WO2022068871A1 - 双官能团香豆素肟酯类化合物及其制备和应用 - Google Patents

双官能团香豆素肟酯类化合物及其制备和应用 Download PDF

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WO2022068871A1
WO2022068871A1 PCT/CN2021/121682 CN2021121682W WO2022068871A1 WO 2022068871 A1 WO2022068871 A1 WO 2022068871A1 CN 2021121682 W CN2021121682 W CN 2021121682W WO 2022068871 A1 WO2022068871 A1 WO 2022068871A1
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alkyl
group
amino
cycloalkyl
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French (fr)
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庞玉莲
樊书珩
邹应全
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湖北固润科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/18—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted otherwise than in position 3 or 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
    • C07D491/14—Ortho-condensed systems
    • C07D491/153—Ortho-condensed systems the condensed system containing two rings with oxygen as ring hetero atom and one ring with nitrogen as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
    • C07D493/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

  • the present invention relates to bifunctional coumarin oxime ester compounds, which can be used as photoinitiators.
  • the invention also relates to the preparation and application of the bifunctional coumarin oxime ester compound.
  • Photoinitiators also known as photosensitizers or photocuring agents, are a type of energy that can absorb a certain wavelength in the ultraviolet region (250-400nm) or visible light region (400-600nm) to generate free radicals, cations, etc., thereby initiating monomers. Polymeric cross-linked cured compounds. In the photocuring system, the photoinitiator generally accounts for 3-5%. Although the content is low, it is the key component and plays a decisive role in the photocuring speed. It is related to whether the oligomer and diluent can be quickly cross-linked and cured when the formulation system is irradiated with light, thereby changing from liquid to solid.
  • the photoinitiator must meet the needs of different photocuring conditions and applications.
  • the main goals are: to improve light sensitivity, improve surface curing efficiency (anti-oxidative polymerization inhibition), improve deep curing performance, improve the solubility of photoinitiators in monomers and resins, reduce toxicity and odor , reduce the migration of uncured initiator after curing and reduce yellowing.
  • Oxime ester photoinitiators have become a class of photoinitiators that have gradually received attention in recent years due to their excellent photosensitivity. They have been well known by researchers in this field, and their activity is outstanding. It is widely used in high-end photoresist fields such as black matrix (BM), photo-spacer (photo-spacer), rib grid (rib), etc.
  • BM black matrix
  • photo-spacer photo-spacer
  • rib grid rib
  • the commonly used oxime ester photoinitiators are mainly carbazole or diphenyl sulfide groups.
  • BASF products OXE-01 and OXE-02 are two representative products of oxime esters that are common in the market.
  • UV-vis LED light source emission wavelength 300-550nm, such as 365nm, 385nm, 395nm, 405nm, 420nm, 470nm, 525nm.
  • LED light source emission wavelength 300-550nm, such as 365nm, 385nm, 395nm, 405nm, 420nm, 470nm, 525nm.
  • oxime ester photoinitiators in China.
  • CN102775527A discloses a diphenylsulfide ketoxime ester photoinitiator and its preparation method
  • CN102492059A discloses substituted diphenylsulfide ketoxime ester photoinitiators. agent, etc.
  • the ultraviolet absorption wavelength of most initiators is 250-350nm, which cannot be matched with the increasingly developed LED light source, which greatly limits the application of oxime ester photoinitiators.
  • CN104817653A discloses an oxime ester photoinitiator suitable for UV-LED light source curing.
  • the initiator compound is a coumarin aldoxime ester compound.
  • studies have shown that the thermal stability of such compounds is not as good as that of OXE-01 [Zhu Guigang] , Synthesis of Coumarin Oxime Ester Derivatives and Its Application in LED Light Curing, Master Thesis, 2016; Dietliker K, Birbaum J L, Hüsler R, et al.Photolatent catalysts[J].CHIMIA International Journal for Chemistry, 2002, 56(5):197-202.].
  • CN1889960A discloses that coumarin ketoxime ester compounds can be used in pharmaceutical compositions or cosmetic compositions to prevent and treat diseases, including immune diseases, chronic inflammation, neurological diseases and skin diseases, tumor diseases, specific viruses (especially SARS) and so on. In this sense, such compounds are safe and non-toxic. Therefore, the development of photoinitiators with high sensitivity, high stability, and easy preparation is still the demand for the rapid development of the photocuring industry. Research and development of photoinitiators with higher performance has always been the core work in this field.
  • the bifunctional coumarin oxime ester has strong ultraviolet absorption in the range of 300-550nm, especially in the range of 365-525nm, and can rapidly transfer energy after absorbing light energy, continue to initiate polymerization, and has good photosensitivity and pattern integrity. It has obvious advantages in terms of properties and has good thermal stability and solubility, so it is suitable for use as a photoinitiator for radiation curing of (UV-vis) LED light sources.
  • the object of the present invention has been achieved based on the foregoing findings.
  • an object of the present invention is to provide a bifunctional coumarin oxime ester compound whose absorption wavelength is not only suitable for (UV-vis) LED light source radiation curing, but also has good thermal stability.
  • Another object of the present invention is to provide a method for preparing the bifunctional coumarin oxime ester compound of the present invention.
  • Another object of the present invention is to provide the use of the bifunctional coumarin oxime ester compound of the present invention as a photoinitiator or a photosensitizer.
  • Ch 1 is
  • A is CR 3 R 4 , NR 5 , S or O;
  • a benzene ring or a fused system with 2-5 benzene rings and each benzene ring in the benzene ring or the fused system has from 0 to the maximum possible number of substituents R 6 (Ch 1 -4);
  • R 1 , R 2 , 'R 1 , 'R 2 independently of one another represent straight-chain or branched C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl , C 4 -C 10 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkyl aryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 - C 20 alkylaryl is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 independently represent hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, C 1 -C 8 carboxylate, Sulfonic acid group, amino group, cyano group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 -C 20 cycloalkyl group, C 4 -C 20 cycloalkyl group Alkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy base, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkynylthio, C 3 -
  • Each R 0 independently of one another represents straight-chain or branched C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl or C 4 -C 10 alkylcycloalkane base;
  • n is 0 to the maximum possible number of substitutions, preferably 0-2.
