CN113527278B - Thioxanthone compound, preparation method thereof and photo-curing composition - Google Patents
Thioxanthone compound, preparation method thereof and photo-curing composition Download PDFInfo
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- CN113527278B CN113527278B CN202010319297.3A CN202010319297A CN113527278B CN 113527278 B CN113527278 B CN 113527278B CN 202010319297 A CN202010319297 A CN 202010319297A CN 113527278 B CN113527278 B CN 113527278B
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- -1 Thioxanthone compound Chemical class 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000016 photochemical curing Methods 0.000 title abstract description 16
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 18
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 18
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 150000001875 compounds Chemical class 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
- 125000000732 arylene group Chemical group 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- ANHLDZMOXDYFMQ-UHFFFAOYSA-N 2-hydroxythioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC(O)=CC=C3SC2=C1 ANHLDZMOXDYFMQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000002541 furyl group Chemical group 0.000 claims description 6
- 125000001041 indolyl group Chemical group 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 125000001544 thienyl group Chemical group 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 238000007142 ring opening reaction Methods 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 3
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003444 phase transfer catalyst Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 125000006267 biphenyl group Chemical group 0.000 claims 1
- 238000013508 migration Methods 0.000 abstract description 14
- 230000005012 migration Effects 0.000 abstract description 14
- 239000011347 resin Substances 0.000 abstract description 12
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 11
- 239000004593 Epoxy Substances 0.000 abstract description 10
- 125000000524 functional group Chemical group 0.000 abstract description 8
- 239000003999 initiator Substances 0.000 abstract description 6
- 239000012044 organic layer Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 125000002993 cycloalkylene group Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 125000003884 phenylalkyl group Chemical group 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052739 hydrogen Inorganic materials 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
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a thioxanthone compound, a preparation method thereof and a photo-curing composition. According to the application, an oligomeric multifunctional structure is introduced into the 2-hydroxyl of the molecular structure of the thioxanthone compound 2-hydroxyl-9H-thioxanthone-9-ketone derivative, on one hand, the introduction of epoxy four-ring groups and various functional groups in the oligomeric multifunctional structure enhances the solubility of the thioxanthone compound and matrix resin, so that the thioxanthone compound can be matched with a light source well and can be used as a sensitizer and other initiators in a matching manner. On the other hand, the polymerizable epoxy four-membered ring group can be further crosslinked and polymerized with the matrix resin, thereby greatly reducing the possibility of migration thereof. Therefore, the photo-curing composition containing the thioxanthone compound has extremely low migration and low odor, and greatly improved adhesive force and shrinkage rate on the basis of retaining the basic performance of the traditional thioxanthone photosensitizer.
Description
Technical Field
The invention relates to the technical field of photosensitizers, in particular to a thioxanthone compound, a preparation method thereof and a photo-curing composition.
Background
Thioxanthone photosensitizers are common hydrogen abstraction type free radical photoinitiators, wherein thioxanthone as a representative product has poor solubility in oligomers and reactive diluents, so that derivatives thereof are used as photosensitizers, such as ITX, CTX, CPTX, DETX, so as to improve the solubility, enable the absorption wavelength to reach 430nm, and can be well matched with UV-LED light sources and often used as a sensitizer and other initiators to be matched.
In recent years, it has been further introduced to introduce various groups into thioxanthone to improve it, thereby improving its solubility in resins, as disclosed in chinese patent application publication No. CN1599735a, by bonding thioxanthone structure and polyhydroxy polymer compound, the thioxanthone derivative photosensitizer is excellent in surface photocuring activity and has lower mobility; the thioxanthone is further modified on the basis of the Chinese patent application with the publication number of CN104892798A, so that the characteristic that the thioxanthone derivative is not easy to store is solved, and the thioxanthone derivative is also suitable for a UV-LED system.
However, these existing modified photosensitizers hardly achieve zero migration, and the adhesion of the materials after use and the shrinkage of the materials after curing are not ideal.
Disclosure of Invention
The invention mainly aims to provide a thioxanthone compound, a preparation method thereof and a photocuring composition, so as to solve the problems that a modified photosensitizer in the prior art is high in mobility, adhesiveness of a used material and shrinkage of a cured material are not ideal.
