EP4157916A1 - A photopolymer epoxy composition and a photoinitiator for curing same - Google Patents
A photopolymer epoxy composition and a photoinitiator for curing sameInfo
- Publication number
- EP4157916A1 EP4157916A1 EP21816917.5A EP21816917A EP4157916A1 EP 4157916 A1 EP4157916 A1 EP 4157916A1 EP 21816917 A EP21816917 A EP 21816917A EP 4157916 A1 EP4157916 A1 EP 4157916A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- weight parts
- photoinitiator
- photopolymer
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 189
- 239000004593 Epoxy Substances 0.000 title claims abstract description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 125000005409 triarylsulfonium group Chemical group 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 67
- 238000000034 method Methods 0.000 claims description 38
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 30
- -1 poly tetramethylene Polymers 0.000 claims description 30
- 239000000377 silicon dioxide Substances 0.000 claims description 29
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 28
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 24
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 229910000077 silane Inorganic materials 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000003365 glass fiber Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 150000002148 esters Chemical class 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 19
- NTNLSICUQDSUMN-UHFFFAOYSA-N 2-(2-benzoylphenoxy)acetic acid Chemical compound OC(=O)COC1=CC=CC=C1C(=O)C1=CC=CC=C1 NTNLSICUQDSUMN-UHFFFAOYSA-N 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 16
- FPHBLZMNRWNJEJ-UHFFFAOYSA-N methyl 2-(prop-2-enoxymethyl)prop-2-enoate Chemical compound COC(=O)C(=C)COCC=C FPHBLZMNRWNJEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000007711 solidification Methods 0.000 claims description 14
- 230000008023 solidification Effects 0.000 claims description 14
- 229910052787 antimony Inorganic materials 0.000 claims description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 12
- 229920005906 polyester polyol Polymers 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- 229920003232 aliphatic polyester Polymers 0.000 claims description 10
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 235000013772 propylene glycol Nutrition 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 claims description 7
- 239000001045 blue dye Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 6
- 230000005764 inhibitory process Effects 0.000 claims description 6
- 235000013799 ultramarine blue Nutrition 0.000 claims description 6
- SHHGHQXPESZCQA-UHFFFAOYSA-N oxiran-2-ylmethylsilicon Chemical compound [Si]CC1CO1 SHHGHQXPESZCQA-UHFFFAOYSA-N 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 4
- 230000001747 exhibiting effect Effects 0.000 claims description 3
- 238000001723 curing Methods 0.000 description 24
- 239000003999 initiator Substances 0.000 description 12
- 239000002114 nanocomposite Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 229910021485 fumed silica Inorganic materials 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 150000004010 onium ions Chemical class 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000012745 toughening agent Substances 0.000 description 4
- SCHZCUMIENIQMY-UHFFFAOYSA-N tris(trimethylsilyl)silicon Chemical compound C[Si](C)(C)[Si]([Si](C)(C)C)[Si](C)(C)C SCHZCUMIENIQMY-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- KSMGAOMUPSQGTB-UHFFFAOYSA-N 9,10-dibutoxyanthracene Chemical compound C1=CC=C2C(OCCCC)=C(C=CC=C3)C3=C(OCCCC)C2=C1 KSMGAOMUPSQGTB-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 102100040796 Glycoprotein hormones alpha chain Human genes 0.000 description 2
- 101001038874 Homo sapiens Glycoprotein hormones alpha chain Proteins 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012949 free radical photoinitiator Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 1
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 description 1
- POYODSZSSBWJPD-UHFFFAOYSA-N 2-methylprop-2-enoyloxy 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOOC(=O)C(C)=C POYODSZSSBWJPD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002019 Aerosil® 380 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 206010070835 Skin sensitisation Diseases 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 238000012663 cationic photopolymerization Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013036 cure process Methods 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000012682 free radical photopolymerization Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910002011 hydrophilic fumed silica Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 231100000370 skin sensitisation Toxicity 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4064—Curing agents not provided for by the groups C08G59/42 - C08G59/66 sulfur containing compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
Definitions
- the invention provides a photoinitiator comprising one or more triarylsulfonium hexafluoro antimonate compounds together with a silane.
- the silane comprises an alkysilane.
- said photoinitiator comprises, in one embodiment, triarylsulfonium hexafluoro antimonate, silane, and an ester of carboxymethoxy-benzophenone with poly methyl ethylene glycol or with poly tetramethylene glycol.
- the composition contains at least one component selected from silica, glass fiber, and aliphatic polyester polyols.
- the photopolymer composition of the invention may further comprise at least one bisphenol A epoxy compound, which, in another specific embodiment constitutes 20-40 wt% of the composition.
- said bisphenol A epoxy compound is bisphenol A diglycidyl ether (BADGE).
- the photopolymer composition of the invention may further comprise at least acrylic compound, which, in another specific embodiment constitutes 5-10 wt% of the composition.
- said acrylic compound is 2-(allyloxymethyl)acrylic acid methyl ester.
- the resultant composition is UV curable.
- the photopolymer composition the acrylic compound is 2-(allyloxymethyl)acrylic acid methyl ester.
- the photopolymer compositions include 2-(allyloxymethyl)acrylic acid methyl ester.
- the 2- (allyloxymethyl)acrylic acid methyl ester constitutes at least 5 wt% of the composition.
- the photopolymer composition is fast solidifying and/or insensitive to oxygen and/or provides a polymer with a high mechanical and dielectric strength.
- Fig. 2. shows the effect of non-settling of added fillers in the formulation due to the incorporation of the nano-composite in the formulation
- Fig. 3. demonstrates the dark cure effect of the epoxy formulation; by presenting the Young modulus as a function of time following initial exposure of 20 sec to 15mW/cm2 of UV-LED @ 395nm under air, at RT; and Fig. 4. thermal acceleration of the dark cure effect is demonstrated through presentation of Young modulus versus time at various temperatures, following initial exposure of 20 sec to 15mW/cm2 of UV-LED @ 395nm under air.
- Said cycloaliphatic epoxy compounds may include one or more materials selected from EEC, hydrogenated bisphenol A diglycidyl ether (HBD), epoxy acrylates, and others.
- Said bisphenol A epoxy compound may include one or more materials selected from bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE), and others.
- Said acrylic compound may include one or more materials selected from 2- (allyloxymethyl)acrylic acid methyl ester, 2-(allyloxyethyl)acrylic acid methyl ester, and others.
- the system of the invention is easy to use, fast cure, and safe, and provides a tough product; the composition before curing has good flowability at room temperature, and it can be stably stored for future use, at least for 2 months, such as at least 3 months or at least 4 months or at least 5 months or at least 6 months.