  • R 1 , R 2 , 'R 1 , 'R 2 independently of one another represent straight-chain or branched C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl, wherein The aforementioned C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkyl alkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl are optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkyl
  • R 1 , R 2 , 'R 1 , 'R 2 independently of one another are selected from linear or branched C 1 -C 8 alkyl, linear or branched C 1 -C 8 perfluoroalkane base, C 5 -C 6 cycloalkyl, C 1 -C 4 alkyl substituted by C 5 -C 6 cycloalkyl, C 1 -C 4 alkyl substituted by phenyl, and phenyl, wherein the aforementioned phenyl Each is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro , amino, mono(C 1 -C 4 alkyl) amino, di(C 1 -C 4 alkyl) amino and mercapto;
  • R 1 and 'R 1 are linear or branched C 1 -C 6 alkyl, linear or branched C 1 -C 4 perfluoroalkyl, C 5 -C 6 cycloalkyl , C 1 -C 2 alkyl substituted by C 5 -C 6 cycloalkyl, or phenyl, the aforementioned phenyl optionally being substituted by one or more groups independently selected from the group consisting of C 1 -C 4 Alkyl, C1 - C4alkylthio, C1 - C4alkoxy , halogen, nitro, amino and mercapto, and
  • R 2 , 'R 2 are linear or branched C 1 -C 7 alkyl or phenyl, wherein the phenyl is optionally substituted with one or more groups independently selected from the group consisting of C 1 - C4 alkyl, halogen, nitro, amino, mono( C1 - C4 alkyl)amino, di( C1 - C4 alkyl)amino and mercapto.
  • R 1 , 'R 1 are linear or branched C 1 -C 6 alkyl or linear or branched C 1 -C 4 perfluoroalkyl.
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are independently of each other selected from hydrogen, halogen, nitro , hydroxyl, mercapto, carboxyl, C 1 -C 6 carboxylate, sulfonic acid, amino, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 - C 8 cycloalkoxy, C 4 -C 8 cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenylthio, C 2 -C 6 alkylthio, C 2 -C 6 alken
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 independently of each other are selected from hydrogen, halogen, nitro, C 1 -C 4 carboxylate, C 1 -C 6 alkyl, C 2 -C 4 alkenyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, mono(C 1 -C 4 alkyl) amino, di(C 1 - C 4 alkyl) amino, phenoxy and phenylthio;
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are independently of each other selected from hydrogen and C 1 -C 6 alkyl.
  • each R 0 independently of one another represents straight-chain or branched C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8cycloalkylalkyl or C4- C8alkylcycloalkyl , preferably straight-chain or branched C1 - C8alkyl .
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 independently of each other are selected from hydrogen, halogen, nitro, C 1 -C 4 carboxylate, C 1 -C 6 Alkyl, C 2 -C 4 alkenyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl) ) amino, phenoxy and phenylthio;
  • R 1 , 'R 1 are linear or branched C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, substituted by C 5 -C 6 cycloalkyl C 1 -C 2 alkyl or phenyl, the aforementioned phenyl is optionally substituted with one or more groups independently selected from the group consisting of fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio and halogenated C 1 -C 4 alkyl, and
  • R 2 , 'R 2 are linear or branched C 1 -C 7 alkyl or phenyl, wherein the phenyl is optionally substituted with one or more groups independently selected from the group consisting of C 1 - C 4 alkyl, halogen, nitro, amino, mono(C 1 -C 4 alkyl) amino and di(C 1 -C 4 alkyl) amino,
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 independently of one another are selected from hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 - C 4 alkylthio, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino, phenoxy and phenylthio;
  • R 1 , 'R 1 are linear or branched C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl or substituted by C 5 -C 6 cycloalkyl C 1 -C 2 alkyl, and
  • R 2 , 'R 2 are straight-chain or branched C 1 -C 6 alkyl or phenyl optionally substituted with nitro.
  • oximation reaction the compound of formula (II) is subjected to oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to obtain the compound of formula (III)
  • R 1 , 'R 1 and M are as defined in any one of claims 1-7;
  • the oximation reaction satisfies one or more of the following conditions:
  • the oximation reaction is carried out in the presence of ethanol or water-containing ethanol as a solvent;
  • the temperature of the oximation reaction is 60-120°C;
  • the oximation reaction time is 0.1-20 hours, preferably 0.5-10 hours;
  • the molar ratio of the compound of formula (II) to the compound selected from hydroxylamine and/or hydroxylamine hydrochloride is 1:2.5-1.25:2, preferably 1:2.2-1.1:2.
  • step (2) is carried out using an esterification reagent selected from the group consisting of compounds of formula (IVa), (IVb) and (IVc) below:
  • X is halogen, especially chlorine, and R 2 is as defined in any one of claims 1-7.
  • a photocurable composition comprising at least one photoinitiator according to any of items 1-7.
  • a method of preparing a photocurable material comprising combining the photocurable combination of item 14 with a light source having an emission wavelength of 300-550 nm, especially 365-525, such as 420-525 nm, such as a (UV-vis) LED light source objects are irradiated.
  • Fig. 1 is the schematic diagram of Ugra (Ugra) printing plate test strip, wherein
  • a first aspect of the present invention provides a bifunctional coumarin oxime ester compound of formula (I):
  • Ch 1 is
  • A is CR 3 R 4 , NR 5 , S or O;
  • a benzene ring or a fused system with 2-5 benzene rings and each benzene ring in the benzene ring or the fused system has from 0 to the maximum possible number of substituents R 6 (Ch 1 -4);
  • R 1 , R 2 , 'R 1 , 'R 2 independently of one another represent straight-chain or branched C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl , C 4 -C 10 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkyl aryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 - C 20 alkylaryl is optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkylthio, C 1
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 independently represent hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, C 1 -C 8 carboxylate, Sulfonic acid group, amino group, cyano group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 -C 20 cycloalkyl group, C 4 -C 20 cycloalkyl group Alkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy base, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkynylthio, C 3 -
  • Each R 0 independently of one another represents straight-chain or branched C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkylalkyl or C 4 -C 10 alkylcycloalkane base;
  • n is 0 to the maximum possible number of substitutions, preferably 0-2.
