CN116162431B - Hybrid curing damp-heat resistant adhesive and preparation method thereof - Google Patents
Hybrid curing damp-heat resistant adhesive and preparation method thereof Download PDFInfo
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- CN116162431B CN116162431B CN202211725050.7A CN202211725050A CN116162431B CN 116162431 B CN116162431 B CN 116162431B CN 202211725050 A CN202211725050 A CN 202211725050A CN 116162431 B CN116162431 B CN 116162431B
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- trigonox
- heat resistant
- polybutadiene
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 24
- 239000000853 adhesive Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title description 5
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 28
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 37
- KQYLUTYUZIVHND-UHFFFAOYSA-N tert-butyl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)C KQYLUTYUZIVHND-UHFFFAOYSA-N 0.000 claims description 17
- -1 (methyl) acryloyloxy Chemical group 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 11
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 10
- 239000012965 benzophenone Substances 0.000 claims description 10
- 239000012949 free radical photoinitiator Substances 0.000 claims description 10
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 claims description 4
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 claims description 2
- NNAHKQUHXJHBIV-UHFFFAOYSA-N 2-methyl-1-(4-methylthiophen-2-yl)-2-morpholin-4-ylpropan-1-one Chemical compound CC1=CSC(C(=O)C(C)(C)N2CCOCC2)=C1 NNAHKQUHXJHBIV-UHFFFAOYSA-N 0.000 claims description 2
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 claims description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- IQJVBAIESAQUKR-UHFFFAOYSA-N isocyanic acid;prop-2-enoic acid Chemical compound N=C=O.OC(=O)C=C IQJVBAIESAQUKR-UHFFFAOYSA-N 0.000 claims description 2
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 2
- 229910000077 silane Inorganic materials 0.000 claims 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims 1
- CQUTXCKGINHWKG-UHFFFAOYSA-N isocyanato prop-2-enoate Chemical compound C=CC(=O)ON=C=O CQUTXCKGINHWKG-UHFFFAOYSA-N 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 14
- 238000003860 storage Methods 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000001029 thermal curing Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 18
- 238000002329 infrared spectrum Methods 0.000 description 16
- 238000005303 weighing Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 238000006356 dehydrogenation reaction Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The hybrid curing wet heat resistant adhesive prepared by the invention comprises A, B components, wherein the component A comprises: 90-100 parts of modified epoxidized polybutadiene resin and 0.5-5 parts of photoinitiator; the component B comprises 100 parts of modified anhydride polybutadiene and 1-10 parts of accelerator. The adhesive prepared by the invention can be photo-thermal dual-cured, has excellent storage stability and high photo-thermal curing strength, has the strength retention rate of more than 95% after high temperature and high humidity, has good high and low temperature impact resistance, still has excellent protective capability on ITO substrate lines under the high temperature and high humidity electrifying condition, and has better water resistance.
Description
Technical Field
The invention relates to a hybrid curing damp-heat resistant adhesive and a preparation method thereof, belonging to the field of adhesive materials.
Background
With the development of technology, the photo-curing adhesive has been widely used in various industrial and electronic fields due to the advantages of high curing speed, low energy consumption, excellent comprehensive properties, environmental friendliness and the like. The photoinitiated free radical curing adhesive can be rapidly cured to form bonding strength within a few seconds under Ultraviolet (UV) light irradiation, so that the efficiency of a production line is greatly improved, but the defects are that the adhesive layer can not be completely cured due to insufficient irradiation of UV light or insufficient irradiation of UV light, the bonding performance of the adhesive layer is reduced, and the problem becomes increasingly prominent along with the higher and higher requirements of the terminal product on reliability such as high temperature and humidity resistance, high and low temperature impact resistance and the like, and the hybrid curing moisture and heat resistant adhesive can solve the problem.
Disclosure of Invention
The invention provides a hybrid curing moisture-heat resistant adhesive and a preparation method thereof, and aims to solve the problem that the shadow part of the existing ultraviolet light curing adhesive cannot be cured completely.
The technical scheme for solving the technical problems is as follows:
a room temperature hybrid cure adhesive comprising A, B two components, component a comprising: 90-100 parts of modified epoxidized polybutadiene resin and 0.5-5 parts of photoinitiator; the component B comprises 100 parts of modified anhydride polybutadiene and 1-10 parts of accelerator.
