CN114316879A - UV (ultraviolet) shading adhesive with good hydrophobicity and low moisture permeability and preparation method thereof - Google Patents
UV (ultraviolet) shading adhesive with good hydrophobicity and low moisture permeability and preparation method thereof Download PDFInfo
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- CN114316879A CN114316879A CN202111618095.XA CN202111618095A CN114316879A CN 114316879 A CN114316879 A CN 114316879A CN 202111618095 A CN202111618095 A CN 202111618095A CN 114316879 A CN114316879 A CN 114316879A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 38
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 38
- 230000035699 permeability Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 229920002635 polyurethane Polymers 0.000 claims abstract description 17
- 239000004814 polyurethane Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 5
- QWYSJTTWCUXHQO-UHFFFAOYSA-N [F].OC(=O)C=C Chemical compound [F].OC(=O)C=C QWYSJTTWCUXHQO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012949 free radical photoinitiator Substances 0.000 claims abstract description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 25
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 14
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- 238000011049 filling Methods 0.000 claims description 11
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 8
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 7
- 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 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 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 5
- 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 5
- 150000002009 diols Chemical class 0.000 claims description 5
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 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 4
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-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
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 claims description 4
- UACSZOWTRIJIFU-UHFFFAOYSA-N hydroxymethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCO UACSZOWTRIJIFU-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- -1 polyethylene adipate Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical compound CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 0.000 claims description 2
- FWYUJGXEYOXHRJ-UHFFFAOYSA-N fluoromethyl prop-2-enoate Chemical compound FCOC(=O)C=C FWYUJGXEYOXHRJ-UHFFFAOYSA-N 0.000 claims description 2
- GJIDOLBZYSCZRX-UHFFFAOYSA-N hydroxymethyl prop-2-enoate Chemical compound OCOC(=O)C=C GJIDOLBZYSCZRX-UHFFFAOYSA-N 0.000 claims description 2
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000921 polyethylene adipate Polymers 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 239000012856 weighed raw material Substances 0.000 claims description 2
- ATYCHUNXPSPHLD-UHFFFAOYSA-N 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylbutan-1-one Chemical compound CCC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 ATYCHUNXPSPHLD-UHFFFAOYSA-N 0.000 claims 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical group CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims 1
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 claims 1
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000000516 sunscreening agent Substances 0.000 claims 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 description 11
- 239000003292 glue Substances 0.000 description 10
- 239000002313 adhesive film Substances 0.000 description 9
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- NSFGOWGWLHAJPC-UHFFFAOYSA-N COCOC.C(C=C)(=O)O Chemical compound COCOC.C(C=C)(=O)O NSFGOWGWLHAJPC-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a UV shading adhesive with good hydrophobicity and low moisture permeability and a preparation method thereof. The UV light-shielding adhesive is prepared from the following components in parts by mass: 30-50 parts of modified polyurethane acrylate oligomer, 30-40 parts of non-fluorine acrylate monomer, 10-20 parts of fluorine-containing acrylic monomer, 5-10 parts of double-bond-containing polyhedral oligomeric silsesquioxane, 1-8 parts of free radical photoinitiator, 1-5 parts of adhesion promoter and 0.1-1 part of black powder. According to the invention, cage-type silsesquioxane is introduced into the modified polyurethane acrylate oligomer, and double-bond cage-type silsesquioxane and fluorocarbon side chain-containing acrylate are introduced into the UV monomer. The UV light-shielding adhesive has good rigidity, thermal stability, water repellency and hardness, and also has good moisture-heat resistance, moisture resistance and scratch resistance.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a UV shading adhesive which is mainly applied to shading and moistureproof of the side edges of an LCD (liquid crystal display) and an OLED (organic light emitting diode) and has good hydrophobicity and low moisture permeability and a preparation method thereof.
Background
Modern high technology is rapidly developed, display screens of electronic products such as mobile phones, flat panels and notebook computers are larger and larger, but frames are narrower and narrower, and sweat stains on hands of corresponding users, residual cosmetics or water vapor in a humid environment can easily enter LCD and OLED display modules and cause damage. This places higher demands on the water repellency, moisture permeability, resistance to cosmetic corrosion, etc. of the UV side edge light-screening adhesive. Therefore, some modification of the conventional UV light-screening paste is necessary.
