CN101717613B - High-temperature resistant copper foil glue and preparation and application thereof - Google Patents
High-temperature resistant copper foil glue and preparation and application thereof Download PDFInfo
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- CN101717613B CN101717613B CN200910200053.7A CN200910200053A CN101717613B CN 101717613 B CN101717613 B CN 101717613B CN 200910200053 A CN200910200053 A CN 200910200053A CN 101717613 B CN101717613 B CN 101717613B
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Abstract
The invention relates to high-temperature resistant copper foil glue containing the following components: 5-15wt percent of trifluoromethyl-contained maleimide resin, 10-30wt percent of polyfunctional ethoxyline resin, 10-40wt percent of bisphenol A epoxy resin, 5-15wt percent of ethylene-contained polyetherimide, 5-10wt percent of curing agent and 25-45wt percent of organic solvent; the preparation comprises the following steps of: adding the trifluoromethyl-contained maleimide resin and the ethylene-contained polyetherimide to the mixture of the polyfunctional ethoxyline resin and the bisphenol A epoxy resin, stirring while heating for reacting, and then cooling to 30-50 DEG C; adding the organic solvent and the curing agent; evenly stirring to obtain the high-temperature resistant copper foil glue the homogeneous phase of which is transparent and clear. The high-temperature resistant copper foil glue has Tonset temperature reaching up to 415 DEG C and excellent comprehensive performance, can be applied to the high-tech fields of electronics and microelectronics, automobiles, electrical machines, aerospace and the like; moreover, the invention has simple preparation process, low cost, convenient operation and available reaction raw materials, thereby being beneficial to realizing industrial production.
Description
Technical field
The invention belongs to organic polymer binder and preparation thereof and Application Areas, particularly relate to a kind of high-temperature resistant copper foil glue and preparation thereof and application.
Background technology
As everyone knows, epoxy resin has many good performances: the adhesiveproperties that (1) is good: bonding strength is high, bonding wide, the bonding strength of it and many metals (as iron, steel, copper, aluminium, metal alloy etc.) or non-metallic material (as glass, pottery, timber, plastics etc.) is very high, what have even surpasses by the intensity of sticky material itself, therefore can be used in many stress members, is one of main component of structure-type tackiness agent; (2) good processing characteristics: the diversity of the handiness of Formulaion of epoxy resin, complete processing and product properties is the most outstanding in macromolecular material; (3) satisfactory stability performance: solidifying of epoxy resin is mainly the ring opening polyaddition that relies on epoxy group(ing), therefore in solidification process, do not produce low-molecular material, its cure shrinkage is one of kind minimum in thermosetting resin, be generally 1%-2%, if select suitable filler can make shrinking percentage be down to 0.2% left and right; Epoxy resin main chain after solidifying is ehter bond, phenyl ring, three-dimensional crosslinking structure, therefore has excellent resistance to acids and bases.
Therefore, epoxy resin is widely used in the every field of national economy: no matter be high-technology field or current techique field, no matter be defence and military or civilian industry, and even all can see its trace in daily life.
At present, also there are some problems in epoxy resin binder system, as lower in thermotolerance, not as good as fragrant heterocyclic polymeric system (as polyimide, polybenzimidazole, polybenzoxazole, polyphenylene quinoxaline, polybenzothiozole etc.), can not meet the application under hot conditions far away.
Relevant fire resistant epoxy adhesive composition 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 epoxy resin, Hydrogenated Bisphenol A, solidifying agent, promotor mix, made heat-resistant solvent-free epoxy adhesive.But its resistance to elevated temperatures still has larger limitation, fail to meet 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 A component contains novolac epoxy, alicyclic type epoxy resin and nbr carboxyl terminal; B component is Isosorbide-5-Nitrae-bis-(2,4-diamino phenoxy) benzene aromatic polyamine solidifying agent.The addition of alicyclic type epoxy resin and nbr carboxyl terminal is respectively 20-35% and the 12%(mass percent of novolac epoxy).The 15-20%(mass percent that the addition of Isosorbide-5-Nitrae-bis-(2,4-diamino phenoxy) benzene aromatic polyamine solidifying agent is novolac epoxy), gained adhesive system good manufacturability, tensile shear strength is up to 25MPa.But its resistance toheat is desirable not enough.
