CN103254573A - High-temperature-resistant mica plate matrix resin and preparation method thereof - Google Patents
High-temperature-resistant mica plate matrix resin and preparation method thereof Download PDFInfo
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- CN103254573A CN103254573A CN2013102078256A CN201310207825A CN103254573A CN 103254573 A CN103254573 A CN 103254573A CN 2013102078256 A CN2013102078256 A CN 2013102078256A CN 201310207825 A CN201310207825 A CN 201310207825A CN 103254573 A CN103254573 A CN 103254573A
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Abstract
The invention relates to a high-temperature-resistant mica plate matrix resin and preparation method thereof. The matrix resin comprises TGBAPOPP epoxy resin, a curing agent, 2-sulfhydryl benzimidazole, N-(toluenesulfonyl)-N'-phenyl para-phenylene diamine, 2-sulfhydryl benzimidazole zinc salt and an organic solvent. The preparation method comprises the following steps: putting the TGBAPOPP epoxy resin, the 2-sulfhydryl benzimidazole zinc salt and the organic solvent into a reaction kettle for mixing and evenly stirring at the temperature of 50 to 70 DEG C, thereby obtaining a component A; mixing the curing agent, the 2-sulfhydryl benzimidazole, the N-(toluenesulfonyl)-N'-phenyl para-phenylene diamine and the organic solvent and evenly stirring at the temperature of 50 to 70 DEG C, thereby obtaining a component B; and during the application, evenly mixing the component A with the component B at the temperature of 50 to 70 DEG C, thereby obtaining the matrix resin. The matrix resin provided by the invention is convenient in raw material obtainment, simple in preparation process, low in cost and excellent in comprehensive performance.
Description
Technical field
The invention belongs to composite matrix resin and preparation field thereof, particularly a kind of high temperature resistant plate mica matrix resin and preparation method thereof.
Background technology
High temperature resistant plate mica material is mainly used in the insulating material of high temperature appliance equipments such as electric arc furnace, steel-smelting electric furnace, furnace of calcium carbide, this just needs the plate mica material to have excellent heat resisting, can be under the condition of high temperature long-term works better, therefore, must have high thermal resistance to the plate mica matrix resin, but also should have good electrical insulation properties, mechanical property, the every property retention rate under particularly hot all can reach more than 80%.
China has developed epoxy mica tape the sixties in 20th century, first Resins, epoxy is applied to the high-voltage motor major insulation of China.This mica tape adopts epoxy-bismaleimides-TOA system as tackiness agent, and with original asphalt cloud parent phase ratio, performance is greatly improved, but still has some defectives, and is relatively poor as hot mechanical property, and mica tape storage period is short etc.Therefore, be to improve the performance of tackiness agent, researcher has been through after the experiment of system, having selected suitable properties-correcting agent, and its performance is studied, and disclosed bibliographical information is arranged:
Yu Xinhai, Meng Huijuan [research of Epoxy Bismaleimide TOA Cured System Properties [J]. Hebei College of Light Chemical Industry's journal, 1997,18(1): 39-42] a kind of mica tape tackiness agent is disclosed, be primarily characterized in that: under the condition of lead benzoate as catalyzer, introduce certain properties-correcting agent, mechanical property, dielectric properties, resistance toheat to epoxy-bismaleimides-TOA system cured article are studied, and have also studied the room temperature storage performance of epoxy-bismaleimides-T OA-lead benzoate-modifier system simultaneously.The result shows: introduces after the properties-correcting agent, and the dielectric spectrogram of this cured article, 161 ℃ of its peak Wen Gaoda, and the peak value of dielectric loss only is 2.21%; Hot bending strength in the time of 155 ℃ reaches 13MPa; 25 ℃ shock strength is 13.6kJ/m
2The heatproof index is greater than 155 ℃; And the room temperature storage phase of its corresponding tackiness agent can reach more than 4 months.Therefore, be very favourable for the tackiness agent of making F level mica paper tape.