At present, most of the existing cage type silsesquioxane (POSS) modified UV adhesives are modified by using POSS as a UV monomer or additive. Moreover, most of the prior art focuses on the problems of hardness, abrasion resistance and water drop angle of the polymer caused by the polyhedral oligomeric silsesquioxane POSS, and the research on the humidity resistance and the heat resistance of the polymer is only focused on. For example, patent CN201910925846.9 proposes that a high-hardness and low-haze UV hardening solution is prepared from self-made POSS polymaleimide and raw materials such as acrylate prepolymer and monomer, and only focuses on several properties of hardness, light transmittance and haze. Patent CN113214770A proposes that a thermal acid generator and an acid-induced color-changing powder are introduced into a UV glue, and the UV glue is heated to become black after being cured, so that the light-shielding property and the curing depth of the UV black glue are mainly studied, and the humidity resistance and the heat resistance of the UV black glue are not studied. In patent CN110184024A, the reliability test of 85 ℃/85% RH of the UV black adhesive prepared by using the aliphatic urethane acrylate oligomer with better water resistance as the main resin only reaches 500h, and the humidity resistance of the UV black adhesive is not further studied. Compared with the method of simultaneously chemically modifying the oligomer by POSS and using POSS as a UV monomer, the UV adhesive prepared by the traditional technology has obviously insufficient adhesive solution compatibility, adhesive film surface water repellency and moist heat resistance.
Therefore, it is an urgent problem in the art to overcome the defects that the existing light-shielding adhesive has only good light-shielding property and curing depth and does not have excellent moisture-heat-resistance and moisture-resistance.
Disclosure of Invention
The invention provides a UV shading adhesive with good hydrophobicity and low moisture permeability and a preparation method thereof, aiming at solving the problem that the functional surface of the shading adhesive in the prior art is poor in moisture resistance, heat resistance and moisture resistance. The UV shading glue has the advantages of good hardness, good scratch resistance, low surface energy and good moisture and heat resistance.
The invention provides a hydrophobic UV shading adhesive with good moisture permeability, which is prepared from the following components in parts by mass:
preferably, the modified polyurethane acrylate oligomer is prepared from the following components in parts by mass:
preferably, the aliphatic diisocyanate is isophorone diisocyanate (IPDI) and/or Hexamethylene Diisocyanate (HDI).
Preferably, the dihydric alcohol is at least one of polycaprolactone diol, polypropylene glycol or polyethylene adipate glycol-1, 4-butanediol diol, and the relative molecular mass is 500-2000.
Preferably, the hydroxyl-containing cage-type silsesquioxane has a structure shown in formula (1):
commercially available products are Hybrid Plastics SO1450, SO1455, SO1458, AL0104, AL 0130;
preferably, the hydroxy acrylate monomer is at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxymethyl methacrylate, hydroxymethyl acrylate or 4-hydroxybutyl acrylate.
Preferably, the non-fluorine acrylic monomer is at least one of isobornyl acrylate, 4-morpholine acrylate, cyclotrimethylolpropane formal acrylate, dicyclopentenyl acrylate, tricyclodecane dimethanol diacrylate or tetrahydrofuran acrylate.
Preferably, the fluorine-containing acrylic monomer is 13 fluoroacrylate and/or 13 fluoromethylacrylate.
Preferably, the double bond-containing cage type silsesquioxane structure is represented by the formula (2):
commercially available products are Hybrid Plastics MA0701, MA0702, MA0703, MA0706, MA0716, MA0717, MA0718, MA0719, and MA 0734;
preferably, the radical type photoinitiator is 2-hydroxy-2-methyl-1-phenyl acetone (1173), 1-hydroxycyclohexyl phenyl ketone (184), -methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone (907), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (TPO-L), 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone (910), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone (659) and phenylbis (2, one or more than two of 4, 6-trimethylbenzoyl) phosphine oxide (819).
Preferably, the adhesion promoter is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and/or gamma-methacryloxypropyl trimethoxy silane.
Preferably, the black powder is at least one of carbon black, titanium black or metal complex black.