- Cationic curing mechanism exhibits curing within seconds under UV LED, or more when employing nano-composite toughening system.
- the nano-composite toughening system renders the product high impact strength and long term weather resistance.
- the product and the method for preparing it are non-hazardous and safe for the environment.
- Photopolymerization system of the invention belongs to green technologies, as it is characterized by low electrical power input and energy requirements, low temperature operation and no volatile organic compound release.
- the photoinitiator according to the invention is a hybrid cationic/free radical photoinitiator for UV LED curable epoxies.
- QPI comprises photo energy shifting ingredients, and/or free-radical photoinitiators.
- the photoinitiator of the invention may comprise a mixture of sulfonium based photo and thermal cure initiators.
- the photoinitiator of the invention may comprise a color purifying additive, such as ultramarine blue.
- nano based toughener (QPN) for cationic cure cycloaliphatic epoxy systems comprising an organic-inorganic nanocomposite and exhibiting transparency which makes it advantageously usable for epoxy based UV curing.
- TMS Tris(trimethylsilyl)silane
- GTS Glycidyloxypropyltrimethoxysilane
- the photoinitiator mixture (mixture 1, abbreviated QPI) was prepared by mixing 2.63 g of TSHA in propylene carbonate 1:1, 0.14 g of silane, 0.81 g of ECBP, and 0.14 g of AH.
- Nano based toughener in accordance with one aspect of the invention was tested and compared with agents generally used for epoxies, including core-shell rubber particles (butadiene/styrene, polybutadiene or acrylate), core shell toughened resins ALBIDUR ® (Siloxane), rubber modified epoxies (butadiene-acrylonitrile rubbers / CTBN), thermoplastic granulated or dissolved polymers. (PES, PEEK or PEI), nanosilica containing epoxy resins NANOPOX ® (surface modified silica), mineral / inorganic fillers.
- the material according to the invention provided better results when measuring material fractures.
- the photoinitiator mixture (mixture 1, abbreviated QPI) was prepared by mixing 2.63 g ofTSHA in propylene carbonate 1:1, 0.14 g of silane, 0.81 g of ECBP, and 0.14 g of AH.
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Abstract
A photopolymer composition comprising at least one cycloaliphatic epoxy compound and a photoinitiator comprising a triarylsulfonium salt.
Description
A PHOTOPOLYMER EPOXY COMPOSITION AND A PHOTOINITIATOR FOR CURING SAME
Details of related applications:
This application claims priority under the Paris convention from IL 275026 filed June 1, 2020 and from IL 283470 filed May 26, 2021, each of which has the same title as the present application and each of which is fully incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates to photopolymer compositions curable with gentle UV light. Particularly, the invention relates to fast solidifying epoxy based compositions, and to photoinitiators for use in said compositions, providing cured polymers with superior mechanical and electrical properties.
BACKGROUND OF THE INVENTION
A photopolymerization process makes a solid polymer from a liquid radiation-curable mixture; the mixture is often called a photopolymer even if comprising only oligomers, and it is mostly cured by light irradiation in the UV range. Photon-induced crosslinking of shorter chains (curing) leads to the solidification. The photopolymer typically contains multifunctional monomers and oligomers, often comprising acrylate derivatives, and further a photoinititiator providing reactive species which start the polymerization process. The predominant mechanism of photopolymerization is based on the formation of free radicals, less frequently it comprises a cationic initiator. The curing treatment results in a solid network of thermoset polymer. The photopolymers are broadly used in medicine and dentistry, in printing, in electronics, in coating, and still more in 3D-printing.
A variety of UV curable resins have been developed, mostly employing acrylic compounds polymerized via the free radical mechanism. Many acrylic-functionalized oligomers are commercially available, including acrylated polyesters, urethanes, silicones, epoxies, and others. However, some of the compositions produce polymers prone to weathering or with a tendency to yellow - particularly in the sunlight, and
other compositions exhibit lower performance in regard to the desired properties, including bond strength, solvent resistance, impact resistance, heat resistance, flexibility, glass-transition temperature (Tg), electrical resistivity, and other. A general problem with the free radical photopolymerization of acrylic compositions lies in their extreme sensitivity to oxygen inhibition. Compositions comprising cationic initiators, based for example on epoxy or vinyl ether compounds, have been described but few are available and, moreover, they are easily deactivated by small amounts of water. Another general difficulty with light-induced solidification is the limited light penetration depth. Further, the need for UV light, which use is strictly regulated in view of health and environmental hazards, also complicates the work with photopolymers. For example, a mercury lamp - the often employed UV source - provides UV light at wavelengths lower than 260 nm, typically in the range of 200-315 nm, which is considered to have serious effects in human. It is therefore an object of this invention to provide a composition avoiding at least some of the above drawbacks.
Summary of the Invention
It is another object of this invention to provide a composition for photopolymerization resistant to oxygen inhibition.
It is also an object of the invention to provide a cationically initiated photopolymerization containing a monomer selected from cycloaliphatic epoxy compounds.
It is a further object of this invention to provide a composition for cationically initiated photopolymerization containing a cycloaliphatic epoxy compound and a photoinitiator comprising an onium ion.
It is still another object of this invention to provide a composition curable with a light outside the wavelength range considered to have serious effects in human.
It is a further object of this invention to provide a composition for cationically initiated photopolymerization containing a cycloaliphatic epoxy compound and a photoinitiator comprising an onium ion, curable with a UV-LED.
This invention aims at providing a composition for cationically initiated photopolymerization containing a cycloaliphatic epoxy compound and a photoinitiator comprising an onium ion, curable with a UV-LED, and providing a solid polymer exhibiting good mechanical and electrical properties.
This invention also aims at providing a UV-LED curable and fast-solidifying composition based on cycloaliphatic epoxy compounds.
It is also an object of this invention to provide a composition for cationically initiated photopolymerization containing a cycloaliphatic epoxy compound and an onium ion, curable with light of a wavelength greater than 350 nm (gentle UV irradiation).
The invention further aims at providing a photoinitiator for cationic photo polymerization of epoxy-based photo-curable mixtures, providing fast mixture solidification when irradiated with a light of a wavelength greater than 350 nm.
The invention also aims at providing a photoinitiator for polymerization of epoxy-based photo-curable mixtures, comprising an aryl-onium ion.
Other objects and advantages of present invention will appear as the description proceeds.
