CN116496741A - Dual-cured epoxy adhesive and preparation method thereof - Google Patents
Dual-cured epoxy adhesive and preparation method thereof Download PDFInfo
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- CN116496741A CN116496741A CN202310585497.7A CN202310585497A CN116496741A CN 116496741 A CN116496741 A CN 116496741A CN 202310585497 A CN202310585497 A CN 202310585497A CN 116496741 A CN116496741 A CN 116496741A
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- 229920006332 epoxy adhesive Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000853 adhesive Substances 0.000 claims abstract description 32
- 230000001070 adhesive effect Effects 0.000 claims abstract description 32
- 239000003085 diluting agent Substances 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 11
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 4
- 238000001723 curing Methods 0.000 claims description 27
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 12
- 230000009977 dual effect Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001029 thermal curing Methods 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical group 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 3
- 238000001816 cooling Methods 0.000 claims description 3
- MZRQZJOUYWKDNH-UHFFFAOYSA-N diphenylphosphoryl-(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MZRQZJOUYWKDNH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims description 3
- QKQSRIKBWKJGHW-UHFFFAOYSA-N morpholine;prop-2-enoic acid Chemical compound OC(=O)C=C.C1COCCN1 QKQSRIKBWKJGHW-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims 1
- FEUIEHHLVZUGPB-UHFFFAOYSA-N oxolan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC1CCCO1 FEUIEHHLVZUGPB-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 10
- 238000003848 UV Light-Curing Methods 0.000 description 8
- 238000013007 heat curing Methods 0.000 description 6
- -1 tetrahydrofuran acrylic ester Chemical class 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
-
- 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
Abstract
The invention discloses a dual-curing epoxy adhesive, which relates to the field of adhesives and comprises the following components in parts by weight: 20-56 parts of epoxy resin; 20-40 parts of epoxy acrylate oligomer; 20-30 parts of a diluent; 1-3 parts of a photoinitiator; 1-8 parts of a thermal initiator; 1-2 parts of a silane coupling agent; 1-5 parts of mercaptan, and the invention also discloses a preparation method of the dual-curing epoxy adhesive, which comprises the following steps: (1) Mixing the formula amount of diluent, photoinitiator and thermal initiator together, and heating at 60 ℃ in a dark place to form a uniform transparent system; (2) The uniform transparent system is cooled to below 18 ℃, the rest materials in the formula are added, the temperature is kept below 18 ℃ and the light is prevented, the uniform transparent system is stirred and mixed uniformly at a low speed, and the final finished product is obtained after defoaming; the invention has the advantages of no solvent, convenient and easily obtained raw materials, low viscosity, larger scope for adjusting the formula according to the actual demands of customers, self-mixing according to the demands, convenient connection process and suitability for assembly line application.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a dual-curing epoxy adhesive and a preparation method thereof.
Background
Along with the rapid development of the electronic industry, the application range of electronic products is wider and wider, and the requirements on the electronic adhesives are also stricter. In recent years, a dual curing method combining ultraviolet light with other curing methods is more and more emphasized, and a dual curing method combining ultraviolet light and thermal curing is also an important development direction.
At present, the UV thermosetting dual-curing is applied to paint and ink products with solvent and a cationic curing epoxy system applied to 3D printing, and the invention relates to a formula design and a corresponding preparation method of a UV thermosetting dual-curing system adhesive which has the advantages of convenient and easily available raw materials, easy preparation, no solvent, low viscosity and rapid free radical curing.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a dual-curing epoxy adhesive and a preparation method thereof, which solve the technical problems in the prior art.
In order to achieve the aim, the invention provides a dual-curing epoxy adhesive and a preparation method thereof, wherein the dual-curing epoxy adhesive comprises the following components in parts by weight:
in the technical scheme, the epoxy resin is bisphenol F type epoxy resin.
In the above technical scheme, the epoxy acrylate oligomer is one or more of Changxing chemical 621A-80, 6202, 6210G,6235 and 6265.
In the technical scheme, the diluent is one or more of tetrahydrofuran acrylic ester, propylene isobornyl ester, hydroxyethyl methacrylate, hydroxybutyl acrylate and morpholine acrylate.
In the technical scheme, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone and/or 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide.
In the technical scheme, the thermal initiator is selected from FXR1081 and/or FXR1020 low-temperature latent modified amine epoxy curing agents.
In the technical scheme, the mercaptan is trimethylolpropane tri (3-mercaptopropionic acid) ester and/or pentaerythritol tetra (3-mercaptopropionic acid) ester.
In the technical scheme, the silane coupling agent is gamma-glycidol ether oxygen propyl trimethoxy silane and/or gamma- (methacryloyloxy) propyl trimethoxy silane.