In order to achieve the above object, according to one aspect of the present invention, there is provided a thioxanthone compound having the following structural formula I:
m is an n-valent substituent, M isC 1 ～C 40 Alkyl, C of (2) 1 ～C 40 Alkylene group, C 7 ～C 40 Aralkyl of (C) 7 ～C 60 Aryl alkylene, C 3 ～C 40 Cycloalkyl, C 3 ～C 40 Cycloalkylene of C 1 ～C 40 Alkoxy, C 6 ～C 60 Aryl, C of (2) 12 ～C 60 Arylene of (C) 4 ～C 12 Any one of the heteroaryl groups of (1), wherein R 5 ' is H, C 1 ～C 40 Alkyl, C of (2) 3 ～C 40 Cycloalkyl, C 7 ～C 40 Aralkyl of (C) 1 ～C 40 Alkoxy, C 6 ～C 60 Aryl, C of (2) 4 ～C 12 Any one of the heteroaryl groups of (a). R is R 1 、R 2 、R 3 、R 4 、R 5 Each independently is H, substituted or unsubstituted phenyl, substituted or unsubstituted C 1 ～C 5 Alkyl, -NO of (C) 2 Substituted or unsubstituted C 1 ～C 5 Any one of the alkoxy groups of (a). n is any integer from 1 to 3, m is any integer from 1 to 6, and q is any integer from 0 to 3.
Further, when q is 0, n is 1 or 2, and when n is 1, M is preferably substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 20 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Aralkyl, substituted or unsubstituted C 3 ～C 20 Cycloalkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, substituted or unsubstituted C 6 ～C 20 Aryl, substituted or unsubstituted C 4 ～C 12 Any one of heteroaryl groups of (a); further preferred M is substituted or unsubstituted C 1 ～C 10 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 10 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Is a phenylalkyl group, a substituted or unsubstituted C 13 ～C 20 Is a biphenylalkyl group, a substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substitutedOr any one of unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted pyridyl, substituted or unsubstituted indolyl; when n is 2, M is preferably substituted or unsubstituted C 1 ～C 20 Alkylene, substituted or unsubstituted C 7 ～C 20 Aryl alkylene, substituted or unsubstituted C 3 ～C 20 Cycloalkylene, substituted or unsubstituted C 12 ～C 20 Any one of arylene groups of (a); further preferred M is substituted or unsubstituted C 1 ～C 10 Alkylene, substituted or unsubstituted C 7 ～C 12 Phenyl alkylene, substituted or unsubstituted C 12 ～C 20 Is a biphenylene group, a substituted or unsubstituted C 3 ～C 12 Cycloalkylene, substituted or unsubstituted C 12 ～C 20 Any one of arylene groups of (a).
Further, when q is 1 to 3, n is 3 and M isPreferably R 5 ' H, substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 2 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Aralkyl, substituted or unsubstituted C 3 ～C 20 Cycloalkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, substituted or unsubstituted C 6 ～C 20 Aryl, substituted or unsubstituted C 4 ～C 12 Any one of heteroaryl groups of (a); further preferably R 5 ' H, substituted or unsubstituted C 1 ～C 10 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 10 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Is a phenylalkyl group, a substituted or unsubstituted C 13 ～C 20 Is a biphenylalkyl group, a substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Alkoxy, substituted or unsubstituted phenyl, substitutedOr any one of unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted pyridyl, and substituted or unsubstituted indolyl.
Further, n is 2, M is a substituted or unsubstituted C 12 ～C 20 Is preferably any one of arylene groups of (2), M is preferably
Wherein, represents a binding position, R 1 ′、R 2 ′、R 3 ′、R 4 ' each independently selected from H, substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 20 Branched alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C 3 ～C 20 Alkyl cycloalkyl, substituted or unsubstituted C 4 ～C 20 Cycloalkyl alkyl, substituted or unsubstituted C 2 ～C 20 Alkenyl groups of (a) and (b) are each independently selected from the group consisting of alkenyl groups.
Further, R is as described above 1 ′、R 2 ′、R 3 ' and R 4 -CH in 2 -CH which may each independently be substituted, preferably substituted, by-O 2 The number is 1 to 5.
Further, the structural formula of the thioxanthone compound is as follows
Any one of the following.
