CN113024690A - Photoinitiator composition, photocuring composition and photocured product - Google Patents
Photoinitiator composition, photocuring composition and photocured product Download PDFInfo
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- CN113024690A CN113024690A CN202011629068.8A CN202011629068A CN113024690A CN 113024690 A CN113024690 A CN 113024690A CN 202011629068 A CN202011629068 A CN 202011629068A CN 113024690 A CN113024690 A CN 113024690A
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- substituted
- alkyl
- independently selected
- unsubstituted
- photoinitiator
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- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 239000012952 cationic photoinitiator Substances 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 125000003435 aroyl group Chemical group 0.000 claims description 28
- 125000001424 substituent group Chemical group 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 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 12
- -1 cyclic carbonate compounds Chemical class 0.000 claims description 11
- 125000001072 heteroaryl group Chemical group 0.000 claims description 11
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 125000002252 acyl group Chemical group 0.000 claims description 9
- 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
- 125000004946 alkenylalkyl group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000005253 heteroarylacyl group Chemical group 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 5
- 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
- 238000000576 coating method Methods 0.000 claims description 4
- 239000000976 ink Substances 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 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
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 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
- 150000002921 oxetanes Chemical class 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims 1
- 230000001235 sensitizing effect Effects 0.000 abstract description 6
- 231100000489 sensitizer Toxicity 0.000 description 42
- 239000000047 product Substances 0.000 description 17
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 14
- 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 11
- 206010070834 Sensitisation Diseases 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000008313 sensitization Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-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
- 238000005516 engineering process Methods 0.000 description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 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
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 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
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-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
- MLOISVRIVMQAEX-UHFFFAOYSA-N C(C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C1=CC=C(C=C1)OCC(C(F)F)(F)F)=O)C(C1=CC=C(C=C1)OCC(C(F)F)(F)F)=O Chemical compound C(C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C1=CC=C(C=C1)OCC(C(F)F)(F)F)=O)C(C1=CC=C(C=C1)OCC(C(F)F)(F)F)=O MLOISVRIVMQAEX-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000607568 Photobacterium Species 0.000 description 1
- 238000010521 absorption reaction 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
- 150000001454 anthracenes Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000012663 cationic photopolymerization Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000021615 conjugation Effects 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
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 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)
- Epoxy Resins (AREA)
- Polymerisation Methods In General (AREA)
- Indole Compounds (AREA)
Abstract
The invention provides a photoinitiator composition, a photocuring composition and a photocuring product. The photoinitiator composition comprises a sensitizer and a cationic photoinitiator, wherein the sensitizer is selected from any one or more of a compound shown in a formula I and a compound shown in a formula II-A to a formula II-I:
Description
Technical Field
The invention relates to the technical field of photocuring, and particularly relates 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, in recent years, LED lamps are used to replace mercury lamps which are toxic to the environment and consume power, and the UV light curing technology has been increasingly used in the fields of printing industry, electronic product manufacturing and the like. However, the output light of the current relatively good cost performance LED lamps is relatively long-wave (365 nm-405 nm), for example, the LED lamps with emission wavelengths of 365nm, 385nm and 395nm are common commercial products, and even the ultraviolet laser products with 405nm are common. The spectrum emission of the ultraviolet light is greatly different from that of a mercury lamp, especially the ultraviolet light with the wavelength of 200-350 nm cannot be commercialized on an LED lamp, and therefore challenges are brought to the photo-curing technology industry. Based on the characteristics of the photocuring technology, the effective absorption range of the photoinitiator and the emission spectrum of the light source should be effectively overlapped to ensure that the photoinitiator is fully photolyzed and generates enough active groups, so that the polymerization rate reaches the standard requirement, and the physical property and the chemical property of the cured material are ensured to meet the use requirement.
There are many photoinitiators absorbing below 350nm, for example, the radical photoinitiators such as Omnirad 1173 and Omnirad907 of IGM resin company, and most cationic photoinitiators such as Omnicat 250, Omnicat 440, Omnicat 432 and Omnicat 270. These products are rejected as failing to match the energy of the light source as the light source is changed, and therefore, it is thought by those skilled in the art to use a sensitizer in combination with an initiator, for example, an anthracene compound used in combination with a cation in the patent application of U.S. 3M company, international patent application No. WO2005051332, for preparing a visible light source cured dental material; Jung-Dae Cho and Jin-Who Hong (nutritional kinetics for the UV-initiated conjugation polymerization of a cyclic lipid system by thioxanthone, Eur.Polymer.J., 2005,41(2),367) investigated the sensitizing effect of thioxanthone compounds on cations; crivello investigated the use of Anthracene compounds (Anthracene electron-transducers for onium salt induced cationic photopolymerization, J.Photochem.Photobacterium.A: Chemistry,2003,159,173) and benzothiazine compounds (Benzophenothiazine and benzophenoxazine photosensticizers for triarylsulfonium salt reactive phosphorus.J.polym.Sci.A: Polymer.Chem.2008, 46(11),3820) as sensitizers with sulfonium salts. However, the sensitizing effect obtained by the combined sensitizer and initiator used in these methods still needs to be further improved.