  • the compound of formula (I) contains both a coumarin-based moiety and an oxime ester moiety and contains two coumarin oxime ester structures.
  • the compound has strong ultraviolet absorption in the range of 350-550nm. After absorbing light energy, it can quickly transfer energy and continuously initiate polymerization. It has obvious advantages in photosensitivity and pattern integrity, and is very suitable for (UV-vis) LEDs.
  • the light source is safe and non-toxic and can be used in food packaging and other fields.
  • the compounds of formula (I) also have good thermal stability.
  • Cn- Cm denotes in each case that the number of carbon atoms contained in the group is nm.
  • Halogen refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferred that the halogen includes F, Cl or a combination thereof.
  • Cn- Cm alkyl as used herein means having nm, such as 1-20, preferably 1-12, more preferably 1-8, particularly preferably 1-6, especially preferably 1-4 Branched or unbranched saturated hydrocarbon radicals of 1 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1 - Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpenty
  • C1 -C8 alkyl may be methyl, ethyl, propyl, isopropyl, n-butyl, 2 -butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl and its isomers.
  • C1 - C6 alkyl groups can be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl and isomers thereof.
  • C 1 -C 4 alkyl may be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl base and its isomers.
  • C2- Cm alkenyl as used herein means having 2 -m, such as 2-20, preferably 2-6, more preferably 2-4 carbon atoms and having one or more carbon atoms at any position Branched or unbranched unsaturated open-chain hydrocarbon radicals of double bonds, such as vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3- Butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl , 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl- 3-butenyl, 3-methyl-3-butenyl, 2-
  • C2 - C6 alkenyl can be vinyl, propenyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, neopentenyl, 1-hexyl Alkenyl, 2-hexenyl, 3-hexenyl, isohexenyl, neohexenyl and isomers thereof.
  • C 2 -C 4 alkenyl can be vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl 1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl and isomers thereof.
  • C2- Cm alkynyl as used herein means having 2 -m, such as 2-20, preferably 2-6, more preferably 2-4 carbon atoms and having one or more carbon atoms at any position Branched or unbranched unsaturated open-chain hydrocarbon radicals with triple bonds, such as ethynyl, propynyl, 1-butynyl, 2-butynyl and isomers thereof.
  • C2 - C6alkynyl can be ethynyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl and isomers thereof.
  • the C2 - C4alkynyl group can be ethynyl, propynyl, 1-butynyl, 2 -butynyl and isomers thereof.
  • C3 - Cm cycloalkyl refers to a saturated alicyclic monocyclic group having 3-m, such as 3-20, preferably 3-8, more preferably 5-6 ring carbon atoms groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
  • C 4 -C m cycloalkylalkyl denotes an alkyl group substituted by a cycloalkyl group and containing a total of 4-m carbon atoms, such as 4-20 carbon atoms, preferably 4-10 carbon atoms, more preferably 4-6 carbon atoms, where alkyl and cycloalkyl apply as defined herein, eg cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutyl cyclopentylethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, Cyclohexylpropyl, cyclo
  • C 4 -C 10 alkylcycloalkyl denotes a cycloalkyl substituted by an alkyl group and containing in total 4-m carbon atoms, eg 4-10 carbon atoms, preferably 4-8 carbon atoms, more preferably 4-6 carbon atoms, where alkyl and cycloalkyl are as defined herein, eg methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethyl Cyclobutyl, propylcyclobutyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl , butylcyclohexyl, etc.
  • C6 - Cm aryl refers to a monocyclic, bicyclic or tricyclic aromatic hydrocarbon group containing 6-m carbon atoms, eg 6-18, preferably 6-10 carbon atoms.
  • C 6 -C m aryl groups mention may be made of phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methylethylphenyl, diethylphenyl, methylphenyl propylphenyl, naphthyl, etc.; preferably phenyl or naphthyl, especially phenyl (also denoted as C 6 H 5 as a substituent).
  • C7 - C20 aralkyl denotes an alkyl group substituted by an aryl group and containing in total 7-20 carbon atoms, eg 7-12, preferably 7-10 carbon atoms, more preferably 7-8 carbon atoms atom, where alkyl and aryl are as defined herein, eg, benzyl, phenethyl, naphthylmethyl, naphthylethyl, and the like.
  • C7 - C20 alkylaryl denotes an aryl group substituted by an alkyl group and containing in total 7-20 carbon atoms, eg 7-12, preferably 7-10 carbon atoms, more preferably 7-8 carbon atoms carbon atoms, where alkyl and aryl are as defined herein, eg methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, methylphenyl naphthyl, ethyl naphthyl, etc.
  • C n -C m alkoxy and “C n -C m alkylthio" mean that at any carbon atom of the open chain C n -C m alkane corresponding to the C n -C m alkyl group is bonded
  • C 1 -C 8 alkoxy may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentyloxy, isopentyloxy group, hexyloxy, heptyloxy, octyloxy, isooctyloxy and their isomers.
  • C 1 -C 4 alkoxy may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and isomers thereof body.
  • C 1 -C 8 alkylthio may be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, 2-butylthio, tert-butylthio, pentylthio, isopentylthio base, hexylthio, heptylthio, octylthio, isooctylthio and their isomers.
  • the C 1 -C 4 alkylthio group may be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio and isomers thereof.