According to another aspect of the present invention, there is provided a process for the preparation of any one of the thioxanthones compounds described above, the process comprising: performing ring-opening reaction on the 2-hydroxy-9H-thioxanthen-9-one derivative and the compound a under alkaline conditions to obtain thioxanthone compounds; wherein, the structural general formula II of the 2-hydroxy-9H-thioxanth-9-ketone derivative and the structural general formula III of the compound a are as follows:
n、m、q、M、R 1 、R 2 、R 3 、R 4 、R 5 n, m, q, M, R of the same general structural formula I 1 、R 2 、R 3 、R 4 、R 5 。
Further, the preparation method comprises the following steps: step S1, mixing a 2-hydroxy-9H-thioxanth-9-ketone derivative, a compound a, a phase transfer catalyst and a solvent to obtain a mixture; and S2, reacting the mixture in an alkaline environment for 3-10 hours to obtain thioxanthone compounds, wherein the reaction is preferably carried out at 50-150 ℃, the alkaline environment is formed by adopting an alkaline solution, the alkaline solution is preferably one or more of a sodium hydroxide solution, a potassium hydroxide solution and a lithium hydroxide solution, the concentration of the alkaline solution is preferably 10-40 wt%, and the solvent is preferably one or more of dichloroethane, acetonitrile, benzene, toluene and xylene.
According to yet another aspect of the present invention, there is provided a photocurable composition comprising a photosensitizer which is any one of the thioxanthones described above.
Further, the composition for coating and photo-curing is any one of paint, ink and adhesive.
By applying the technical scheme of the invention, an oligomeric multifunctional structure is introduced at the 2-hydroxy of the molecular structure of the thioxanthone compound 2-hydroxy-9H-thioxanthone-9-ketone derivative, and one sideEpoxy four-membered ring groups and multiple functional groups in the surface-oligomeric multifunctional structures (M, R) 2 、R 3 、R 4 、R 5 ) The introduction of the thioxanthone derivative enhances the solubility of the thioxanthone compound and matrix resin while retaining the molecular structure of the thioxanthone derivative, so that the thioxanthone compound can be matched with a light source well and used as a sensitizer and other initiators in a matching way. On the other hand, the polymerizable epoxy four-membered ring group can be further crosslinked and polymerized with the matrix resin, so that the thioxanthone compound is not solely present in the system, but forms a crosslinked network together with the polymer, thereby greatly reducing the possibility of migration thereof. Therefore, the photo-curing composition containing the thioxanthone compound has extremely low migration and low odor, and greatly improved adhesive force and shrinkage rate on the basis of retaining the basic performance of the traditional thioxanthone photosensitizer.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As analyzed by the background technology, the problems of high mobility of the modified photosensitizer, unsatisfactory adhesiveness of the used material and shrinkage of the cured material exist in the prior art, and the invention provides a thioxanthone compound, a preparation method thereof and a photocuring composition for solving the problems.
In one exemplary embodiment of the present application, a thioxanthone compound is provided, which has the following structural formula I:
m is an n-valent substituent, M isC 1 ～C 40 Alkyl, C of (2) 1 ～C 40 Alkylene group, C 7 ～C 40 Aralkyl of (C) 7 ～C 60 Aryl alkylene, C 3 ～C 40 Cycloalkyl, C 3 ～C 40 Cycloalkylene of C 1 ～C 40 Alkoxy, C 6 ～C 60 Aryl, C of (2) 12 ～C 60 Arylene of (C) 4 ～C 12 Any one of the heteroaryl groups of (1), wherein R 5 ' is H, C 1 ～C 40 Alkyl, C of (2) 3 ～C 40 Cycloalkyl, C 7 ～C 40 Aralkyl of (C) 1 ～C 40 Alkoxy, C 6 ～C 60 Aryl, C of (2) 4 ～C 12 Any one of the heteroaryl groups of (a). R is R 1 、R 2 、R 3 、R 4 、R 5 Each independently is H, substituted or unsubstituted phenyl, substituted or unsubstituted C 1 ～C 5 Alkyl, -NO of (C) 2 Substituted or unsubstituted C 1 ～C 5 Any one of the alkoxy groups of (a). n is any integer from 1 to 3, m is any integer from 1 to 6, and q is any integer from 0 to 3.
The thioxanthone compound introduces an oligomeric multifunctional structure at the 2-hydroxy of the molecular structure of the 2-hydroxy-9H-thioxanthone-9-ketone derivative, on the one hand, the epoxy four-membered ring group and a plurality of functional groups (M, R) 2 、R 3 、R 4 、R 5 ) The introduction of the thioxanthone derivative enhances the solubility of the thioxanthone compound and matrix resin while retaining the molecular structure of the thioxanthone derivative, so that the thioxanthone compound can be matched with a light source well and used as a sensitizer and other initiators in a matching way. On the other hand, the polymerizable epoxy four-membered ring group can be further crosslinked and polymerized with the matrix resin, so that the thioxanthone compound is not solely present in the system, but forms a crosslinked network together with the polymer, thereby greatly reducing the possibility of migration thereof. Thus, the photocurable composition comprising the thioxanthone compound of the present application has extremely low migration and low odor properties while retaining the basic properties of conventional thioxanthone photosensitizersAnd the adhesive force and the shrinkage are greatly improved.