Relevant high-temperature resistant epoxy oxygen system is reported to some extent: Chinese patent CN101148656A discloses a kind of preparation method of heat-resistant solvent-free epoxy adhesive, be primarily characterized in that: TGDDM Resins, epoxy, toughner, Hydrogenated Bisphenol A, solidifying agent, promotor mix, and have made the heat-resistant solvent-free epoxy adhesive.But its resistance to elevated temperatures still has bigger limitation, fails to satisfy the practical application under many hot environments.
Chinese patent CN101397486A discloses a kind of preparation method of two-pack solvent-free epoxy resin tackiness agent, be primarily characterized in that: it comprises A component and B component, and wherein the A component contains novolac epoxy, alicyclic type epoxy resin and nbr carboxyl terminal; The B component is two (2,4-diamino phenoxy) the benzene aromatic polyamine solidifying agent of 1,4-.The addition of alicyclic type epoxy resin and nbr carboxyl terminal is respectively 20-35% and the 12%(mass percent of novolac epoxy).The addition of two (2,4-diamino phenoxy) the benzene aromatic polyamine solidifying agent of 1,4-is the 15-20%(mass percent of novolac epoxy), gained adhesive system good manufacturability.But its resistance toheat is desirable not enough.
Chinese invention patent CN101962436A discloses a kind of used for advanced composite material heat resist modification multi-functional epoxy matrix resin and preparation method thereof, be primarily characterized in that: adopt 1,4-two (2,4-dimaleimide phenoxyl) four maleimide resins of benzene and polyfunctional epoxy resin, nbr carboxyl terminal CTBN reaction obtain the novel fire resistant resin of high tenacity, add organic solvent, stirring and dissolving is even, obtains the viscous liquid of homogeneous phase transparent, i.e. the A component; Solidifying agent mixes with organic solvent, and stirring and dissolving is even, namely gets the B component; A, B component are mixed, stir, namely get used for advanced composite material heat resist modification multi-functional epoxy substrate resin solution.
People such as Yu Xinhai [development of high-temperature resistant single-component epoxy tackiness agent [J]. bonding, 2008,29 (12): 16-19] a kind of preparation method of high-temperature resistant single-component epoxy tackiness agent is disclosed, be primarily characterized in that: be end-capping reagent with maleic anhydride (MA), with 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa (BAHPFP) of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPOPP) of 2-, 2,2-two [4-(3,4-di carboxyl phenyloxy) phenyl] propane dianhydride (BPADA) has obtained phenolic hydroxy group polyetherimide resin (HPEI) for main raw material synthesizes; The HPEI that obtains is resistant, toughened dose with synthesized, with N, and N, N', N'-four glycidyl group-4,4'-diaminodiphenylmethane (TGDDM), hydrogenated bisphenol A epoxy resin (HBPAE), latent curing agent etc., preparation has obtained the high-temperature resistant single-component epoxy tackiness agent of excellent combination property.
Present method is though by the synthetic polyetherimide resin (HPEI) that contains active reactive group (hydroxyl, unsaturated double-bond), carried out toughening modifying to Resins, epoxy, and obtained better technical effect.But, also there are some shortcomings:
(1) the reactable group is limited, and particularly the content of unsaturated double-bond is on the low side.Because maleic anhydride uses as end-capping reagent, the consumption of maleic anhydride seldom.
Two (3-amino-4-hydroxy phenyl) the HFC-236fa monomers such as (BAHPFP) of (2) 2,2-are expensive, cause the cost of polyetherimide resin (HPEI) and tackiness agent very high, are unfavorable for large-scale promotion application, can only be confined to some special dimension.
Summary of the invention
Technical problem to be solved by this invention provides a kind of high temperature resistant plate mica matrix resin and preparation method thereof, and this matrix resin has good hot mechanical property and electrical insulation properties, and excellent combination property; Preparation technology is simple, cost is low, easy to operate, the reaction raw materials convenient sources can be finished preparation process in general-purpose equipment, be conducive to realize suitability for industrialized production.