Further, the modified epoxidized polybutadiene resin refers to polybutadiene containing (methyl) acryloyloxy, epoxy, alkoxy and hydroxyl on the molecular chain, and the molecular structure is schematically shown in the following scheme:
Wherein R 1 is-H or-CH 3, and n is a positive integer of 1-100.
Further, the method for synthesizing the modified epoxidized polybutadiene resin comprises the steps of adding 1mol of the dehydrated epoxidized hydroxyl-terminated polybutadiene resin, 1-3mol of vinyl-terminated siloxane and a thermal initiator accounting for 0.01% -2% of the total weight of the two raw materials into a reaction kettle, and reacting for 2-8 hours at 70-90 ℃; adding 0.1-2mol of isocyanate acrylate, and reacting at 70-90 ℃ for 2-8 hours until the isocyanate (-NCO) disappears, thus obtaining the modified epoxidized polybutadiene resin.
Still further, the thermal initiator is an azo or peroxide thermal initiator, including but not limited to TRIGONO 181,TRIGONOX SBP,TRIGONOX 23,TRIGONOX 425-C75, TRIGONO 36-C75, PERCADOX AIBN from Nouryon, preferably a liquid thermal initiator, TRIGONO 23.
Further, the vinyl-terminated siloxane refers to a siloxane containing both vinyl and siloxane in the molecular chain, and includes, but is not limited to, 3- (methacryloxy) propylmethyldimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, 3- (methacryloxy) propyltrimethoxysilane vinyltris (. Beta. -methoxyethoxy) silane.
Still further, the epoxidized hydroxyl terminated polybutadiene resin comprises Polybd E or Polybd 605E from Crayvalley, and has the molecular structural formula shown below:
further, the isocyanate-based acrylate refers to a acrylate having both an acryloyloxy group and an-NCO group in the molecular chain, and includes BEI, MOI, AOI, MOI-EG from Japanese Showa Denko Co., ltd., and has the following molecular structure:
Further, the photoinitiator refers to a free radical photoinitiator, which comprises benzoin dimethyl ether 651, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide TPO, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide 819, 1-hydroxycyclohexyl phenyl ketone 184, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholinyl-1-propanone 907, 2-phenylbenzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone 369, isopropyl thioxanthone ITX, benzophenone BP, 4-hydroxybenzophenone, 2-hydroxybenzophenone, and preferably a cleavage type initiator and a hydrogen abstraction type initiator are used simultaneously.
Further, the modified anhydrated polybutadiene refers to polybutadiene molecular chain containing (methyl) acryloyloxy and anhydride groups, and the molecular structure is schematically shown as follows:
Further, the method for synthesizing the modified anhydridized polybutadiene resin comprises the steps of adding 1mol of the anhydridized polybutadiene resin subjected to water, 1-4mol of isocyanate-based acrylate and a thermal initiator accounting for 0.01% -2% of the total weight of the two into a reaction kettle, and reacting for 2-8 hours at 70-90 ℃; adding 1-5mol of hydroxy acrylic ester, and reacting at 70-90 ℃ for 2-8 hours until isocyanate (-NCO) disappears, thus obtaining the modified anhydride polybutadiene resin.
Still further, the anhydrified polybutadiene resin comprises Polyvest MA 75,Polyvest EP MA100 of Evonik company, the molecular structural formula of which is shown as follows:
Further, the accelerator is an accelerator containing tertiary amine and comprises 2,4, 6-tris [ (dimethoxy) methyl ] phenol, diethylaminopropylamine, benzyl dimethylamine, triethylamine, triethanolamine, o-hydroxybenzyl dimethylamine and the like.
The preparation method of the hybrid curing moisture-heat resistant adhesive comprises the following steps: weighing 90-100 parts of modified epoxidized polybutadiene resin and 0.5-5 parts of photoinitiator, stirring, dissolving and uniformly mixing to obtain a component A; weighing 90-100 parts of modified anhydride polybutadiene resin and 1-10 parts of accelerator, stirring, dissolving and uniformly mixing to obtain a component B; A. the mass ratio of the two components B is 1:1-10:1, preferably 1:1.