Polyimide resin is to have an extremely family macromolecule material of excellent heat resistance.Conventional polyimide structures, its heat decomposition temperature is general all more than 500 ℃, also has obdurability simultaneously.Therefore, also usually for thermosetting resin, as the heat-resisting plasticized modifier of epoxy resin, bimaleimide resin etc.But the consistency of polyimide system and epoxy resin is poor, is difficult to make and has polyimide high temperature-resistant concurrently and have again cohesiveness and a technological adhesive composition of epoxy resin excellence.So, with conventional polyimide resin, carry out modified epoxy resin system, to obtain the tackiness agent of excellent combination property, be more difficult.
Therefore the consistency that, how to improve thermoplastic polyether imide resin and epoxy resin is a very significant problem.The scientific worker of this area has done a large amount of research work, and has obtained certain technique effect.
Chinese patent CN1927908A discloses a kind of preparation method of phenolic hydroxyl group containing polyimide powder, existence due to phenolic hydroxyl group, its polyimide powder can with epoxy reaction, form covalent linkage, thereby can improve the consistency of thermoplastic polyimide resin and epoxy resin, and can further make epoxy-resin systems reach good toughening effect.
The 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: the maleic anhydride (MA) of take is end-capping reagent, with 2, two (3-amino-4-hydroxylphenyl) HFC-236fa (BAHPFP) of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPOPP) of 2-, 2, two [the 4-(3 of 2-, 4-di carboxyl phenyloxy) phenyl] propane dianhydride (BPADA) obtained phenolic hydroxy group polyetherimide resin (HPEI) for main raw material is synthetic, the HPEI that the synthesized of take obtains is resistant, toughened dose, with N, 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.
Aforesaid method, although by the synthetic polyetherimide resin (HPEI) containing active reactive group (hydroxyl, unsaturated double-bond), carried out toughening modifying to epoxy resin, and obtained good technique effect.But, also there are some shortcomings: (1) reactable group is limited, and particularly the content of unsaturated double-bond is on the low side.Because maleic anhydride is used as end-capping reagent, the consumption of maleic anhydride seldom; (2) polyetherimide resin (HPEI) content in system (≤10%) on the low side, causes the improved heat resistance of adhesive composition limited.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of high-temperature resistant copper foil glue and preparation and application, this high-temperature resistant copper foil glue consistency is good, excellent combination property, in high-tech areas such as electronics microelectronics, automobile, motor, aerospace, has broad application prospects; And preparation technology is simple, cost is low, easy to operate, reaction raw materials is easy to get, and is conducive to realize suitability for industrialized production.
A kind of high-temperature resistant copper foil glue of the present invention, comprises that following component: 5wt%～15wt%'s contains active ethylene group polyetherimide, the solidifying agent of 5wt%～10wt% and the organic solvent of 25wt%～45wt% containing trifluoromethyl bimaleimide resin, the polyfunctional epoxy resin of 10wt%～30wt%, the bisphenol A type epoxy resin of 10wt%～40wt%, 5wt%～15wt%.
The thermolysis Tonset temperature of described high-temperature resistant copper foil glue is up to 415 ℃;
The tensile shear strength of described high-temperature resistant copper foil glue (base material: copper-copper) up to 35MPa, 90 degree stripping strength (base materials: copper-phenolic hydroxyl group Kapton) up to 2.2kg/cm;