A kind of high temperature resistant plate mica matrix resin of the present invention; its composition: mass ratio is the N of 100:10-80:1-5:1-5:1-5:100-300; N; N'; N'-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane Resins, epoxy, solidifying agent, 2 mercapto benzimidazole, N-(p-toluenesulfonyl)-N '-diphenyl-para-phenylene diamine, 2 mercapto benzimidazole zinc salt and organic solvent.
The structural formula of described 2 mercapto benzimidazole zinc salt is:
Described solidifying agent is selected from 1,4-two (2, the 4-diamino phenoxy) benzene, 1,3-two (2, the 4-diamino phenoxy) benzene, 2,2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] propane, 2,2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa, 4,4'-two (2, the 4-diamino phenoxy) diphenyl sulfide, 4,4'-two (2, the 4-diamino phenoxy)-3,3', 5, the 5'-tetramethyl biphenyl, 4,4'-two (2, the 4-diamino phenoxy) biphenyl, 4,4'-two (2, the 4-diamino phenoxy) phenyl ether, 4,4'-two (2, the 4-diamino phenoxy) ditane, 4,4'-two (2, the 4-diamino phenoxy) sulfobenzide, 4,4'-two (2, the 4-diamino phenoxy) benzophenone, 4,4'-two (2, the 4-diamino phenoxy)-3,3', 5, the 5'-tetramethyl diphenyl sulfone, 2,6-two (2, the 4-diamino phenoxy) toluene, 4,4 '-diamino-dicyclohexyl methane, 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane, 1, the 2-diamino-cyclohexane, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] propane of 2,2-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two [4-(2, the 4-diamino phenoxy) phenyl] propane of 2-, 2,2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa, 1, two (2, the 4-diamino phenoxy) benzene of 4-, 1,3-two (2, the 4-diamino phenoxy) benzene, 2, two [4-(2, the 4-diamino phenoxy) phenyl] propane of 2-, 2,2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa, 4, two (2, the 4-diamino phenoxy) diphenyl sulfides of 4'-, 4,4'-two (2, the 4-diamino phenoxy)-3,3', 5,5'-tetramethyl biphenyl, 4,4'-two (2, the 4-diamino phenoxy) biphenyl, two (2, the 4-diamino phenoxy) phenyl ether of 4,4'-, 4,4'-two (2, the 4-diamino phenoxy) ditane, two (2, the 4-diamino phenoxy) sulfobenzides of 4,4'-, 4,4'-two (2, the 4-diamino phenoxy) benzophenone, two (2, the 4-diamino phenoxies)-3 of 4,4'-, 3', 5,5'-tetramethyl diphenyl sulfone, 2,6-two (2, the 4-diamino phenoxy) toluene, 2-ethyl-4-methylimidazole, 2,4,6-three (dimethylamino methyl) phenol, benzyldimethylamine, trolamine, in 1,8-diaza-dicyclo [5.4.0] hendecene-7 one or more.
Described organic solvent is selected from one or more in ethanol, acetone, methylethylketone, methyl alcohol, ethylene glycol, butyleneglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, the ethyl acetate.
The preparation method of a kind of high temperature resistant plate mica matrix resin of the present invention comprises the steps:
(1) in 50 ℃-70 ℃, with N, N, N', N'-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane Resins, epoxy, 2 mercapto benzimidazole zinc salt and organic solvent are put into reactor and are mixed, and stir, and obtain the A component;
(2) in 50 ℃-70 ℃, solidifying agent, 2 mercapto benzimidazole, N-(p-toluenesulfonyl)-N '-diphenyl-para-phenylene diamine and organic solvent are mixed, stir, obtain the B component;
When (3) using, in 50 ℃-70 ℃, A, B component are mixed, namely get high temperature resistant plate mica matrix resin.
The curing process of the described high temperature resistant plate mica matrix resin that obtains is: begin heating from room temperature, be warming up to 60 ℃, keep continuing to be warming up to 100 ℃ after 1 hour, kept 1 hour, continue to be warming up to 130 ℃, kept 1 hour, and continued to be warming up to 170 ℃, kept 1 hour, close heating system, naturally cool to room temperature.