In order to further improve the solubility of the thioxanthone compound in the matrix resin, it is preferable that when q is 0, n is 1 or 2, and when n is 1, M is preferably substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 20 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Aralkyl, substituted or unsubstituted C 3 ～C 20 Cycloalkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, substituted or unsubstituted C 6 ～C 20 Aryl, substituted or unsubstituted C 4 ～C 12 Any one of heteroaryl groups of (a); further preferred M is substituted or unsubstituted C 1 ～C 10 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 10 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Is a phenylalkyl group, a substituted or unsubstituted C 13 ～C 20 Is a biphenylalkyl group, a substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted pyridyl, substituted or unsubstituted indolyl. When n is 2, M is preferably substituted or unsubstituted C 1 ～C 20 Alkylene, substituted or unsubstituted C 7 ～C 20 Aryl alkylene, substituted or unsubstituted C 3 ～C 20 Cycloalkylene, substituted or unsubstituted C 12 ～C 20 Any one of arylene groups of (a); further preferred M is substituted or unsubstituted C 1 ～C 10 Alkylene, substituted or unsubstituted C 7 ～C 12 Phenyl alkylene, substituted or unsubstituted C 12 ～C 20 Is a biphenylene group, a substituted or unsubstituted C 3 ～C 12 Cycloalkylene, substituted or unsubstituted C 12 ～C 20 Any of arylene groups of (2)Meaning one.
In order to further enhance the polymerizability of the thioxanthone compound to increase the crosslinking density and reactivity thereof upon curing to satisfy the requirements of more photocurable compositions, it is preferable that when q is 1 to 3, n is 3 and M isPreferably R 5 ' H, substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 2 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Aralkyl, substituted or unsubstituted C 3 ～C 20 Cycloalkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, substituted or unsubstituted C 6 ～C 20 Aryl, substituted or unsubstituted C 4 ～C 12 Any one of heteroaryl groups of (a); further preferably R 5 ' H, substituted or unsubstituted C 1 ～C 10 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 10 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Is a phenylalkyl group, a substituted or unsubstituted C 13 ～C 20 Is a biphenylalkyl group, a substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted pyridyl, substituted or unsubstituted indolyl.
In one embodiment of the present application, n is 2 and M is a substituted or unsubstituted C 12 ～C 20 Is preferably any one of arylene groups of (2), M is preferably
Wherein, represents a binding position, R 1 ′、R 2 ′、R 3 ′、R 4 ' each independently selected from H, substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 20 Branched alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C 3 ～C 20 Alkyl cycloalkyl, substituted or unsubstituted C 4 ～C 20 Cycloalkyl alkyl, substituted or unsubstituted C 2 ～C 20 Alkenyl groups of (a) and (b) are each independently selected from the group consisting of alkenyl groups.
When n is 2, M further enriches the functional group structure of the thioxanthone compound, so that the modification of the thioxanthone compound on the 2-hydroxy-9H-thioxanthone-9-ketone derivative is improved, and the thioxanthone compound has better performance.
In order to further enrich the variety of the arylene-substituted functional group, the R is preferably 1 ′、R 2 ′、R 3 ' and R 4 -CH in 2 -CH which may each independently be substituted, preferably substituted, by-O 2 The number is 1 to 5.
In one embodiment of the present application, the thioxanthone compound has the structural formula
Any one of the following.
The thioxanthone compound has a polymerizable epoxy group and various substituted functional groups, and also has any substituted or unsubstituted substituent of 1 to 3 valences, so that the thioxanthone compound can meet the requirements of various photocuring compositions.