  • C 2 -C m alkenyloxy and “C 2 -C m alkenylthio” refer to bonding at any saturated carbon atom in the C 2 -C m alkene corresponding to the C 2 -C m alkenyl group
  • a C 2 -C m alkenyl group having an oxygen atom or a sulfur atom as a linking group such as a C 2 -C 20 alkenyloxy (or thio) group, preferably a C 2 -C 12 alkenyloxy (or thio) group, more Preference is given to C 2 -C 8 alkenyloxy (or thio) groups, particularly preferred C 2 -C 6 alkenyloxy (or thio) groups, especially preferred C 2 -C 4 alkenyloxy (or thio) groups, such as vinyloxy, propylene Oxygen, isopropenyloxy, n-butenyloxy, sec-butenyloxy, isobuteny
  • C 2 -C m alkynyloxy and “C 2 -C m alkynylthio” refer to a bond at any saturated carbon atom in the C 2 -C m alkyne corresponding to the C 2 -C m alkynyl group
  • a C 2 -C m alkynyl group having an oxygen atom or a sulfur atom as a linking group such as a C 2 -C 20 alkynyloxy (or thio) group, preferably a C 2 -C 12 alkynyloxy (or thio) group, More preferably C 2 -C 8 alkynyloxy (or thio) group, particularly preferably C 2 -C 6 alkynyloxy (or thio) group, especially preferably C 2 -C 4 alkynyloxy (or thio) group, such as ethynyloxy, Propynyloxy, n-butynyloxy, sec-buty
  • C 3 -C m cycloalkoxy and “C 3 -C m cycloalkylthio” refer to any ring carbon atom in the C 3 -C m cycloalkane corresponding to the C 3 -C m cycloalkyl group
  • a C 3 -C m cycloalkyl group having an oxygen atom or a sulfur atom bonded to it as a linking group such as a C 3 -C 20 cycloalkoxy (or sulfur) group, preferably a C 3 -C 8 cycloalkoxy ( or thio) group, more preferably C 5 -C 6 cycloalkoxy (or thio) group, such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy , cyclooctyloxy, cyclodecyloxy and its isomers, cyclopropyloxy
  • C 4 -C m cycloalkylalkoxy and “C 4 -C m cycloalkylalkylthio” refer to alkoxy(thio) groups substituted with cycloalkyl and contain a total of 4-m carbons atoms, such as 4-20 carbon atoms, preferably 4-8 carbon atoms, where cycloalkyl and alkoxy(thio) groups are as defined herein, such as cyclopropylmethoxy, cyclopropylethoxy, cyclopropyl Propylpropoxy, cyclopropylbutoxy, cyclobutylmethoxy, cyclobutylethoxy, cyclobutylpropoxy, cyclobutylbutoxy, cyclopentylmethoxy, cyclopentylethyl Oxy, cyclopentylpropoxy, cyclopentylbutoxy, cyclohexylmethoxy, cyclohexylethoxy, cyclohe
  • C 6 -C m aryloxy and “C 6 -C m arylthio” as used herein refer to any aromatic carbon atom in the C 6 -C m arene corresponding to the C 6 -C m aryl group
  • R 1 , R 2 , 'R 1 , and 'R 2 independently represent linear or branched C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 Cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkyl and C 7 -C 20 alkylaryl, wherein the aforementioned C 1 -C 20 alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 cycloalkyl alkyl, C 4 -C 10 alkylcycloalkyl, C 6 -C 20 aryl, C 7 -C 20 aralkane and C 7 -C 20 alkylaryl groups are optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 6 alkylthio, C 1 -C 6 alkoxy, C 1 -C
  • R 1 , R 2 , 'R 1 , 'R 2 independently of one another represent straight-chain or branched C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 ring Alkylalkyl, C 4 -C 8 alkylcycloalkyl, C 6 -C 10 aryl, C 7 -C 11 aralkyl and C 7 -C 11 alkylaryl, wherein the aforementioned C 1 -C 8 Alkyl, C3- C8cycloalkyl , C4 - C8cycloalkylalkyl , C4 - C8alkylcycloalkyl , C6 - C10aryl , C7 - C11aralkyl and C 7 -C 11 alkylaryl optionally substituted with one or more groups independently selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C
  • R 1 , R 2 , 'R 1 , 'R 2 independently of one another are selected from linear or branched C 1 -C 8 alkyl, C 5 -C 6 cycloalkyl, C 5 -C C 6 cycloalkyl substituted C 1 -C 4 alkyl, phenyl substituted C 1 -C 4 alkyl and phenyl, wherein each of the aforementioned phenyl groups is optionally independently selected from the group consisting of one or more Group substitution of: C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, halogen, nitro, amino, mono(C 1 -C 4 alkyl)amino, Di(C 1 -C 4 alkyl)amino and mercapto.
  • R 1 and 'R 1 are linear or branched C 1 -C 6 alkyl, linear or branched C 1 -C 4 perfluoroalkyl, C 5 -C 6 cycloalkyl , C 1 -C 2 alkyl substituted by C 5 -C 6 cycloalkyl, or phenyl, the aforementioned phenyl optionally being substituted by one or more groups independently selected from the group consisting of C 1 -C 4 Alkyl, C1 - C4alkylthio, C1 - C4alkoxy , halogen, nitro, amino and mercapto, and
  • R 2 , 'R 2 are linear or branched C 1 -C 7 alkyl or phenyl, wherein the phenyl is optionally substituted with one or more groups independently selected from the group consisting of C 1 - C4 alkyl, halogen, nitro, amino, mono( C1 - C4 alkyl)amino, di( C1 - C4 alkyl)amino and mercapto.
  • R 1 , 'R 1 are linear or branched C 1 -C 6 alkyl or linear or branched C 1 -C 4 perfluoroalkyl.
  • R 1 and 'R 1 may have the same or different meanings, preferably have the same meaning, ie 'R 1 has the definition mentioned for R 1 .
  • R 2 and 'R 2 may have the same or different meanings, preferably have the same meaning, ie 'R 2 has the definition mentioned for R 2 .
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 independently of each other are selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, C 1 -C 8 Carboxylic acid ester group, sulfonic acid group, amino group, cyano group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 -C 20 cycloalkyl group, C 4 -C 20 cycloalkylalkyl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 3 -C 20 cycloalkoxy, C 4 -C 20 cycloalkylalkoxy, C 1 -C 20 alkylthio, C 2 -C 20 alkenylthio, C 2 -C 20 alkeny
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 independently of each other are selected from hydrogen, halogen, nitro, hydroxyl, mercapto, carboxyl, C 1 -C 6 Carboxylate, sulfonic acid, amino, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 4 - C 8 cycloalkylalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 8 cycloalkoxy, C 4 -C 8 Cycloalkylalkoxy, C 1 -C 6 alkylthio, C 2 -C 6 alkenylthio, C 2 -C 6 alkynylthio, C 3 -
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are independently of each other selected from hydrogen, halogen, nitro, C 1 -C 4 carboxylate, C 1 -C 6 alkyl, C 2 -C 4 alkenyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl)amino, phenoxy and phenylthio.
