CN113024690B - Photoinitiator composition, photo-curing composition and photo-curing product - Google Patents
Photoinitiator composition, photo-curing composition and photo-curing product Download PDFInfo
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- CN113024690B CN113024690B CN202011629068.8A CN202011629068A CN113024690B CN 113024690 B CN113024690 B CN 113024690B CN 202011629068 A CN202011629068 A CN 202011629068A CN 113024690 B CN113024690 B CN 113024690B
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- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 58
- 239000012952 cationic photoinitiator Substances 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 51
- 125000003435 aroyl group Chemical group 0.000 claims description 27
- 125000001424 substituent group Chemical group 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000005843 halogen group Chemical group 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- -1 cyclic carbonate compounds Chemical class 0.000 claims description 14
- 125000001072 heteroaryl group Chemical group 0.000 claims description 12
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 7
- 125000004946 alkenylalkyl group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000005257 alkyl acyl group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 238000001723 curing Methods 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000005548 dental material Substances 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 125000005253 heteroarylacyl group Chemical group 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 4
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims 1
- 150000002921 oxetanes Chemical class 0.000 claims 1
- 206010070834 Sensitisation Diseases 0.000 abstract description 22
- 230000008313 sensitization Effects 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 17
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- TXOZSRCVHASUCW-UHFFFAOYSA-N 1,3,3,3-tetrafluoropropan-1-ol Chemical compound OC(F)CC(F)(F)F TXOZSRCVHASUCW-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GHXXDRXSFYGBLJ-UHFFFAOYSA-N [9-ethyl-6-(4-fluorobenzoyl)carbazol-3-yl]-(4-fluorophenyl)methanone Chemical compound C(C)N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C(=O)C1=CC=C(C=C1)F)C(=O)C1=CC=C(C=C1)F GHXXDRXSFYGBLJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000001454 anthracenes Chemical class 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- CSUFEOXMCRPQBB-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropan-1-ol Chemical compound CC(F)(F)C(O)(F)F CSUFEOXMCRPQBB-UHFFFAOYSA-N 0.000 description 1
- XSYIOOOYIJWUNF-UHFFFAOYSA-N 11-(2-ethylhexyl)benzo[a]carbazole Chemical compound C1=CC=CC2=C3N(CC(CC)CCCC)C4=CC=CC=C4C3=CC=C21 XSYIOOOYIJWUNF-UHFFFAOYSA-N 0.000 description 1
- PGIGZWJIJSINOD-UHFFFAOYSA-N 12h-benzo[a]phenothiazine Chemical compound C1=CC=CC2=C3NC4=CC=CC=C4SC3=CC=C21 PGIGZWJIJSINOD-UHFFFAOYSA-N 0.000 description 1
- YOSZEPWSVKKQOV-UHFFFAOYSA-N 12h-benzo[a]phenoxazine Chemical compound C1=CC=CC2=C3NC4=CC=CC=C4OC3=CC=C21 YOSZEPWSVKKQOV-UHFFFAOYSA-N 0.000 description 1
- RAAGZOYMEQDCTD-UHFFFAOYSA-N 2-fluorobenzoyl chloride Chemical compound FC1=CC=CC=C1C(Cl)=O RAAGZOYMEQDCTD-UHFFFAOYSA-N 0.000 description 1
- UJVBZCCNLAAMOV-UHFFFAOYSA-N 2h-1,2-benzothiazine Chemical class C1=CC=C2C=CNSC2=C1 UJVBZCCNLAAMOV-UHFFFAOYSA-N 0.000 description 1
- CZKLEJHVLCMVQR-UHFFFAOYSA-N 4-fluorobenzoyl chloride Chemical compound FC1=CC=C(C(Cl)=O)C=C1 CZKLEJHVLCMVQR-UHFFFAOYSA-N 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000012663 cationic photopolymerization Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
-
- 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
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F16/32—Monomers containing two or more unsaturated aliphatic radicals
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Epoxy Resins (AREA)
- Indole Compounds (AREA)
Abstract
The application provides a photoinitiator composition, a photo-curing composition and a photo-curing product. The photoinitiator composition comprises a sensitizer and a cationic photoinitiator, wherein the sensitizer is selected from any one or more of compounds shown in a formula I and compounds shown in a formula II-A to a formula II-I:
Description
Technical Field
The application relates to the technical field of photocuring, in particular to a photoinitiator composition, a photocuring composition and a photocuring product.
Background
The UV light curing technology has been widely used since the 70 s, and in the aspect of curing light sources, LED lamps are used in recent years to replace mercury lamps which are toxic to the environment and consume electricity, and are increasingly used in the fields of printing industry, electronic product manufacturing and the like. However, at present, the output light of the LED lamp with better cost performance is relatively long wave (365 nm-405 nm), for example, the LED lamp with emission wavelengths of 365nm, 385nm and 395nm as main materials is a common commercial product, and even a 405nm ultraviolet laser product is common. This is very different from the spectral emission of mercury lamps, especially ultraviolet light of 200-350 nm, which has not been commercially available on LED lamps, and this presents a challenge to the photo-curing technology industry. Based on the characteristics of the photo-curing technology, the effective absorption range of the photo-initiator and the emission spectrum of the light source should be effectively overlapped to enable the photo-initiator to be fully photolyzed and generate enough active groups, so that the polymerization rate reaches the standard requirement, and further the physical property and the chemical property of the cured material are ensured to reach the use requirement.