Disclosure of Invention
The invention mainly aims to provide a photoinitiator composition, a photocuring composition and a photocuring product, and aims to solve 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 invention, there is provided a photoinitiator composition comprising a sensitizer and a cationic photoinitiator, the sensitizer being 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 is1、R2、R4、R5、R7、R8、R24、R25、R27、R28、R31、R34、R35、R37、R38、R41、R42、R45、R47、R48、R54、R55、R61、R62、R67、R68、R71、R72、R74、R75、R102、R103、R104、R105、R107、R108、R112、R114、R115、R117、R118、R121、R122、R124、R125、R127Each independently selected from H, halogen atom, C1～C8Alkyl of (C)1～C8Any one of alkoxy and carbon-nitrogen triple bond of (1); r70Selected from H, C1～C10Any one of the alkoxy groups of (1), R73Selected from H,
C6～C20Any one of the aroyl groups of (a); r6、R26、R36、R46、R56、R66、R106、R116、R126Each independently selected from H, halogen atom, carbon-nitrogen triple bond, C1～C8Alkyl of (C)1～C12Alkyl acyl of (2), C6～C20Substituted or unsubstituted aroyl, C4～C20Substituted or unsubstituted heteroarylacyl group,
Any one of the above; r6、R26、R36、R46、R56、R66、R106、R116Each independently can form a 5-7 membered ring with the adjacent substituent; r9、R29、R39、R49、R59、R69Each independently selected from substituted or unsubstituted C1～C12Straight chain alkyl group of (1), C3～C12Branched alkyl of C2～C12Alkenyl of, C3～C12Alkenylalkyl of (C)6～C20Any one of the aryl groups of (a); ar (Ar)1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7、Ar8Each independently selected from C6～C20Substituted or unsubstituted aryl, C4～C20Any of the substituted or unsubstituted heteroaryl groups of (a); r119Is selected from C6～C20Substituted or unsubstituted aryl, C4～C20Substituted or unsubstituted heteroaryl, C1～C20Any one of the alkyl groups of (a); y is selected from C1～C3Straight chain alkyl or C3A branched alkylene group of (a); m is 0 or 1 and the molar ratio of sensitizer to cationic photoinitiator is greater than 0.2.
Further, the above R6、R26、R36、R46、R56、R66、R106、R116、R126Each independently selected from H, C6～C20Substituted aroyl or C4～C20When substituted heteroaroyl group of (a), C is preferred6～C20Substituted aroyl with C4～C20Each substituent on the substituted heteroaroyl group of (a) is independently selected from the group consisting of a halogen atom, R40、-OR50、-SR50、-NR51R52、-COOR50、-CONR51R52Any one or more of; wherein R is40、R50Each independently selected from C1～C8Substituted or unsubstituted alkyl, C containing one or two hetero atoms5～C6Any one of the cycloalkyl, substituted or unsubstituted phenyl; preferably the heteroatom is selected from any one or more of O, S, N, preferably C1～C8The substituent in the substituted alkyl is selected from any one or more of-F, -Cl and hydroxyl; preferably R40、R50Each independently selected from C3～C8Any of the substituted alkyl groups of (1), preferably C3～C8The substituent in the substituted alkyl is selected from any one or more of-O-, hydroxyl and acetoxy; r51、R52Each independently selected from C1～C4Substituted or unsubstituted alkyl, substituted or unsubstituted C5～C7Any of the heterocycloalkyl groups of (1), preferably C1～C4The substituent in the substituted alkyl is selected from any one or more of methyl, ethyl and hydroxyl; further, NR is preferable51R52Each independently selected from
Is preferably any of the above, more preferably
Preferably R6、R26、R36、R46、R56、R66、R106、R116、R126Each independently selected from C1～C4Straight chain alkyl group of (1), C3～C5Branched alkyl of C6～C10Alkyl acyl of (2), C6～C10Substituted or unsubstituted aroyl, C4～C10Any of the substituted or unsubstituted heteroarylacyl groups of (1), further preferably R6、R26、R36、R46、R56、R66、R106、R116、R126Each independently selected from
Any one of them.