According to one aspect of some embodiments of the invention relates to a photopolymer composition comprising at least one epoxy compound and a photoinitiator comprising a triarylsulfonium salt. In some exemplary embodiments of the invention, the epoxy compound is a cycloaliphatic epoxy compound. Alternatively or additionally, in some embodiments the cycloaliphatic epoxy compound usually constitutes 20-40 wt% and said photoinitiator usually constitutes 2-6 wt% of the
composition. Alternatively or additionally, in some embodiments, the cycloaliphatic epoxy compound is 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate (EEC). In another embodiment, the invention provides a photoinitiator comprising one or more triarylsulfonium hexafluoro antimonate compounds together with a silane. In some exemplary embodiments of the invention, the silane comprises an alkysilane.Said photoinitiator comprises, in one embodiment, triarylsulfonium hexafluoro antimonate, silane, and an ester of carboxymethoxy-benzophenone with poly methyl ethylene glycol or with poly tetramethylene glycol. In some exemplary embodiments of the invention, the composition contains at least one component selected from silica, glass fiber, and aliphatic polyester polyols. In another embodiment, the photopolymer composition of the invention comprises 5-15 wt% silica. The composition of the invention usually comprises 10-30 wt% aliphatic polyester polyols. An important component for enhancing the mechanical and other properties of the final polymer are glass fibers, included according to the need in an amount of up to about 28 wt%. Alternatively or additionally, in some embodiments the photopolymer composition of the invention contains 5-15 wt% silica, 10-30 wt% aliphatic polyester polyols, up to 28 wt% glass fibers such as 10-25 wt%. Alternatively or additionally, in some embodiments the photopolymer composition of the invention may further comprise up to 0.5 wt% of dibutoxyanthracene. Alternatively or additionally, in some embodiments photopolymer composition of the invention may further comprise up to 0.5 wt%. Alternatively or additionally, in some embodiments the photopolymer composition of the invention may further comprise at least one blue dye. In one embodiment of the invention, the composition to be cured includes methylene blue (MB) as a curing indicator. The cured composition advantageously comprises a blue dye to rid the reaction mixture before curing of yellowish color, such as an ultramarine dye-based agent.
In some exemplary embodiments of the invention, the photopolymer composition of the invention may further comprise at least one bisphenol A epoxy compound, which, in another specific embodiment constitutes 20-40 wt% of the composition. In yet another specific embodiment, said bisphenol A epoxy compound is bisphenol A diglycidyl ether (BADGE). According to another embodiment, the photopolymer composition of the invention may further comprise at least acrylic compound, which, in another specific
embodiment constitutes 5-10 wt% of the composition. In yet another specific embodiment, said acrylic compound is 2-(allyloxymethyl)acrylic acid methyl ester. In some exemplary embodiments of the invention, the resultant composition is UV curable. For example, UV irradiation with a wavelength greater than 350 nm, such as 365 nm or more, for example that of UV LED sources emitting light at 395 nm contribute to an increase in the rate of crosslinking which contributes to solidification . Alternatively or additionally, in some embodiments the polymer exhibits good mechanical and electrical properties (e.g. di-electric).
Another aspect of some embodiments of the invention is directed to a quickly acting photoinitiator for photopolymer compositions that comprise cycloaliphatic epoxy compounds, which in other specific embodiments may be in an amount of 20-40 wt%, the weight % being based on the composition including the initiator, and where said photoinitiator is usually employed in an amount of 2-6 wt%, weight % being based on the composition including the initiator, the initiator comprising a triarylsulfonium hexafluoro antimonate, silane, and an ester of carboxymethoxy-benzophenone with poly tetramethylene glycol.
Alternatively or additionally, in some embodiments the photopolymer compositions comprise BADGE (e.g. least 20 wt% of the composition) and/or 2-(allyloxymethyl)acrylic acid methyl ester, (e.g. at least 5 wt% of the composition). Alternatively or additionally, in some embodiments the photoinitiator comprises an antimony hexafluoride based catalyst for thermal initiated cationic polymerization. For example, in some embodiments the photoinitiator comprises at least 25 wt% triarylsulfonium hexafluoro antimonate, such as 25-45 wt%, at least 2 wt% silane, such as 2-6 wt%, at least 10 wt% ester of carboxymethoxy-benzophenone with poly tetramethylene glycol, such as 10-30 wt%, and at least 2 wt% antimony hexafluoride based catalyst for thermal initiated cationic polymerization, such as 2-6 wt%. In some exemplary embodiments of the invention, photoinitiator (PI) is resistant to oxygen inhibition and works with light of a wavelength greater than 350 nm, while enabling very quick solidification.
Another aspect of some embodiments of the invention relates to a process for manufacturing a photopolymer composition comprising at least one cycloaliphatic epoxy compound and a photoinitiator comprising a triarylsulfonium salt, the composition being fast solidifying and insensitive to oxygen, and providing a polymer with a high mechanical and dielectric strength, the process comprising the step of i) preparing a photoinitiator (QPI), mixture 1, by mixing a) 1-4 weight parts of triarylsulfonium hexafluoro antimonate in propylene carbonate 1:1, b) 0.02-0.2 weight parts of silane, c) 0.2-2 weight parts of ester of carboxymethoxy-benzophenone with poly tetramethylene glycol, and d) 0.02-0.2 weight parts of antimony hexafluoride based catalyst for thermal initiated cationic polymerization. In a specific embodiment of the invention, said process for manufacturing a photopolymer composition further comprises the steps of ii) preparing a curing indicator, mixture 2, by dissolving a blue dye in EEC; iii) preparing a color purifying solution, mixture B, by dissolving an ultramarine blue material in a polyester polyol; iv) preparing an EEC mixture, mixture 4, by mixing 20-40 weight parts of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate (EEC), 0.1-0.5 weigh parts of said mixture 2, up to 1 weight parts of polyether, and up to 0.4 weigh parts of dibutoxyanthracene, and intensively stirring with 1-2 weigh parts of silica; v) preparing a glycidyl silane mixture, mixture 5, by mixing 0.2-0.8 weight parts of (glycidyloxypropyl)trimethoxysilane, 10-30 weigh parts of a polyester polyol, and intensively stirring with 2-6 weight parts of silica at 150°C for 10 to 60 minutes; and vi) combining mixtures 4 and 5 while well stirring for about 15 minutes, followed by admixing 10-25 weight parts of glass fibers, 1-3 weight parts of silica, and up to 1 weight part of said mixture 3, followed by admixing 7-30 weight parts of hydrogenated bisphenol A diglycidyl ether and, in other more specific embodiments, either or both of 7-30 weight parts of bisphenol A diglycidyl ether (BADGE) and 5-10 weight parts of 2-(allyloxymethyl)acrylic acid methyl ester, while mixing at 50°C for about 10 minutes; followed by adding 2-8 weight parts of mixture 1 while stirring about 10 more minutes, and adjusting the final viscosity by admixing about 1-3 weight parts of silica; thereby obtaining a photocomposition for curing with a light of a wavelength greater than 350 nm.