In the above technical solution, the curing mode of the adhesive is thermal curing or UV-before-thermal curing.
The technical scheme also provides a preparation method in the technical scheme, which comprises the following steps:
(1) Mixing the formula amount of diluent, photoinitiator and thermal initiator together, and heating at 60 ℃ in a dark place to form a uniform transparent system;
(2) And cooling the uniform transparent system to below 18 ℃, adding the rest materials in the formula, keeping the temperature below 18 ℃ and keeping out of light, stirring and mixing uniformly at a low speed, and defoaming to obtain the final finished adhesive.
Compared with the prior art, the invention has the beneficial effects that:
1. the adhesive prepared by the invention can be cured by adopting a single UV curing mode, a thermosetting mode or a UV+thermosetting mode, and has the advantages of high curing speed, deep curing depth and good bonding strength.
2. The prepared adhesive can be rapidly cured and positioned under the UV curing condition for 5-10S, the curing thickness can reach 15-20mm, and the prepared adhesive can be cured under the thermal curing condition (110 ℃) for 20-40min, so that the obtained adhesive has high hardness and high strength.
3. The raw materials adopted by the technical scheme are convenient and easy to obtain, the selection range is wide, the solvent is not used, the operation is simple, in addition, the viscosity of the technical scheme is low, the scope of formula adjustment for a customer according to actual demands is large, the formula can be selected and allocated according to the demands, and the technical scheme is convenient in connection process and suitable for mass and assembly line application.
Detailed Description
All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that all directional indications (such as up, down, left, right, front, and rear … …) in the embodiments of the present invention are merely used to explain the relative positional relationship between the components, the movement condition, etc. in a specific posture, and if the specific posture is changed, the directional indication is changed accordingly.
In the present invention, unless specifically stated and limited otherwise, the terms "connected," "affixed," and the like are to be construed broadly, and for example, "affixed" may be a fixed connection, a removable connection, or an integral body; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In addition, if there is a description of "first", "second", etc. in the embodiments of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
Example 1
The embodiment provides a dual-curing epoxy adhesive, which comprises the following components in parts by weight:
the curing mode of the technical scheme can be heat curing or UV-before-heat curing, double bonds in the epoxy acrylate oligomer are quickly cured after being irradiated by a UV lamp, the adhesiveness is quickly increased, the effect of primary bonding is achieved, then epoxy group polymerization is initiated under the action of heat, the bonding strength is further improved, and deep curing can be achieved. Preferably, the epoxy resin is bisphenol F type epoxy resin. The epoxy acrylate oligomer is one or more of Changxing chemical 621A-80, 6202, 6210G,6235 and 6265.
Preferably, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone (184) and/or 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide (TOP). The TOP is light yellow powder, the effective absorption peak value is 350-400nm, the TOP is absorbed to about 420nm, the TOP is a high-efficiency free radical (I) photoinitiator, the absorption peak is longer, benzoyl and phosphoryl two free radicals can be generated after illumination, polymerization can be initiated, the photo-curing speed is high, the TOP also has a photo-bleaching effect, the photo-bleaching effect is low in volatility, the TOP can be used for transparent coatings, and the TOP is especially suitable for products with low odor requirements. 184 is white crystal powder, the effective absorption peak value is 246nm and 278nm, the free radical (I) solid photoinitiator is high-efficiency and does not cause yellowing, and even if the cured coating is exposed to sunlight for a long time, no benzyl is generated due to photolysis, and the yellowing degree is very small. The two photoinitiators adopted in the technical scheme have the characteristic of no yellowing, so that the cured product of the technical scheme can be used after being exposed to sunlight for a long time.
The thermal initiator of the technical scheme is selected from FXR1081 and/or FXR1020 low-temperature latent modified amine epoxy curing agents. FXR-1081 and FXR1020 are easily dispersed in epoxy resin, and the mixed resin has good storage stability at normal temperature, and when FXR-1081 and FXR1020 are mixed, the addition amount can greatly reduce the hardening temperature even if the addition amount is very small, but the storage stability of the whole mixing system is not damaged.
Preferably, the thiol is trimethylolpropane tris (3-mercaptopropionate) (TMPMP) and/or pentaerythritol tetrakis (3-mercaptopropionate) (PETMP). According to the technical scheme, the speed of the adhesive in heat curing can be improved by adding the mercaptan. The silane coupling agent in the technical scheme is preferably gamma-glycidoxypropyl trimethoxysilane (KH 560) and/or gamma- (methacryloyloxy) propyl trimethoxysilane (KH 570), so that the bonding strength in the technical scheme can be improved. The diluent in the technical scheme is preferably one or more of tetrahydrofuran acrylic ester (THFA), propylene isobornyl ester (IBOA), hydroxyethyl methacrylate (HEMA), hydroxybutyl acrylate (4 HBA) and Acryloylmorpholine (ACMO).