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are independently of each other selected from hydrogen and C 1 -C 6 alkyl.
  • each R 0 independently represents a straight-chain or branched C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 4 -C 8 cycloalkyl alkyl or C 4 -C 8 alkylcycloalkyl, preferably straight-chain or branched C 1 -C 8 alkyl.
  • n is each independently 0-2, such as 0, 1 or 2.
  • R 1 , 'R 1 are linear or branched C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl, C 1 -C 2 alkyl substituted with C 5 -C 6 cycloalkyl or phenyl optionally substituted with one or more groups independently selected from the group consisting of fluorine, chlorine, bromine, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio and halogenated C 1 -C 4 alkyl, and
  • R 2 , 'R 2 are linear or branched C 1 -C 7 alkyl or phenyl, wherein the phenyl is optionally substituted with one or more groups independently selected from the group consisting of C 1 - C 4 alkyl, halogen, nitro, amino, mono(C 1 -C 4 alkyl) amino and di(C 1 -C 4 alkyl) amino,
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 independently of each other are selected from hydrogen, halogen, nitro, C 1 -C 4 carboxylate, C 1 -C 6 Alkyl, C 2 -C 4 alkenyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, mono(C 1 -C 4 alkyl)amino, di(C 1 -C 4 alkyl) ) amino, phenoxy and phenylthio.
  • the fused system having 2-5 benzene rings may be a naphthalene ring, an anthracene ring, a phenanthrene ring, a benzo(a)anthracene, a tetracene or a pentacene structure.
  • the benzene ring or each benzene ring in the condensed system preferably has 0-2, such as 0, 1 or 2 substituents R 6 . In one embodiment, only 1 or 2 of the benzene rings in the fused system have 1 or 2 substituents R6.
  • the (Ch 1 -4) structure is a benzene ring or a fused system with 2-4 benzene rings, such as a naphthalene ring, anthracene ring, phenanthrene ring, benzo(a)anthracene or tetracene structure .
  • the compound of formula (I) is selected from compounds 1-64 of Table 1 below.
  • Compounds 1-64 were prepared in Examples 1-64, respectively.
  • oximation reaction the compound of formula (II) is subjected to oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to obtain the compound of formula (III)
  • R 1 , 'R 1 and M are as defined above,
  • an oximation reaction can be carried out first to introduce an oxime group, and then the hydroxyl group in the oxime group is converted into a corresponding ester group through an esterification reaction, thereby obtaining the bifunctional coumarin of the present invention Oxime ester compounds.
  • the oximation reaction usually starts from a carbonyl compound.
  • the compound of formula (II) is subjected to an oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to obtain the compound of formula (III)
  • R 1 , 'R 1 and M in formulae (II) and (III) are as defined above.
  • hydroxylamine hydrochloride NH 2 OH.HCl
  • hydroxylamine NH 2 OH
  • a mixture thereof a mixture thereof as an oximation reagent.
  • the oximation reaction is usually carried out in an organic solvent, preferably in an organic polar solvent.
  • Solvents that can be used are, for example, ethanol or aqueous ethanol. If aqueous ethanol is used, the volume ratio of ethanol to water may be 10:1-1:10, preferably 5:1-1:5, eg 3:1, 1:1 or 1:2.
  • the temperature of the oximation reaction is generally the reflux temperature of the solvent, and the temperature is usually in the range of 60-120°C, for example, 60-90°C.
  • the oximation reaction time is also not particularly limited, and is usually carried out for 0.1-20 hours, preferably 0.3-10 hours.
  • the relative amount of the compound of formula (II) and the compound selected from hydroxylamine and/or hydroxylamine hydrochloride is not particularly limited, for example, the molar ratio of the two is 1:2.5-1.25:2, preferably 1:2.2-1.1:2, such as about 1:2.
  • Each oxime ester group may exist in two configurations, (Z) form or (E) form.
  • Isomers can be separated by conventional methods, but it is also possible to use isomer mixtures as photoinitiating species. Accordingly, the present invention also relates to mixtures of configurational isomers of compounds of formula (I).
  • Esterification of compounds of formula (III) is conventional, and by this reaction, the hydroxyl group in the oxime group is converted into an ester group, thereby obtaining compounds of formula (I).
  • the esterification reagent is not particularly limited as long as it can convert the hydroxyl group in the oxime group of the compound of formula (III) into an ester group.
  • esterification reagents it is possible to use the corresponding acid halides, such as acid chlorides, as well as the corresponding carboxylic acids, and also the corresponding acid anhydrides. These compounds can be represented by formulae (IVa), (IVb) and (IVc), respectively:
  • X is halogen, especially chlorine, and R2 is as defined above.
  • the above-mentioned esterification reaction is usually carried out in the presence of a catalyst suitable for the esterification reaction.
  • a catalyst suitable for the esterification reaction.
  • an acidic catalyst or a basic catalyst can be used.
  • a catalyst one or more selected from the group consisting of sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate can be used , sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride, tetramethylammonium hydroxide and tertiary amines such as trialkylamines such as trimethylamine and triethylamine.
  • the amount of catalyst used is conventional and can be determined by common knowledge in the art, or by several routine preliminary experiments.
  • the above-mentioned esterification reaction is usually carried out in a solvent, preferably an organic solvent.
  • a solvent preferably an organic solvent.
  • the selection of the type of solvent is not particularly limited as long as it can dissolve the compound of formula (III) and the esterification reagent and is chemically inert to the esterification reaction, that is, it does not participate in the esterification reaction.
  • solvents mention may be made of tetrahydrofuran, benzene, toluene, N,N-dimethylformamide, dichloromethane and acetone.
  • a single solvent may be used, or a mixture of two or more solvents may be used.