In some exemplary embodiments of the invention, the photoinitiator in accordance with the invention, employs primarily cycloaliphatic epoxy materials, such as epoxycyclohexylmethyl epoxycyclohexane carboxylate, which avoids drawbacks of other epoxy materials, such as bisphenol A epoxy (when used as a major constituent), including limited depth of cure or low resistance to prolonged exposure to UV light. The solidification process employs thermally activated components, activated by the heat of the polymerization process. The solidification process employs mixed cation/radical initiation. These compositions include the following: Triarylsulfonium hexafluoro antimonate (THA), which may be obtained, for example, from Sigma Aldrich as 50% material in propylene carbonate. Ester of carboxymethoxy-benzophenone and poly methyl ethylene glycol or ester of carboxymethoxy-benzophenone and poly tetramethylene glycol. MB-99% Quantum blue is a curing indicator; upon full cure it changes color from blue to yellowish. Ultramarine Blue is preferred dye, to be dissolved in a dendritic polymer, such as dendritic polyester polyols, specifically a branched ester of a polyol like PEG with low fatty acids. A polyether, such as silicone free polyether. Polyester polyol, such as aliphatic polyester diol.
In some exemplary embodiments of the invention there is provided a photopolymer composition including at least one cycloaliphatic epoxy compound and a photoinitiator comprising a triarylsulfonium salt. In some embodiments the at least one cycloaliphatic epoxy compound constitutes 20-40 wt% and the photoinitiator constitutes 2-6 wt% of the composition. Alternatively or additionally, in some embodiments the cycloaliphatic epoxy compound comprises 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate (EEC). Alternatively or additionally, in some embodiments the photoinitiator comprises triarylsulfonium hexafluoro antimonate and silane. Alternatively or additionally, in some embodiments the photoinitiator comprises triarylsulfonium hexafluoro antimonate, silane, and an ester of carboxymethoxy- benzophenone with poly methyl ethylene glycol or with poly tetramethylene glycol. Alternatively or additionally, in some embodiments the composition includes at least one component selected from silica, glass fiber, and aliphatic polyester polyol. Alternatively or additionally, in some embodiments the composition includes 5-15 wt% silica, 10-30 wt% aliphatic polyester polyol, and up to 28 wt% glass fiber. Alternatively or additionally, in some embodiments the composition includes up to 0.5 wt% of
dibutoxyanthracene. Alternatively or additionally, in some embodiments the composition includes up to 0.5 wt% antimony hexafluoride. Alternatively or additionally, in some embodiments the composition includes at least one blue dye.
Alternatively or additionally, in some embodiments the composition includes at least one bisphenol A epoxy compound. In some embodiments the at least one bisphenol A epoxy compound constitutes 20-40 wt% of the composition. Alternatively or additionally, in some embodiments the bisphenol A epoxy compound is bisphenol A diglycidyl ether (BADGE).
Alternatively or additionally, in some embodiments the composition includes at least one acrylic compound. Alternatively or additionally, in some embodiments the at least one acrylic compound constitutes 5-10 wt% of the composition.
Alternatively or additionally, in some embodiments the photopolymer composition the acrylic compound is 2-(allyloxymethyl)acrylic acid methyl ester.
Alternatively or additionally, in some embodiments the photopolymer composition is curable with a gentle UV irradiation.
Alternatively or additionally, in some embodiments the photopolymer composition exhibits fast solidification, and good mechanical and dielectrical properties.
In some exemplary embodiments of the invention there is provided a quickly acting photoinitiator (PI) for use in photopolymer compositions comprising at least one cycloaliphatic epoxy compound, the composition comprising a triarylsulfonium hexafluoro antimonate, silane, an ester of carboxymethoxy-benzophenone with poly methyl ethylene glycol or poly tetramethylene glycol, and antimony hexafluoride.
In some embodiments the PI includes at least 25 wt% triarylsulfonium hexafluoro antimonate, at least 2 wt% silane, at least 10 wt% ester of carboxymethoxy- benzophenone with poly tetramethylene glycol, and at least 2 wt% antimony hexafluoride.
Alternatively or additionally, in some embodiments the photopolymer composition is resistant to oxygen inhibition and curable with a light of a wavelength greater than 350 nm. Alternatively or additionally, in some embodiments the at least one cycloaliphatic epoxy compound constitutes 20-40 wt% of the composition.
Alternatively or additionally, in some embodiments the photopolymer compositions includes BADGE. In some embodiments the BADGE constitutes at least 20 wt% of the composition.
Alternatively or additionally, in some embodiments the photopolymer compositions include 2-(allyloxymethyl)acrylic acid methyl ester. In some embodiments the 2- (allyloxymethyl)acrylic acid methyl ester constitutes at least 5 wt% of the composition.
In some exemplary embodiments of the invention there is provided a process for manufacturing a photopolymer composition. In some embodiments, the photopolymer composition is fast solidifying and/or insensitive to oxygen and/or provides a polymer with a high mechanical and dielectric strength. The process includes the step i) of preparing a photoinitiator, mixture 1, by mixing a) 1-4 weight parts of triarylsulfonium hexafluoro antimonate in propylene carbonate 1:1, b) 0.02-0.2 weight parts of silane, c) 0.2-2 weight parts of an ester of carboxymethoxy-benzophenone with poly tetramethylene glycol or with poly methyl ethylene glycol, and d) 0.02-0.2 weight parts of antimony hexafluoride based catalyst for thermal initiated cationic polymerization.
In some embodiments the process includes: ii) preparing a curing indicator, mixture 2, by dissolving a blue dye in 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate; iii) preparing a color purifying solution, mixture 3, by dissolving an ultramarine blue material in a polyester polyol; iv) preparing a cycloaliphatic epoxy mixture, mixture 4, by mixing 20-40 weight parts of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 0.1-0.5 weigh parts of said mixture 2, up to 1 weight parts of a polyether, and up to 0.4 weigh parts of dibutoxyanthracene, and intensively stirring with 1-2 weigh parts of silica; v) preparing a glycidyl silane mixture, mixture 5, by mixing 0.2-0.8 weight parts of (glycidyloxypropyl)trimethoxysilane, 10-30 weigh parts of a polyester polyol, and
intensively stirring with 2-6 weight parts of silica at 150°C for 10-60 minutes; and vi) combining mixtures 4 and 5 while well stirring for about 15 minutes, followed by admixing 10-25 weight parts of glass fibers, 1-3 weight parts of silica, and up to 1 weight part of said mixture 3, followed by admixing 7-30 weight parts of hydrogenated bisphenol A diglycidyl ether while mixing at 50°C for about 10 minutes; followed by adding 2-6 weight parts of mixture 1 while stirring about 10 more minutes, and adjusting the final viscosity by admixing about 1-3 weight parts of silica; thereby obtaining a photocomposition for curing with a light of a wavelength greater than 350 nm, such as between 380 and 395 nm.