Further, the above R9、R29、R39、R49、R59、R69Wherein the hydrogen is substituted with one or more of the following substituents: phenyl radical, C5～C6Cycloalkyl of, C3～C6Heterocyclyl, halogen, -COOR20、-OR20、-SR20、-PO(OCnH2n+1)2、-Si(CnH2n+1)3Wherein n is an integer of 1-4; preferably R9、R29、R39、R49、R59、R69Each independently selected from substituted or unsubstituted C3～C12Alkyl of (C)3～C12Any of the alkenylalkyl groups of (1), further preferably C3～C12Alkyl and C3～C12Each independently inserted into one or more carbon chains of the alkenylalkyl group of (a) O, S, S ═ O, SO2CO or carboxyl; superior foodR is selected9、R29、R39、R49、R59、R69Each independently selected from substituted or unsubstituted C1～C10Straight chain alkyl group of (1), C3～C10Branched alkyl of C2～C6Alkenyl of, C3～C6Alkenylalkyl of (C)6～C10Any of the aryl groups of (1), preferably R9、R29、R39、R49、R59、R69Each independently selected from phenyl or substituted phenyl, preferably substituted phenyl substituted with one or more of the following substituents: c1～C8Alkyl, halogen atoms, -OR20、-SR20、-COR30-CN, -COOH; further, R is preferable29、R39、R49、R59、R69Each independently selected from
Any one of them.
Further, Ar mentioned above1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7、Ar8Each independently selected from C6～C10Substituted or unsubstituted aryl, C4～C10Any of the substituted or unsubstituted heteroaryl groups of (1), preferably Ar1、Ar2、Ar5The carbon atoms adjacent to the acyl groups are independently connected with any carbon atom on the carbazole ring through-O-or-S-; further preferably Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7、Ar8Each independently selected from
Any one of them.
Further, the above R119Is selected from C6～C10Substituted or unsubstituted aryl, C4～C10Substituted or unsubstituted heteroaryl, C1～C10Any one of the alkyl groups of (a); preferably R119Is selected from
Any one of them.
Further, R73Is C6～C20When it is aroyl, C6～C20At least one hydrogen atom in the aroyl group of (a) is replaced by a halogen atom, and/or at C6～C20The side chain of the aroyl group of (2) is inserted with an O atom, further preferably R73Is composed of
Any one of them.
Further, the above R70Is methoxy.
Further, the cationic photoinitiator is one or more selected from the group consisting of sulfonium salt photoinitiators and iodonium salt photoinitiators.
According to another aspect of the present invention, there is provided a photo-curable composition comprising 1 to 10 wt% of a photo-initiator component and 90 to 99 wt% of a cationically polymerizable compound, wherein the photo-initiator component comprises the photo-initiator composition.
Further, the above cationically polymerizable compound is selected from any one or more of epoxy compounds, vinyl ether compounds, oxetane compounds and cyclic carbonate compounds, and further, preferably, the cationically polymerizable compound is selected from
According to still another aspect of the present invention, there is provided a photocurable product formed by photocuring a photocurable composition, the photocurable composition being as described above, preferably the photocurable product is selected from any one of a coating, an adhesive, a printing ink, and a dental material.
By applying the technical scheme of the invention, the sensitizer takes carbazole as a core structure, has various variable structures from a formula I, a formula II-A to a formula II-I, and has various substituents such as alkyl, aroyl, alkoxy, halogen and the like on the structure of each variable 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 a cationic photoinitiator is more than 0.2, the photoinitiator composition has a strong sensitization effect.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background technology, the problem of low sensitization effect of the combined sensitizer exists in the prior art, and in order to solve the problem, the invention 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 compounds represented by formula I, compounds represented by formula II-A, compounds represented by formula II-B, compounds represented by formula II-C, compounds represented by formula II-D, compounds represented by formula II-E, compounds represented by formula II-F, compounds represented by formula II-G, compounds represented by formula II-H, and compounds represented by formula II-I:
wherein R is1、R2、R4、R5、R7、R8、R24、R25、R27、R28、R31、R34、R35、R37、R38、R41、R42、R45、R47、R48、R54、R55、R61、R62、R67、R68、R71、R72、R74、R75、R102、R103、R104、R105、R107、R108、R112、R114、R115、R117、R118、R121、R122、R124、R125、R127Each independently selected from H, halogen atom, C1～C8Alkyl of (C)1～C8Any one of alkoxy and carbon-nitrogen triple bond of (1); r70Selected from H, C1～C10Any one of the alkoxy groups of (1), R73Selected from H,
C6～C20Any one of the aroyl groups of (a); r6、R26、R36、R46、R56、R66、R106、R116、R126Each independently selected from H, halogen atom, carbon-nitrogen triple bond, C1～C8Alkyl of (C)1～C12Alkyl acyl of (2), C6～C20Substituted or unsubstituted aroyl, C4～C20Substituted or unsubstituted heteroarylacyl group,
Any one of the above; r6、R26、R36、R46、R56、R66、R106、R116Each independently can form a 5-7 membered ring with the adjacent substituent; r9、R29、R39、R49、R59、R69Each independently selected from substituted or unsubstituted C1～C12Straight chain alkyl group of (1), C3～C12Branched alkyl of C2～C12Alkenyl of, C3～C12Alkenylalkyl of (C)6～C20Any one of the aryl groups of (a); ar (Ar)1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7、Ar8Each independently selected from C6～C20Substituted or unsubstituted aryl, C4～C20Any of the substituted or unsubstituted heteroaryl groups of (a); r119Is selected from C6～C20Substituted or unsubstituted aryl, C4～C20Substituted or unsubstituted heteroaryl, C1～C20Any one of the alkyl groups of (a); y is selected from C1～C3Straight chain alkyl or C3A branched alkylene group 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 and has various variable structures from a formula I, a formula II-A to a formula II-I, and a compound structure of each variable structure has various substituent groups such as alkyl, aroyl, alkoxy, halogen and the like, 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 a cationic photoinitiator is more than 0.2, the photoinitiator composition has a strong sensitization effect.