The beneficial effects of the invention are as follows: the mixed curing wet heat resistant adhesive prepared by the invention has the advantages that A component resin contains acryloyloxy, epoxy, alkoxy and hydroxyl on a polybutadiene molecular chain, and B component resin contains acryloyloxy and anhydride on the polybutadiene molecular chain; after the two components are mixed, the part containing acryloyloxy of the component A, B reacts and crosslinks rapidly under the irradiation of UV light to form initial bonding strength, and in the process, a hydrogen abstraction type photoinitiator in the component A and an accelerator containing tertiary amine in the component B form a compound, and the compound and the cracking type photoinitiator trigger photopolymerization together, so that the initial curing strength is greatly improved; the heating and curing process is that epoxy groups on the A component molecules and anhydride groups on the B component molecules react and crosslink mutually under the action of the accelerator, so that the intermolecular crosslinking density is further increased, and the bonding strength is improved. It is worth mentioning that the hydroxyl groups on the A-component resin have a significant promoting effect on the reaction process.
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1
Respectively weighing 0.8g of TRIGONOX 23, 250g of 3- (methacryloyloxy) propyl trimethoxysilane, 1300g Polybd 605E g of the TRIGONOX propyl trimethoxysilane, adding the TRIGONOX propyl trimethoxysilane and the TRIGONOX propyl trimethoxysilane into a reaction kettle, and reacting for 4 hours at 75-85 ℃; 114g of AOI is added for continuous reaction for 4 hours, and infrared spectrum is measured until the-NCO group disappears; under the condition of avoiding ultraviolet light, 23g of free radical photoinitiator 184 and 10g of hydrogen abstraction photoinitiator benzophenone are added, and the mixture is stirred until the photoinitiator is dissolved and uniformly mixed to obtain a component A. Respectively weighing 2g TRIGONOX 23, 3000g Polyvest MA75 g and 114g of AOI, adding into a reaction kettle, and reacting for 4 hours at 75-85 ℃; 118g of hydroxyethyl acrylate is added, the reaction is continued for 3 hours, the infrared spectrum is measured until the-NCO group disappears, the temperature is reduced to the room temperature, 160g of 2,4, 6-tris (dimethylaminomethyl) phenol is added, and the component B is obtained after uniform stirring.
Example 2
Respectively weighing 0.8g of TRIGONOX 23, 250g of 3- (methacryloyloxy) propyl trimethoxysilane, 1300g Polybd 605E g of the TRIGONOX propyl trimethoxysilane, adding the TRIGONOX propyl trimethoxysilane and the TRIGONOX propyl trimethoxysilane into a reaction kettle, and reacting for 4 hours at 75-85 ℃; 240g of BEI is added for continuous reaction for 4 hours, and infrared spectrum is measured until the-NCO group disappears; under the condition of avoiding ultraviolet light, 23g of free radical photoinitiator 184 and 10g of hydrogen abstraction photoinitiator benzophenone are added, and the mixture is stirred until the photoinitiator is dissolved and uniformly mixed to obtain a component A. Respectively weighing 2g TRIGONOX 23, 3000g Polyvest MA75 g and 114g of AOI, adding into a reaction kettle, and reacting for 4 hours at 75-85 ℃; 118g of hydroxyethyl acrylate is added, the reaction is continued for 3 hours, the infrared spectrum is measured until the-NCO group disappears, the temperature is reduced to the room temperature, 160g of 2,4, 6-tris (dimethylaminomethyl) phenol is added, and the component B is obtained after uniform stirring.