Alternatively or additionally, in some embodiments step vi) consists of combining mixtures 4 and 5 while well stirring for about 15 minutes, followed by admixing 10-25 weight parts of glass fibers, 1-3 weight parts of silica, and up to 1 weight part of said mixture 3, followed by admixing 7-30 weight parts of hydrogenated bisphenol A diglycidyl ether and either or both of 7-30 weight parts of bisphenol A diglycidyl ether (BADGE) and 5-10 weight parts of 2-(allyloxymethyl)acrylic acid methyl ester while mixing at 50°C for about 10 minutes; followed by adding 2-6 weight parts of mixture 1 while stirring about 10 more minutes, and adjusting the final viscosity by admixing about 1-3 weight parts of silica.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although suitable methods and materials are described below, methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. In case of conflict, the patent specification, including definitions, will control. All materials, methods, and examples are illustrative only and are not intended to be limiting. As used herein, the terms "comprising" and "including" or grammatical variants thereof are to be taken as specifying inclusion of the stated features, integers, actions or components without precluding the addition of one or more additional features, integers, actions, components or groups thereof. This term is broader than, and
includes the terms "consisting of" and "consisting essentially of" as defined by the Manual of Patent Examination Procedure of the United States Patent and Trademark Office. Thus, any recitation that an embodiment "includes" or "comprises" a feature is a specific statement that sub embodiments "consist essentially of" and/or 'consist of" the recited feature.
The phrase "consisting essentially of" or grammatical variants thereof when used herein are to be taken as specifying the stated features, integers, steps or components but do not preclude the addition of one or more additional features, integers, steps, components or groups thereof but only if the additional features, integers, steps, components or groups thereof do not materially alter the basic and novel characteristics of the claimed composition, device or method.
The phrase "adapted to" as used in this specification and the accompanying claims imposes additional structural limitations on a previously recited component.
The terms "method" and "process" refers to manners, means, techniques and procedures for accomplishing a given task including, but not limited to, those manners, means, techniques and procedures either known to, or readily developed from known manners, means, techniques and procedures by practitioners of the art.
Percentages, such as percentage by weight abbreviated wt%, are W/W (weight per weight) unless otherwise indicated. Brief Description of the Drawings
In order to understand the invention and to see how it may be carried out in practice, embodiments will now be described, by way of non-limiting example only, with reference to the accompanying figures, wherein:
Fig. 1. shows a schematic drawing of the synthesis production process of the nanocomposite;
Fig. 2. shows the effect of non-settling of added fillers in the formulation due to the
incorporation of the nano-composite in the formulation;
Fig. 3. demonstrates the dark cure effect of the epoxy formulation; by presenting the Young modulus as a function of time following initial exposure of 20 sec to 15mW/cm2 of UV-LED @ 395nm under air, at RT; and Fig. 4. thermal acceleration of the dark cure effect is demonstrated through presentation of Young modulus versus time at various temperatures, following initial exposure of 20 sec to 15mW/cm2 of UV-LED @ 395nm under air.
Detailed Description of the Invention
It has now been found that a photopolymer composition containing epoxy compounds, triarylsulfonium hexafluoro antimonite, and tris(trimethylsilyl)silane, solidifies quickly when cured with a gentle UV light of UV LED, while forming a polymer with good mechanical and electric properties. The quickly acting photoinitiator in accordance with the invention, abbreviated QPI throughout the description (QPI standing for Quick Photo Initiator), enabled solidification of 2-3 mm thick layers by UV of 395 nm within 20 seconds or less. The solidification times are lower for a PI according to an exemplary embodiment of the invention than for standard PI employed in the field. In some exemplary embodiments of the invention, cure parameters, including time and thickness, are advantageous for 3D printing formulations.
A photopolymer composition according to some embodiments includes at least one cycloaliphatic epoxy compound and a photoinitiator comprising a triarylsulfonium salt is suitable for providing a toughened cured resin, particularly by adding a nano composite toughening agent. In one preferred embodiment of the invention, a photopolymer composition according to the invention, comprising photoinitiator QPI described above, is combined with a Si0 -Polyester Nano composite Toughening & Anti settling agent based on fumed silica particles whose hydroxyl groups are esterified with fatty acids, preferably via a reaction of silica with a diester of an aliphatic diol polyster. In a preferred embodiment of the invention, said reaction includes adding silane at a higher temperature, while obtaining transparent organic-inorganic nanocomposite (Fig. 1) to be employed as a toughening additive to the photopolymer composition of the invention. The toughener nano composite is added to the composition before curing, resulting in two improved properties: firstly the cured polymer is tougher, and secondly
the nanocomposite stabilizes an eventual suspension of glass fiber or other fillers in the composition before curing and prevents settling glass fibers (Fig. 2). The Quick-curing Photopolymer Nanocomposite (QPN) additive, comprising derivatized silica, is used with glass fibers and provides very strong nanocomposite comprising product.
In some exemplary embodiments of the invention, the compositon includes cycloaliphatic epoxy compounds, and a photoinitiator comprising at least triarylsulfonium hexafluoro antimonate, and, in various embodiments of the invention, components selected at least from esters of carboxymethoxy-benzophenone, aliphatic polyester polyols, dibutoxyanthracene, tris(trimethylsilyl)silane, a bisphenol A epoxy compound and acrylic compound, exhibits advantageous features when the composition is UV-cured, particularly when the composition further comprises silica and glass fibers. The advantageous features include fast curing/solidifying, no oxygen inhibition, reduced shrinkage, dark post-cure (which is continuing the cure process after UV initiation even when the light source is removed, "in dark"), whereas the product has high Tg, high tensile and flexure strength, good electrical properties (excellent arc and tracking resistance, low dielectric constant and dissipation), UV stability and weatherability due to the aliphatic backbone of the polymer and, moreover, the system exhibits a low skin sensitization due to the high light wavelength. Using LED sources of gentle UV radiation, such as comprising 395 nm, is not only significantly less dangerous from the viewpoint of eventual inadvertent skin irradiation, but it also obviates the elimination of ozone, which is produced by mercury light sources.
Said cycloaliphatic epoxy compounds may include one or more materials selected from EEC, hydrogenated bisphenol A diglycidyl ether (HBD), epoxy acrylates, and others. Said bisphenol A epoxy compound may include one or more materials selected from bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE), and others. Said acrylic compound may include one or more materials selected from 2- (allyloxymethyl)acrylic acid methyl ester, 2-(allyloxyethyl)acrylic acid methyl ester, and others.
