of tackiness agents, be numbered 1,2,3.Be applied on request on the aluminium flake, two aluminium flakes are bonding, ambient cure 24h, and characterize adhesion characteristic (as shown in table 1).Experimental result shows that prepared adhesive has well can hot unsticking performance.
Table 1 different rings epoxy resins/poly-own lactones quality specific adhesion agent performance relatively
Claims (10)
1. reversible adhesive-debinding epoxy resin binder is characterized in that this tackiness agent is made by the following weight parts feed composition:
(a) 5～70 weight part Resins, epoxy, epoxy equivalent (weight) is less than 550g/mol;
(b) 3～50 weight part organic amine curing agent, molecular weight is less than 900g/mol;
(c) 0～50 weight part thermoplastic resin, molecular weight is between 1000-100000g/mol;
(d) 0～70 parts by weight solvent;
Wherein, (a) and (b), (c) and (d) be independent component or mix with other components in the described component that described weight part is to be as the criterion with 100 parts of tackiness agents.
2. by the described reversible adhesive of claim 1-debinding epoxy resin binder, it is characterized in that described Resins, epoxy is selected from: one or more in bisphenol A diglycidyl ether, Bisphenol F diglycidylether, epoxidization phenolic resin or the cycloaliphatic epoxy resin.
3. by claim 1 or 2 described reversible adhesive-debinding epoxy resin binders, it is characterized in that, contain plural epoxide group in each molecule of described Resins, epoxy.
4. by the described reversible adhesive of claim 1-debinding epoxy resin binder, it is characterized in that described organic amine is selected from: one or more in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, diaminobenzene sulfone, benzidine, aminoethyl piperazine, polytrimethylene ether diamines or the polytrimethylene ether triamine.
5. by the described reversible adhesive of claim 1-debinding epoxy resin binder, it is characterized in that described thermoplastic resin is selected from: one or more in thermoplastic acrylic resin, thermoplastic polyester or the polyvinyl alcohol.
6. by the described reversible adhesive of claim 5-debinding epoxy resin binder, it is characterized in that described thermoplastic acrylic resin is selected from polymethylmethacrylate, Jia Jibingxisuanyizhi, poly-n-butyl methacrylate or their multipolymer.
7. by the described reversible adhesive of claim 5-debinding epoxy resin binder, it is characterized in that described thermoplastic polyester mainly comprises polylactide, polycaprolactone, polybutyl terapthalate or their mixture.
8. by claim 1 or 5 described reversible adhesive-debinding epoxy resin binders, it is characterized in that described thermoplastic resin has linearity or branched structure.
9. by the described reversible adhesive of claim 1-debinding epoxy resin binder, it is characterized in that described solvent choosing: toluene, dimethylbenzene, vinyl acetic monomer, N-BUTYL ACETATE, acetone, butanone, pimelinketone, chloroform, chlorobenzene, methylene dichloride, ethylene dichloride or their mixture.
10. by the described reversible adhesive of claim 1-debinding epoxy resin binder, it is characterized in that described tackiness agent has thermoset, under the situation of being heated, keep the solid form of its glued membrane.
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Cited By (10)
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| CN104277419A (en) * | 2013-07-09 | 2015-01-14 | 上海杰事杰新材料(集团)股份有限公司 | Tough epoxy resin curing system and preparation method thereof |
| CN104371602A (en) * | 2014-10-31 | 2015-02-25 | 青岛昌安达药业有限公司 | High-temperature-resistant adhesive |
| CN104817991A (en) * | 2015-04-30 | 2015-08-05 | 黄琳 | Preparation method of high-temperature-resistant epoxy resin adhesive |
| CN105694790A (en) * | 2016-02-29 | 2016-06-22 | 中国工程物理研究院材料研究所 | Epoxy adhesive capable of being removed quickly and preparing and removing methods thereof |
| CN107177317A (en) * | 2017-07-10 | 2017-09-19 | 苏州润德新材料有限公司 | A kind of water boils sections glass sheet synthetic resin adhesive |
| WO2018068268A1 (en) * | 2016-10-13 | 2018-04-19 | 宁德新能源科技有限公司 | Binder and electrochemical energy storage device thereof |
| CN111154438A (en) * | 2020-01-14 | 2020-05-15 | 深圳市华天河科技有限公司 | Thermoplastic conductive silver adhesive containing high polymer resin |
| CN112592689A (en) * | 2021-02-26 | 2021-04-02 | 山东万圣博化工有限公司 | Electronic adhesive and preparation method thereof |
| ES2852674A1 (en) * | 2020-03-10 | 2021-09-14 | Fresmak Sa | Thermally reversible adhesive composition (Machine-translation by Google Translate, not legally binding) |
| CN115895214A (en) * | 2022-11-21 | 2023-04-04 | 北京航空航天大学 | Variable-rigidity high polymer material and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277419A (en) * | 2013-07-09 | 2015-01-14 | 上海杰事杰新材料(集团)股份有限公司 | Tough epoxy resin curing system and preparation method thereof |
| CN104371602A (en) * | 2014-10-31 | 2015-02-25 | 青岛昌安达药业有限公司 | High-temperature-resistant adhesive |
| CN104817991A (en) * | 2015-04-30 | 2015-08-05 | 黄琳 | Preparation method of high-temperature-resistant epoxy resin adhesive |
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| CN105694790B (en) * | 2016-02-29 | 2018-06-29 | 中国工程物理研究院材料研究所 | It is a kind of can the epoxy adhesive of rapid disassembling and its preparation and disassembling method |
| WO2018068268A1 (en) * | 2016-10-13 | 2018-04-19 | 宁德新能源科技有限公司 | Binder and electrochemical energy storage device thereof |
| CN107177317A (en) * | 2017-07-10 | 2017-09-19 | 苏州润德新材料有限公司 | A kind of water boils sections glass sheet synthetic resin adhesive |
| CN111154438A (en) * | 2020-01-14 | 2020-05-15 | 深圳市华天河科技有限公司 | Thermoplastic conductive silver adhesive containing high polymer resin |
| ES2852674A1 (en) * | 2020-03-10 | 2021-09-14 | Fresmak Sa | Thermally reversible adhesive composition (Machine-translation by Google Translate, not legally binding) |
| CN112592689A (en) * | 2021-02-26 | 2021-04-02 | 山东万圣博化工有限公司 | Electronic adhesive and preparation method thereof |
| CN115895214A (en) * | 2022-11-21 | 2023-04-04 | 北京航空航天大学 | Variable-rigidity high polymer material and preparation method and application thereof |
| CN115895214B (en) * | 2022-11-21 | 2024-06-07 | 北京航空航天大学 | Variable-rigidity polymer material and preparation method and application thereof |
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Application publication date: 20130703 |