Example 3
Respectively weighing 0.8g of TRIGONOX 23, 250g of 3- (methacryloyloxy) propyl trimethoxysilane, 1300g Polybd 605E g of the TRIGONOX propyl trimethoxysilane, adding the TRIGONOX propyl trimethoxysilane and the TRIGONOX propyl trimethoxysilane into a reaction kettle, and reacting for 4 hours at 75-85 ℃; 240g of BEI is added for continuous reaction for 4 hours, and infrared spectrum is measured until the-NCO group disappears; under the condition of avoiding ultraviolet light, 23g of free radical photoinitiator 184 and 10g of hydrogen abstraction photoinitiator benzophenone are added, and the mixture is stirred until the photoinitiator is dissolved and uniformly mixed to obtain a component A. Respectively weighing 2g TRIGONOX 23, 3000g Polyvest MA75 g BEI and 240g BEI, adding into a reaction kettle, and reacting for 4 hours at 75-85 ℃; 118g of hydroxyethyl acrylate is added, the reaction is continued for 3 hours, the infrared spectrum is measured until the-NCO group disappears, the temperature is reduced to the room temperature, 160g of 2,4, 6-tris (dimethylaminomethyl) phenol is added, and the component B is obtained after uniform stirring.
Example 4
Respectively weighing 0.8g of TRIGONOX 23, 250g of 3- (methacryloyloxy) propyl trimethoxysilane, 1300g Polybd 605E g of the TRIGONOX propyl trimethoxysilane, adding the TRIGONOX propyl trimethoxysilane and the TRIGONOX propyl trimethoxysilane into a reaction kettle, and reacting for 4 hours at 75-85 ℃; 360g of BEI is added to continue the reaction for 4 hours, and the infrared spectrum is measured until the-NCO group disappears; under the condition of avoiding ultraviolet light, 23g of free radical photoinitiator 184 and 10g of hydrogen abstraction photoinitiator benzophenone are added, and the mixture is stirred until the photoinitiator is dissolved and uniformly mixed to obtain a component A. Respectively weighing 2g TRIGONOX 23, 3000g Polyvest MA75 g BEI and 240g BEI, adding into a reaction kettle, and reacting for 4 hours at 75-85 ℃; 118g of hydroxyethyl acrylate is added, the reaction is continued for 3 hours, the infrared spectrum is measured until the-NCO group disappears, the temperature is reduced to the room temperature, 160g of 2,4, 6-tris (dimethylaminomethyl) phenol is added, and the component B is obtained after uniform stirring.
Comparative example 1
1.6G TRIGONOX 23, 250g 3- (methacryloyloxy) propyl trimethoxysilane, 2800g Polybd R-45M were weighed out separately, and the molecular structure is shown below:
Adding the mixture into a reaction kettle, and reacting for 4 hours at 75-85 ℃; 114g of AOI is added for continuous reaction for 4 hours, and infrared spectrum is measured until the-NCO group disappears; under the condition of avoiding ultraviolet light, 40g of free radical photoinitiator 184 and 20g of hydrogen abstraction photoinitiator benzophenone are added, and the mixture is stirred until the photoinitiator is dissolved and uniformly mixed to obtain the component A. Respectively weighing 2gTRIGONOX 23, 3000g Polyvest MA75 g and 114g of AOI, adding into a reaction kettle, and reacting for 4 hours at 75-85 ℃; 118g of hydroxyethyl acrylate is added, the reaction is continued for 3 hours, the infrared spectrum is measured until the-NCO group disappears, the temperature is reduced to the room temperature, 160g of 2,4, 6-tris (dimethylaminomethyl) phenol is added, and the component B is obtained after uniform stirring.
Comparative example 2
1.6G TRIGONOX 23, 250g 3- (methacryloyloxy) propyl trimethoxysilane and 2800-g Polybd R-45M are respectively weighed and added into a reaction kettle to react for 4 hours at 75-85 ℃; 114g of AOI is added for continuous reaction for 4 hours, and infrared spectrum is measured until the-NCO group disappears; 727g of epoxy E55 are added; under the condition of avoiding ultraviolet light, 55g of free radical photoinitiator 184 and 35g of hydrogen abstraction photoinitiator benzophenone are added, and the mixture is stirred until the photoinitiator is dissolved and uniformly mixed to obtain the component A. Respectively weighing 2g TRIGONOX 23, 3000g Polyvest MA75 g and 114g of AOI, adding into a reaction kettle, and reacting for 4 hours at 75-85 ℃; 118g of hydroxyethyl acrylate is added, the reaction is continued for 3 hours, the infrared spectrum is measured until the-NCO group disappears, the temperature is reduced to the room temperature, 160g of 2,4, 6-tris (dimethylaminomethyl) phenol is added, and the component B is obtained after uniform stirring.
