CN115947948B - Photo-curing composition and preparation method and application thereof - Google Patents
Photo-curing composition and preparation method and application thereof Download PDFInfo
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- CN115947948B CN115947948B CN202211624605.9A CN202211624605A CN115947948B CN 115947948 B CN115947948 B CN 115947948B CN 202211624605 A CN202211624605 A CN 202211624605A CN 115947948 B CN115947948 B CN 115947948B
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- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 238000000016 photochemical curing Methods 0.000 title abstract description 9
- 229920001971 elastomer Polymers 0.000 claims abstract description 28
- 239000005060 rubber Substances 0.000 claims abstract description 28
- -1 modified acrylic ester Chemical class 0.000 claims abstract description 13
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 19
- 239000003085 diluting agent Substances 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 229920000459 Nitrile rubber Polymers 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 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
- 238000000034 method Methods 0.000 claims description 4
- 239000013008 thixotropic agent Substances 0.000 claims description 4
- 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 description 3
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 claims description 3
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- LAIJAUHBAWLPCO-UHFFFAOYSA-N (4-tert-butylcyclohexyl) prop-2-enoate Chemical compound CC(C)(C)C1CCC(OC(=O)C=C)CC1 LAIJAUHBAWLPCO-UHFFFAOYSA-N 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
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 2
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000008033 biological extinction Effects 0.000 claims 1
- 239000013530 defoamer Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000010292 electrical insulation Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 14
- 238000001723 curing Methods 0.000 description 13
- 239000004642 Polyimide Substances 0.000 description 10
- 229920001721 polyimide Polymers 0.000 description 10
- 229910000679 solder Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- PMMYEEVYMWASQN-DMTCNVIQSA-N Hydroxyproline Chemical compound O[C@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-DMTCNVIQSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention provides a photo-curing composition, a preparation method and application thereof, and provides rubber modified acrylic ester as shown in formula I, wherein the photo-curing composition containing the rubber modified acrylic ester can be cured under the condition of a UV cold light source and has a good surface drying effect; the electrical insulation performance is good, and the low water absorption rate can be still maintained under the long-term high-temperature high-humidity condition or the continuous water soaking condition; has excellent adhesion to PI substrate and high reliability.
Description
Technical Field
The invention belongs to the technical field of high molecular functional materials, and particularly relates to a photo-curing composition, a preparation method and application thereof.
Background
In recent years, under the background of increasing demands for intelligent devices, a large number of flexible circuit boards (FPCs) are used for the intelligent devices in order to pursue light weight, flexibility, high efficiency and the like. The FPC and the traditional PCB hard board surface are exposed with welding spots, and the welding spots are required to be covered and protected. The traditional PCB hard board adopts solvent type or UV type three-proofing paint to protect welding spots, however, the paint film has too high rigidity and is not suitable for flexible FPC. On the other hand, the solder joint protective adhesive for the FPC is also required to have enough adhesive force on a Polyimide (PI) film of the FPC, and failure phenomena such as cracking, interface debonding and the like can not occur under extreme conditions. In addition, the solder joint protective adhesive is also required to have excellent electrical insulation performance, so that the influence of the external environment on the FPC circuit is prevented. The welding spot protective adhesive has good self-insulation performance, and has certain requirements on water absorption and water vapor transmittance so as to isolate external water from penetrating into welding spots to influence the electrical performance. At present, the glue of the solder joint protective glue is usually cured by adopting a high-efficiency ultraviolet curing method. From the perspective of efficient production, the long-wave cold light source ultraviolet light curing has the advantages of more energy conservation and high efficiency compared with the traditional mercury lamp low-wave band curing, but the limitation of the long-wave cold light source ultraviolet light curing is that the solder joint protective adhesive is difficult to surface dry after curing, and dust is easy to be stained to influence the appearance. The ultraviolet light curing solder joint protective adhesive on the market at present is difficult to solve the problems at the same time, such as cracking or interfacial adhesive opening of part of existing or high-low temperature aging impact adhesives, overhigh water absorption, overhigh water vapor transmittance or no surface drying after curing, and the like. These problems limit the application of ultraviolet curing adhesive in the field of solder joint protection, and greatly reduce the production efficiency of flexible circuit boards.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. To this end, the first aspect of the present invention proposes a rubber-modified acrylate capable of improving the reactivity.
In a second aspect, the present invention provides a photocurable composition comprising said rubber modified acrylate.