In another exemplary embodiment of the present application, there is provided a method for preparing the aforementioned thioxanthone compound, the method comprising: performing ring-opening reaction on the 2-hydroxy-9H-thioxanthen-9-one derivative and the compound a under alkaline conditions to obtain thioxanthone compounds; wherein, the structural general formula II of the 2-hydroxy-9H-thioxanth-9-ketone derivative and the structural general formula III of the compound a are as follows:
n、m、q、M、R 1 、R 2 、R 3 、R 4 、R 5 n, m, q, M, R of the same general structural formula I 1 、R 2 、R 3 、R 4 、R 5 。
The application adopts a common 2-hydroxy-9H-thioxanthen-9-one derivative and a multifunctional group oligomeric compound with a three-membered ring and a four-membered ring to carry out a one-step ring opening reaction under an alkaline condition to obtain the thioxanthone compound with an epoxy four-membered ring group, thereby modifying the 2-hydroxy-9H-thioxanthen-9-one derivative molecule, and the reaction general formula is as follows:
compared with the existing thioxanthone macromolecular photosensitizer, the synthesis method is simple, the thioxanthone compound introduces a low-polymerization multifunctional structure at the 2-hydroxy of the 2-hydroxy-9H-thioxanthone-9-ketone derivative molecular structure, on one hand, epoxy four-membered ring groups and various functional groups (M, R 2 、R 3 、R 4 、R 5 ) The introduction of the thioxanthone derivative enhances the solubility of the thioxanthone compound and matrix resin while retaining the molecular structure of the thioxanthone derivative, so that the thioxanthone compound can be matched with a light source well and used as a sensitizer and other initiators in a matching way. On the other hand polymerizabilityThe epoxy four-ring group of (c) is capable of further cross-linking polymerization with the matrix resin such that the thioxanthone compound is not present alone in the system but forms a cross-linked network with the polymer, thereby greatly reducing the possibility of migration thereof. Therefore, the photo-curing composition containing the thioxanthone compound has extremely low migration and low odor, and greatly improved adhesive force and shrinkage rate on the basis of retaining the basic performance of the traditional thioxanthone photosensitizer.
In order to improve the synthesis efficiency of thioxanthone compounds, the preparation method preferably comprises the steps of S1, mixing 2-hydroxy-9H-thioxanthene-9-ketone derivatives, a compound a, a phase transfer catalyst and a solvent to obtain a mixture; and S2, reacting the mixture in an alkaline environment for 3-10 hours to obtain thioxanthone compounds, wherein the reaction is preferably carried out at 50-150 ℃, the alkaline environment is formed by adopting an alkaline solution, the alkaline solution is preferably one or more of a sodium hydroxide solution, a potassium hydroxide solution and a lithium hydroxide solution, the concentration of the alkaline solution is preferably 10-40 wt%, and the solvent is preferably one or more of dichloroethane, acetonitrile, benzene, toluene and xylene.
In yet another exemplary embodiment of the present application, a photocurable composition is provided that includes a photosensitizer that is any of the thioxanthones described previously.
The photo-curing composition prepared by adopting the thioxanthone compound has excellent performance.
In yet another embodiment of the present application, the above-described photocurable composition is any one of a paint, an ink, and an adhesive.
The photo-curing composition has extremely low migration property, low odor and greatly improved adhesion and shrinkage rate as any one of paint, ink and adhesive.
The beneficial effects of the present application will be described below with reference to specific examples.
Example 1
50mL of toluene, 2-hydroxy-9H-thioxanth-9-one 2.8g, compound 1a 130.2g and tetrabutylammonium bromide 0.5g are added into a 250mL four-neck flask, the mixture is stirred and heated to 100 ℃, 40g of 1% sodium hydroxide solution is slowly added dropwise, the addition is completed for 30min, the stirring is continued for 5H, and the reaction is stopped. When the temperature of the system is reduced to room temperature, 60g of water is added, the system is layered, an organic layer is separated, and the organic layer is washed 3 times with 200g of water until the organic layer is neutral. The organic phase was poured into a 250mL four-necked flask, and the solvent was distilled off to give a yellow viscous liquid, which gave thioxanthone 1, MS (M/z): 531 (M+1) +.
Example 2
50mL of toluene, 22.8g of 2-hydroxy-9H-thioxanth-9-one, 35.5g of compound 2a and 0.5g of tetrabutylammonium bromide are added into a 250mL four-neck flask, the mixture is stirred and heated to 100 ℃, 40g of 1% sodium hydroxide solution is slowly added dropwise, the mixture is added for 30min, the stirring is continued for 5H, and the reaction is stopped. When the temperature of the system is reduced to room temperature, 60g of water is added, the system is layered, an organic layer is separated, and the organic layer is washed 3 times with 200g of water until the organic layer is neutral. The organic phase is poured into a 250mL four-necked flask, and the solvent is distilled off to obtain yellow viscous liquid, thus obtaining thioxanthone compound 2, MS (M/z): 1141 (M+1) +.