Beneficial effect
(1) preparation technology of the present invention is simple, cost is low, easy to operate, the reaction raw materials convenient sources can be finished preparation process in general-purpose equipment, be conducive to realize suitability for industrialized production;
(2) high temperature resistant plate mica matrix resin of the present invention has good hot mechanical property and electrical insulation properties, and excellent combination property, has broad application prospects.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
In 70 ℃, with 100 gram N, N, N', N'-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane (TGBAPOPP) Resins, epoxy, 1 gram 2 mercapto benzimidazole zinc salt and 50 gram ethanol are put into reactor and are mixed, stir, obtain 151 gram A components, note is made A1.
In 50 ℃, with 100 gram N, N, N', N'-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane (TGBAPOPP) Resins, epoxy, 3 gram 2 mercapto benzimidazole zinc salts, 50 gram acetone and 50 gram ethanol are put into reactor and are mixed, and stir, obtain 203 gram A components, note is made A2.
In 60 ℃, with 100 gram N, N, N', N'-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane (TGBAPOPP) Resins, epoxy, 5 gram 2 mercapto benzimidazole zinc salts and 150 gram ethanol are put into reactor and are mixed, stir, obtain 255 gram A components, note is made A3.
Embodiment 2
In 60 ℃; with 5 grams 1; 4-two (2; the 4-diamino phenoxy) benzene and 5 grams 1; 8-diaza-dicyclo [5.4.0] hendecene-7,1 gram 2 mercapto benzimidazole, 3 gram N-(p-toluenesulfonyl)-N '-diphenyl-para-phenylene diamines, 80 gram ethanol and 100 gram acetone mix; stir, obtain 194 gram B components, note is made B1.
In 70 ℃; two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 80 grams, 2,2-, 5 gram 2 mercapto benzimidazoles, 1 gram N-(p-toluenesulfonyl)-N '-diphenyl-para-phenylene diamine, 200 gram acetone are mixed, stir; obtain 286 gram B components, note is made B2.
In 50 ℃, two [4-(4-amino-benzene oxygen) phenyl] propane of 30 grams, 2,2-, 4 gram 2 mercapto benzimidazoles, 5 gram N-(p-toluenesulfonyl)-N '-diphenyl-para-phenylene diamines, 150 gram acetone are mixed, stir, obtain 189 gram B components, note is made B3.
Embodiment 3
In 50 ℃, the A component of above-described embodiment 1 and the B component of embodiment 2 are mixed, namely get a kind of high temperature resistant plate mica matrix resin.Concrete performance is as follows:
151 gram A1 and 194 gram B1 mix, and obtain the high temperature resistant plate mica matrix resin of 345 grams, and note is made A1B1.
203 gram A2 and 194 gram B1 mix, and obtain the high temperature resistant plate mica matrix resin of 397 grams, and note is made A2B1.
255 gram A3 and 286 gram B2 mix, and obtain the high temperature resistant plate mica matrix resin of 541 grams, and note is made A3B2.
151 gram A1 and 189 gram B3 mix, and obtain the high temperature resistant plate mica matrix resin of 340 grams, and note is made A1B3.
Embodiment 4
Get the high temperature resistant plate mica matrix resin of an amount of embodiment 3, i.e. A1B1, A2B1, A3B2, A1B3, and evenly be coated on respectively in the test piece of standard stainless steel, hang after 0.5 hour superimposedly under the room temperature, clamp, put into convection oven and be cured: be heated to 80 ℃ from room temperature, be incubated 1 hour, continue to be warming up to 100 ℃, be incubated 1 hour, continue to be warming up to 160 ℃, be incubated 2 hours, continue to be warming up to 180 ℃, be incubated 2 hours, naturally cool to room temperature.It is as shown in table 1 to record tensile shear strength.