The invention also provides a preparation method of the hydrophobic UV shading adhesive with good moisture permeability and low moisture permeability, which comprises the following steps:
step 1, weighing the raw materials according to the proportion of the hydrophobic UV shading adhesive with good moisture permeability and low moisture permeability: modified polyurethane acrylate oligomer, fluorine-containing acrylic acid monomer, non-fluorine acrylate monomer, double-bond-containing polyhedral oligomeric silsesquioxane, adhesion promoter, free radical photoinitiator and black powder;
step 2: adding the weighed raw materials into a planetary stirrer, and stirring, dissolving, mixing and dispersing for 3-4 hours in a vacuum state to uniformly dissolve and disperse all the raw materials;
and 3, screening and filtering the uniformly dissolved and dispersed raw materials by more than 500 meshes, then carrying out vacuum defoaming treatment, and filling.
Preferably, the preparation of the modified urethane acrylate oligomer comprises the following steps:
1. reacting the aliphatic diisocyanate with the dihydric alcohol under the action of the catalyst dibutyltin dilaurate at 70-90 ℃ for 1-2 hours to obtain a polyurethane prepolymer;
2. dropwise adding the hydroxyl-containing polyhedral oligomeric silsesquioxane into a reactor containing the polyurethane prepolymer at 70-90 ℃, and reacting for 1-3 hours to obtain a modified polyurethane prepolymer;
3. and adding the hydroxyl acrylic monomer added with the p-hydroxy toluidine and the dibutyltin dilaurate into the reactor at 60-75 ℃, and reacting for 2-4 hours to obtain the modified polyurethane acrylate oligomer.
Compared with the prior art, the invention has the following beneficial effects:
the main resin-modified polyurethane acrylate oligomer is prepared by introducing cage type silsesquioxane; and cage type silsesquioxane containing double bonds and acrylic ester containing fluorocarbon side chains are introduced into the UV monomer. Therefore, the shading glue disclosed by the invention can keep better rigidity, thermal stability, water repellency and hardness, and can also ensure that the UV glue still has excellent moisture resistance in a high-temperature high-humidity damp-heat environment for a long time. In addition, the higher hardness provides the UV glue with good scratch resistance.
Drawings
FIG. 1 is a schematic view of the microstructure of the UV light-shielding adhesive according to the embodiment of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples. The present invention includes the following examples but is not limited thereto.
Example 1
1. Synthesizing a polyurethane prepolymer:
at 80 ℃, reacting 20 parts of isophorone diisocyanate (IPDI) with 50 parts of polypropylene glycol with the molecular weight of 1000 for 2 hours under the action of 0.1 part of dibutyltin dilaurate serving as a catalyst to obtain a polyurethane prepolymer;
2. synthesizing a modified polyurethane prepolymer:
at 80 ℃, dropwise adding 7 parts of hydroxyl-containing polyhedral oligomeric silsesquioxane SO1450 into a reactor containing a polyurethane prepolymer, and reacting for 1 hour to obtain a modified polyurethane prepolymer;
3. synthesizing a modified polyurethane acrylate oligomer:
25 parts of 4-hydroxybutyl acrylate to which 0.01 part of p-hydroxytoluene and 0.05 part of dibutyltin dilaurate were added was charged into the reactor at 65 ℃ and reacted for 2 hours to obtain a modified urethane acrylate oligomer.
4. Preparing the UV shading adhesive with good hydrophobicity and low moisture permeability:
adding 40 parts of modified polyurethane acrylate oligomer, 10 parts of 13 fluoroacrylate, 30 parts of isobornyl acrylate, 5 parts of tricyclodecane dimethanol diacrylate, 8 parts of double-bond-containing polyhedral oligomeric silsesquioxane MA0701, 2 parts of 1-hydroxycyclohexyl phenyl ketone (184), 3 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), 1 part of gamma-methacryloxypropyl trimethoxysilane and 0.1 part of titanium black powder into a planetary stirrer, stirring, dissolving, mixing and dispersing under a vacuum state for 4 hours, after all raw materials are dissolved and uniformly dispersed, screening and filtering by a 500-mesh sieve, carrying out vacuum defoaming treatment, and finally filling by a filling machine.