The technical scheme also provides a preparation method of the dual-curing epoxy adhesive, which comprises the following steps:
(1) Mixing the formula amount of diluent, photoinitiator and thermal initiator together, and heating at 60 ℃ in a dark place to form a uniform transparent system;
(2) And cooling the uniform transparent system to below 18 ℃, adding the rest materials in the formula, keeping the temperature below 18 ℃, grinding the materials by using a stirrer or a three-roller mill, stirring and mixing the materials uniformly at a low speed, and taking light-shielding measures and defoaming in the stirring process to obtain the final finished adhesive.
Example 1
In this embodiment, the components of the adhesive of the first embodiment are configured differently, and specific parts by weight of each component are shown in the following table.
Table 1 shows the composition of the adhesive in example 1
| The components | Name of the name | Parts by weight of |
| Cycloaliphatic epoxy resins | 621A-80 6202 6210G25 | 25 |
| Bisphenol F type epoxy resin | South Asia 170 | 40 |
| Diluent agent | THFA 4HBA | 26 |
| Photoinitiator | 184 | 2 |
| Thermal initiator | FXR1081 FXR1020 | 6 |
| Silane coupling agent | KH560 KH570 | 1 |
2. The preparation method of the adhesive comprises the following steps:
(1) Mixing the formula amount of diluent, photoinitiator and thermal initiator together, and heating at 60 ℃ in a dark place to form a uniform transparent system;
(2) The uniform transparent system is cooled to below 18 ℃, the rest materials in the formula are added, the mixture is kept at a low temperature (below 18 ℃) and dispersed in a low-speed light-shielding way, the mixture is stirred and mixed uniformly (a stirrer can be used for stirring at a low speed or a three-roll mill can be used for grinding, light-shielding measures are taken), and the dual-curing epoxy adhesive is obtained after defoaming.
3. Results testing
The adhesive prepared by the steps has the viscosity of 2200CPS.
Table 2 shows the adhesive performance test results of example 1
Shear strength data:
the testing method comprises the following steps: the same batch of PC sheets (specification 20 x 50 mm) was used, the glue to be tested was adhered and cured sufficiently, test pieces were made and left at room temperature for 1 hour, the adhesion area was measured with a vernier caliper, the shear force was measured with a tensile tester, and specific experimental data are shown in table 3:
table 3 shows the shear strength test results of the adhesive of example 1
| Test piece | Shear strength MPa |
| Pure UV curing | 1.17 |
| UV curing and baking at +80 ℃ for 60min | 6.33 |
| Pure heat curing (110 ℃ baking 20 min) | 4.45 |
Example 2
In this embodiment, the components of the adhesive of the first embodiment are configured differently, and specific parts by weight of each component are shown in the following table.
Table 4 shows the composition of the adhesive in example 2
| The components | Name of the name | Parts by weight of |
| Cycloaliphatic epoxy resins | 6210G 6235 6202 | 23 |
| Bisphenol F type epoxy resin | South Asia 170 | 40 |
| Diluent agent | THFA IBOA ACMO | 26 |
| Photoinitiator | TPO | 1 |
| Thermal initiator | FXR1081 | 4 |
| Silane coupling agent | KH560 KH570 | 1 |
| Thiols | TMPMP PETMP | 5 |
2. The preparation method of the adhesive comprises the following steps:
(1) Mixing the formula amount of diluent, photoinitiator and thermal initiator together, and heating at 60 ℃ in a dark place to form a uniform transparent system;
(2) The uniform transparent system is cooled to below 18 ℃, the rest materials in the formula are added, the mixture is kept at a low temperature (below 18 ℃) and dispersed in a low-speed light-shielding way, the mixture is stirred and mixed uniformly (a stirrer can be used for stirring at a low speed or a three-roll mill can be used for grinding, light-shielding measures are taken), and the dual-curing epoxy adhesive is obtained after defoaming.
3. Results testing
The viscosity of the adhesive prepared by the steps is 2400CPS.