The system of the invention is easy to use, fast cure, and safe, and provides a tough product; the composition before curing has good flowability at room temperature, and
it can be stably stored for future use, at least for 2 months, such as at least 3 months or at least 4 months or at least 5 months or at least 6 months. Cationic curing mechanism exhibits curing within seconds under UV LED, or more when employing nano-composite toughening system. The nano-composite toughening system renders the product high impact strength and long term weather resistance. The product and the method for preparing it are non-hazardous and safe for the environment. Photopolymerization system of the invention belongs to green technologies, as it is characterized by low electrical power input and energy requirements, low temperature operation and no volatile organic compound release.
The photoinitiator according to the invention, QPI, may be employed as a hybrid photo/thermal cationic cure initiator providing ultra-fast and also deep curing of cycloaliphatic epoxy resin systems, enabling photo-cure by using UV-LED lamps eventually combined with thermal cure.
The photoinitiator according to the invention, QPI, is a hybrid cationic/free radical photoinitiator for UV LED curable epoxies. In one aspect of the invention, QPI comprises photo energy shifting ingredients, and/or free-radical photoinitiators. The photoinitiator of the invention may comprise a mixture of sulfonium based photo and thermal cure initiators. The photoinitiator of the invention may comprise a color purifying additive, such as ultramarine blue.
In another aspect of the invention, nano based toughener (QPN) for cationic cure cycloaliphatic epoxy systems is employed, comprising an organic-inorganic nanocomposite and exhibiting transparency which makes it advantageously usable for epoxy based UV curing.
The additional objects, advantages, and novel features of various embodiments of the invention will become apparent to one ordinarily skilled in the art upon examination of the following examples, which are not limiting. Additionally, each of the various embodiments and aspects of the present invention as delineated hereinabove and as
claimed in the claims section below finds experimental support in the following examples.
Examples
Reference is now made to the following examples, which together with the above descriptions, illustrate the invention in a non limiting fashion.
MATERIALS AND METHODS
The following materials and methods are used in performance of experiments described in examples hereinbelow:
• Triarylsulfonium hexafluoro antimonate (TSHA, such as 50% in 50% material in propylene carbonate of Sigma Aldrich or of Insight High Technology IHT-PI 436);
• Ester of carboxymethoxy-benzophenone with poly tetramethylene glycol or with poly methylethylene glycol (ECBP), such as Omnipol BP of IGM Resins;
• Tris(trimethylsilyl)silane (TTS);
• Antimony hexafluoride based catalyst (AHC) for thermal initiated cationic polymerization, such as K-PURE® CXC-1612 of King Industries;
• 3,4-Epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate (EEC), such as Celloxide 2021P of Daicel;
• Methylene Blue (MB);
• Ester of a polyol such as a dendritic polyester polyol, for example a branched ester of a polyol like PEG with low fatty acids (EP), such as Boltorn™ H2004 of Perstorp;
• Ultramarine Blue 08 (UMB);
• 9,10-Dibutoxyanthracene (DBA), for example of Kawasaki Kasei Chemicals Ltd.;
• Polyether crosslinkable additive (PEC), such as of BYK Additives & Instruments;
• Fumed silica (FS), Aerosil R 805 of Evonic Industries;
• Hydrophilic fumed silica, Aerosil 380;
• Polyester polyol (PEP), such as of King Industries;
• Glycidyloxypropyl)trimethoxysilane (GTS), of Sigma-Aldrich;
• Glass fibers (GF);
• Hydrogenated bisphenol A diglycidyl ether (HBD), such as of Nagase;
• Bisphenol A diglycidyl ether (BADGE), also known as diglycidyl ether of bisphenol A (DGEBA), CAS number 25068-38-6, such as of Sigma; and
• 2-(allyloxymethyl)acrylic acid methyl ester, also known as methyl 2- ((allyloxy)methyl)acrylate, CAS number 219828-90-9.
Example 1
Preparation procedure
In one experiment, a photopolymer composition in accordance with the invention was prepared by performing the following steps.
A) The photoinitiator mixture (mixture 1, abbreviated QPI) was prepared by mixing 2.63 g of TSHA in propylene carbonate 1:1, 0.14 g of silane, 0.81 g of ECBP, and 0.14 g of AH.
B) The curing indicator mixture (mixture2) was prepared by dissolving MB in EEC to 0.25 wt% solution.
C) The color purifying solution (mixture 3) was prepared by dissolving UMB to 1% solution in DP.
D) The EEC mixture (mixture 4) was prepared by mixing 29.5 g of EEC, 0.3 g parts of said mixture 2, 0.58 g of PE, and 0.19 g of DBA, while intensively stirring with 1.54 g of.
E) The glycidyl silane mixture (mixture 5) was prepared by mixing 0.53 g of GTS, 22.03 g of PEP, while intensively stirring with 3.98 g of FS at 150°C for about 30 minutes; and
F) Mixtures 4 and 5 were combined while well stirring for about 15 minutes, followed by admixing 18.0 g of GF, 2.0 g of FS, and 0.6 g of mixture 3, followed by admixing 15.04 g of HBD while mixing at 50°C for about 10 minutes; followed by adding 3.70 g of QPI (mixture 1) while stirring about 10 more minutes, and adjusting the final viscosity by admixing about 2.00 g of FS.
About 100 g photopolymer composition was obtained and examined during curing with 395 nm UV LED. The composition did not show sensitivity to oxygen, and it quickly solidified, providing a polymer of which mechanical and electric properties were characterized.
Viscosity before curing and thixotropic character of the mixture were found to be
between 15,000 cP and 1,000,000 cP, I.T being > 4. The cured material exhibited tensile strength of 74 MPa, elongation 2.5, and hardness D85. Example 2
The photoinitiator according to the invention (QPI-2000) and a standard photoinitiator (PI-436) used in the field were employed for curing three resins: A) resin based on EEC prepared as described in Example 1, B) resin based on epoxy-methacrylate, and C) resin based on epoxy-bisphenol A. Three different initiator concentrations in the range of 2- 5% were employed, and two different irradiation intensities in the range of about 0.2-
0.4 W/cm2 were employed. The solidification times were measured, according to visual test and hardness test. The results are presented in following Table 1.
Table 1 Cure and solidification times (in seconds) at different initiator concentrations (wt%) and different irradiations (in W/cm2) at wavelength of 395 nm, for different resins and for the initiator of invention (QPI) and for a standard initiator (PI-436).