In order to further improve the sensitisation of the corresponding sensitisers of formulae I, II-A to II-H above, preference is given to R above6、R26、R36、R46、R56、R66、R106、R116、R126Each independently selected from H, C6～C20Substituted aroyl or C4～C20When substituted heteroaroyl group of (a), C is preferred6～C20Substituted aroyl with C4～C20Each substituent on the substituted heteroaroyl group of (a) is independently selected from the group consisting of a halogen atom, R40、OR50、SR50、NR51R52、COOR50、CONR51R52Any one or more of; wherein R is40、R50Each independently selected from C1～C8Substituted or unsubstituted alkyl, C containing one or two hetero atoms5～C6Any one of the cycloalkyl, substituted or unsubstituted phenyl; preferably the heteroatom is selected from any one or more of O, S, N, preferably C1～C8The substituent in the substituted alkyl is selected from any one or more of-F, -Cl and hydroxyl; preferably R40、R50Each independently selected from C3～C8Any of the substituted alkyl groups of (1), preferably C3～C8The substituent in the substituted alkyl is selected from any one or more of-O-, hydroxyl and acetoxy; r51、R52Each independently selected from C1～C4Substituted or unsubstituted alkyl, substituted or unsubstituted C5～C7Any of the heterocycloalkyl groups of (1), preferably C1～C4In substituted alkyl groups ofThe substituent is selected from one or more of methyl, ethyl and hydroxyl; further, NR is preferable51R52Each independently selected from
Is preferably any of the above, more preferably
Preferably R6、R26、R36、R46、R56、R66、R106、R116、R126Each independently selected from C1～C4Straight chain alkyl group of (1), C3～C5Branched alkyl of C6～C10Alkyl acyl of (2), C6～C10Substituted or unsubstituted aroyl, C4～C10Any of the substituted or unsubstituted heteroarylacyl groups of (1), further preferably R6、R26、R36、R46、R56、R66、R106、R116、R126Each independently selected from
Any one of them.
In order to further enhance the sensitizing effect of the sensitizer by allowing the substituent on carbazole N to act on the carbazole ring, the above-mentioned R is preferably used9、R29、R39、R49、R59、R69Wherein the hydrogen is substituted with one or more of the following substituents: phenyl radical, C5～C6Cycloalkyl of, C3～C6Heterocyclyl, halogen, -COOR20、-OR20、-SR20、-PO(OCnH2n+1)2、-Si(CnH2n+1)3Wherein n is an integer of 1-4; preferably R9、R29、R39、R49、R59、R69Each independently selected from substituted or unsubstituted C3～C12Alkyl of (C)3～C12Any of the alkenylalkyl groups of (1), further preferably C3～C12Alkyl and C3～C12Each independently inserted into one or more carbon chains of the alkenylalkyl group of (a) O, S, S ═ O, SO2CO or carboxyl; preferably R9、R29、R39、R49、R59、R69Each independently selected from substituted or unsubstituted C1～C10Straight chain alkyl group of (1), C3～C10Branched alkyl of C2～C6Alkenyl of, C3～C6Alkenylalkyl of (C)6～C10Any of the aryl groups of (1), preferably R9、R29、R39、R49、R59、R69Each independently selected from phenyl or substituted phenyl, preferably substituted phenyl substituted with one or more of the following substituents: c1～C8Alkyl, halogen atoms, -OR20、-SR20、-COR30-CN, -COOH; further, R is preferable29、R39、R49、R59、R69Each independently selected from
Any one of them.