Described is selected from Isosorbide-5-Nitrae-bis-(4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene containing trifluoromethyl bimaleimide resin, Isosorbide-5-Nitrae-bis-(4-dimaleoyl imino-3-4-trifluoromethylphenopendant) benzene, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 1,3-, two (4-dimaleoyl imino-3-4-trifluoromethylphenopendant) benzene of 1,3-, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 1,2-, two (4-dimaleoyl imino-3-4-trifluoromethylphenopendant) benzene of 1,2-, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) toluene of 2,5-, two (4-dimaleoyl imino-3-4-trifluoromethylphenopendant) toluene of 2,5-, Isosorbide-5-Nitrae-bis-(4-dimaleoyl imino-2-4-trifluoromethylphenopendant)-2-tert-butylbenzene, Isosorbide-5-Nitrae-bis-(4-dimaleoyl imino-3-4-trifluoromethylphenopendant)-2-tert-butylbenzene, Isosorbide-5-Nitrae-bis-(4-dimaleoyl imino-2-4-trifluoromethylphenopendant)-2,5-di-t-butylbenzene, Isosorbide-5-Nitrae-bis-(4-dimaleoyl imino-3-4-trifluoromethylphenopendant)-2,5-di-t-butylbenzene, 2,2-pair [4-(4-dimaleoyl imino-2-4-trifluoromethylphenopendant) phenyl] propane, 2,2-pair [4-(4-dimaleoyl imino-3-4-trifluoromethylphenopendant) phenyl] propane, 2,2-pair [4-(4-dimaleoyl imino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 2,2-pair [4-(4-dimaleoyl imino-3-4-trifluoromethylphenopendant) phenyl] HFC-236fa, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) biphenyl of 4,4'-, two (4-dimaleoyl imino-3-4-trifluoromethylphenopendant) biphenyl of 4,4'-, two (the 4-dimaleoyl imino-2-4-trifluoromethylphenopendants)-3 of 4,4'-, 3', 5,5'-tetramethyl biphenyl, two (the 4-dimaleoyl imino-3-4-trifluoromethylphenopendants)-3 of 4,4'-, 3', 5,5'-tetramethyl biphenyl, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) phenyl ether of 4,4'-, two (4-dimaleoyl imino-3-4-trifluoromethylphenopendant) phenyl ether of 4,4'-, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) diphenyl sulfides of 4,4'-, two (4-dimaleoyl imino-3-4-trifluoromethylphenopendant) diphenyl sulfides of 4,4'-, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) sulfobenzides of 4,4'-, two (4-dimaleoyl imino-3-4-trifluoromethylphenopendant) sulfobenzides of 4,4'-, two (the 4-dimaleoyl imino-2-4-trifluoromethylphenopendants)-3 of 4,4'-, 3', 5,5'-tetramethyl diphenyl sulfone, two (the 4-dimaleoyl imino-3-4-trifluoromethylphenopendants)-3 of 4,4'-, 3', the mixture of one or more in 5,5'-tetramethyl diphenyl sulfone,
Described polyfunctional epoxy resin is selected from N, N, N', N'-four glycidyl group-4,4'-diaminodiphenylmethane, N, N, N', N'-four glycidyl group-4,4'-diaminodiphenyl oxide, N, N, N', N'-four glycidyl group-4,4'-diaminodiphenylsulfone(DDS), N, N, N', N'-four glycidyl group-3,3'-dimethyl-4,4 '-diaminodiphenylmethane, N, N, N', N'-four glycidyl group-3,3'-bis-is chloro-4, the mixture of one or more in 4'-diaminodiphenylmethane;
The described molecular structural formula containing active ethylene group polyetherimide is:
N wherein
1: n
2=1:5;
Described solidifying agent is selected from 2-ethyl-4-methylimidazole, Dyhard RU 100, 4,4'-diaminodiphenylsulfone(DDS), Isosorbide-5-Nitrae-bis-(2,6-diamino-4-4-trifluoromethylphenopendant) benzene, two (2, the 6-diamino-4-4-trifluoromethylphenopendant) benzene of 1,3-, two [4-(2, the 6-diamino-4-4-trifluoromethylphenopendant) phenyl] propane of 2,2-, two [4-(2, the 6-diamino-4-4-trifluoromethylphenopendant) phenyl] HFC-236fa of 2,2-, two (2, the 6-diamino-4-4-trifluoromethylphenopendant) sulfobenzides of 4,4'-, two (2, the 6-diamino-4-4-trifluoromethylphenopendant) biphenyl of 4,4'-, two (2, the 6-diamino-4-4-trifluoromethylphenopendants)-3 of 4,4'-, 3'5,5'-tetramethyl diphenyl sulfone, two (2, the 6-diamino-4-4-trifluoromethylphenopendants)-3 of 4,4'-, 3'5,5'-tetramethyl biphenyl, pyromellitic acid anhydride, oxygen supports two phthalic anhydrides, 3,3', 4,4'-tetracarboxylic acid benzophenone dianhydride, biphenyl dianhydride, two [4-(3,4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2,2-, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydrides of 2,2-, phthalic anhydride, methyl tetrahydro phthalic anhydride, maleic anhydride, Nai Dike acid anhydrides, methyl Nai Dike acid anhydrides, 4,4'-diaminodiphenylmethane, 4,4'-benzidine, 3,3'-diaminodiphenylsulfone(DDS), 3,3'-dimethyl-4,4 '-diaminodiphenylmethane, two [4-(3-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, 4,4'-diaminodiphenyl oxide, 3,4'-diaminodiphenyl oxide, 3,3'-diaminodiphenyl oxide, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) cyanobenzenes of 2,6-, two (3-amino-benzene oxygen) cyanobenzenes of 2,6-, two (4-amino-benzene