There are many photoinitiators having an absorption of 350nm or less, for example, such as Omnirad 1173, omnirad907, or such as OMNICAT from IGM resin company, and such as Omnicat 250, omnicat 440, omnicat 432, or Omnicat 270. As the light source changes, these products are eliminated from being able to match the energy of the light source, and thus those skilled in the art contemplate the use of sensitizers in combination with initiators, such as anthracene compounds in combination with cations, as used by the american 3M company in its international patent application No. WO2005051332, for the preparation of visible light source cured dental materials; the sensitization of thioxanthones to cations was studied in Jung-Dae Cho and Jin-Who Hong papers (Photocuring kinetics for the UV-initiated cationic polymerization of a cycloaliphatic diepoxide system photosensitized by thioxanthone. Eur. Polym. J,2005,41 (2), 367); crivello studied the use of anthracene compounds (Anthracene electron-transfer photosensitizers for onium salt induced cationic photopolymerizations, J.Photochem. Photobrio. A: chemistry,2003,159,173) and benzothiazine compounds (Benzophenothiazine and benzophenoxazine photosensitizers for triarylsulonium salt cationic photoinitiators. J.polym. Sci. A: polym. Chem.,2008,46 (11), 3820) as sensitizers with sulfonium salts. However, the sensitization effect obtained by the combined sensitizer and initiator used in the above methods is still to be further improved.
Disclosure of Invention
The application mainly aims to provide a photoinitiator composition, a photocuring composition and a photocuring product, which are used for solving the problem of low sensitization effect of a combined sensitizer in the prior art.
In order to achieve the above object, according to one aspect of the present application, there is provided a photoinitiator composition comprising a sensitizer selected from any one or more of a compound represented by formula I, a compound represented by formula II-a, a compound represented by II-B, a compound represented by II-C, a compound represented by formula II-D, a compound represented by formula II-E, a compound represented by formula II-F, a compound represented by formula II-G, a compound represented by II-H, and a compound represented by II-I, and a cationic photoinitiator:
wherein R is 1 、R 2 、R 4 、R 5 、R 7 、R 8 、R 24 、R 25 、R 27 、R 28 、R 31 、R 34 、R 35 、R 37 、R 38 、R 41 、R 42 、R 45 、R 47 、R 48 、R 54 、R 55 、R 61 、R 62 、R 67 、R 68 、R 71 、R 72 、R 74 、R 75 、R 102 、R 103 、R 104 、R 105 、R 107 、R 108 、R 112 、R 114 、R 115 、R 117 、R 118 、R 121 、R 122 、R 124 、R 125 、R 127 Each independently selected from H, halogen atom, C 1 ～C 8 Alkyl, C of (2) 1 ～C 8 Any one of alkoxy, carbon-nitrogen triple bond; r is R 70 Selected from H, C 1 ～C 10 R is any one of alkoxy groups of (C) 73 Selected from H,C 6 ～C 20 Any one of aroyl groups of (a); r is R 6 、R 26 、R 36 、R 46 、R 56 、R 66 、R 106 、R 116 、R 126 Each independently selected from H, halogen atoms, carbon-nitrogen triple bonds, C 1 ～C 8 Alkyl, C of (2) 1 ～C 12 Alkyl acyl, C 6 ～C 20 Is substituted or unsubstitutedAroyl, C 4 ～C 20 Substituted or unsubstituted heteroarylacyl, < >>Any one of them; r is R 6 、R 26 、R 36 、R 46 、R 56 、R 66 、R 106 、R 116 Each independently may form a 5-7 membered ring with its adjacent substituents; r is R 9 、R 29 、R 39 、R 49 、R 59 、R 69 Each independently selected from substituted or unsubstituted C 1 ～C 12 Straight chain alkyl, C 3 ～C 12 Branched alkyl, C 2 ～C 12 Alkenyl, C 3 ～C 12 Alkenyl alkyl, C 6 ～C 20 Any one of the aryl groups of (a); ar (Ar) 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 、Ar 8 Each independently selected from C 6 ～C 20 Substituted or unsubstituted aryl, C 4 ～C 20 Any one of substituted or unsubstituted heteroaryl groups; r is R 119 Selected from C 6 ～C 20 Substituted or unsubstituted aryl, C 4 ～C 20 Substituted or unsubstituted heteroaryl, C 1 ～C 20 Any one of the alkyl groups of (a); y is selected from C 1 ～C 3 Straight chain alkyl or C 3 Branched alkylene of (a); m is 0 or 1, and the molar ratio of sensitizer to cationic photoinitiator is greater than 0.2.
Further, R is as described above 6 、R 26 、R 36 、R 46 、R 56 、R 66 、R 106 、R 116 、R 126 Each independently selected from H, C 6 ～C 20 Substituted aroyl or C 4 ～C 20 Preferably C when substituted heteroaroyl 6 ～C 20 Substituted aroyl groups of (C) 4 ～C 20 Each of the substituents on the substituted heteroaroyl groups is independently selected from halogen atoms, R 40 、-OR 50 、-SR 50 、-NR 51 R 52 、-COOR 50 、-CONR 51 R 52 Any one or more of the following; wherein R is 40 、R 50 Each independently selected from C 1 ～C 8 Substituted or unsubstituted alkyl, C containing one or two hetero atoms 5 ～C 6 Any one of cycloalkyl, substituted or unsubstituted phenyl; preferably the heteroatom is selected from any one or more of O, S, N, preferably C 1 ～C 8 The substituent in the substituted alkyl of (a) is selected from any one or more of-F, -Cl and hydroxyl; preferably R 40 、R 50 Each independently selected from C 3 ～C 8 Any of the substituted alkyl groups of (2), preferably C 3 ～C 8 The substituent in the substituted alkyl of (a) is selected from any one or more of-O-, hydroxyl and acetoxy; r is R 51 、R 52 Each independently selected from C 1 ～C 4 Substituted or unsubstituted alkyl, substituted or unsubstituted C 5 ～C 7 Any one of the heterocycloalkyl groups of (C) is preferred 1 ～C 4 The substituent in the substituted alkyl of (a) is selected from any one or more of methyl, ethyl and hydroxyl; further, NR is preferred 51 R 52 Each independently selected fromAny one of them, further preferably +.>Preferably R 6 、R 26 、R 36 、R 46 、R 56 、R 66 、R 106 、R 116 、R 126 Each independently selected from C 1 ～C 4 Straight chain alkyl, C 3 ～C 5 Branched alkyl, C 6 ～C 10 Alkyl acyl, C 6 ～C 10 Substituted or unsubstituted aroyl, C 4 ～C 10 Is further preferably R 6 、R 26 、R 36 、R 46 、R 56 、R 66 、R 106 、R 116 、R 126 Each independently selected from->
Any one of the following.