To enhance the electron interaction between the aroyl group and the carbazole ring, thereby enhancing the sensitizerThe sensitizing Effect of (3), Ar is preferable1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7、Ar8Each independently selected from C6～C10Substituted or unsubstituted aryl, C4～C10Any of the substituted or unsubstituted heteroaryl groups of (1), preferably Ar1、Ar2、Ar5The carbon atoms adjacent to the acyl groups are independently connected with any carbon atom on the carbazole ring through-O-or-S-; further preferably Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7、Ar8Each independently selected from
Any one of them.
To increase R119With II-G carbazole, and preferably R is the above-mentioned compound119Is selected from C6～C10Substituted or unsubstituted aryl, C4～C10Substituted or unsubstituted heteroaryl, C1～C10Any one of the alkyl groups of (a); preferably R119Is selected from
Any one of them.
To further increase R73With II-G carbazole, and preferably R is the above-mentioned compound73Is C6～C20When it is aroyl, C6～C20At least one hydrogen atom in the aroyl group of (a) is replaced by a halogen atom, and/or at C6～C20The side chain of the aroyl group of (2) is inserted with an O atom, further preferably R73Is composed of
Any one of them.
In one embodiment of the present application, R is as defined above70Is methoxy, to be further passed through R70The substituent increases the sensitivity of the corresponding sensitizer of II-I.
In order to improve the sensitivity of the sensitizer and to obtain a photoinitiator composition with excellent overall sensitivity by better synergy with the cationic photoinitiator, the sensitizer is preferably selected from any one or more of the following structural formulas:
in order to achieve sufficient synergistic effect between the sensitizer and the cationic photoinitiator, the cationic photoinitiator is preferably selected from any one or more of sulfonium salt photoinitiators and iodonium salt photoinitiators.
In order to further improve the synergistic effect of the sulfonium salt photoinitiator and the iodonium salt photoinitiator with the sensitizer of the present application to obtain a photoinitiator composition with better sensitization, any one or more of the following sulfonium salt photoinitiators and iodonium salt photoinitiators are preferred:
of course, one skilled in the art can select the conventional sulfonium salt type photoinitiator and iodonium salt type photoinitiator according to actual needs, and details are not described herein.
In another exemplary embodiment of the present application, there is provided a photocurable composition including 1 to 10 wt% of a photoinitiator component and 90 to 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 sensitivity.
In order to sufficiently carry out the polymerization reaction of the cationically polymerizable compound by the action of the photoinitiator composition, it is preferable that the cationically polymerizable compound is selected from the group consisting of epoxy compounds, vinyl ether compounds, oxetane compounds and cyclic carbonatesAny one or more of the compounds, further, preferably the cationically polymerizable compound is selected from
In still another exemplary embodiment of the present application, there is provided a photo-curable product formed by photo-curing a photo-curable composition, preferably a photo-curable product selected from any one of coatings, adhesives, printing inks, dental materials, as described above.
The photocuring product obtained by curing the photocuring composition has excellent performance and can be widely applied to photocuring products, and the photocuring product is preferably selected from any one of coatings, adhesives, printing ink and dental materials.
The advantageous effects of the present application will be described below with reference to specific examples and comparative examples.
Examples of preparation of sensitizers
Sensitizer preparation example 1
Adding 19.5g of N-ethyl carbazole into 250mL of dichloroethane for dissolving, then adding 34g of aluminum trichloride, keeping the temperature between 0 ℃ and-5 ℃, dropwise adding 40g of p-fluorobenzoyl chloride into the solution, and then keeping the reaction liquid at the temperature between 0 ℃ and 5 ℃ for reacting for 15 hours. The reaction mixture was added portionwise to 100mL 10% HCl solution at 0 ℃ and stirred for 30 min. After standing for 30 minutes, the mixture 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 obtain 30.5g of 9-ethyl-3, 6-bis (4-fluorobenzoyl) carbazole product with 98.5% white powder content and 69.5% yield.