In a third aspect of the invention, a process for preparing the rubber modified acrylate is provided.
In a fourth aspect the present invention provides the use of said rubber modified acrylate and/or said photocurable composition.
According to a first aspect of the present invention, there is provided a rubber modified acrylate of formula I:
wherein R is 1 Selected from-H, -CH 3 ；R 2 Comprises any one of bisphenol A epoxy resin residue, bisphenol F epoxy resin residue or hydrogenated bisphenol A epoxy resin residue with partial deletion of epoxy groups at two ends; m is selected from any integer from 1 to 60; n is selected from any integer from 1 to 6;
R 3 selected from:
wherein, in the step (1),the mass fraction of (2) is 20% -65%; />Is->And->5-15% of the sum of the mass; (2) In (I)>The mass fraction of (2) is 20-65%.
In some embodiments of the invention, in (1),is 20% by mass; />Is thatAnd->10% of the sum of the masses; (2) In (I)>Is 20% by mass.
In some preferred embodiments of the present invention, the rubber modified acrylate of formula I is selected from:
according to a second aspect of the present invention, a photocurable composition comprising said rubber modified acrylate is presented.
In some embodiments of the invention, the photocurable composition comprises: 30 to 60 percent of rubber modified acrylic ester, 35 to 65 percent of (methyl) acrylic acid reactive diluent, 0.5 to 5 percent of additive and 0.5 to 4 percent of photoinitiator.
In some preferred embodiments of the present invention, the photocurable composition comprises: 38 to 58 percent of rubber modified acrylic ester, 45 to 60 percent of (methyl) acrylic acid reactive diluent, 0.5 to 5 percent of additive and 0.5 to 4 percent of photoinitiator.
In some more preferred embodiments of the present invention, the (meth) acrylic reactive diluent comprises at least one of isobornyl acrylate, isobornyl methacrylate, benzyl acrylate, isodecyl acrylate, dicyclopentenyl ethoxylated methacrylate, 2-phenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, or cyclotrimethylolpropane formal acrylate; preferably, the (meth) acrylic reactive diluent comprises at least one of isobornyl acrylate or 2-phenoxyethyl acrylate.
In some more preferred embodiments of the present invention, the photoinitiator comprises at least one of diphenyl- (2, 4, 6-trimethylbenzoyl) phosphine oxide, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, isopropylthioxanthone, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ]; preferably, the photoinitiator comprises a mixture of diphenyl- (2, 4, 6-trimethylbenzoyl) phosphine oxide, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, and 1,1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ].
In some more preferred embodiments of the present invention, the additive comprises at least one of a thixotropic agent, an antifoaming agent, a leveling agent, a matting powder; preferably, the additives include thixotropic agents and matting agents.
According to a third aspect of the present invention, there is provided a method for producing the rubber-modified acrylic ester, comprising the steps of:
s1: mixing carboxyl-terminated nitrile rubber, epoxy resin and a catalyst to react, so as to prepare a prepolymer;
s2: and (3) adding a polymerization inhibitor into the prepolymer prepared in the step (S1) after cooling, and dropwise adding acrylic acid for reaction until the acid value is less than or equal to 3mg KOH/g, thereby preparing the rubber modified acrylic ester.
In some embodiments of the invention, the reaction temperature of S1 is 100℃to 130℃for a period of 3h to 6h.
In some preferred embodiments of the invention, the reaction temperature of S2 is 70℃to 90 ℃.
In some more preferred embodiments of the present invention, the epoxy resin comprises any one of bisphenol a epoxy resin, bisphenol F epoxy resin, or hydrogenated bisphenol a epoxy resin.
In some more preferred embodiments of the present invention, the polymerization inhibitor includes any one of hydroquinone, p-hydroxyanisole or 2, 6-di-tert-butyl-p-cresol.
In some more preferred embodiments of the invention, the catalyst comprises at least one of triphenylphosphine, N dimethylbenzylamine, or triethylamine.
In some more preferred embodiments of the present invention, in S1, the molar ratio of the carboxyl terminated nitrile rubber to the epoxy resin is 1 (2-3); preferably 1 (2) to 2.2).
In some more preferred embodiments of the invention, in S2, the molar ratio of the carboxylated nitrile rubber to the acrylic acid is 1: (1-2); preferably 1: (1-1.1).
According to a fourth aspect of the present invention, there is provided the use of said rubber modified acrylate and/or said photocurable composition in flexible circuit boards.