oxygen) toluene of 2,6-, two (4-amino-benzene oxygen) phenylfluoroforms of 2,6-, two (4-amino-benzene oxygen) toluene of 2,5-, two (4-amino-benzene oxygen) tert-butylbenzenes of 2,5-, 2,5-di-t-butyl-Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzophenone of 4,4'-, two (4-amino-benzene oxygen) sulfobenzides of 4,4'-, two (3-amino-benzene oxygen) benzophenone of 4,4'-, two (3-amino-benzene oxygen) sulfobenzides of 4,4'-, Isosorbide-5-Nitrae-bis-(2-trifluoromethyl-4-aminophenoxyl) benzene, two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] propane of 2,2-, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] HFC-236fa of 2,2-, two (2-trifluoromethyl-4-aminophenoxyl) toluene of 2,5-, two (2-trifluoromethyl-4-aminophenoxyl) tert.-butylbenzenes of 2,5-, 2,5-di-t-butyl-Isosorbide-5-Nitrae-bis-(2-trifluoromethyl-4-aminophenoxyl) benzene, two (2-trifluoromethyl-4-aminophenoxyl) sulfobenzides of 4,4'-, two (the 2-trifluoromethyl-4-aminophenoxyls)-3 of 4,4'-, 3'5,5'-tetramethyl diphenyl sulfone, two (2-trifluoromethyl-4-aminophenoxyl) biphenyl of 4,4'-, two (the 2-trifluoromethyl-4-aminophenoxyls)-3 of 4,4'-, 3'5,5'-tetramethyl biphenyl, two (2-trifluoromethyl-4-aminophenoxyl) phenyl ether of 4,4'-, two (4-amino-benzene oxygen) phenyl ether of 4,4'-, two (3-amino-benzene oxygen) phenyl ether of 4,4'-, two (3-amino-benzene oxygen) diphenyl sulfides of 4,4'-, two (4-amino-benzene oxygen) diphenyl sulfides of 4,4'-, two (the 4-amino-benzene oxygens)-3 of 4,4'-, 3'5,5'-tetramethyl biphenyl, two (the 3-amino-benzene oxygens)-3 of 4,4'-, 3'5,5'-tetramethyl biphenyl, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (3-amino-benzene oxygen) benzene of 1,3-, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4'-diamino-4 " hydroxyl tritane, 3,3'-diamino-4,4' dihydroxy diphenyl, 3,3'-dihydroxyl-4,4'-benzidine, two (3-amino-4-hydroxylphenyl) propane of 2,2-, two (3-amino-4-hydroxylphenyl) HFC-236fa of 2,2-, 3,3'-diamino-4,4'-dihydroxy diphenylsulphone, 3,5-diaminobenzoic acid, glyoxal ethyline, 2,4-methylimidazole, 2-ethyl imidazol(e), 2,4,6-tri-(dimethylamino methyl) phenol, benzyldimethylamine, triethylamine, tripropyl amine, Tributylamine, 1,8-diaza-dicyclo [5.4.0] hendecene-7, to SA two hydrazides, m-phthalic acid hydrazides, Whitfield's ointment hydrazides, hexanodioic acid hydrazides, boron trifluoride-2, the mixture of one or more in 4-dimethyl benzene amine complex,
Described organic solvent is selected from a kind of or several in methylene dichloride, trichloromethane, DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, tetrahydrofuran (THF), methyltetrahydrofuran, dimethyl sulfoxide (DMSO).
Described bisphenol A type epoxy resin is selected from E-51(oxirane value 0.51), E-44(oxirane value 0.44), ES-216(oxirane value 0.216) in one or more mixture.
The preparation method of a kind of high-temperature resistant copper foil glue of the present invention, comprising:
According to said ratio, to join in the mixture of polyfunctional epoxy resin and bisphenol A type epoxy resin containing trifluoromethyl bimaleimide resin with containing active ethylene group polyetherimide, be heated to 90 ℃～120 ℃, after stirring reaction 30min-90min, be cooled to 30～50 ℃, add organic solvent, be stirred to after dissolving completely, add solidifying agent, stir, obtain the high-temperature resistant copper foil glue of homogeneous phase transparent clarification.
A kind of high-temperature resistant copper foil glue of the present invention can be applicable to the high-tech areas such as electronics microelectronics, flexible copper clad foil plate (FCCL), flexible printed circuit board (FPC), rigid copper coated foil plate (PCB), automobile, motor, aerospace.
Get appropriate high-temperature resistant copper foil glue of the present invention, and be evenly coated on thick copper test piece or phenolic hydroxyl group Kapton surface, make copper-glue-copper, copper-glue-phenolic hydroxyl group polyimide film sample, be cured: from room temperature, be heated to 100 ℃, insulation 1h, continue to be warming up to 120 ℃, insulation 2h, continues to be warming up to 150 ℃, insulation 2h, continue to be warming up to 170 ℃, insulation 0.5h, naturally cools to room temperature.