30g of 9-ethyl-3, 6-bis (4-fluorobenzoyl) carbazole, 25g of 2,2,3, 3-tetrafluoropropanol and 8g of sodium hydroxide were dissolved in 200mL of pyridine, and reacted at 70 ℃ for 18 hours. ReducingAnd (4) distilling under pressure to remove pyridine and redundant 2,2,3, 3-tetrafluoropropanol. To the residue were added 100mL of water and 250mL of dichloroethane, and the mixture was stirred for 1 hour. The aqueous phase was separated and the dichloroethane solution was washed 2 times with 100mL of water. Distilling under reduced pressure to recover dichloroethane, adding 150mL of ethyl acetate and 2g of activated carbon to the residue, heating and refluxing for 1 hour, filtering the activated carbon, distilling the filtrate under reduced pressure to remove about 100mL of ethyl acetate, cooling to crystallize, filtering, and drying the filter cake to obtain 27.8g of light yellow powder 9-ethyl-3, 6-bis [4- (2,2,3, 3-tetrafluoropropoxy) benzoyl]Carbazole (formula I-30), its content is 98.5%, yield is 61.4%. It is composed of1H-NMR formula CDCl3Is 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
In a 50mL single-neck flask, 2.0g of 11- (2-ethylhexyl) -11H-benzo [ a ] carbazole was added, 20mL of dichloroethane was added and dissolved, 0.2g of zinc chloride and 2.3g of o-fluorobenzoyl chloride were added, and the reaction was stirred at 80 ℃ for 10 hours. After the temperature is reduced, the reaction solution is washed twice by 20mL of water, and the dichloroethane solution is decompressed and concentrated to be dry to obtain brown sticky substances of 11- (2-ethylhexyl) -5, 8-bis (4-fluorobenzoyl) -11H-benzo [ a ] carbazole.
4.0g of 11- (2-ethylhexyl) -5, 8-bis (4-fluorobenzoyl) -11H-benzo [ a ]]Carbazole was dissolved in 20mL of pyridine in a 50mL single-neck flask, and 2.2g of tetrafluoropropanol and 1.2g of sodium hydroxide were added, and the mixture was heated to 80 ℃ and stirred for 5 hours. The reaction solution was added dropwise to 100mL of water, followed by stirring with 100mL of dichloroethane for 1 hour and then standing for separation. The separated dichloroethane solution was concentrated to dryness under reduced pressure to give 4.7g of a coffee-colored solid. Dissolving the solid in mixed solvent of 20mL ethyl acetate and 20mL ethanol under heating, adding 0.25g activated carbon, refluxing for 1 hr, heat filtering, cooling the filtrate to precipitate yellow crystal 11- (2-ethylhexyl) -5, 8-bis [2- (2,2,3, 3-tetrafluoropropoxy) benzoyl]-11H-benzo [ a]Carbazole (formula II-5), weighing 2.5g after drying, the total yield of the two steps is 51.3%, and the content is 98.51%. Of formula II-51H-NMR(CDCl3)，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 examples of photoinitiator compositions
Preparation of photoinitiator composition example 1
6g of Omnicat 270 and 6g of the compound represented by the formula I-30 are put into a mortar for grinding and mixing to obtain light yellow powder, namely a sample with the molar ratio of the sensitizer to the active groups of the cationic photoinitiator being 1.29.
Preparation of photoinitiator composition example 2
6g of Omnicat 270 and 4.2g of the compound represented by the formula I-30 are put into a mortar for grinding and mixing to obtain light yellow powder, namely a sample with the molar ratio of the sensitizer to the active groups of the cationic photoinitiator of 0.91.
Preparation of photoinitiator composition example 3
6g of Omnicat 270 and 13.2g of the compound represented by the formula I-30 are put into a mortar for grinding and mixing to obtain light yellow powder, namely a sample with the molar ratio of the sensitizer to the active groups of the cationic photoinitiator 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 heated to 70 ℃ for dissolution and mixing to obtain yellow liquid, namely a sample with the molar ratio of the sensitizer to the active groups of the cationic photoinitiator being 2.28.
Preparation of photoinitiator composition example 5
6g of Esacure 1187 and 6g of the compound shown as the formula I-30 are heated to 70 ℃ to be dissolved and mixed to obtain yellow liquid, namely the product with the molar ratio of the sensitizer to the active groups of the cationic photoinitiator being 1.00.
Photoinitiator composition preparation example 6
6g of Omnicat 270 and 1.96g of the compound of the formula II-5 are put in a mortar for grinding and mixing to obtain light yellow powder, namely a sample with the molar ratio of the sensitizer to the active groups of the cationic photoinitiator being 0.35.
Photoinitiator composition preparation example 7
6g of Omnicat 250 and 6g of the compound of formula II-5 are heated to 70 ℃ for dissolution and mixing to obtain yellow liquid, namely a sample with the molar ratio of the sensitizer to the active groups of the cationic photoinitiator being 0.83.