Further, R is as described above 9 、R 29 、R 39 、R 49 、R 59 、R 69 Is substituted with one or more of the following substituents: phenyl, C 5 ～C 6 Cycloalkyl, C 3 ～C 6 Heterocyclic groups of (C), halogen, -COOR 20 、-OR 20 、-SR 20 、-PO(OC n H 2n+1 ) 2 、-Si(C n H 2n+1 ) 3 Wherein n is an integer of 1 to 4; preferably R 9 、R 29 、R 39 、R 49 、R 59 、R 69 Each independently selected from substituted or unsubstituted C 3 ～C 12 Alkyl, C of (2) 3 ～C 12 Is further preferably C 3 ～C 12 Alkyl and C of (C) 3 ～C 12 Each independently inserted into one or more of the carbon chains in the alkenyl alkyl group of O, S, S = O, SO 2 CO or carboxyl; preferably R 9 、R 29 、R 39 、R 49 、R 59 、R 69 Each independently selected from substituted or unsubstituted C 1 ～C 10 Straight chain alkyl, C 3 ～C 10 Branched alkyl, C 2 ～C 6 Alkenyl, C 3 ～C 6 Alkenyl alkyl, C 6 ～C 10 Any one of the aryl groups of (2), preferably R 9 、R 29 、R 39 、R 49 、R 59 、R 69 Each independently selected from phenyl or substituted phenyl, preferably substituted phenyl substituted with one or more of the following substituents: c (C) 1 ～C 8 Alkyl, halogen atom, -OR 20 、-SR 20 、-COR 30 -CN, -COOH; further, R is preferably 29 、R 39 、R 49 、R 59 、R 69 Each independently selected from
Any one of the following.
Further, ar is as described above 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 、Ar 8 Each independently selected from C 6 ～C 10 Substituted or unsubstituted aryl, C 4 ～C 10 Any of the substituted or unsubstituted heteroaryl groups, preferably Ar 1 、Ar 2 、Ar 5 The acyl ortho carbon atoms on the carbazole ring are each independently linked to any carbon atom on the carbazole ring through-O-or-S-; further preferred Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 、Ar 8 Each independently selected from
Any one of the following.
Further, the method comprises the steps of,r is as described above 119 Selected from C 6 ～C 10 Substituted or unsubstituted aryl, C 4 ～C 10 Substituted or unsubstituted heteroaryl, C 1 ～C 10 Any one of the alkyl groups of (a); preferably R 119 Selected from the group consisting of
Any one of the following.
Further, R 73 Is C 6 ～C 20 C at aroyl group of (C) 6 ～C 20 At least one hydrogen atom in the aroyl group of (2) is substituted by a halogen atom, and/or at C 6 ～C 20 Is further preferred by inserting an O atom into the side chain of the aroyl group of R 73 Is that Any one of the following.
Further, R is as described above 70 Is methoxy.
Further, the cationic photoinitiator is selected from any one or more of sulfonium salt photoinitiators and iodonium salt photoinitiators.
According to another aspect of the present application, there is provided a photocurable composition comprising 1 to 10wt% of a photoinitiator component and 90 to 99wt% of a cationically polymerizable compound, wherein the photoinitiator component comprises the aforementioned photoinitiator composition.
Further, the cationically polymerizable compound is selected from any one or more of an epoxy compound, a vinyl ether compound, an oxetane compound, and a cyclic carbonate compound, and further, preferably, the cationically polymerizable compound is selected from
Any one or more of the following.
According to still another aspect of the present application, there is provided a photocurable product formed by photocuring a photocurable composition as described above, preferably a photocurable product selected from any one of paint, adhesive, printing ink, dental material.
By applying the technical scheme of the application, the sensitizer takes carbazole as a core structure, has various variant structures of the formulas I, II-A to II-I, and has various substituents such as alkyl, aroyl, alkoxy, halogen and the like on the structure of each variant compound, so that the molecular structure of the sensitizer is further enriched, the sensitization effect of the sensitizer is improved, and when the molar ratio of the sensitizer to the cationic photoinitiator is greater than 0.2, the photoinitiator composition has a stronger sensitization effect.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
As analyzed by the background art, the problem of lower sensitization effect of the combined sensitizer exists in the prior art, and in order to solve the problem, the application provides a photoinitiator composition, a photocuring composition and a photocuring product.