Example 2
1. Synthesizing a polyurethane prepolymer:
at 90 ℃, reacting 30 parts of Hexamethylene Diisocyanate (HDI) and 40 parts of polycaprolactone diol with the molecular weight of 1000 for 1 hour under the action of 0.07 part of catalyst dibutyltin dilaurate to obtain a polyurethane prepolymer;
2. synthesizing a modified polyurethane prepolymer:
at 90 ℃, dropwise adding 10 parts of hydroxyl-containing polyhedral oligomeric silsesquioxane SO1455 into a reactor containing a polyurethane prepolymer, and reacting for 2 hours to obtain a modified polyurethane prepolymer;
3. synthesizing a modified polyurethane acrylate oligomer:
30 parts of hydroxyethyl methacrylate to which 0.01 part of p-hydroxytoluene and 0.03 part of dibutyltin dilaurate were added to the reactor at 75 ℃ and reacted for 3 hours to obtain a modified urethane acrylate oligomer.
4. Preparing the UV shading adhesive with good hydrophobicity and low moisture permeability:
50 parts of modified polyurethane acrylate oligomer, 15 parts of 13-fluoro methacrylate, 30 parts of cyclotrimethylolpropane methylal acrylate, 10 parts of dicyclopentenyl acrylate, 10 parts of double-bond-containing polyhedral oligomeric silsesquioxane MA0706, 3 parts of 1-hydroxycyclohexyl phenyl ketone (184), 5 parts of phenyl bis (2,4, 6-trimethyl benzoyl) phosphine oxide (819), 5 parts of gamma-methacryloxypropyl trimethoxy silane and 0.6 part of carbon black powder are added into a planetary stirrer, stirred, dissolved, mixed and dispersed in a vacuum state for 3 hours, after all raw materials are dissolved and uniformly dispersed, the raw materials are screened and filtered by a 500-mesh sieve, subjected to vacuum defoaming treatment and finally filled by a filling machine.
Example 3
1. Synthesizing a polyurethane prepolymer:
at 70 ℃, reacting 25 parts of Hexamethylene Diisocyanate (HDI) and 45 parts of polycaprolactone diol with the molecular weight of 2000 for 1.5 hours under the action of 0.04 part of catalyst dibutyltin dilaurate to obtain a polyurethane prepolymer;
2. synthesizing a modified polyurethane prepolymer:
dropwise adding 4 parts of hydroxyl-containing polyhedral oligomeric silsesquioxane SO1455 into a reactor containing a polyurethane prepolymer at 70 ℃, and reacting for 3 hours to obtain a modified polyurethane prepolymer;
3. synthesizing a modified polyurethane acrylate oligomer:
at 60 ℃, 20 parts of hydroxymethyl methacrylate added with 0.01 part of p-hydroxy toluidine and 0.01 part of dibutyltin dilaurate is added into a reactor and reacted for 4 hours to obtain the modified urethane acrylate oligomer.
4. Preparing the UV shading adhesive with good hydrophobicity and low moisture permeability:
adding 30 parts of modified polyurethane acrylate oligomer, 20 parts of 13 fluoroacrylate, 20 parts of cyclotrimethylolpropane methylal acrylate, 10 parts of dicyclopentenyl acrylate, 5 parts of double-bond-containing polyhedral oligomeric silsesquioxane MA0706, 0.5 part of 1-hydroxycyclohexyl phenyl ketone (184), 0.5 part of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819), 3 parts of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 1 part of titanium black powder into a planetary stirrer, stirring, dissolving, mixing and dispersing for 3.5 hours in a vacuum state, sieving and filtering by a sieve of 500 meshes after all raw materials are dissolved and uniformly dispersed, defoaming, and finally filling by a filling machine.
Comparative example 1
1. Synthesizing a polyurethane prepolymer:
at 85 ℃, reacting 25 parts of Hexamethylene Diisocyanate (HDI) and 50 parts of polycaprolactone diol with the molecular weight of 2000 for 2 hours under the action of 0.1 part of catalyst dibutyltin dilaurate to obtain a polyurethane prepolymer;
2. polyurethane acrylate oligomer synthesis:
25 parts of methylol methacrylate to which 0.01 part of p-hydroxytoluene ether and 0.05 part of dibutyltin dilaurate were added to a reactor at 65 ℃ and reacted for 2 hours to obtain a urethane acrylate oligomer.
3. Preparing UV shading glue:
adding 40 parts of urethane acrylate oligomer, 45 parts of cyclotrimethylolpropane formal acrylate, 15 parts of dicyclopentenyl acrylate, 1 part of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 2 parts of 1-hydroxycyclohexyl phenyl ketone (184), 3 parts of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819) and 0.2 part of titanium black powder into a planetary stirrer, stirring, dissolving, mixing and dispersing for 4 hours in a vacuum state, screening and filtering by a 500-mesh sieve after all raw materials are dissolved and uniformly dispersed, and finally filling by a filling machine.