  • the relative amount of the esterification reagent of the compound of formula (III) and the compound of formula (IVa), (IVb) and (IVc) is not particularly limited, and the molar ratio of the two is 1:1.6-1:2.5, preferably 1:1.8- 1:2.2, eg about 1:2.
  • the esterification reaction can be carried out over a very wide temperature range.
  • the esterification reaction is carried out at a temperature of -10°C to 150°C, preferably 0°C to 100°C, preferably at ambient temperature.
  • the esterification reaction time is also not particularly limited, and is usually carried out for 0.5-24 hours, preferably 0.8-12 hours.
  • a reaction mixture comprising the compound of formula (I). Therefore, the reaction mixture can be worked up to obtain purified compounds of formula (I). Generally, the reaction mixture obtained by the esterification reaction is first filtered, and a portion of the filtrate is taken out. Then, the filtrate was washed to remove the catalyst and unreacted raw materials.
  • the washing liquid is not particularly limited as long as the catalyst and unreacted raw materials can be removed.
  • washing solutions mention may be made of dilute hydrochloric acid (aqueous solution), saturated aqueous sodium bicarbonate solution and water. The concentration of dilute hydrochloric acid is not particularly limited, and generally, dilute hydrochloric acid with a concentration of 5-12% is used.
  • washing with the lotion can be performed once or multiple times; in the case of multiple times, a single lotion can be used, or different lotions can be used in sequence.
  • the filtrate obtained by filtering the reaction mixture obtained by the esterification reaction is washed successively with dilute hydrochloric acid, saturated aqueous sodium bicarbonate solution and water.
  • the organic phase needs to be washed with the next washing solution after the aqueous phase is poured out.
  • drying is required to remove residual water.
  • drying is usually carried out using anhydrous sodium sulfate. After drying, residual organic solvent is removed.
  • the means for removing the organic solvent here is not particularly limited, and the organic solvent is usually removed by distillation under reduced pressure. After removal of residual organic solvent, the crude product of the compound of formula (I) is obtained. If it is desired to further improve the purity of the compound of formula (I), the compound may be further purified, for example by means of recrystallization.
  • the selection of the recrystallization solvent is conventional and not particularly limited. According to the present invention, the crude product of the compound of formula (I) is advantageously recrystallized from methanol.
  • the compound of formula (I) of the present invention has strong absorption in the wavelength range of 300-550nm, especially 350-525nm, especially 365-525nm, such as 420-525nm, so it can be applied to (UV-vis) LED light in the curing system.
  • the preparation raw materials of the compound of formula (I) of the present invention are all coumarin ketone compounds with less toxicity, and compared with traditional photoinitiators, the degree of harm to the human body and the environment is reduced.
  • a compound of formula (I) according to the present invention as a photoinitiator.
  • the compound of formula (I) of the present invention can be used as a photoinitiator in a (UV-vis) LED light curing system, and can effectively initiate a curing reaction.
  • the compounds of formula (I) can be used as photoinitiators or photosensitizers in the fields of coatings, inks, microelectronics, printing and the like.
  • a compound of formula (I) is used as a photoinitiator or photosensitizer, the amount thereof is conventional or can be determined by routine preliminary experiments.
  • Another aspect of the present invention relates to photocurable compositions comprising at least one photoinitiator of the present invention.
  • the amount of photoinitiator of the present invention is generally 0.01-10% by weight, such as 0.02% by weight, 0.05% by weight, 0.08% by weight, 0.1% by weight, 0.2% by weight, 0.5% by weight, 0.8% by weight, 1% by weight, 1.2% by weight %, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.5%, 5% by weight, 5.5% by weight, 6% by weight, 6.5% by weight, 7% by weight, 7.5% by weight, 8% by weight, 8.5% by weight, 9% by weight, 9.5% by weight, preferably 0.1-6% by weight, such as 0.2- 5% by weight, based on the active ingredient amount of the photocurable composition.
  • active ingredients refer to ingredients in the photocurable composition other than the solvent.
  • the photocurable composition further includes a photocurable resin.
  • a photocurable resin refers to an oligomer or prepolymer containing unsaturated carbon-carbon double bonds. After the oligomer or prepolymer is irradiated with light, a photoinitiator can initiate a polymerization reaction, and then cross-link curing occurs.
  • Photocurable resins are the main components of photocurable products (such as UV coatings, UV inks, UV adhesives, etc.).
  • epoxy (meth)acrylate resins As the photocurable resin, epoxy (meth)acrylate resins, polyester-based (meth)acrylates, urethane (meth)acrylates, ethylenically unsaturated polyesters, amino (meth)acrylates can be mentioned Resin, photoimageable alkali-soluble resin, etc.
  • epoxy (meth)acrylate resins, polyester (meth)acrylates, polyurethane (meth)acrylates or combinations thereof are employed.
  • the epoxy (meth)acrylate resin is preferably bisphenol A epoxy (meth)acrylate, bisphenol A epoxy acrylate diluted with tripropylene glycol di (meth)acrylate or a combination thereof, such as Wuxi Resin Factory's Bisphenol A Epoxy Acrylate WSR-U125, 20% Tripropylene Glycol Diacrylate Diluted Bisphenol A Epoxy Acrylate 621A-80 from Taiwan Changxing Chemical Co., Ltd., Modified Bisphenol A Epoxy Acrylic from Taiwan Changxing Chemical Co., Ltd. Ester 623-100, Modified Bisphenol A Epoxy Acrylate 6231A-80 diluted with 20% Tripropylene Glycol Diacrylate, Changxing Chemical Company, Taiwan.
  • the polyester (meth)acrylate is preferably a hyperbranched polyester acrylic resin with a high functionality, especially a hyperbranched polyester acrylic resin with a functionality of 5-30, such as a hyperbranched polymer with a functionality of 6-20.
  • Ester acrylate prepolymer such as Wuxi Knox company's hyperbranched polyester acrylate prepolymer 932-100 (6 functional), American Sartomer company's hyperbranched polyester acrylate prepolymer CN2300 (8 functional) degree), CN2301 (9 functionality), CN2302 (16 functionality), etc.