In a typical embodiment of the present application, there is provided a photoinitiator composition comprising a sensitizer and a cationic photoinitiator, wherein the sensitizer is selected from any one or more of a compound represented by formula I, a compound represented by formula II-A, a compound represented by formula II-B, a compound represented by formula II-C, a compound represented by formula II-D, a compound represented by formula II-E, a compound represented by formula II-F, a compound represented by formula II-G, a compound represented by formula II-H, and a compound represented by formula II-I:
wherein R is 1 、R 2 、R 4 、R 5 、R 7 、R 8 、R 24 、R 25 、R 27 、R 28 、R 31 、R 34 、R 35 、R 37 、R 38 、R 41 、R 42 、R 45 、R 47 、R 48 、R 54 、R 55 、R 61 、R 62 、R 67 、R 68 、R 71 、R 72 、R 74 、R 75 、R 102 、R 103 、R 104 、R 105 、R 107 、R 108 、R 112 、R 114 、R 115 、R 117 、R 118 、R 121 、R 122 、R 124 、R 125 、R 127 Each independently selected from H, halogen atom, C 1 ～C 8 Alkyl, C of (2) 1 ～C 8 Any one of alkoxy, carbon-nitrogen triple bond; r is R 70 Selected from H, C 1 ～C 10 R is any one of alkoxy groups of (C) 73 Selected from H,C 6 ～C 20 Any one of aroyl groups of (a); r is R 6 、R 26 、R 36 、R 46 、R 56 、R 66 、R 106 、R 116 、R 126 Each independently selected from H, halogen atoms, carbon-nitrogen triple bonds, C 1 ～C 8 Alkyl, C of (2) 1 ～C 12 Alkyl acyl, C 6 ～C 20 Substituted or unsubstituted aroyl, C 4 ～C 20 Substituted or unsubstituted heteroarylacyl, < >>Any one of them; r is R 6 、R 26 、R 36 、R 46 、R 56 、R 66 、R 106 、R 116 Each independently may form a 5-7 membered ring with its adjacent substituents; r is R 9 、R 29 、R 39 、R 49 、R 59 、R 69 Each independently selected from substituted or unsubstituted C 1 ～C 12 Straight chain alkyl, C 3 ～C 12 Branched alkyl, C 2 ～C 12 Alkenyl, C 3 ～C 12 Alkenyl alkyl, C 6 ～C 20 Any one of the aryl groups of (a); ar (Ar) 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 、Ar 8 Each independently selected from C 6 ～C 20 Substituted or unsubstituted aryl, C 4 ～C 20 Any one of substituted or unsubstituted heteroaryl groups; r is R 119 Selected from C 6 ～C 20 Substituted or unsubstituted aryl, C 4 ～C 20 Substituted or unsubstituted heteroaryl, C 1 ～C 20 Any one of the alkyl groups of (a); y is selected from C 1 ～C 3 Straight chain alkyl or C 3 Branched alkylene of (a); m is 0 or 1, and the molar ratio of sensitizer to cationic photoinitiator is greater than 0.2.
The sensitizer takes carbazole as a core structure, has various variant structures from formula I, formula II-A to formula II-I, and has various substituents such as alkyl, aroyl, alkoxy, halogen and the like on the structure of each variant compound, so that the molecular structure of the sensitizer is further enriched, the sensitization effect of the sensitizer is improved, and when the molar ratio of the sensitizer to the cationic photoinitiator is greater than 0.2, the photoinitiator composition has a stronger sensitization effect.
To further enhance the sensitization of the corresponding sensitizers of formulas I, II-A to II-H, R is preferably as defined above 6 、R 26 、R 36 、R 46 、R 56 、R 66 、R 106 、R 116 、R 126 Each independently selected from H, C 6 ～C 20 Substituted aroyl or C 4 ～C 20 Preferably C when substituted heteroaroyl 6 ～C 20 Substituted aroyl groups of (C) 4 ～C 20 Each of the substituents on the substituted heteroaroyl groups is independently selected from halogen atoms, R 40 、OR 50 、SR 50 、NR 51 R 52 、COOR 50 、CONR 51 R 52 Any one or more of the following; wherein R is 40 、R 50 Each independently selected from C 1 ～C 8 Substituted or unsubstituted alkyl, C containing one or two hetero atoms 5 ～C 6 Any one of cycloalkyl, substituted or unsubstituted phenyl; preferably the heteroatom is selected from any one or more of O, S, N, preferably C 1 ～C 8 The substituent in the substituted alkyl of (a) is selected from any one or more of-F, -Cl and hydroxyl; preferably R 40 、R 50 Each independently selected from C 3 ～C 8 Any of the substituted alkyl groups of (2), preferably C 3 ～C 8 The substituent in the substituted alkyl of (a) is selected from any one or more of-O-, hydroxyl and acetoxy; r is R 51 、R 52 Each independently selected from C 1 ～C 4 Substituted or unsubstituted alkyl, substituted or unsubstituted C 5 ～C 7 Any one of the heterocycloalkyl groups of (C) is preferred 1 ～C 4 The substituent in the substituted alkyl of (a) is selected from any one or more of methyl, ethyl and hydroxyl; further, the bestSelect NR 51 R 52 Each independently selected from Any one of them, further preferably +.> Preferably R 6 、R 26 、R 36 、R 46 、R 56 、R 66 、R 106 、R 116 、R 126 Each independently selected from C 1 ～C 4 Straight chain alkyl, C 3 ～C 5 Branched alkyl, C 6 ～C 10 Alkyl acyl, C 6 ～C 10 Substituted or unsubstituted aroyl, C 4 ～C 10 Is further preferably R 6 、R 26 、R 36 、R 46 、R 56 、R 66 、R 106 、R 116 、R 126 Each independently selected from-> Any one of the following.
The R is preferably selected so as to further act on the carbazole N substituent and the carbazole ring to enhance the sensitization effect of the sensitizer 9 、R 29 、R 39 、R 49 、R 59 、R 69 Is substituted with one or more of the following substituents: phenyl, C 5 ～C 6 Cycloalkyl, C 3 ～C 6 Heterocyclic groups of (C), halogen, -COOR 20 、-OR 20 、-SR 20 、-PO(OC n H 2n+1 ) 2 、-Si(C n H 2n+1 ) 3 Wherein n is an integer of 1 to 4; preferably R 9 、R 29 、R 39 、R 49 、R 59 、R 69 Each independently selected from substituted or unsubstituted C 3 ～C 12 Alkyl, C of (2) 3 ～C 12 Is further preferably C 3 ～C 12 Alkyl and C of (C) 3 ～C 12 Each independently inserted into one or more of the carbon chains in the alkenyl alkyl group of O, S, S = O, SO 2 CO or carboxyl; preferably R 9 、R 29 、R 39 、R 49 、R 59 、R 69 Each independently selected from substituted or unsubstituted C 1 ～C 10 Straight chain alkyl, C 3 ～C 10 Branched alkyl, C 2 ～C 6 Alkenyl, C 3 ～C 6 Alkenyl alkyl, C 6 ～C 10 Any one of the aryl groups of (2), preferably R 9 、R 29 、R 39 、R 49 、R 59 、R 69 Each independently selected from phenyl or substituted phenyl, preferably substituted phenyl substituted with one or more of the following substituents: c (C) 1 ～C 8 Alkyl, halogen atom, -OR 20 、-SR 20 、-COR 30 -CN, -COOH; further, R is preferably 29 、R 39 、R 49 、R 59 、R 69 Each independently selected from
Any one of the following.