The beneficial effects of the invention are as follows:
1. the rubber modified acrylic ester has high reactivity.
2. The photo-curing composition has the following technical effects: (1) The paint can be cured under the condition of a UV cold light source and has a good surface drying effect; (2) The electrical insulation performance is good, and the low water absorption rate can be still maintained under the long-term high-temperature high-humidity condition or the continuous water soaking condition; (3) excellent adhesion to PI substrate and high reliability. The composition has the advantages that the composition can be matched with the use requirement of the solder joint protective adhesive of the flexible circuit board, and the reliability and the service life of the solder joint protective adhesive can be improved.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
In the following examples or comparative examples, the rubber modified acrylate was synthesized as:
the synthesis scheme of the rubber modified acrylic ester is as follows, 400g of carboxyl terminated nitrile liquid rubber (Hypro 1300X 47), 82.5g of hydrogenated epoxy resin (Mitsubishi, YX 8000) and 2g of triphenylphosphine are added into a reaction vessel for reaction for 5h at 100 ℃. After the temperature is reduced to 80 ℃, 0.4g of p-hydroxyanisole is added, then 14.42g of acrylic acid is slowly dripped into the mixture, and the mixture reacts until the acid value is lower than 3mg KOH/g, thus obtaining the rubber modified acrylic ester S-1 (formula I-A).
Examples 1 to 5 and comparative examples 1 to 5
Examples 1 to 5 and comparative examples 1 to 5 an adhesive was prepared, the specific amounts of the components being shown in Table 1, the specific procedure being: adding the photoinitiator and the reactive diluent into a reactor equipped with a mechanical stirrer and a heating sleeve, stirring, continuing to add the acrylic resin after the photoinitiator is completely dissolved in the reactive diluent, stirring until the resin is uniformly dispersed, adding the additive, stirring for 20min at a high speed of 1200-2000 rpm, and finally vacuum defoaming for 3min to obtain the photocuring composition.
CN9014: rubber modified acrylates supplied by Sartomer company;
CN8888: polyurethane acrylates supplied by Sartomer company;
BR-641E: rubber modified acrylates supplied by Bomar company;
EP400V: rubber modified acrylates supplied by Kaneka corporation;
TEAI-1000: rubber modified acrylates supplied by Nippon-soda company;
IBXA: reactive diluents supplied by osaka organic company;
CTFA: reactive diluents supplied by Sartomer company;
photoinitiators supplied by the company TPO, 819, 127:IGM;
TS720: fumed silica thixotropic agent available from CABOT corporation;
ACEMATT OK607: matting powder supplied by Evonik corporation.
TABLE 1
Test examples
The compositions prepared in the examples and comparative examples were tested for their properties. Wherein:
the surface dry test method comprises the following steps: the composition was cured to a 2mm thick slab and cured under a 365nm or 395nm UV-LED lamp, and its surface drying properties were evaluated by touch.
Hardness: : the composition was cured to a gel block with a thickness of 2mm, cured under a UV-LED lamp at 365nm or 395nm, and after 2 hours of constant temperature at 25℃the hardness was measured with a Shore durometer
Shear strength test: and fixing the PI film on a PC sheet, coating the photo-curing composition on the PI film, then curing under a 365nm or 395nm UV-LED lamp after lamination of the PC sheet, and testing the shearing strength of the PC substrate to the PI substrate, wherein the adhesive thickness is 0.2 mm.
Water absorption test: after curing the photocurable composition, cut into 60mm X2 mm specimens, and the initial weight m was recorded 0 Sample weight m after 24h is tested, and calculated by a formula
c-the water absorption mass fraction of the sample, the numerical value being expressed in%
Volume resistivity test: the photocurable composition was cured to a volume resistivity after 1 minute at 500V measured at a thick film of 1mm to 2 mm.
The test results are shown in Table 2:
table 2 results of adhesive Property test of the compositions
Note that: surface dryness is very good; "O" slightly tacky; "×" no surface dry. Cold and hot impact, "NG" colloid cracks.