Application examples of photocurable compositions:
the following photocurable composition application/comparative examples relate to the following experimental equipment and reagents and materials:
a light source device:
365nm LED area light source, blue sky lamp development ltd;
395nm LED area light source, blue sky lamp development ltd;
testing equipment:
a pendulum hardness tester;
reagents and materials:
omnilane OC 1005: 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylmethyl ester, commercially available from IGM resins;
omnicat 270: containing a compound of formula III-5, commercially available from IGM resins;
omnicat 250: containing a compound of formula III-14, commercially available from IGM resins;
omnicat 432: containing 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 with a solid content of 75%; IGM resins.
The photocurable compositions of practical examples/comparative examples (pre-mixing) were prepared according to the components and amounts shown in tables 1 to 7, and after uniformly mixing and dissolving, the glass plate was coated with a film using a 25 μm wire bar, and then cured by irradiating for 1s with the light source in each table, and after curing, the pendulum hardness of each sample was measured at 1h, 3h, and 24h, respectively, and the test results were set in tables 8 to 14 correspondingly.
TABLE 1
Wherein, the mol ratio of the sensitizer to the active groups of the cationic photoinitiator is as follows: (number of moles of sensitizer active groups)/(number of moles of cation active groups).
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
TABLE 7
TABLE 8
TABLE 9
Watch 10
TABLE 11
TABLE 12
Watch 13
TABLE 14
A comprehensive analysis of the above tables 1 to 14 reveals that the photoinitiator composition of the present application has an excellent sensitizing effect.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the sensitizer takes carbazole as a core structure and has various variable structures from a formula I, a formula II-A to a formula II-I, and a compound structure of each variable structure has various substituent groups such as alkyl, aroyl, alkoxy, halogen and the like, 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 a cationic photoinitiator is more than 0.2, the photoinitiator composition has a strong sensitization effect.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A 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 is1、R2、R4、R5、R7、R8、R24、R25、R27、R28、R31、R34、R35、R37、R38、R41、R42、R45、R47、R48、R54、R55、R61、R62、R67、R68、R71、R72、R74、R75、R102、R103、R104、R105、R107、R108、R112、R114、R115、R117、R118、R121、R122、R124、R125、R127Each independently selected from H, halogen atom, C1～C8Alkyl of (C)1～C8Any one of alkoxy and carbon-nitrogen triple bond of (1);
R70selected from H, C1～C10Any one of the alkoxy groups of (1), R73Selected from H,
C6～C20Any one of the aroyl groups of (a);
R6、R26、R36、R46、R56、R66、R106、R116、R126each independently selected from H, halogen atom, carbon-nitrogen triple bond, C1～C8Alkyl of (C)1～C12Alkyl acyl of (2), C6～C20Substituted or unsubstituted aroyl, C4～C20Substituted or unsubstituted heteroarylacyl group,
Any one of the above;
the R is6The R is26The R is36The R is46The R is56The R is66The R is106The R is116Each independently can form a 5-7 membered ring with the adjacent substituent;
R9、R29、R39、R49、R59、R69each independently selected from substituted or unsubstituted C1～C12Straight chain alkyl group of (1), C3～C12Branched alkyl of C2～C12Alkenyl of, C3～C12Alkenylalkyl of (C)6～C20Any one of the aryl groups of (a);
Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7、Ar8each independently selected from C6～C20Substituted or unsubstituted aryl, C4～C20Any of the substituted or unsubstituted heteroaryl groups of (a);
R119is selected from C6～C20Substituted or unsubstituted aryl, C4～C20Substituted or unsubstituted heteroaryl, C1～C20Any one of the alkyl groups of (a);
y is selected from C1～C3Straight chain alkyl or C3A branched alkylene group of (a); m is 0 or 1, and the molar ratio of the sensitizer to the cationic photoinitiator is greater than 0.2.
2. The photoinitiator composition of claim 1 wherein R is6The R is26The R is36The R is46The R is56The R is66The R is106The R is116The R is126Each independently selected from H, C6～C20Substituted aroyl of said C4～C20In the case of the substituted heteroaroyl group of (1), the C group is preferred6～C20Substituted aroyl of (A) and (C)4～C20Each substituent on the substituted heteroaroyl group of (a) is independently selected from the group consisting of a halogen atom, R40、-OR50、-SR50、-NR51R52、-COOR50、-CONR51R52Any one or more of;
wherein R is40、R50Each independently selected from C1～C8Substituted or unsubstituted alkyl, C containing one or two hetero atoms5～C6Any one of the cycloalkyl, substituted or unsubstituted phenyl; preferably the heteroatom is selected from any one or more of O, S, N, preferably C1～C8The substituent in the substituted alkyl is selected from any one or more of-F, -Cl and hydroxyl; preferably said R40The R is50Each independently selected from C3～C8Preferably said C is3～C8Substituted alkyl of (2)Any one or more of-O-, hydroxyl and acetoxy;
the R is51The R is52Each independently selected from C1～C4Substituted or unsubstituted alkyl, substituted or unsubstituted C5～C7Any of the heterocycloalkyl groups of (1), preferably C1～C4The substituent in the substituted alkyl is selected from any one or more of methyl, ethyl and hydroxyl; further, it is preferable to use-NR51R52Each independently selected from
Is preferably any of the above, more preferably
Preferably said R6The R is26The R is36The R is46The R is56The R is66The R is106The R is116The R is126Each independently selected from C1～C4Straight chain alkyl group of (1), C3～C5Branched alkyl of C6～C10Alkyl acyl of (2), C6～C10Substituted or unsubstituted aroyl, C4～C10Any of the substituted or unsubstituted heteroarylacyl groups of (1), further preferably said R6The R is26The R is36The R is46The R is56The R is66The R is106The R is116The R is126Each independently selected from
Any one of them.