To enhance the electron action of aroyl groups with carbazole rings,thereby improving the sensitization effect of the sensitizer, preferably Ar as described above 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 、Ar 8 Each independently selected from C 6 ～C 10 Substituted or unsubstituted aryl, C 4 ～C 10 Any of the substituted or unsubstituted heteroaryl groups, preferably Ar 1 、Ar 2 、Ar 5 The acyl ortho carbon atoms on the carbazole ring are each independently linked to any carbon atom on the carbazole ring through-O-or-S-; further preferred Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 、Ar 8 Each independently selected from
/>
Any one of the following.
To improve R 119 The sensitizer having excellent sensitization by the action effect with carbazole of II-G is preferably the above R 119 Selected from C 6 ～C 10 Substituted or unsubstituted aryl, C 4 ～C 10 Substituted or unsubstituted heteroaryl, C 1 ～C 10 Any one of the alkyl groups of (a); preferably R 119 Selected from the group consisting of
Any one of the following.
To further increase R 73 The sensitizer having excellent sensitization by the action effect with carbazole of II-G is preferably the above R 73 Is C 6 ～C 20 C at aroyl group of (C) 6 ～C 20 At least one hydrogen atom in the aroyl group of (2) is substituted by a halogen atom, and/or at C 6 ～C 20 Is further preferred by inserting an O atom into the side chain of the aroyl group of R 73 Is that Any one of the following.
In one embodiment of the application, R is 70 Methoxy, to further pass R 70 The substituent increases the sensitization of the II-I corresponding sensitizer.
In order to improve the sensitization of the sensitizer and enable the sensitizer to better cooperate with the cationic photoinitiator to obtain a photoinitiator composition with excellent comprehensive sensitization, the sensitizer is preferably selected from any one or more of the following structural formulas:
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in order to allow the sensitizer and the cationic photoinitiator to perform a more sufficient synergistic effect, it is preferable that the cationic photoinitiator is selected from any one or more of sulfonium salt type photoinitiators and iodonium salt type photoinitiators.
In order to further enhance the synergistic effect of the sulfonium salt photoinitiator, the iodonium salt photoinitiator and the sensitizer of the present application to obtain a photoinitiator composition with better sensitization, any one or more of the following sulfonium salt photoinitiator and iodonium salt photoinitiator are preferred:
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of course, the person skilled in the art can select the conventional sulfonium salt photoinitiator and iodonium salt photoinitiator according to actual needs, and the description is omitted here.
In another exemplary embodiment of the present application, a photocurable composition is provided that includes 1-10 wt% of a photoinitiator component and 90-99 wt% of a cationically polymerizable compound, wherein the photoinitiator component includes the aforementioned photoinitiator composition.
The photocurable composition comprising the aforementioned photoinitiator composition has excellent sensitization.
In order to allow the cationically polymerizable compound to undergo polymerization reaction more sufficiently under the action of the above photoinitiator composition, it is preferable that the cationically polymerizable compound is selected from any one or more of an epoxy compound, a vinyl ether compound, an oxetane compound, and a cyclic carbonate compound, and further, it is preferable that the cationically polymerizable compound is selected from
Any one or more of the following.
In still another exemplary embodiment of the present application, there is provided a photo-cured product formed by photo-curing a photo-curing composition as described above, preferably a photo-curing product selected from any one of paint, adhesive, printing ink, dental material.
The photo-cured product obtained by curing the photo-cured composition has excellent performance and can be widely applied to photo-cured products, and the photo-cured products are preferably selected from any one of paint, adhesive, printing ink and dental materials.
The advantageous effects of the present application will be described below with reference to specific examples and comparative examples.
Sensitizer preparation examples
Sensitizer preparation example 1
19.5g of N-ethyl carbazole is added into 250mL of dichloroethane for dissolution, 34g of aluminum trichloride is added, the temperature is kept between 0 ℃ and minus 5 ℃, 40g of p-fluorobenzoyl chloride is added into the solution in a dropwise manner, and then the reaction solution is kept at 0 ℃ to 5 ℃ for reaction for 15 hours. The reaction mixture was added in portions to 100ml of 10% HCl at 0deg.C and stirred for 30min. After standing for 30 minutes, the solution was separated, and the dichloroethane phase was washed with 50mL of 2% sodium hydroxide solution for 30 minutes, to separate the dichloroethane phase. The dichloroethane solution was distilled under reduced pressure and dichloroethane was recovered, and 80mL of ethyl acetate was added to the residue for crystallization to give 30.5g of a 9-ethyl-3, 6-bis (4-fluorobenzoyl) carbazole product having a white powder content of 98.5% and a yield of 69.5%.
30g of 9-ethyl-3, 6-bis (4-fluorobenzoyl) carbazole, 25g of 2, 3-tetrafluoropropanol and 8g of sodium hydroxide were dissolved in 200mL of pyridine and reacted at 70℃for 18 hours. Vacuum distillation, and distilling off pyridine and redundant 2, 3-tetrafluoropropanol. To the residue was added 100mL of water, 250mL of dichloroethane, and stirred for 1h. The aqueous phase was separated and the dichloroethane solution was washed 2 times with 100mL of water. Recovering dichloroethane by distillation under reduced pressure, adding 150mL of ethyl acetate and 2g of activated carbon to the residue, refluxing under heating for 1 hour, filtering the activated carbon, removing about 100mL of ethyl acetate from the filtrate by distillation under reduced pressure, cooling to crystallize, filtering, drying the filter cake to obtain 27.8g, and obtaining 9-ethyl-3, 6-bis [4- (2, 3-tetrafluoropropoxy) benzoyl as pale yellow powder]Carbazole (formula I-30) was 98.5% in yield of 61.4%. Which is a kind of 1 H-NMR CDCl 3 Delta [ ppm ]]:1.512(t,3H),4.425-4.483(m,6H),5.949-6.277(m,2H),7.016-7.045(m,4H),7.496-7.517(d,2H),7.844-7.868(d,4H),7.990-8.011(d,2H),8.534(s,2H)。
Sensitizer preparation example 2
To a 50mL single flask, 2.0g of 11- (2-ethylhexyl) -11H-benzo [ a ] carbazole was added, and 20mL of dichloroethane was added to dissolve the mixture, 0.2g of zinc chloride was added, 2.3g of o-fluorobenzoyl chloride was added, and the mixture was stirred at 80℃to react for 10 hours. After cooling, the reaction mixture was washed twice with 20mL of water, and the dichloroethane solution was concentrated to dryness under reduced pressure to give 11- (2-ethylhexyl) -5, 8-bis (4-fluorobenzoyl) -11H-benzo [ a ] carbazole as a brown viscous material.