Beneficial effect
(1) the viscosity controllability of high-temperature resistant copper foil glue of the present invention is good, can in broader scope, regulate, good manufacturability, the Tonset temperature of its thermolysis is up to more than 410 ℃, and excellent to the adhesiveproperties of metallic copper-copper base material and copper-phenolic hydroxyl group Kapton, its tensile shear strength (base material: copper-copper) up to 35MPa, 90 degree stripping strength (base materials: copper-phenolic hydroxyl group Kapton) up to 2.2kg/cm;
(2) this high-temperature resistant copper foil glue, in high-tech areas such as electronics microelectronics, flexible copper clad foil plate (FCCL), flexible printed circuit board (FPC), rigid copper coated foil plate (PCB), automobile, motor, aerospace, has broad application prospects;
(3) and preparation technology is simple, cost is low, easy to operate, reaction raw materials convenient sources can complete preparation process in general-purpose equipment, is conducive to realize suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the molecular structural formula containing active ethylene group polyetherimide.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
By 5.0 grams, contain active ethylene group polyetherimide (AEPEI) powder, 15.0 gram 1, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-, 10.0 gram N, N, N', N'-four glycidyl group-3, 3'-dimethyl-4, 4'-diaminodiphenylmethane and 40.0 grams of ES-216 bisphenol A type epoxy resins add in reactor, after 90 ℃～120 ℃ reaction 30min-90min, be cooled to 40 ℃, add 25.0 grams of N, N-N,N-DIMETHYLACETAMIDE organic solvent, be stirred to after dissolving completely, add 5.0 grams of dicy-curing agents, stir, obtain the high-temperature resistant copper foil glue of homogeneous phase transparent clarification, be denoted as CFA-1.
Get the addition of C FA-1 high-temperature resistant copper foil glue, be coated on equably on thick copper test piece or phenolic hydroxyl group Kapton surface, make copper-glue-copper, copper-glue-phenolic hydroxyl group polyimide film sample, be cured: from room temperature, be heated to 100 ℃, insulation 1h, continue to be warming up to 120 ℃, insulation 2h, continues to be warming up to 150 ℃, insulation 2h, continue to be warming up to 170 ℃, insulation 0.5h, naturally cools to room temperature.
This CFA-1 high-temperature resistant copper foil adhesive capacity controllability is good, can in broader scope, regulate, good manufacturability, the Tonset temperature of its thermolysis is up to 415 ℃, and excellent to the adhesiveproperties of metallic copper-copper base material and copper-phenolic hydroxyl group Kapton, its tensile shear strength (base material: copper-copper) up to 35MPa, 90 degree stripping strength (base materials: copper-phenolic hydroxyl group Kapton) up to 2.2kg/cm.
Embodiment 2
By 15.0 grams, contain active ethylene group polyetherimide (AEPEI) powder, 5.0 gram 2, 2-pair [4-(4-dimaleoyl imino-2-4-trifluoromethylphenopendant) phenyl] propane, 20.0 gram N, N, N', N'-four glycidyl group-4, 4'-diaminodiphenyl oxide, 5.0 grams of E-51 and 5.0 grams of ES-216 bisphenol A type epoxy resins add in reactor, after 90 ℃～120 ℃ reaction 30min-90min, be cooled to 40 ℃, add 35.0 grams of N, dinethylformamide and 10.0 grams of methylene dichloride organic solvents, be stirred to after dissolving completely, add 3.0 gram 4, 4'-diaminodiphenylsulfone(DDS) and 2.0 gram 1, 4-two (2, 6-diamino-4-4-trifluoromethylphenopendant) benzene solidifying agent, stir, obtain the high-temperature resistant copper foil glue of homogeneous phase transparent clarification, be denoted as CFA-2.
Get the addition of C FA-2 high-temperature resistant copper foil glue, be coated on equably on thick copper test piece or phenolic hydroxyl group Kapton surface, make copper-glue-copper, copper-glue-phenolic hydroxyl group polyimide film sample, be cured: from room temperature, be heated to 100 ℃, insulation 1h, continue to be warming up to 120 ℃, insulation 2h, continues to be warming up to 150 ℃, insulation 2h, continue to be warming up to 170 ℃, insulation 0.5h, naturally cools to room temperature.