Example 3
50mL of toluene, 22.8g of 2-hydroxy-9H-thioxanth-9-one, 25.9g of compound 3a and 0.5g of tetrabutylammonium bromide are added into a 250mL four-neck flask, the mixture is stirred and heated to 100 ℃, 40g of 1% sodium hydroxide solution is slowly added dropwise, the mixture is added for 30min, the stirring is continued for 5H, and the reaction is stopped. When the temperature of the system is reduced to room temperature, 60g of water is added, the system is layered, an organic layer is separated, and the organic layer is washed 3 times with 200g of water until the organic layer is neutral. The organic phase was poured into a 250mL four-necked flask, and the solvent was distilled off to give a yellow viscous liquid, which gave thioxanthone 3, MS (M/z): 1492 (M+1) +.
According to the reaction procedure similar to that in examples 1 to 3, the substrates were replaced and the reaction conditions were adapted to give the corresponding thioxanthones, and the substrates in all examples were listed in Table 1, and the corresponding thioxanthones prepared in all examples were listed in Table 2, respectively.
The raw materials and sources used in the following experiments:
2-hydroxy-9H-thioxanthen-9-one (Shenzhen Biotechnology Co., ltd.) compound a is commercially available or synthesized by known synthetic methods, and the specific synthetic method can be prepared by referring to the synthetic method disclosed in the Chinese patent application publication No. CN 107619399A.
TABLE 1
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TABLE 2
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Photo-curable compositions were prepared according to the compositions of table 3:
TABLE 3 Table 3
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Any one of thioxanthone compounds, thioxanthone (Jiangxi Lot chemical Co., ltd.), ITX (Nanjing Ponno Biotechnology Co., ltd.) and Compound A (commercially available or prepared by the disclosed synthetic method of CN 100360524A) obtained in examples 1 to 13 above was used as a photosensitizer to prepare corresponding photocurable compositions (flexo ink formulations) 1 to 16 in the proportions of Table 3, which were evaluated for properties by the following property test methods, and the test results were shown in Table 4.
Sensitivity test:
about 1mg of the composition sample was weighed and spread on an aluminum crucible, and the sample was scanned using a Perkin Elmer differential scanning calorimeter (DSC 8000) equipped with a mercury arc lamp ultraviolet light source (OmniCure-S2000) to cure the sample. The time until the UV initiates the maximum curing exotherm was recorded, the shorter the time to peak apex, indicating better curing performance.
Migration evaluation:
the photosensitizer is prepared into 1X 10 by using ethyl alcohol as solvent -5 The absorption peak of the mol/L solution is measured by a UV3010 ultraviolet spectrophotometer; weighing 0.05g of the cured film prepared under the high-pressure mercury lamp of the photo-curing composition, respectively soaking in 30g of ethanol, standing at normal temperature for 24 hours, taking the soaking solution with the same volume, measuring the absorption peak at the maximum absorption wavelength by using an ultraviolet spectrophotometer, and observing whether the two are overlapped at the maximum absorption position or not, if so, indicating migration.
Adhesive force evaluation:
the composition was applied to PET film at a thickness of 25 μm and received 200mj/cm 2 To allow it to cure substantially completely. The coating film was cut into hundred cells, the knife edge was cut to the substrate and the knife edge was sharpened, the knife edge being at an angle of 45 degrees to the coating film, with reference to the paint film scoring evaluation criteria specified in GB/T9286-1998. Brushing paint scraps with a soft brush, adhering the 3M transparent adhesive tape to the scratched hundred lattices, and applying force to firmly adhere the adhesive tape to the coating surface and the scratched lattice part. One end of the 3M tape was held at an angle of 60 degrees in 2min, and the tape was peeled off smoothly in 1 second and evaluated according to the following criteria.
Level 0: the cutting edge is completely smooth and free from falling off;
stage 1: a little coating is dropped at the intersection of the incisions, but the cross cutting area cannot be affected by more than 5%;
2 stages: the coating is peeled off at the intersection of the incisions and/or along the edges of the incisions, being affected by significantly more than 5%, but not significantly more than 15%;
3 stages: the coating is partially or completely peeled off in large fragments along the cutting edge and/or partially or completely peeled off at different parts of the grid, the affected cross cutting area is obviously more than 15 percent, but not more than 35 percent;
4 stages: the coating flakes off along the cut edge, and/or some or all of the squares flake off, with the affected cross cut area being significantly greater than 35%, but not significantly greater than 65%;
5 stages: the extent of exfoliation exceeded 4 stages.