The photocuring compositions prepared in the embodiments 1-5 have the advantages of high curing speed and high efficiency through ultraviolet curing, and the cured composition has the advantages of proper shear strength, adhesion force (the shear strength test is that the interface between the PI and the composition is debonded) of more than 2MPa, good insulating property and water absorption of less than 0.5 percent. In examples 1 to 3, the effect of the reactive diluent on the adhesion of the composition on PI is shown in that the composition contains IBXA, so that the adhesion strength can be improved, but the excessive amount of IBXA leads to excessively high colloid hardness, reduced flexibility, and easy colloid cracking or PI substrate interface adhesive opening and debonding in the cold and hot impact process, so that the hardness and modulus of the system can be reduced by the IBXA in combination with CTFA, and the better adhesion performance after aging test is ensured. In examples 1 and 4, the surface dryness after curing with a cold light source was slightly improved due to the red shift in the 819 and 127 mixed absorption spectra after the addition of 127 initiator. In examples 4 and 5, after the matting agent was added to the hydrophobic aliphatic acrylate S1 having a good surface drying property, the adhesive property of the entire composition was slightly lowered, but the surface drying property was improved from slightly tacky to good surface drying property and the insulating property was further improved.
Compared with the examples, the polybutadiene acrylate is adopted in the comparative examples 1-4, and the adhesion to PI is lower than that of S-1, which is due to the cyano group in the S-1 polyacrylonitrile structure, and the cyano group is introduced into the rubber chain segment, so that the polarity of the main chain segment is improved, and the adhesion to the base material is improved; on the other hand, the surface drying performance of the resin is optimized in comparison with the surface drying performance of the resin S-1, which is not easy to dry and is slightly adhered due to the structure of the hydrogenated bisphenol A epoxy resin contained in the S-1. In comparative example 5, the conventional polyurethane acrylate has good adhesion, but the thermal shock resistance is still insufficient; furthermore, the barrier ability of such resins to water (water absorption higher than 1.5%) remains a problem compared to rubber modified hydrophobic acrylates.
In conclusion, the composition is suitable for the solder joint protection of the flexible circuit board, can withstand the influence of complex environmental conditions such as cold and hot impact, high temperature and high humidity, has excellent insulating property, has the effects of cold light source solidification and good surface dryness, and can improve and solve the problems of high water absorption rate, poor surface dryness, ageing and glue spreading and the like of partial UV solder joint protection glue on the market.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A rubber modified acrylate of the formula:
wherein m is selected from any integer from 1 to 60; n is selected from any integer from 1 to 6;
wherein,the mass fraction of (2) is 20% -65%; />Is->And->5-15% of the sum of the mass; (2) In (I)>The mass fraction of (2) is 20-65%.
2. A photocurable composition comprising the rubber-modified acrylate of claim 1.
3. The photocurable composition according to claim 2, characterized in that: the photocurable composition comprises: 30 to 60 percent of rubber modified acrylic ester, 35 to 65 percent of (methyl) acrylic acid reactive diluent, 0.5 to 5 percent of additive and 0.5 to 4 percent of photoinitiator.
4. A photocurable composition according to claim 3, characterized in that: the (meth) acrylic reactive diluent includes at least one of isobornyl acrylate, isobornyl methacrylate, benzyl acrylate, isodecyl acrylate, dicyclopentenyl ethoxylated methacrylate, 2-phenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, or cyclotrimethyolpropane formal acrylate.
5. A photocurable composition according to claim 3, characterized in that: the photoinitiator comprises at least one of diphenyl- (2, 4, 6-trimethylbenzoyl) phosphine oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, benzophenone, 2-benzyl-2-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, isopropylthioxanthone, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ].
6. A photocurable composition according to claim 3, characterized in that: the additive comprises at least one of thixotropic agent, defoamer, flatting agent and extinction powder.
7. A process for the preparation of the rubber modified acrylate of claim 1 wherein: the method comprises the following steps:
s1: mixing carboxyl-terminated nitrile rubber, epoxy resin and a catalyst to react, so as to prepare a prepolymer;
s2: and (3) adding a polymerization inhibitor into the prepolymer prepared in the step (S1) after cooling, and dropwise adding acrylic acid for reaction until the acid value is less than or equal to 3mg KOH/g, thereby preparing the rubber modified acrylic ester.
8. The method for producing a rubber-modified acrylic ester according to claim 7, characterized in that: in S1, the mol ratio of the carboxyl-terminated nitrile rubber to the epoxy resin is 1 (2-3).
9. The method for producing a rubber-modified acrylic ester according to claim 7, characterized in that: in S2, the molar ratio of the carboxyl terminated nitrile rubber to the acrylic acid is 1: (1-2).
10. Use of the rubber modified acrylate of claim 1 and/or the photocurable composition of any one of claims 2-6 in flexible circuit boards.
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