Get the high temperature resistant plate mica matrix resin of an amount of embodiment 3, be A1B1, A2B1, A3B2, A1B3, pour diameter into and be in the stainless steel disk of 10cm (disk applies releasing agent in advance), thermofixation: be heated to 80 ℃ from room temperature, be incubated 1 hour, continue to be warming up to 100 ℃, be incubated 1 hour, continue to be warming up to 160 ℃, be incubated 2 hours, continue to be warming up to 180 ℃, be incubated 2 hours, naturally cool to room temperature.Obtain the circular specimen of the about 1mm of thickness, diameter 10cm, after 72 hours, survey its water-intake rate with distilled water immersion, the result is as shown in table 1.
Get the high temperature resistant plate mica matrix resin of an amount of embodiment 3, be A1B1, A2B1, A3B2, A1B3, flood mica paper, alkali-free glass fiber cloth strongthener respectively, carry out preliminary drying to remove organic solvent in 50 ℃-70 ℃, get prepreg, stacked (mica paper and alkali-free glass cloth are stacked alternately, and skin is alkali-free glass cloth) pressing, thermofixation, its pressure range is: 0.2MPa-2.5MPa; Its solidification value timing relationship is: be heated to 80 ℃ from room temperature, be incubated 1 hour, continue to be warming up to 100 ℃, be incubated 1 hour, continue to be warming up to 160 ℃, be incubated 2 hours, continue to be warming up to 180 ℃, be incubated 2 hours, naturally cool to room temperature, the release demoulding obtains high performance plate mica matrix material, and its salient features is as shown in table 2.
Tensile shear strength and the water-intake rate of table 1 is high temperature resistant mica tape tackiness agent
Table 2 plate mica performance of composites
Claims (6)
1. high temperature resistant plate mica matrix resin; its composition: mass ratio is the N of 100:10-80:1-5:1-5:1-5:100-300; N; N'; N'-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane Resins, epoxy, solidifying agent, 2 mercapto benzimidazole, N-(p-toluenesulfonyl)-N '-diphenyl-para-phenylene diamine, 2 mercapto benzimidazole zinc salt and organic solvent.
2. a kind of high temperature resistant plate mica matrix resin according to claim 1, it is characterized in that: the structural formula of described 2 mercapto benzimidazole zinc salt is:
3. a kind of high temperature resistant plate mica matrix resin according to claim 1, it is characterized in that: described solidifying agent is selected from 1,4-two (2, the 4-diamino phenoxy) benzene, 1,3-two (2, the 4-diamino phenoxy) benzene, 2,2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] propane, 2,2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa, 4,4'-two (2, the 4-diamino phenoxy) diphenyl sulfide, 4,4'-two (2, the 4-diamino phenoxy)-3,3', 5, the 5'-tetramethyl biphenyl, 4,4'-two (2, the 4-diamino phenoxy) biphenyl, 4,4'-two (2, the 4-diamino phenoxy) phenyl ether, 4,4'-two (2, the 4-diamino phenoxy) ditane, 4,4'-two (2, the 4-diamino phenoxy) sulfobenzide, 4,4'-two (2, the 4-diamino phenoxy) benzophenone, 4,4'-two (2, the 4-diamino phenoxy)-3,3', 5, the 5'-tetramethyl diphenyl sulfone, 2,6-two (2, the 4-diamino phenoxy) toluene, 4,4 '-diamino-dicyclohexyl methane, 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane, 1, the 2-diamino-cyclohexane, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] propane of 2,2-, 2, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] propane of 2-, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, 2,2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] propane, 2, two [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa of 2-, 1,4-two (2, the 4-diamino phenoxy) benzene, 1, two (2, the 4-diamino phenoxy) benzene of 3-, 2,2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] propane, 2, two [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa of 2-, 4,4'-two (2, the 4-diamino phenoxy) diphenyl sulfide, 4, two (2, the 4-diamino phenoxies)-3 of 4'-, 3', 5, the 5'-tetramethyl biphenyl, two (2, the 4-diamino phenoxy) biphenyl of 4,4'-, 4,4'-two (2, the 4-diamino phenoxy) phenyl ether, two (2, the 4-diamino phenoxy) ditanes of 4,4'-, 4,4'-two (2, the 4-diamino phenoxy) sulfobenzide, two (2, the 4-diamino phenoxy) benzophenone of 4,4'-, 4,4'-two (2, the 4-diamino phenoxy)-3,3', 5, the 5'-tetramethyl diphenyl sulfone, 2, two (2, the 4-diamino phenoxy) toluene of 6-, 2-ethyl-4-methylimidazole, 2,4,6-three (dimethylamino methyl) phenol, benzyldimethylamine, trolamine, in 1,8-diaza-dicyclo [5.4.0] hendecene-7 one or more.