The results clearly show that the photoinitiator according to the invention provides shorter curing/solidification times than the standard intitiator for all resins and all concentrations and all irradiations.
Example 3
The effect also known as "dark cure", relating to a phenomena when the photopolymer continues to cure after initial illumination even when the UV LED light source is removed, was verified by evaluating Young modulus vs. time and is presented in Fig. 3. Twenty samples of 1mm thick layer of a composition as described in Example 1 were exposed for 20 sec to 15mW/cm2 of UV-LED, 395nm, under air. The samples were then placed in a "black box" in order to prevent additional exposure to illumination. Every 10 min, Young modulus was measured in a sample using DMA (Dynamic Mechanical Analysis) with maximum force of 18N, at RT. The data, fitted to an exponential, demonstrate that full cure was achieved after approximately 150 min. After about 200 minutes samples do not break under the DMA's maximal force of 18N.
Fig. 4 demonstrates the effect of temperature on the rate of "dark cure". The experiment described in Fig. 3 was repeated, with DMA measurements at various elevated temperatures. The results presented in Fig 4 show that exposure to 90°C will shorten the cure time at "dark cure" from appx 150 min to 30 sec.
Example 4
Toughened cured polymer was prepared by incorporating the nano-material of the derivatized silica (Fig.l) into the material as described in Example 1, employing high shear mixing and elevated temperature, while obtaining quickly-cured photopolymer.
Nano based toughener in accordance with one aspect of the invention, was tested and compared with agents generally used for epoxies, including core-shell rubber particles (butadiene/styrene, polybutadiene or acrylate), core shell toughened resins ALBIDUR® (Siloxane), rubber modified epoxies (butadiene-acrylonitrile rubbers / CTBN), thermoplastic granulated or dissolved polymers. (PES, PEEK or PEI), nanosilica containing epoxy resins NANOPOX® (surface modified silica), mineral / inorganic fillers.
The material according to the invention provided better results when measuring material fractures.
Example 5
Preparation procedure
In order to improve impact resistance and increase heat deflection temperature of a resin as describe in Example 1, a photopolymer composition in accordance with the invention was prepared by performing the following steps.
A) The photoinitiator mixture (mixture 1, abbreviated QPI) was prepared by mixing 2.63 g ofTSHA in propylene carbonate 1:1, 0.14 g of silane, 0.81 g of ECBP, and 0.14 g of AH.
B) The EEC mixture was prepared by mixing 7 gr of 2-(allyloxymethyl)acrylic acid methyl ester, 0.06 gr of 9,10-Dibutoxyanthracene, 42.5 g of (3', 4'- Epoxycyclohexane)methyl 3,4-epoxycyclohexylcarboxylate( EEC), 5.4gr of epoxy compound blend (ODP-OH-B0177-02), 5.4gr of Aliphatic polyester diol with primary hydroxyl groups, 0.75gr [3-(2,3-epoxypropoxy)propyl]trimethoxysilane, 0.35gr Polyether.
Mix the above components for approx. lOmin so as to obtain a homogeneous liquid.
C) Add 2gr of Silane, trimethoxyoctyl-, hydrolysis products with silica make sure proper wetting, slowly add 18gr of Fibrous glass (composition consisting principally of oxides of silicon, calcium, aluminum, magnesium and boron fused in an amorphous vitreous state), and additional 4gr of Silane, trimethoxyoctyl-, hydrolysis products with silica. Make sure temp does not exceed 70C.
D) Add lOgr of Hydrogenated bisphenol A diglycidyl ether diacrylate and mix well for 10 min. temp of mixture should not exceed 50C. Finally add 4.0 gr of QPI (mixture 1) while stirring about 10 more minutes.
About 100 g photopolymer composition was obtained and examined during curing with 395 nm UV LED. The composition did not show sensitivity to oxygen, and it quickly solidified, providing a polymer of which mechanical and electric properties were
characterized.
Table 2 compares the mechanical properties of two different exemplary embodiments of the invention.
Table 2: Comparison of properties of two different exemplary embodiments of the invention
While the invention has been described using some specific examples, many modifications and variations are possible. It is therefore understood that the invention is not limited in any way, other than by the scope of the appended claims.
It is expected that during the life of this patent many variations thereon will be developed and the scope of the invention includes all such new technologies a priori.
As used herein the term "about" refers to ±10 % of the recited value.
Although the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art. Accordingly, it is intended to embrace all such alternatives, modifications and variations that fall within the spirit and broad scope of the appended claims.
Specifically, a variety of numerical indicators have been utilized. It should be understood that these numerical indicators could vary even further based upon a variety of engineering principles, materials, intended use and designs incorporated into the various embodiments of the invention. Additionally, components and/or actions ascribed to exemplary embodiments of the invention and depicted as a single unit may be divided into subunits. Conversely, components and/or actions ascribed to exemplary
embodiments of the invention and depicted as sub-units/individual actions may be combined into a single unit/action with the described/depicted function.
Alternatively, or additionally, features used to describe a method or a process can be used to characterize an apparatus and features used to describe an apparatus can be used to characterize a method or a process.
It should be further understood that the individual features described hereinabove can be combined in all possible combinations and sub-combinations to produce additional embodiments of the invention. The examples given above are exemplary in nature and are not intended to limit the scope of the invention which is defined solely by the following claims.
Each recitation of an embodiment of the invention that includes a specific feature, part, component, module or process is an explicit statement that additional embodiments of the invention not including the recited feature, part, component, module or process exist.
Alternatively or additionally, various exemplary embodiments of the invention exclude any specific feature, part, component, module, process or element which is not specifically disclosed herein.
All publications, references, patents and patent applications mentioned in this specification are herein incorporated in their entirety by reference into the specification, to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated herein by reference. In addition, citation or identification of any reference in this application shall not be construed as an admission that such reference is available as prior art to the present invention.
The terms "include", and "have" and their conjugates as used herein mean "including but not necessarily limited to".
Claims
1. A photopolymer composition comprising at least one cycloaliphatic epoxy compound and a photoinitiator comprising a triarylsulfonium salt.
2. The photopolymer composition of claim 1, wherein said at least one cycloaliphatic epoxy compound constitutes 20-40 wt% and said photoinitiator constitutes 2-6 wt% of the composition.
3. The photopolymer composition of claim 1, wherein said cycloaliphatic epoxy compound is 3, 4-epoxycyclohexylmethyl-3', 4' -epoxycyclohexane carboxylate (EEC).
4. The photopolymer composition of any one of claims 1 to 3, wherein said photoinitiator comprises triarylsulfonium hexafluoro antimonate and silane.