This CFA-2 high-temperature resistant copper foil adhesive capacity controllability is good, can in broader scope, regulate, good manufacturability, the Tonset temperature of its thermolysis is up to 412 ℃, and excellent to the adhesiveproperties of metallic copper-copper base material and copper-phenolic hydroxyl group Kapton, its tensile shear strength (base material: copper-copper) up to 27MPa, 90 degree stripping strength (base materials: copper-phenolic hydroxyl group Kapton) up to 1.6kg/cm.
Embodiment 3
By 8.0 grams, contain active ethylene group polyetherimide (AEPEI) powder, 3.0 gram 4, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) biphenyl of 4'-and 8.0 gram 1, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 3-, 10.0 gram N, N, N', N'-four glycidyl group-3, 3'-dimethyl-4, 4'-diaminodiphenylmethane, 20.0 gram N, N, N', N'-four glycidyl group-4, 4'-diaminodiphenyl oxide, 5.0 grams of E-44 and 6.0 grams of ES-216 bisphenol A type epoxy resins add in reactor, after 90 ℃～120 ℃ reaction 30min-90min, be cooled to 40 ℃, add 30.0 grams of N, N-N,N-DIMETHYLACETAMIDE organic solvent, be stirred to after dissolving completely, add 5.0 grams of 2-ethyl-4-methylimidazoles and 5.0 grams of dicy-curing agents, stir, obtain the high-temperature resistant copper foil glue of homogeneous phase transparent clarification, be denoted as CFA-3.
Get the addition of C FA-3 high-temperature resistant copper foil glue, be coated on equably on thick copper test piece or phenolic hydroxyl group Kapton surface, make copper-glue-copper, copper-glue-phenolic hydroxyl group polyimide film sample, be cured: from room temperature, be heated to 100 ℃, insulation 1h, continue to be warming up to 120 ℃, insulation 2h, continues to be warming up to 150 ℃, insulation 2h, continue to be warming up to 170 ℃, insulation 0.5h, naturally cools to room temperature.
This CFA-3 high-temperature resistant copper foil adhesive capacity controllability is good, can in broader scope, regulate, good manufacturability, the Tonset temperature of its thermolysis is up to 411 ℃, and excellent to the adhesiveproperties of metallic copper-copper base material and copper-phenolic hydroxyl group Kapton, its tensile shear strength (base material: copper-copper) up to 21MPa, 90 degree stripping strength (base materials: copper-phenolic hydroxyl group Kapton) up to 1.9kg/cm.
Claims (8)
1. a high-temperature resistant copper foil glue, comprises that following component: 5wt%～15wt%'s contains active ethylene group polyetherimide, the solidifying agent of 5wt%～10wt% and the organic solvent of 25wt%～45wt% containing trifluoromethyl bimaleimide resin, the polyfunctional epoxy resin of 10wt%～30wt%, the bisphenol A type epoxy resin of 10wt%～40wt%, 5wt%～15wt%; Wherein, the molecular structural formula containing active ethylene group polyetherimide is:
N wherein
1: n
2=1:5.
2. a kind of high-temperature resistant copper foil glue according to claim 1, is characterized in that: the thermolysis Tonset temperature of described high-temperature resistant copper foil glue is up to 415 ℃, and its tensile shear strength reaches 35MPa, and 90 degree stripping strengths reach 2.2kg/cm.