4.0g of 11- (2-ethylhexyl) -5,8 bis (4-fluorobenzoyl) -11H-benzo [ a ]]Carbazole was dissolved in a 50mL single-necked flask with 20mL pyridine, 2.2g of tetrafluoropropanol and 1.2g of sodium hydroxide were added thereto, and the mixture was stirred at 80℃for 5 hours. The reaction was added dropwise to 100mL of water, and then stirred with 100mL of dichloroethane for 1h, followed by standing for delamination. The separated dichloroethane solution was concentrated to dryness under reduced pressure to give 4.7g of a coffee coloured solid. The solid is heated and dissolved by a mixed solvent of 20mL of ethyl acetate and 20mL of ethanol, 0.25g of active carbon is added for refluxing for 1 hour, hot filtration is carried out, and yellow crystals of 11- (2-ethylhexyl) -5,8 bis [2- (2, 3-tetrafluoropropoxy) benzoyl are separated out after the filtrate is cooled]-11H-benzeneAnd [ a ]]Carbazole (formula II-5), weighing 2.5g after drying, and obtaining the total yield of 51.3% and 98.51% in two steps. Formula II-5 1 H-NMR(CDCl 3 )，δ[ppm]:0.754-0.789(m,6H),1.126-1.328(m,8H),2.113(s,1H),4.369-4.452(t,2H),4.513-4.599(t,2H),4.928(m,2H),4.994-5.342(m,1H),5.537-5.885(m,1H),7.251-7.272(m,4H),7.430-7.455(d,1H),7.566-7.811(m,6H),7.950-7.979(d,1H),8.430(s,1H),8.571(s,1H),8.668-8.695(d,1H),8.736-8.764(d,1H)。
Preparation of photoinitiator composition examples
Preparation of photoinitiator composition example 1
6g of Omnicat 270 and 6g of the compound shown in the formula I-30 are taken, put into a mortar for grinding and mixing, and light yellow powder is obtained, namely, a sample with the molar ratio of sensitizer to cationic photoinitiator active group being 1.29.
Preparation of photoinitiator composition example 2
6g of Omnicat 270 and 4.2g of the compound shown in the formula I-30 are taken, put into a mortar for grinding and mixing, and light yellow powder is obtained, namely, a sample with the molar ratio of sensitizer to cationic photoinitiator active group being 0.91.
Preparation of photoinitiator composition example 3
6g of Omnicat 270 and 13.2g of the compound shown in the formula I-30 are taken, put into a mortar for grinding and mixing, and light yellow powder is obtained, namely, a sample with the molar ratio of sensitizer to cationic photoinitiator active group being 2.85.
Preparation of photoinitiator composition example 4
6g of Omnicat 432 and 6g of the compound shown in the formula I-30 are taken, heated to 70 ℃ for dissolution and mixing, and yellow liquid is obtained, namely the sample with the molar ratio of sensitizer to cationic photoinitiator active group being 2.28.
Preparation of photoinitiator composition example 5
6g of Esacure 1187 and 6g of the compound shown in the formula I-30 are heated to 70 ℃ for dissolution and mixing to obtain yellow liquid, namely the product with the molar ratio of sensitizer to cationic photoinitiator active group of 1.00.
Preparation of photoinitiator composition example 6
6g of Omnicat 270 and 1.96g of the compound of formula II-5 are taken, put into a mortar for grinding and mixing, and light yellow powder is obtained, namely, a sample with the molar ratio of sensitizer to cationic photoinitiator active group being 0.35 is obtained.
Preparation of photoinitiator composition example 7
6g of Omnicat 250 and 6g of the compound of the formula II-5 are heated to 70 ℃ for dissolution and mixing, and yellow liquid is obtained, namely the sample with the molar ratio of sensitizer to cationic photoinitiator active group of 0.83.
Application examples of photocurable compositions:
the following experimental equipment and reagents and materials involved in the application of the photocurable composition to the examples/comparative examples are as follows:
light source device:
365nm LED area light source, blue sky light development Co., ltd;
395nm LED area light source, blue sky light development Co., ltd;
test equipment:
pendulum sclerometer;
reagents and materials:
omnilane OC 1005:3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylmethyl ester, commercially available from IGM resins company;
omnicat 270: comprises a compound of formula III-5, a commodity of IGM resin company;
omnicat 250: comprises a compound of formula III-14, a commodity of IGM resin company;
omnicat 432: comprises compounds of the formulae III-1 and III-2, with a solids content of 45%, commercially available from IGM resins;
esacure 1187: contains a compound of formula III-12, and has a solid content of 75%; IGM resins company.
The photo-curable compositions were prepared according to the respective components and amounts shown in tables 1 to 7, applied to the examples/comparative examples (pre-mixing), dissolved and uniformly mixed, and then coated on a glass plate using a 25 μm bar, and cured by irradiation with a light source for 1s in each table, and pendulum hardness of each sample was measured at 1h, 3h, and 24h after curing, and the measurement results were set in tables 8 to 14, respectively.