Comparative example 3
Respectively weighing 0.8g of TRIGONOX 23, 250g of 3- (methacryloyloxy) propyl trimethoxysilane, 1300g Polybd 605E g of the TRIGONOX propyl trimethoxysilane, adding the TRIGONOX propyl trimethoxysilane and the TRIGONOX propyl trimethoxysilane into a reaction kettle, and reacting for 4 hours at 75-85 ℃; 240g of BEI is added for continuous reaction for 4 hours, and infrared spectrum is measured until the-NCO group disappears; under the condition of avoiding ultraviolet light, 23g of free radical photoinitiator 184 and 10g of hydrogen abstraction photoinitiator benzophenone are added, and the mixture is stirred until the photoinitiator is dissolved and uniformly mixed to obtain a component A. 2g of TRIGONOX 23, 3000g Polyvest 130 were weighed out separately and the molecular structure was as follows:
114g of AOI is added into a reaction kettle to react for 4 hours at 75-85 ℃; 118g of hydroxyethyl acrylate is added, the reaction is continued for 3 hours, the infrared spectrum is measured until the-NCO group disappears, the temperature is reduced to the room temperature, 160g of 2,4, 6-tris (dimethylaminomethyl) phenol is added, and the component B is obtained after uniform stirring.
Comparative example 4
Respectively weighing 0.8g of TRIGONOX 23, 250g of 3- (methacryloyloxy) propyl trimethoxysilane, 1300g Polybd 605E g of the TRIGONOX propyl trimethoxysilane, adding the TRIGONOX propyl trimethoxysilane and the TRIGONOX propyl trimethoxysilane into a reaction kettle, and reacting for 4 hours at 75-85 ℃; 240g of BEI is added for continuous reaction for 4 hours, and infrared spectrum is measured until the-NCO group disappears; under the condition of avoiding ultraviolet light, 23g of free radical photoinitiator 184 and 10g of hydrogen abstraction photoinitiator benzophenone are added, and the mixture is stirred until the photoinitiator is dissolved and uniformly mixed to obtain a component A. 2g TRIGONOX 23 and 3000g Polyvest 130 g AOI are respectively weighed and 114g AOI is added into a reaction kettle to react for 4 hours at 75-85 ℃; 118g of hydroxyethyl acrylate is added, the reaction is continued for 3 hours, the infrared spectrum is measured until the-NCO group disappears, 200g of ethylene glycol bis (trimellitic anhydride ester) is added, the mixture is stirred until the mixture is dissolved, the temperature is reduced to the room temperature, 160g of 2,4, 6-tris (dimethylaminomethyl) phenol is added, and the mixture is stirred uniformly to obtain a component B.
The storage stability, the bonding strength after photo-curing, the bonding strength after photo + thermosetting and the reliability of a hybrid cured wet heat resistant adhesive of the present invention were tested by the following tests.
Storage stability test method: the A, B components are respectively sealed and shaded for 6 months at room temperature, and whether precipitation and gel phenomena and the viscosity rising rate are observed.
The following adhesive property tests were carried out by uniformly mixing A, B=1:1 (mass ratio) and preparing samples.
Shear strength test: substrate-stainless steel sheet and transparent PC.
Photo-curing adhesive strength test: an LED365nm light source, 300mW/cm 2, a light time of 20s,
Bonding strength test after light + heat set: after the sample was photo-cured, it was heated at 120℃for 60 min.
And (3) high-temperature and high-humidity testing, namely placing the sample after light and thermosetting in 85 ℃ and 85% RH for 600h to test the strength.
High-low temperature impact test: and (3) respectively placing the prepared light and thermosetting sample pieces in 600 cycles of high and low temperature impact (-40 ℃/30 min-85 ℃/30 min) to observe whether the sample pieces crack or not.
High-temperature and high-humidity electrifying test: the glue was applied TO the ito glass (surface with circuit) surface, the thickness was controlled at 100 μm, cured according TO the above uv+thermosetting conditions, and then placed in a high temperature and high humidity environment box (85 ℃,85% rh, applied voltage 12V) for 500h.