5. The photopolymer composition of any one of claims 1 to 4, wherein said photoinitiator comprises triarylsulfonium hexafluoro antimonate, silane, and an ester of carboxymethoxy-benzophenone with poly methyl ethylene glycol or with poly tetramethylene glycol.
6. The photopolymer composition of any one of claims 1 to 5, further comprising at least one component selected from silica, glass fiber, and aliphatic polyester polyol.
7. The photopolymer composition of any one of claims 1 to 6, comprising 5-15 wt% silica, 10-30 wt% aliphatic polyester polyol, and up to 28 wt% glass fiber.
8. The photopolymer composition of any one of claims 1 to 7, further comprising up to 0.5 wt% of dibutoxyanthracene.
9. The photopolymer composition of any one of claims 1 to 8, further comprising up to 0.5 wt% antimony hexafluoride.
10. The photopolymer composition of any one of claims 1 to 9, further comprising at least one blue dye.
11. The photopolymer composition of any one of claims 1 to 10, further comprising at least one bisphenol A epoxy compound.
12. The photopolymer composition of claim 11, wherein said at least one bisphenol A epoxy compound constitutes 20-40 wt% of the composition.
IB. The photopolymer composition of claim 11 or 12, wherein said bisphenol A epoxy compound is bisphenol A diglycidyl ether (BADGE).
14. The photopolymer composition of any one of claims 1 to 13, further comprising at least one acrylic compound.
15. The photopolymer composition of claim 14, wherein said at least acrylic compound constitutes 5-10 wt% of the composition.
16. The photopolymer composition of claim 14 or 15, wherein said acrylic compound is 2-(allyloxymethyl)acrylic acid methyl ester.
17. The photopolymer composition of any one of claims 1 to 16, curable with a gentle UV irradiation.
18. The photopolymer composition of any one of claims 1 to 16, exhibiting fast solidification, and good mechanical and dielectrical properties.
19. A quickly acting photoinitiator for use in photopolymer compositions comprising at least one cycloaliphatic epoxy compound, the composition comprising a triarylsulfonium hexafluoro antimonate, silane, an ester of carboxymethoxy- benzophenone with poly methyl ethylene glycol or poly tetramethylene glycol, and antimony hexafluoride.
20. The photoinitiator for use of claim 19, comprising at least 25 wt% triarylsulfonium hexafluoro antimonate, at least 2 wt% silane, at least 10 wt% ester of
carboxymethoxy-benzophenone with poly tetramethylene glycol, and at least 2 wt% antimony hexafluoride.
21. The photoinitiator for use of claims 19 or 20, wherein said photopolymer composition is resistant to oxygen inhibition and curable with a light of a wavelength greater than 350 nm, and wherein said at least one cycloaliphatic epoxy compound constitutes 20-40 wt% of the composition.
22. The photoinitiator for use of any one of claims 19 to 21, wherein said photopolymer compositions further comprise BADGE.
23. The photoinitiator for use of claim 22, wherein BADGE constitutes at least 20 wt% of the composition.
24. The photoinitiator for use of any one of claims 19 to 23, wherein said photopolymer compositions further comprise 2-(allyloxymethyl)acrylic acid methyl ester.
25. The photoinitiator for use of claim 24, wherein 2-(allyloxymethyl)acrylic acid methyl ester constitutes at least 5 wt% of the composition.
26. A process for manufacturing a photopolymer composition of claim 1, wherein said photopolymer composition is fast solidifying, insensitive to oxygen and provides a polymer with a high mechanical and dielectric strength, the process comprising the step i) of preparing a photoinitiator, mixture 1, by mixing a) 1-4 weight parts of triarylsulfonium hexafluoro antimonate in propylene carbonate 1:1, b) 0.02-0.2 weight parts of silane, c) 0.2-2 weight parts of an ester of carboxymethoxy- benzophenone with poly tetramethylene glycol or with poly methyl ethylene glycol, and d) 0.02-0.2 weight parts of antimony hexafluoride based catalyst for thermal initiated cationic polymerization.
27. A process for manufacturing a photopolymer composition according to claim 26 further comprising steps of
ii) preparing a curing indicator, mixture 2, by dissolving a blue dye in 3,4- epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate; iii) preparing a color purifying solution, mixture 3, by dissolving an ultramarine blue material in a polyester polyol; iv) preparing a cycloaliphatic epoxy mixture, mixture 4, by mixing 20-40 weight parts of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 0.1- 0.5 weigh parts of said mixture 2, up to 1 weight parts of a polyether, and up to 0.4 weigh parts of dibutoxyanthracene, and intensively stirring with 1-2 weigh parts of silica; v) preparing a glycidyl silane mixture, mixture 5, by mixing 0.2-0.8 weight parts of (glycidyloxypropyl)trimethoxysilane, 10-30 weigh parts of a polyester polyol, and intensively stirring with 2-6 weight parts of silica at 150°C for 10- 60 minutes; and vi) combining mixtures 4 and 5 while well stirring for about 15 minutes, followed by admixing 10-25 weight parts of glass fibers, 1-3 weight parts of silica, and up to 1 weight part of said mixture 3, followed by admixing 7-30 weight parts of hydrogenated bisphenol A diglycidyl ether while mixing at 50°C for about 10 minutes; followed by adding 2-6 weight parts of mixture 1 while stirring about 10 more minutes, and adjusting the final viscosity by admixing about 1- 3 weight parts of silica; thereby obtaining a photocomposition for curing with a light of a wavelength greater than 350 nm, such as between 380 and 395 nm.
28. A process for manufacturing a photopolymer composition according to claim 27, wherein step vi) consists of combining mixtures 4 and 5 while well stirring for about 15 minutes, followed by admixing 10-25 weight parts of glass fibers, 1-3 weight parts of silica, and up to 1 weight part of said mixture 3, followed by admixing 7-30 weight parts of hydrogenated bisphenol A diglycidyl ether and either or both of 7-30 weight parts of bisphenol A diglycidyl ether (BADGE) and 5- 10 weight parts of 2-(allyloxymethyl)acrylic acid methyl ester while mixing at 50°C for about 10 minutes; followed by adding 2-6 weight parts of mixture 1 while
stirring about 10 more minutes, and adjusting the final viscosity by admixing about 1-3 weight parts of silica.
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IL275026A IL275026A (en) | 2020-06-01 | 2020-06-01 | A photopolymer epoxy composition and a photoinitiator for curing same |
IL2020050833 | 2020-07-28 | ||
PCT/IL2021/050623 WO2021245650A1 (en) | 2020-06-01 | 2021-05-26 | A photopolymer epoxy composition and a photoinitiator for curing same |
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IL (1) | IL283470A (en) |
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