TABLE 1
Wherein, the mol ratio of sensitizer to cationic photoinitiator active group: (sensitizer mole number of active groups)/(cation mole number of active groups).
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
TABLE 9
Table 10
TABLE 11
Table 12
TABLE 13
TABLE 14
As can be seen from a comprehensive analysis of the above tables 1 to 14, the photoinitiator composition of the present application has excellent sensitization effect.
From the above description, it can be seen that the above embodiments of the present application achieve the following technical effects:
the sensitizer takes carbazole as a core structure, has various variant structures from formula I, formula II-A to formula II-I, and has various substituents such as alkyl, aroyl, alkoxy, halogen and the like on the structure of each variant compound, so that the molecular structure of the sensitizer is further enriched, the sensitization effect of the sensitizer is improved, and when the molar ratio of the sensitizer to the cationic photoinitiator is greater than 0.2, the photoinitiator composition has a stronger sensitization effect.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (30)
1. A photocurable composition comprising 1 to 10wt% of a photoinitiator component and 90 to 99wt% of a cationically polymerizable compound, wherein the photoinitiator component comprises the photoinitiator composition;
the cationically polymerizable compound is selected fromAny one or more of vinyl ether compounds, oxetane compounds and cyclic carbonate compounds;
the photoinitiator composition comprises a sensitizer and a cationic photoinitiator, and is characterized in that the sensitizer is selected from any one or more of a compound shown in a formula I, a compound shown in a formula II-A, a compound shown in a formula II-B, a compound shown in a formula II-C, a compound shown in a formula II-D, a compound shown in a formula II-E, a compound shown in a formula II-F, a compound shown in a formula II-G, a compound shown in a formula II-H and a compound shown in a formula II-I:
wherein R is 1 、R 2 、R 4 、R 5 、R 7 、R 8 、R 24 、R 25 、R 27 、R 28 、R 31 、R 34 、R 35 、R 37 、R 38 、R 41 、R 42 、R 45 、R 47 、R 48 、R 54 、R 55 、R 61 、R 62 、R 67 、R 68 、R 71 、R 72 、R 74 、R 75 、R 102 、R 103 、R 104 、R 105 、R 107 、R 108 、R 112 、R 114 、R 115 、R 117 、R 118 、R 121 、R 122 、R 124 、R 125 、R 127 Each independently selected from H, halogen atom, C 1 ～C 8 Alkyl, C of (2) 1 ～C 8 Any one of alkoxy, carbon-nitrogen triple bond;
R 70 selected from H, C 1 ～C 10 R is any one of alkoxy groups of (C) 73 Selected from H,C 6 ～C 20 Any one of aroyl groups of (a);
R 6 selected from the group consisting of
Any one of them;
R 26 、R 36 、R 46 、R 56 、R 66 、R 106 、R 116 、R 126 each independently selected from H, halogen atoms, carbon-nitrogen triple bonds, C 1 ～C 8 Alkyl, C of (2) 1 ～C 12 Alkyl acyl, C 6 ～C 20 Substituted or unsubstituted aroyl, C 4 ～C 20 Substituted or unsubstituted heteroaryl acyl,Any one of them;
the R is 6 Said R is 26 Said R is 36 Said R is 46 Said R is 56 Said R is 66 Said R is 106 Said R is 116 Each independently may form a 5-7 membered ring with its adjacent substituents;
R 9 、R 29 、R 39 、R 49 、R 59 、R 69 each independently selected from substituted or unsubstituted C 1 ～C 12 Straight chain alkyl, C 3 ～C 12 Branched alkyl, C 2 ～C 12 Alkenyl, C 3 ～C 12 Alkenyl alkyl, C 6 ～C 20 Any one of the aryl groups of (a);
Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 、Ar 7 、Ar 8 each independently selected from C 6 ～C 20 Substituted or unsubstituted aryl, C 4 ～C 20 Any one of substituted or unsubstituted heteroaryl groups;
R 119 selected from C 6 ～C 20 Substituted or unsubstituted aryl, C 4 ～C 20 Substituted or unsubstituted heteroaryl, C 1 ～C 20 Any one of the alkyl groups of (a);
y is selected from C 1 ～C 3 Straight chain alkyl or C 3 Branched alkylene of (a); m is 0 or 1, and the molar ratio of the sensitizer to the cationic photoinitiator is 0.83-3.24;
the cationic photoinitiator is selected from any one or more of sulfonium salt photoinitiators and iodonium salt photoinitiators;
the pendulum hardness of the photo-curing composition after curing for 1h is 0.30-0.49, the pendulum hardness of the photo-curing composition after curing for 3h is 0.39-0.71, and the pendulum hardness of the photo-curing composition after curing for 24h is 0.70-0.85.
2. The photocurable composition of claim 1, wherein R 26 Said R is 36 Said R is 46 Said R is 56 Said R is 66 Said R is 106 Said R is 116 Said R is 126 Each independently selected from H, C 6 ～C 20 Substituted aroyl or said C 4 ～C 20 In the case of a substituted heteroaroyl group, said C 6 ～C 20 Substituted aroyl groups of (C) with said C 4 ～C 20 Each of the substituents on the substituted heteroaroyl groups is independently selected from halogen atoms, R 40 、-OR 50 、-SR 50 、-NR 51 R 52 、-COOR 50 、-CONR 51 R 52 Any one or more of the following; wherein R is 40 、R 50 Each independently selected from C 1 ～C 8 Substituted or unsubstituted alkyl, C containing one or two hetero atoms 5 ～C 6 Any one of cycloalkyl, substituted or unsubstituted phenyl; the R is 51 Said R is 52 Each independently selected from C 1 ～C 4 Substituted or unsubstituted alkyl, substituted or unsubstituted C 5 ～C 7 Any one of the heterocycloalkyl groups of (a).
3. The photocurable composition according to claim 2, characterized in that said heteroatom is selected from any one or more of O, S, N.
4. The photocurable composition according to claim 2, characterized in that said C 1 ～C 8 The substituent in the substituted alkyl of (a) is selected from any one or more of-F, -Cl and hydroxyl.