Shrinkage rate evaluation:
further, the photocurable composition of the example was cured with reference to the application and curing conditions described in the above adhesion evaluation. And calculating the ratio of the volume difference before and after the primary curing to the volume before curing according to the related regulations of the international standard ISO3521, and calculating the shrinkage.
TABLE 4 Table 4
Wherein, the structural formula of the compound A is as follows:
from the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
the thioxanthone compound introduces an oligomeric multifunctional structure at the 2-hydroxy of the molecular structure of the 2-hydroxy-9H-thioxanthone-9-ketone derivative, on the one hand, the epoxy four-membered ring group and a plurality of functional groups (M, R) 2 、R 3 、R 4 、R 5 ) Is introduced, while retaining the molecular structure of thioxanthone derivatives, to enhance thioxanthonesThe solubility of the compound and matrix resin enables the compound to be matched with a light source well and be used as a sensitizer and other initiators in a matching way. On the other hand, the polymerizable epoxy four-membered ring group can be further crosslinked and polymerized with the matrix resin, so that the thioxanthone compound is not solely present in the system, but forms a crosslinked network together with the polymer, thereby greatly reducing the possibility of migration thereof. Therefore, the photo-curing composition containing the thioxanthone compound has extremely low migration and low odor, and greatly improved adhesive force and shrinkage rate on the basis of retaining the basic performance of the traditional thioxanthone photosensitizer.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. The thioxanthone compound is characterized by having the following structural general formula I:
R 1 、R 2 、R 3 、R 4 、R 5 each independently H, unsubstituted phenyl, unsubstituted C 1 ～C 5 Alkyl, -NO of (C) 2 Unsubstituted C 1 ～C 5 Any one of the alkoxy groups of (a);
n is any integer from 1 to 3, m is any integer from 1 to 6, and q is any integer from 0 to 3;
when q is 0, n is 1 or 2,
when n is 1, M is unsubstituted C 1 ～C 20 Straight-chain alkyl, unsubstituted C 3 ～C 20 Is unsubstituted, or branched, alkylC 7 ～C 20 Aralkyl of (C) unsubstituted 3 ～C 20 Cycloalkyl, unsubstituted C 1 ～C 20 Alkoxy, unsubstituted C 6 ～C 20 Aryl, unsubstituted C 4 ～C 12 Any one of heteroaryl groups of (a);
when n is 2, M is unsubstituted C 1 ～C 20 Alkylene of (C) unsubstituted 7 ～C 20 Arylalkylene, unsubstituted C 3 ～C 20 Cycloalkyl, unsubstituted C 12 ～C 20 Arylene group of (2),Any one of them;
when q is 1-3, n is 3, and M isThe R is 5 ' H, unsubstituted C 1 ～C 20 Straight-chain alkyl, unsubstituted C 3 ～C 2 Branched alkyl, unsubstituted C 7 ～C 20 Aralkyl of (C) unsubstituted 3 ～C 20 Cycloalkyl, unsubstituted C 1 ～C 20 Alkoxy, unsubstituted C 6 ～C 20 Aryl, unsubstituted C 4 ～C 12 Any one of the heteroaryl groups of (a).
2. Thioxanthone compound according to claim 1, characterized in that when n is 1, M is unsubstituted C 1 ～C 10 Straight-chain alkyl, unsubstituted C 3 ～C 10 Branched alkyl, unsubstituted C 7 ～C 20 Is unsubstituted C 13 ～C 20 Is (C) unsubstituted 3 ～C 10 Cycloalkyl, unsubstituted C 1 ～C 10 Alkoxy, unsubstituted phenyl, unsubstituted biphenyl, unsubstituted naphthyl, unsubstituted thiopheneAny one of a group, an unsubstituted furyl group, an unsubstituted pyridyl group, and an unsubstituted indolyl group.
3. Thioxanthone compound according to claim 1, characterized in that when n is 2, M is unsubstituted C 1 ～C 10 Alkylene of (C) unsubstituted 7 ～C 12 Is unsubstituted C 12 ～C 20 Is (C) unsubstituted 3 ～C 12 Cycloalkyl, unsubstituted C 12 ～C 20 Any one of arylene groups of (a).