Comparative example 2
1. Synthesizing a polyurethane prepolymer:
at 80 ℃, reacting 20 parts of isophorone diisocyanate (IPDI) with 50 parts of polypropylene glycol with the molecular weight of 1000 for 2 hours under the action of 0.1 part of dibutyltin dilaurate serving as a catalyst to obtain a polyurethane prepolymer;
2. polyurethane acrylate oligomer synthesis:
30 parts of 4-hydroxybutyl acrylate to which 0.01 part of p-hydroxytoluene and 0.05 part of dibutyltin dilaurate were added was charged into a reactor at 65 ℃ and reacted for 2 hours to obtain a urethane acrylate oligomer.
3. Preparing UV shading glue:
adding 40 parts of urethane acrylate oligomer, 50 parts of isobornyl acrylate, 8 parts of tricyclodecane dimethanol diacrylate, 1 part of gamma-methacryloxypropyltrimethoxysilane, 2 parts of 1-hydroxycyclohexyl phenyl ketone (184), 3 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO) and 0.1 part of titanium black powder into a planetary stirrer, stirring, dissolving, mixing and dispersing for 4 hours in a vacuum state, screening and filtering through a 500-mesh sieve after all raw materials are dissolved and uniformly dispersed, and finally filling by a filling machine.
Researches show that the cage-type silsesquioxane (POSS) has extremely low surface energy, the tetragonal structure can increase the surface micro roughness of the polymer and improve the surface hydrophobicity, and the cage-shaped structure and Si-O-Si bonds with higher bond energy can endow the polymer with excellent thermal stability. Meanwhile, various reactive groups or non-reactive groups can be connected to the periphery of the POSS, different reactions and functionalities can be endowed to the POSS, and if a large number of methyl groups are connected, the hydrophobicity of the POSS is greatly improved. In general, excellent moist heat resistance can be imparted to the polymer.
According to the UV adhesive prepared by the invention, double-bond-containing cage-type silsesquioxane and fluorocarbon side chain-containing acrylate are introduced into a UV monomer, and the cage-type silsesquioxane with larger particle size and the fluorocarbon side chain-containing acrylate form a micro rough structure (shown in figure 1) on the surface of the UV adhesive after film forming, wherein the micro rough structure is similar to a microstructure formed by protrusions and villi on the surface of lotus leaves and has a hydrophobic structure similar to the surface of the lotus leaves. Simultaneously, the components of constructing the microcosmic rough structure are all nonpolar functional groups with low surface energy, so that the surface energy of the adhesive film is greatly reduced, the water contact angle of the adhesive film is greatly improved, the contact area of water vapor and the adhesive film is reduced, and the whole moisture-proof and moisture-proof performance of the UV adhesive is greatly improved.
The UV adhesive prepared in the embodiment 1-3 and the comparative example 1-2 of the invention is prepared by using a 405nm LED-UV lamp at 500mJ/cm2The energy was used for curing, and the adhesive film was subjected to a performance test, the results of which are shown in table 1. Wherein the performance test standards are as follows:
hardness: reference GB/T2411-;
water contact angle: reference GB/T30693-;
water absorption: referring to ASTM D570-98 standard, measuring the water absorption of the adhesive film after being soaked in distilled water at 25 ℃ for 24 hours;
moisture permeability: referring to JIS Z0208 standard, covering adhesive film on 200mL beaker with proper amount of color-changing water-absorbing silica gel/anhydrous calcium chloride, sealing, weighing the weight change of the silica gel/anhydrous calcium chloride before and after placing for 24h under 40 ℃/90% RH condition by using an analytical balance, and calculating moisture permeability;
and (3) reliability testing: referring to GB/T2423.3 constant temperature and humidity test, designing 85 ℃/85% RH/1000H reliability test, and observing whether the adhesive film cracks, degums and the like after the reliability test.