3. a kind of high-temperature resistant copper foil glue according to claim 1, is characterized in that: described is selected from Isosorbide-5-Nitrae-bis-(4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene containing trifluoromethyl bimaleimide resin, Isosorbide-5-Nitrae-bis-(4-dimaleoyl imino-3-4-trifluoromethylphenopendant) benzene, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 1,3-, two (4-dimaleoyl imino-3-4-trifluoromethylphenopendant) benzene of 1,3-, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) benzene of 1,2-, two (4-dimaleoyl imino-3-4-trifluoromethylphenopendant) benzene of 1,2-, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) toluene of 2,5-, two (4-dimaleoyl imino-3-4-trifluoromethylphenopendant) toluene of 2,5-, Isosorbide-5-Nitrae-bis-(4-dimaleoyl imino-2-4-trifluoromethylphenopendant)-2-tert-butylbenzene, Isosorbide-5-Nitrae-bis-(4-dimaleoyl imino-3-4-trifluoromethylphenopendant)-2-tert-butylbenzene, Isosorbide-5-Nitrae-bis-(4-dimaleoyl imino-2-4-trifluoromethylphenopendant)-2,5-di-t-butylbenzene, Isosorbide-5-Nitrae-bis-(4-dimaleoyl imino-3-4-trifluoromethylphenopendant)-2,5-di-t-butylbenzene, 2,2-pair [4-(4-dimaleoyl imino-2-4-trifluoromethylphenopendant) phenyl] propane, 2,2-pair [4-(4-dimaleoyl imino-3-4-trifluoromethylphenopendant) phenyl] propane, 2,2-pair [4-(4-dimaleoyl imino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 2,2-pair [4-(4-dimaleoyl imino-3-4-trifluoromethylphenopendant) phenyl] HFC-236fa, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) biphenyl of 4,4'-, two (4-dimaleoyl imino-3-4-trifluoromethylphenopendant) biphenyl of 4,4'-, two (the 4-dimaleoyl imino-2-4-trifluoromethylphenopendants)-3 of 4,4'-, 3', 5,5'-tetramethyl biphenyl, two (the 4-dimaleoyl imino-3-4-trifluoromethylphenopendants)-3 of 4,4'-, 3', 5,5'-tetramethyl biphenyl, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) phenyl ether of 4,4'-, two (4-dimaleoyl imino-3-4-trifluoromethylphenopendant) phenyl ether of 4,4'-, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) diphenyl sulfides of 4,4'-, two (4-dimaleoyl imino-3-4-trifluoromethylphenopendant) diphenyl sulfides of 4,4'-, two (4-dimaleoyl imino-2-4-trifluoromethylphenopendant) sulfobenzides of 4,4'-, two (4-dimaleoyl imino-3-4-trifluoromethylphenopendant) sulfobenzides of 4,4'-, two (the 4-dimaleoyl imino-2-4-trifluoromethylphenopendants)-3 of 4,4'-, 3', 5,5'-tetramethyl diphenyl sulfone, two (the 4-dimaleoyl imino-3-4-trifluoromethylphenopendants)-3 of 4,4'-, 3', the mixture of one or more in 5,5'-tetramethyl diphenyl sulfone.
4. a kind of high-temperature resistant copper foil glue according to claim 1, is characterized in that: described polyfunctional epoxy resin is selected from N, N, N', N'-four glycidyl group-4,4'-diaminodiphenylmethane, N, N, N', N'-four glycidyl group-4,4'-diaminodiphenyl oxide, N, N, N', N'-four glycidyl group-4,4'-diaminodiphenylsulfone(DDS), N, N, N', N'-four glycidyl group-3,3'-dimethyl-4,4 '-diaminodiphenylmethane, N, N, N', N'-four glycidyl group-3,3'-bis-is chloro-4, the mixture of one or more in 4'-diaminodiphenylmethane.
5. a kind of high-temperature resistant copper foil glue according to claim 1, is characterized in that: described solidifying agent is selected from 2-ethyl-4-methylimidazole, Dyhard RU 100, 4,4'-diaminodiphenylsulfone(DDS), Isosorbide-5-Nitrae-bis-(2,6-diamino-4-4-trifluoromethylphenopendant) benzene, two (2, the 6-diamino-4-4-trifluoromethylphenopendant) benzene of 1,3-, two [4-(2, the 6-diamino-4-4-trifluoromethylphenopendant) phenyl] propane of 2,2-, two [4-(2, the 6-diamino-4-4-trifluoromethylphenopendant) phenyl] HFC-236fa of 2,2-, two (2, the 6-diamino-4-4-trifluoromethylphenopendant) sulfobenzides of 4,4'-, two (2, the 6-diamino-4-4-trifluoromethylphenopendant) biphenyl of 4,4'-, two (2, the 6-diamino-4-4-trifluoromethylphenopendants)-3 of 4,4'-, 3'5,5'-tetramethyl diphenyl sulfone, two (2, the 6-diamino-4-4-trifluoromethylphenopendants)-3 of 4,4'-, 3'5,5'-tetramethyl biphenyl, pyromellitic acid anhydride, oxygen supports two phthalic anhydrides, 3,3', 4,4'-tetracarboxylic acid benzophenone dianhydride, biphenyl dianhydride, two [4-(3,4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2,2-, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydrides of 