  • the urethane (meth)acrylate is preferably an aliphatic urethane acrylate.
  • HDDA 1,6-hexanediol diacrylate
  • the amount of the photocurable resin in the photocurable composition is usually 10-90% by weight, such as 15% by weight, 20% by weight, 25% by weight, 30% by weight, 40% by weight, 50% by weight, 60% by weight, 70% by weight % by weight, 80% by weight, 85% by weight, preferably 55-80% by weight, based on the active ingredient amount of the photocurable composition.
  • active ingredients refer to ingredients in the photocurable composition other than the solvent.
  • the photocurable composition may further contain a multifunctional reactive diluent.
  • a polyfunctional reactive diluent refers to a monomer containing two or more photopolymerizable groups. Multifunctional reactive diluents have lower viscosity and stronger solubility. After being irradiated by a light source, the polyfunctional reactive diluent can be polymerized by reactive radicals to form a cross-linked network structure.
  • the multifunctional reactive diluent is a multifunctional (meth)acrylate reactive diluent. It refers to a monomer containing two or more (meth)acrylate polymerizable groups.
  • multifunctional (meth)acrylate crosslinkers mention may be made of trimethylolpropane triacrylate (TMPTA), pentaerythritol tetraacrylate (PETTA), propoxylated trimethylolpropane triacrylate (PO-TMPTA) ) or ethoxylated trimethylolpropane triacrylate (EO-TMPTA), pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentaacrylate (DPEPA), dipentaerythritol hexaacrylate ( DPHA), glycol diacrylates such as tripropylene glycol diacrylate (TPGDA),
  • TPGDA triprop
  • the multifunctional reactive diluent is usually used in the photocurable composition in an amount of 8-60% by weight, such as 10% by weight, 20% by weight, 25% by weight, 30% by weight, 40% by weight, 50% by weight, 60% by weight , preferably 15 to 45% by weight, based on the active ingredient amount of the photocurable composition.
  • the photocurable composition may further comprise a monofunctional reactive diluent.
  • a monofunctional reactive diluent refers to a monomer containing one photopolymerizable group. It has low viscosity and strong dissolving ability, and can act as part of organic solvents. After the monofunctional reactive diluent is irradiated by a light source, a reactive radical can initiate a polymerization reaction.
  • Monofunctional reactive diluents mainly include (meth)acrylate compounds and vinyl compounds.
  • methyl methacrylate (MMA), n-butyl acrylate (BA), isooctyl acrylate (2-EHA), isodecyl acrylate (IDA) can be mentioned
  • lauryl acrylate (LA) hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and some (meth)acrylates with cyclic structures.
  • vinyl-based monofunctional reactive diluent styrene (St), vinyl acetate (VA), N-vinylpyrrolidone (NVP) and the like can be mentioned.
  • the amount of monofunctional reactive diluent in the photocurable composition is usually 5-50% by weight, such as 10% by weight, 20% by weight, 25% by weight, 30% by weight, 40% by weight, 50% by weight, preferably 8- 40% by weight, based on the active ingredient amount of the photocurable composition.
  • the photocurable composition of the present invention may optionally contain an organic solvent.
  • organic solvent aromatic hydrocarbons such as benzene, toluene, halogenated alkanes such as chloroform, dichloromethane, chloroethane, ketones such as acetone, butanone, pentanone, etc., alcohols such as methanol, ethanol, propylene Alcohol, isopropanol, ethylene glycol, and glycol ethers, glycol ether acetates, propylene glycol ethers, propylene glycol ether acetates, etc.
  • the photocurable compositions of the present invention may also optionally contain other additives, such as leveling agents, antioxidants, anti-settling agents, colorants, microbicides, such as antimicrobial agents and thermal insulation materials additives.
  • the leveling agent is selected from Eucalyptus Series of leveling agents, particularly preferably 360S, 361S, 362S, 372S, 375S, 376S, 380S, 384S, 392S, 400U, 415U, etc.
  • the preparation of the photocurable composition of the present invention is conventional, and each component of the photocurable composition of the present invention may be uniformly mixed together.
  • a cured material obtainable from the photocurable composition of the present invention is provided.
  • the resulting cured material may be a photocurable coating, which includes coatings containing functional materials, coatings of color filters for UV light and/or visible light; sealants; photolithographic materials; holographic recording materials; 3D printing materials; Lithographic materials; preparation materials for optical devices and materials for improving mechanical properties, such as carbon fiber composite materials and/or inorganic nanoparticles and/or organic nanoparticles, etc.
  • a method for preparing a photocurable material from the photocurable composition of the present invention comprising using a light source with an emission wavelength of 300-550 nm, especially 365-525 nm, such as 420-525 nm, such as (UV- A vis) LED light source irradiates the photocurable composition of the present invention.
  • Example 1 The method of Example 1 was repeated, and the reaction raw materials were appropriately changed to obtain the following compounds 2-64 and their nuclear magnetic data respectively.
  • the photosensitivity of the photoinitiator was tested using Ugra plate-printing test strips as a mask.
  • the segments of the Ugra plate test strip are shown in Figure 1.
  • the Ugra printing test strip is divided into 5 control sections, from left to right: continuous density ladder section (1); yin and yang micron isoline concentric circle section (2); full-scale tone dot section (3); Shadow control section (4); highlight and shadow control section (5).
  • the second segment yin and yang micrometer isolines
  • concentric circle segment a concentric circle diagram composed of 12 yin and yang micrometer isolines, which are 4, 6, 8, 10, 12, 15, 20, 25, 30, 40, 55, 70, used to detect the exposure and development of the PS version.
  • the third section full-scale tone point section: it consists of 10%-100% and a range of 10%. Measure the change curve of film dots and copying, proofing and printing online shop.
  • the fourth segment ghost control segment: it consists of thin lines with a line width of 60 lines/cm and an area rate of 60%.
  • the photocurable composition was evaluated by applying a photocurable composition containing a photoinitiator on an aluminum substrate, followed by exposure and development, and evaluating the sensitivity from the continuous scale of the obtained image and evaluating the accuracy from the micro-line test block area.