5. A photocurable composition according to claim 3, characterized in that said R 40 Said R is 50 Each independently selected from C 3 ～C 8 Any one of the substituted alkyl groups of (a).
6. The photocurable composition of claim 5, wherein said C 3 ～C 8 The substituent in the substituted alkyl of (a) is selected from any one or more of-O-, hydroxy and acetoxy.
7. The photocurable composition of claim 6, wherein said C 1 ～C 4 The substituent in the substituted alkyl of (a) is selected from any one or more of methyl, ethyl and hydroxyl.
8. A photocurable composition according to claim 3, characterized in that, -NR 51 R 52 Each independently selected from Any one of the following.
9. The photocurable composition of claim 8, wherein said-NR 51 R 52 Is that
10. The photocurable composition of claim 1, wherein R 26 Said R is 36 Said R is 46 Said R is 56 Said R is 66 Said R is 106 Said R is 116 Said R is 126 Each independently selected from C 1 ～C 4 Straight chain alkyl, C 3 ～C 5 Branched alkyl, C 6 ～C 10 Alkyl acyl, C 6 ～C 10 Substituted or unsubstituted aroyl, C 4 ～C 10 Any one of substituted or unsubstituted heteroaryl acyl groups.
11. The photocurable composition of claim 10, wherein R 26 Said R is 36 Said R is 46 Said R is 56 Said R is 66 Said R is 106 Said R is 116 Said R is 126 Each independently selected from
Any one of the following.
12. The photocurable composition of claim 1, wherein R 9 Said R is 29 Said R is 39 Said R is 49 Said R is 59 Said R is 69 Is substituted with one or more of the following substituents: phenyl, C 5 ～C 6 Cycloalkyl, C 3 ～C 6 Heterocyclic groups of (C), halogen, -COOR 20 、-OR 20 、-SR 20 、-PO(OC n H 2n+1 ) 2 、-Si(C n H 2n+1 ) 3 Wherein, the method comprises the steps of, wherein,
n is an integer of 1 to 4.
13. The photocurable composition of claim 12, wherein R 9 Said R is 29 Said R is 39 Said R is 49 Said R is 59 Said R is 69 Each independently selected from substituted or unsubstituted C 3 ～C 12 Alkyl, C of (2) 3 ～C 12 Any one of alkenyl alkyl groups of (a).
14. The photocurable composition of claim 13, wherein said C 3 ～C 12 Alkyl of (C) and said C 3 ～C 12 Each independently inserted into one or more of the carbon chains in the alkenyl alkyl group of O, S, S = O, SO 2 CO or carboxyl.
15. The photocurable composition of claim 12, wherein R 9 Said R is 29 Said R is 39 Said R is 49 Said R is 59 Said R is 69 Each independently selected from substituted or unsubstituted C 1 ～C 10 Straight chain alkyl, C 3 ～C 10 Branched alkyl, C 2 ～C 6 Alkenyl, C 3 ～C 6 Alkenyl alkyl, C 6 ～C 10 Any one of the aryl groups of (a).
16. The photocurable composition of claim 15, wherein said R 9 Said R is 29 Said R is 39 Said R is 49 Said R is 59 Said R is 69 Each independently selected from phenyl or substituted phenyl.
17. According to the weightsThe photocurable composition according to claim 16, wherein said substituted phenyl is substituted with one or more of the following substituents: c (C) 1 ～C 8 Alkyl, halogen atom, -OR 20 、-SR 20 、-COR 30 、-CN、-COOH。
18. The photocurable composition of claim 17, wherein said R 29 Said R is 39 Said R is 49 Said R is 59 Said R is 69 Each independently selected from
Any one of the following.
19. The photocurable composition of claim 1, wherein said Ar 1 Ar of said 2 Ar of said 3 Ar of said 4 Ar of said 5 Ar of said 6 Ar of said 7 Ar of said 8 Each independently selected from C 6 ～C 10 Substituted or unsubstituted aryl, C 4 ～C 10 Any one of substituted or unsubstituted heteroaryl groups.
20. The photocurable composition of claim 19, wherein said Ar 1 Ar of said 2 Ar of said 5 The acyl ortho carbon atoms on the carbazole ring are each independently linked to any carbon atom on the carbazole ring by-O-or-S-.
21. The light of claim 20A curable composition characterized in that the Ar 1 Ar of said 2 Ar of said 3 Ar of said 4 Ar of said 5 Ar of said 6 Ar of said 7 Ar of said 8 Each independently selected from
Any one of the following.
22. The photocurable composition of claim 1, wherein R 119 Selected from C 6 ～C 10 Substituted or unsubstituted aryl, C 4 ～C 10 Substituted or unsubstituted heteroaryl, C 1 ～C 10 Any one of the alkyl groups of (a).
23. The photocurable composition of claim 22, wherein said R 119 Selected from the group consisting of
Any one of the following.
24. The photocurable composition of claim 1, wherein R 73 Is C 6 ～C 20 Aroyl of (C) 6 ～C 20 At least one hydrogen atom of the aroyl group of (2) is substituted by a halogen atom, and/or at said C 6 ～C 20 An O atom is inserted in the side chain of the aroyl group.
25. The photocurable composition of claim 24, wherein said R 73 Is that Any one of the following.
26. The photocurable composition according to any one of claims 2-11, characterized in that R 70 Is methoxy.
27. The photocurable composition according to claim 1, wherein the sensitizer is selected from any one or more of the following structural formulas:
/>
28. the photocurable composition according to any one of claims 1-25, characterized in that said cationically polymerizable compound is selected from the group consisting of />
Any one or more of the following.
29. A photo-cured product formed by photo-curing a photo-curable composition, wherein the photo-curable composition is the photo-curable composition according to any one of claims 1 to 28.
30. The light-cured product of claim 29, wherein the light-cured product is selected from any one of a paint, an adhesive, a printing ink, a dental material.
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