2,2-, phthalic anhydride, methyl tetrahydro phthalic anhydride, maleic anhydride, Nai Dike acid anhydrides, methyl Nai Dike acid anhydrides, 4,4'-diaminodiphenylmethane, 4,4'-benzidine, 3,3'-diaminodiphenylsulfone(DDS), 3,3'-dimethyl-4,4 '-diaminodiphenylmethane, two [4-(3-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, 4,4'-diaminodiphenyl oxide, 3,4'-diaminodiphenyl oxide, 3,3'-diaminodiphenyl oxide, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) cyanobenzenes of 2,6-, two (3-amino-benzene oxygen) cyanobenzenes of 2,6-, two (4-amino-benzene oxygen) toluene of 2,6-, two (4-amino-benzene oxygen) phenylfluoroforms of 2,6-, two (4-amino-benzene oxygen) toluene of 2,5-, two (4-amino-benzene oxygen) tert-butylbenzenes of 2,5-, 2,5-di-t-butyl-Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzophenone of 4,4'-, two (4-amino-benzene oxygen) sulfobenzides of 4,4'-, two (3-amino-benzene oxygen) benzophenone of 4,4'-, two (3-amino-benzene oxygen) sulfobenzides of 4,4'-, Isosorbide-5-Nitrae-bis-(2-trifluoromethyl-4-aminophenoxyl) benzene, two (2-trifluoromethyl-4-aminophenoxyl) benzene of 1,3-, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] propane of 2,2-, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] HFC-236fa of 2,2-, two (2-trifluoromethyl-4-aminophenoxyl) toluene of 2,5-, two (2-trifluoromethyl-4-aminophenoxyl) tert.-butylbenzenes of 2,5-, 2,5-di-t-butyl-Isosorbide-5-Nitrae-bis-(2-trifluoromethyl-4-aminophenoxyl) benzene, two (2-trifluoromethyl-4-aminophenoxyl) sulfobenzides of 4,4'-, two (the 2-trifluoromethyl-4-aminophenoxyls)-3 of 4,4'-, 3'5,5'-tetramethyl diphenyl sulfone, two (2-trifluoromethyl-4-aminophenoxyl) biphenyl of 4,4'-, two (the 2-trifluoromethyl-4-aminophenoxyls)-3 of 4,4'-, 3'5,5'-tetramethyl biphenyl, two (2-trifluoromethyl-4-aminophenoxyl) phenyl ether of 4,4'-, two (4-amino-benzene oxygen) phenyl ether of 4,4'-, two (3-amino-benzene oxygen) phenyl ether of 4,4'-, two (3-amino-benzene oxygen) diphenyl sulfides of 4,4'-, two (4-amino-benzene oxygen) diphenyl sulfides of 4,4'-, two (the 4-amino-benzene oxygens)-3 of 4,4'-, 3'5,5'-tetramethyl biphenyl, two (the 3-amino-benzene oxygens)-3 of 4,4'-, 3'5,5'-tetramethyl biphenyl, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (3-amino-benzene oxygen) benzene of 1,3-, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4'-diamino-4 " hydroxyl tritane, 3,3'-diamino-4,4' dihydroxy diphenyl, 3,3'-dihydroxyl-4,4'-benzidine, two (3-amino-4-hydroxylphenyl) propane of 2,2-, two (3-amino-4-hydroxylphenyl) HFC-236fa of 2,2-, 3,3'-diamino-4,4'-dihydroxy diphenylsulphone, 3,5-diaminobenzoic acid, glyoxal ethyline, 2,4-methylimidazole, 2-ethyl imidazol(e), 2,4,6-tri-(dimethylamino methyl) phenol, benzyldimethylamine, triethylamine, tripropyl amine, Tributylamine, 1,8-diaza-dicyclo [5.4.0] hendecene-7, to SA two hydrazides, m-phthalic acid hydrazides, Whitfield's ointment hydrazides, hexanodioic acid hydrazides, boron trifluoride-2, the mixture of one or more in 4-dimethyl benzene amine complex.
6. a kind of high-temperature resistant copper foil glue according to claim 1, it is characterized in that: described organic solvent is selected from methylene dichloride, trichloromethane, N, a kind of or several in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, tetrahydrofuran (THF), methyltetrahydrofuran, dimethyl sulfoxide (DMSO).
7. a preparation method for high-temperature resistant copper foil glue as claimed in claim 1, comprising:
According to the proportioning in claim 1, to join in the mixture of polyfunctional epoxy resin and bisphenol A type epoxy resin containing trifluoromethyl bimaleimide resin with containing active ethylene group polyetherimide, be heated to 90 ℃～120 ℃, after stirring reaction 30min-90min, be cooled to 30～50 ℃, add organic solvent, be stirred to after dissolving completely, add solidifying agent, stir, obtain the high-temperature resistant copper foil glue of homogeneous phase transparent clarification.
8. a high-temperature resistant copper foil glue as claimed in claim 1 is applied to electronics microelectronics, flexible copper clad foil plate FCCL, flexible printed circuit board FPC, rigid copper coated foil plate PCB, automobile, motor or aerospace field.
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