The hardness of the traditional UV shading adhesive in proportion is improved to a certain extent, so that the scratch resistance of the adhesive layer is correspondingly improved; the water contact angle is greatly improved, so that the contact area between the water vapor in the humid air and the adhesive layer is greatly reduced, the water absorption rate and the moisture permeability of the adhesive layer are directly and greatly reduced, and the super-hydrophobic and low-moisture-permeability gain is obtained on the adhesive layer; meanwhile, the reliability test of 85 ℃/85% RH is carried out for 1000h, which also shows that the humidity resistance of the adhesive layer is greatly increased. As can be seen from the results of the performance test of the adhesive film, the UV shading adhesive provided by the invention has good hydrophobicity and low moisture permeability and has unexpected beneficial effects.
While the present invention has been described in detail with reference to the embodiments, those skilled in the art may make various changes or modifications to the embodiments, and such changes and modifications should fall within the scope of the present invention.
Claims (10)
1. The UV shading adhesive with good hydrophobicity and low moisture permeability is prepared from the following components in parts by mass:
2. the UV light-shielding adhesive of claim 1, wherein the modified polyurethane acrylate oligomer is prepared from the following components in parts by mass:
3. the UV-opaque past of claim 2, wherein said aliphatic diisocyanate is isophorone diisocyanate and/or hexamethylene diisocyanate; the dihydric alcohol is at least one of polycaprolactone diol, polypropylene glycol or polyethylene adipate glycol-1, 4-butanediol glycol, and the relative molecular mass is 500-2000; the hydroxyl acrylic ester monomer is at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxymethyl methacrylate, hydroxymethyl acrylate or 4-hydroxybutyl acrylate.
4. The UV-opaque adhesive of claim 2, wherein said hydroxyl-containing cage-type silsesquioxane has the structure according to formula (1):
5. the UV-opaque adhesive of claim 1, wherein said non-fluorinated acrylic monomer is at least one of isobornyl acrylate, morpholine 4-acrylate, cyclotrimethylolpropane formal acrylate, dicyclopentenyl acrylate, tricyclodecane dimethanol diacrylate or tetrahydrofuran acrylate; the fluorine-containing acrylic monomer is 13 fluoroacrylate and/or 13 fluoromethyl acrylate.
6. The UV-opaque adhesive of claim 1, wherein said double bond containing cage-type silsesquioxane has the structure according to formula (2):
7. the UV light-shielding adhesive of claim 1, wherein the radical photoinitiator is 2-hydroxy-2-methyl-1-phenylpropanone (1173), 1-hydroxycyclohexyl phenyl ketone (184), -methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone (907), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (TPO-L), 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone (910), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-butanone (910) -at least one of acetone (659) and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819).
8. The UV-sunscreen adhesive of claim 1 wherein said adhesion promoter is gamma- (2, 3-glycidoxy) propyltrimethoxysilane and/or gamma-methacryloxypropyltrimethoxysilane; the black toner is at least one of carbon black, titanium black or metal complex black.
9. A method for preparing the hydrophobic UV light-screening adhesive with good moisture permeability as claimed in any one of claims 1 to 8, comprising the steps of:
step 1, weighing the raw materials according to the proportion of the hydrophobic UV shading adhesive with good moisture permeability and low moisture permeability: modified polyurethane acrylate oligomer, fluorine-containing acrylic acid monomer, non-fluorine acrylate monomer, double-bond-containing polyhedral oligomeric silsesquioxane, adhesion promoter, free radical photoinitiator and black powder;
step 2: adding the weighed raw materials into a planetary stirrer, and stirring, dissolving, mixing and dispersing for 3-4 hours in a vacuum state to uniformly dissolve and disperse all the raw materials;
and 3, screening and filtering the uniformly dissolved and dispersed raw materials by more than 500 meshes, then carrying out vacuum defoaming treatment, and filling.
10. The method of claim 9, wherein the modified urethane acrylate oligomer is prepared by the steps of:
reacting the aliphatic diisocyanate with the dihydric alcohol under the action of the catalyst dibutyltin dilaurate at 70-90 ℃ for 1-2 hours to obtain a polyurethane prepolymer;
dropwise adding the hydroxyl-containing polyhedral oligomeric silsesquioxane into a reactor containing the polyurethane prepolymer at 70-90 ℃, and reacting for 1-3 hours to obtain a modified polyurethane prepolymer;
and adding the hydroxyl acrylic monomer added with the p-hydroxy toluidine and the dibutyltin dilaurate into the reactor at 60-75 ℃, and reacting for 2-4 hours to obtain the modified polyurethane acrylate oligomer.
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