4. a kind of high temperature resistant plate mica matrix resin according to claim 1, it is characterized in that: described organic solvent is selected from one or more in ethanol, acetone, methylethylketone, methyl alcohol, ethylene glycol, butyleneglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, the ethyl acetate.
5. the preparation method of a high temperature resistant plate mica matrix resin as claimed in claim 1 comprises the steps:
(1) in 50 ℃-70 ℃, with N, N, N', N'-four glycidyl group-2,2-two [4-(4-amino-benzene oxygen) phenyl] propane Resins, epoxy, 2 mercapto benzimidazole zinc salt and organic solvent are put into reactor and are mixed, and stir, and obtain the A component;
(2) in 50 ℃-70 ℃, solidifying agent, 2 mercapto benzimidazole, N-(p-toluenesulfonyl)-N '-diphenyl-para-phenylene diamine and organic solvent are mixed, stir, obtain the B component;
When (3) using, in 50 ℃-70 ℃, A, B component are mixed, namely get high temperature resistant plate mica matrix resin.
6. the preparation method of a kind of high temperature resistant plate mica matrix resin according to claim 5, it is characterized in that: the curing process of the described high temperature resistant plate mica matrix resin that obtains is: begin heating from room temperature, be warming up to 60 ℃, keep after 1 hour, continue to be warming up to 100 ℃, kept 1 hour, and continued to be warming up to 130 ℃, kept 1 hour, continue to be warming up to 170 ℃, kept 1 hour, and closed heating system, naturally cool to room temperature.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111477379A (en) * | 2020-04-10 | 2020-07-31 | 北京倚天凌云科技股份有限公司 | Mica tape with less glue and preparation method thereof |
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| KR100201708B1 (en) * | 1997-06-16 | 1999-06-15 | 유현식 | Epoxy resin composition for encapsulation of semiconductor |
| CN101265402A (en) * | 2008-05-04 | 2008-09-17 | 深圳市长园新材料股份有限公司 | Water-proof sealing adhesive tape and its preparation method |
| CN102031082A (en) * | 2010-12-10 | 2011-04-27 | 东华大学 | Benzimidazole diamine curing type epoxy adhesive and preparation method thereof |
| CN103030787A (en) * | 2012-12-28 | 2013-04-10 | 东华大学 | Benzimidazole-epoxy matrix resin and preparation method thereof |
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2013
- 2013-05-30 CN CN201310207825.6A patent/CN103254573B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100201708B1 (en) * | 1997-06-16 | 1999-06-15 | 유현식 | Epoxy resin composition for encapsulation of semiconductor |
| CN101265402A (en) * | 2008-05-04 | 2008-09-17 | 深圳市长园新材料股份有限公司 | Water-proof sealing adhesive tape and its preparation method |
| CN102031082A (en) * | 2010-12-10 | 2011-04-27 | 东华大学 | Benzimidazole diamine curing type epoxy adhesive and preparation method thereof |
| CN103030787A (en) * | 2012-12-28 | 2013-04-10 | 东华大学 | Benzimidazole-epoxy matrix resin and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111477379A (en) * | 2020-04-10 | 2020-07-31 | 北京倚天凌云科技股份有限公司 | Mica tape with less glue and preparation method thereof |
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