Table 5 shows the adhesive performance test results of example 2
Shear strength data:
the testing method comprises the following steps: the same batch of PC sheets (specification 20 x 50 mm) was used, the glue to be tested was adhered and cured sufficiently, test pieces were made and left at room temperature for 1 hour, the adhesion area was measured with a vernier caliper, the shear force was measured with a tensile tester, and specific experimental data are shown in table 6:
table 6 shows the shear strength test results for the adhesive of example 2
| Test piece | Shear strength MPa |
| Pure UV curing | 1.42 |
| UV curing and baking at +80 ℃ for 60min | 5.31 |
| Pure heat curing (110 ℃ baking 20 min) | 3.77 |
Example 3
In this example, the components of the adhesive of example one were used for different formulations, and the specific parts by weight of each component are shown in table 7.
TABLE 7 composition of adhesive in example 3
| The components | Name of the name | Parts by weight of |
| Cycloaliphatic epoxy resins | 621A-80 6265 | 23 |
| Bisphenol F type epoxy resin | South Asia 170 | 40 |
| Diluent agent | HEMA 4HBA IBOA | 29 |
| Photoinitiator | TPO | 1 |
| Thermal initiator | FXR1081 FXR1020 | 6 |
| Silane coupling agent | KH560 KH570 | 1 |
2. The preparation method of the adhesive comprises the following steps:
(1) Mixing the formula amount of diluent, photoinitiator and thermal initiator together, and heating at 60 ℃ in a dark place to form a uniform transparent system;
(2) The uniform transparent system is cooled to below 18 ℃, the rest materials in the formula are added, the mixture is kept at a low temperature (below 18 ℃) and dispersed in a low-speed light-shielding way, the mixture is stirred and mixed uniformly (a stirrer can be used for stirring at a low speed or a three-roll mill can be used for grinding, light-shielding measures are taken), and the dual-curing epoxy adhesive is obtained after defoaming.
3. Results testing
The viscosity of the adhesive prepared by the steps is 1800CPS.
Table 8 shows the shear strength test results for the adhesive of example 3
Shear strength data:
the testing method comprises the following steps: the same batch of PC sheets (specification 20 x 50 mm) was used, the glue to be tested was adhered and cured sufficiently, test pieces were made and left at room temperature for 1 hour, the adhesion area was measured with a vernier caliper, the shear force was measured with a tensile tester, and specific experimental data are shown in table 3:
table 8 shows the shear strength test results for the adhesive of example 3
| Test piece | Shear strength MPa |
| Pure UV curing | 1.66 |
| UV curing and baking at +80 ℃ for 60min | 5.63 |
| Pure heat curing (110 ℃ baking 20 min) | 5.12 |
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The dual-curing epoxy adhesive is characterized by comprising the following components in parts by weight:
2. the dual cure epoxy adhesive of claim 1 wherein the epoxy resin is bisphenol F type epoxy resin.
3. The dual cure epoxy adhesive of claim 1, wherein the epoxy acrylate oligomer is one or more of the long-standing chemical 621A-80, 6202, 6210g,6235, 6265.
4. The dual-curing epoxy adhesive according to claim 1, wherein the diluent is one or more of tetrahydrofuranyl acrylate, isobornyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate and morpholine acrylate.
5. A dual cure epoxy adhesive according to claim 1, wherein the photoinitiator is 1-hydroxycyclohexyl phenyl ketone and/or 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide.
6. The dual cure epoxy adhesive process of claim 1 wherein the thermal initiator is selected from the group consisting of low temperature latent modified amine epoxy curatives rich in FXR1081 and/or FXR 1020.
7. A dual cure epoxy adhesive according to claim 1, wherein the thiol is trimethylolpropane tris (3-mercaptopropionate) and/or pentaerythritol tetrakis (3-mercaptopropionate).
8. The dual cure epoxy adhesive of claim 1, wherein the silane coupling agent is gamma-glycidoxypropyl trimethoxysilane and/or gamma- (methacryloyloxy) propyl trimethoxysilane.
9. The dual cure epoxy adhesive of claim 1 wherein the adhesive cures by thermal curing or UV-before-thermal curing.
10. The method for preparing the dual-curing epoxy adhesive according to any one of claims 1 to 9, comprising the following steps:
(1) Mixing the formula amount of diluent, photoinitiator and thermal initiator together, and heating at 60 ℃ in a dark place to form a uniform transparent system;
(2) And cooling the uniform transparent system to below 18 ℃, adding the rest materials in the formula, keeping the temperature below 18 ℃ and keeping out of light, stirring and mixing uniformly at a low speed, and defoaming to obtain the final finished adhesive.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117264469A (en) * | 2023-11-23 | 2023-12-22 | 苏州凡赛特材料科技有限公司 | Delayed-curing UV adhesive for inkjet printing |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117264469A (en) * | 2023-11-23 | 2023-12-22 | 苏州凡赛特材料科技有限公司 | Delayed-curing UV adhesive for inkjet printing |
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