The test results are shown in table 1:
Table 1 results of comparative tests of examples and comparative examples
From the above results, compared with the existing photo-curing adhesive of the common technology, the hybrid curing moisture-heat resistant adhesive of the invention has the advantages that the molecular dual crosslinking curing is realized, the strength after photo-thermal curing is greatly improved, the strength retention rate is higher than 95% after high temperature and high humidity is obviously higher than that of the comparative example, the high-low temperature impact resistance and the cracking resistance are excellent, and the adhesive still has excellent protection capability on ITO substrate circuits under the high temperature and high humidity electrifying condition.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (5)
1. A hybrid cured wet heat resistant adhesive comprising A, B two components, component a comprising: 90-100 parts of modified epoxidized polybutadiene resin and 0.5-5 parts of photoinitiator; the component B comprises: 100 parts of modified anhydride polybutadiene and 1-10 parts of accelerator; the modified epoxidized polybutadiene resin contains (methyl) acryloyloxy, epoxy, alkoxy and hydroxyl on the molecular chain of polybutadiene, and the synthesis method comprises the following steps of adding 1mol of the dehydrated epoxidized hydroxyl-terminated polybutadiene resin, 1-3mol of vinyl-terminated silane and a thermal initiator accounting for 0.01-2% of the total weight of the two into a reaction kettle, and reacting for 2-8h at 70-90 ℃; adding 0.1-2mol of isocyanate acrylate, and reacting at 70-90 ℃ for 2-8 hours until isocyanate (-NCO) disappears, thus obtaining modified epoxidized polybutadiene resin; the vinyl-terminated silane comprises one of 3- (methacryloxy) propyl methyl dimethoxy silane, vinyl triethoxy silane, 3-methacryloxy propyl triethoxy silane, vinyl trimethoxy silane, 3- (methacryloxy) propyl trimethoxy silane and vinyl tri (beta-methoxyethoxy) silane; the epoxidized hydroxyl terminated polybutadiene resin comprises one of Polybd E or Polybd 605E from Crayvalley; the modified anhydrated polybutadiene refers to that the molecular chain of the polybutadiene simultaneously contains (methyl) acryloyloxy and anhydride groups, and the synthetic method comprises the following steps of adding 1mol of anhydrated polybutadiene resin subjected to water, 1-4mol of isocyanato acrylate and a thermal initiator accounting for 0.01-2% of the total weight of the two into a reaction kettle, and reacting for 2-8h at 70-90 ℃; adding 1-5mol of hydroxy acrylic ester, and reacting at 70-90 ℃ for 2-8 hours until isocyanate groups (-NCO) disappear, thus obtaining modified anhydride polybutadiene resin; the anhydrified polybutadiene resin includes Polyvest MA or Polyvest EP MA from Evonik corporation.
2. The hybrid cured wet heat resistant adhesive according to claim 1, wherein the mass ratio of the A, B components is 1:1-10:1.
3. The hybrid cured wet heat resistant adhesive according to claim 1, wherein the thermal initiator is azo or peroxide thermal initiator, including one of TRIGONOX 181,TRIGONOX SBP,TRIGONOX 23,TRIGONOX 425-C75, TRIGONOX 36-C75, PERKADOX AIBN, nouryon.
4. The hybrid curing wet heat resistant adhesive according to claim 1, wherein the isocyanate-based acrylate refers to one of BEI, MOI, AOI, MOI-EG of Japanese Showa electric Co., ltd, wherein the molecular chain contains both acryloyloxy and-NCO groups, and the molecular structure is as follows:
5. the hybrid curing wet heat resistant adhesive according to claim 1, wherein the photoinitiator is a free radical photoinitiator comprising one or more of benzoin dimethyl ether 651, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide TPO, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide 819, 1-hydroxycyclohexyl phenyl ketone 184, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholinyl-1-propanone 907, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylphenyl) butanone 369, isopropylthioxanthone ITX, benzophenone BP, 4-hydroxybenzophenone, 2-hydroxybenzophenone; the accelerator is an accelerator containing tertiary amine and comprises one of 2,4, 6-tris (dimethylaminomethyl) phenol, diethylaminopropylamine, benzyl dimethylamine, triethylamine, triethanolamine and o-hydroxybenzyl dimethylamine.
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