4. Thioxanthone compound according to claim 1, characterized in that R 5 ' H, unsubstituted C 1 ～C 10 Straight-chain alkyl, unsubstituted C 3 ～C 10 Branched alkyl, unsubstituted C 7 ～C 20 Is unsubstituted C 13 ～C 20 Is (C) unsubstituted 3 ～C 10 Cycloalkyl, unsubstituted C 1 ～C 10 An unsubstituted phenyl group, an unsubstituted biphenyl group, an unsubstituted naphthyl group, an unsubstituted thienyl group, an unsubstituted furyl group, an unsubstituted pyridyl group, an unsubstituted indolyl group.
5. Thioxanthone compound according to claim 1, characterized in that n is 2 and M is unsubstituted C 12 ～C 20 Any one of arylene groups of (a).
6. Thioxanthone compound according to claim 1, characterized in that M is
Wherein, represents a binding position, R 1 ′、R 2 ′、R 3 ′、R 4 ' each independently selected from H, unsubstituted C 1 ～C 20 Straight-chain alkyl, unsubstituted C 3 ～C 20 Branched alkyl, unsubstituted phenyl, unsubstituted C 3 ～C 20 Alkyl cycloalkyl, unsubstituted C 4 ～C 20 Cycloalkyl alkyl, unsubstituted C 2 ～C 20 Alkenyl groups of (a) and (b) are each independently selected from the group consisting of alkenyl groups.
7. Thioxanthone compound according to claim 1, characterized in that the structural formula of the thioxanthone compound is
Any one of the following.
8. A process for the preparation of thioxanthones according to any one of claims 1 to 7, characterized in that the process comprises:
performing ring-opening reaction on the 2-hydroxy-9H-thioxanthen-9-one derivative and the compound a under alkaline conditions to obtain thioxanthone compounds;
wherein the structural general formula II of the 2-hydroxy-9H-thioxanth-9-one derivative and the structural general formula III of the compound a are as follows:
said n, m, q, M, R 1 、R 2 、R 3 、R 4 、R 5 As described in said n, m, q, M, R in said general structural formula I 1 、R 2 、R 3 、R 4 、R 5 。
9. The method of manufacturing according to claim 8, characterized in that the method of manufacturing comprises:
step S1, mixing the 2-hydroxy-9H-thioxanth-9-one derivative, the compound a, a phase transfer catalyst and a solvent to obtain a mixture;
and step S2, reacting the mixture in an alkaline environment for 3-10 hours to obtain the thioxanthone compound.
10. The preparation method according to claim 9, wherein the reaction is carried out at 50 to 150 ℃ and the alkaline environment is formed using an alkaline solution.
11. The method according to claim 10, wherein the alkaline solution is one or more of sodium hydroxide solution, potassium hydroxide solution, and lithium hydroxide solution.
12. The preparation method according to claim 10, wherein the concentration of the alkaline solution is 10 to 40wt%.
13. The method of claim 9, wherein the solvent is one or more of dichloroethane, acetonitrile, benzene, toluene, and xylene.
14. A photocurable composition comprising a photosensitizer, characterized in that the photosensitizer is a thioxanthone compound according to any one of claims 1 to 7.
15. The photocurable composition of claim 14, wherein said photocurable composition is any one of a paint, an ink, and an adhesive.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025408A (en) * | 1997-03-27 | 2000-02-15 | First Chemical Corporation | Liquid thioxanthone photoinitiators |
| CN110713561A (en) * | 2018-07-12 | 2020-01-21 | 常州强力电子新材料股份有限公司 | Epoxy modified acrylic resin and preparation method thereof |
| CN110713593A (en) * | 2018-07-12 | 2020-01-21 | 常州强力电子新材料股份有限公司 | Epoxy modified polyester resin, preparation method thereof, composition containing epoxy modified polyester resin and application thereof |
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| EP3562819A4 (en) * | 2016-12-28 | 2020-06-03 | Henkel AG & Co. KGaA | Thioxanthone derivative photoinitiator |
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| US6025408A (en) * | 1997-03-27 | 2000-02-15 | First Chemical Corporation | Liquid thioxanthone photoinitiators |
| CN110713561A (en) * | 2018-07-12 | 2020-01-21 | 常州强力电子新材料股份有限公司 | Epoxy modified acrylic resin and preparation method thereof |
| CN110713593A (en) * | 2018-07-12 | 2020-01-21 | 常州强力电子新材料股份有限公司 | Epoxy modified polyester resin, preparation method thereof, composition containing epoxy modified polyester resin and application thereof |
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