3. The photoinitiator composition of claim 1 wherein R is9The R is29The R is39The R is49The R is59The R is69Wherein the hydrogen is substituted with one or more of the following substituents: phenyl radical, C5～C6Cycloalkyl of, C3～C6Heterocyclyl, halogen, -COOR20、-OR20、-SR20、-PO(OCnH2n+1)2、-Si(CnH2n+1)3Wherein n is an integer of 1-4; preferably said R9The R is29The R is39The R is49The R is59The R is69Each independently selected from substituted or unsubstituted C3～C12Alkyl of (C)3～C12Any of the alkenylalkyl groups of (1), further preferably said C3～C12And said C3～C12Each independently inserted into one or more carbon chains of the alkenylalkyl group of (a) O, S, S ═ O, SO2CO or carboxyl; preferably said R9The R is29The R is39The R is49The R is59The R is69Each independently selected from substituted or unsubstituted C1～C10Straight chain alkyl group of (1), C3～C10Branched alkyl of C2～C6Alkenyl of, C3～C6Alkenylalkyl of (C)6～C10Preferably said R is9The R is29The R is39The R is49The R is59The R is69Each independently selected from phenyl or substituted phenyl, preferably said substituted phenyl is substituted with one or more of the following substituents: c1～C8Alkyl, halogen atoms, -OR20、-SR20、-COR30-CN, -COOH; further, it is preferable that R is29The R is39The R is49The R is59The R is69Each independently selected from
Any one of them.
4. The photoinitiator composition of claim 1 wherein Ar is present1Ar described in2Ar described in3Ar described in4Ar described in5Ar described in6Ar described in7Ar described in8Each independently selected from C6～C10Substituted or unsubstituted aryl, C4～C10Preferably Ar is1Ar described in2Ar described in5The carbon atoms adjacent to the acyl groups are independently connected with any carbon atom on the carbazole ring through-O-or-S-; further preferably Ar is1Ar described in2Ar described in3Ar described in4Ar described in5Ar described in6Ar described in7Ar described in8Each independently selected from
Any one of them.
5. The photoinitiator composition of claim 1 wherein R is119Is selected from C6～C10Substituted or unsubstituted aryl, C4～C10Substituted or unsubstituted heteroaryl, C1～C10Any one of the alkyl groups of (a); preferably said R119Is selected from
Any one of them.
6. The photoinitiator composition of claim 1 wherein R is73Is C6～C20When it is aroyl, said C6～C20At least one hydrogen atom in the aroyl group of (a) is substituted by a halogen atom, and/or at the C6～C20The side chain of the aroyl group of (2) is inserted with an O atom, further preferably the R group73Is composed of
Any one of them.
7. The photoinitiator composition of claim 2 wherein R is70Is methoxy.
8. The photoinitiator composition according to claim 1 wherein the sensitizer is selected from any one or more of the following structural formulas:
9. the photoinitiator composition according to claim 1, wherein the cationic photoinitiator is selected from any one or more of sulfonium-based photoinitiators and iodonium-based photoinitiators.
10. A photocurable composition comprising 1 to 10 wt% of a photoinitiator component and 90 to 99 wt% of a cationically polymerizable compound, wherein the photoinitiator component comprises the photoinitiator composition according to any one of claims 1 to 9.
11. The photocurable composition according to claim 10, wherein the cationically polymerizable compound is selected from any one or more of epoxy compounds, vinyl ether compounds, oxetane compounds, and cyclic carbonate compounds, and preferably the cationically polymerizable compound is selected from
12. A photo-curable product formed by photo-curing a photo-curable composition according to claim 10 or 11, wherein the photo-curable composition is a photo-curable composition, preferably the photo-curable product is selected from any one of coatings, adhesives, printing inks, dental materials.
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