  • the pros and cons of the recipe was evaluated by applying a photocurable composition containing a photoinitiator on an aluminum substrate, followed by exposure and development, and evaluating the sensitivity from the continuous scale of the obtained image and evaluating the accuracy from the micro-line test block area. The pros and cons of the recipe.
  • the bifunctional coumarin ketoxime ester compound of formula (I) of the present invention or a photoinitiator known in the prior art (for comparison) see Table 2 for details.
  • the acrylate resin is a resin with the trade name of FS2600K purchased from Shanghai Fushun International Trade Co., Ltd., the functionality is 2, and the number average molecular weight is 1400.
  • Dipentaerythritol hexaacrylate was purchased from Shanghai Fushun International Trade Co., Ltd. under the trade name of GM66G0C.
  • the crystal violet dye was purchased from Shanghai Sinopharm under the trade name of hexamethyl rosaniline hydrochloride.
  • each composition is stirred and mixed evenly under yellow light, utilize centrifuge spin-coating on the PS aluminum plate base that is processed in advance and satisfies the following conditions:
  • Aluminum plate base size 1030mm ⁇ 800mm
  • Aluminum plate base thickness 0.28-0.3mm
  • the photopolymerizable compound undergoes a polymerization reaction in the presence of an initiator and is insoluble in the developing solution, while the non-exposed area is soluble, thus obtaining a negative image.
  • the sensitivity of the photoinitiator was evaluated from the continuous scale of the obtained image by exposure development.
  • the initiator system sensitivity is characterized by the retention (ie, polymerized) of the highest grayscale number after development. The higher the gray level, the higher the sensitivity of the test system. The results are shown in Table 2.
  • OXE-01 represents 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime)
  • OXE-02 represents 1-(6- o-Toluoyl-9-ethylcarbazol-3-yl)-(3-ethanone)-1-oxime acetate
  • COXE-15 represents a monofunctional coumarin oxime ester compound.
  • the structural formulas of OXE-01, OXE-02 and COXE-15 are as follows:
  • the bifunctional coumarin oxime ester photoinitiator of the present invention has more excellent photosensitivity at wavelengths of 365nm, 385nm, 395nm, 405nm, 420nm, 470nm and 525nm, and is suitable for use in 365nm, 385nm, 395nm , 405nm, 420nm, 470nm and 525nm ultraviolet visible (UV-Vis) LED light source.
  • UV-Vis ultraviolet visible
  • the photosensitivity performance of the bifunctional coumarin oxime ester photoinitiator of the present invention is obviously better than that of the monofunctional coumarin oxime ester photoinitiator at wavelengths of 420 nm, 470 nm and 525 nm.
  • the bifunctional coumarin oxime ester photoinitiator represented by the formula (I) of the present invention has better photosensitivity at wavelengths of 365nm, 385nm, 395nm, 405nm, 420nm, 470nm and 525nm, which is better than Currently commercially available ketoxime ester photoinitiators such as OXE-01 and OXE-02 have significantly better photosensitivity than monofunctional coumarin oxime ester photoinitiators at wavelengths of 420 nm, 470 nm and 525 nm.
  • the compound disclosed in the invention has a simple production process and high yield, and is very suitable for industrial production.
  • Such compounds have good matching with 365nm, 385nm, 395nm, 405nm, 420nm, 470nm and 525nm (UV-vis) LED light sources, and can be widely used in (UV-vis) LED light curing fields such as coatings, inks , microelectronics, printing and other fields as a photoinitiator. Such substances have good market prospects.

Abstract

本发明涉及一种式(I)的双官能团香豆素肟酯光引发剂，其中各变量如说明书中所定义。该化合物在300-550nm范围内具有很强的紫外吸收，吸收光能后能够迅速发生能量转移，持续引发聚合，在感光性及图案完整性方面具有明显优势，非常适合于(UV-vis)LED光源辐射固化。此外，式(I)化合物还具有良好的热稳定性和溶解性。本发明还涉及式(I)化合物的制备方法和该化合物的用途，该化合物适合在(UV-vis)LED光固化体系中作为光引发剂，适合(UV-vis)LED光固化的辐射波长。

Description

双官能团香豆素肟酯类化合物及其制备和应用 技术领域
本发明涉及双官能团香豆素肟酯类化合物，该类化合物可用作光引发剂。本发明还涉及双官能团香豆素肟酯类化合物的制备及应用。
背景技术
光引发剂又称光敏剂或光固化剂，是一类能在紫外光区(250-400nm)或可见光区(400-600nm)吸收一定波长的能量，产生自由基、阳离子等，从而引发单体聚合交联固化的化合物。在光固化体系中，光引发剂一般占3-5％，含量虽低，却是其中的关键组分，对光固化速度起决定作用。它关系到配方体系在光辐照时，低聚物及稀释剂能否迅速交联固化，从而由液态转变为固态。目前，光固化技术已广泛应用在涂料、油墨、微电子、印刷等传统领域，另外还用于制备激光录像及三维元件等新型领域。作为光固化体系的重要组分，光引发剂必须满足不同光固化条件和应用的需要。在自由基光引发剂领域，主要目标是：提高光敏感度，提高表面固化效率(抗氧阻聚)，提高深层固化性能，提高光引发剂在单体及树脂中的溶解性，降低毒性和气味，降低固化后未固化引发剂的迁移性，降低黄变性。
肟酯类光引发剂因其具有优异的感光性能成为近年来逐渐受到重视的一类光引发剂，已被该领域的研究人员所熟知，其活性突出，在彩色滤光片膜(RGB)、黑色矩阵(BM)、光间隔物(photo-spacer)、肋栅(rib)等高端光刻胶领域中应用广泛，常用的肟酯类光引发剂以咔唑或二苯硫醚基团为主体基团，其中巴斯夫产品OXE-01和OXE-02是目前市场上常见的两种肟酯类代表性产品，这两种产品具有较高的光敏度，但是它们的紫外吸收波长偏短，并不适用于(UV-vis)LED光源(发射波长300-550nm，如365nm、385nm、395nm、405nm、420nm、470nm、525nm)的需求。国内也有一些关于肟酯类光引发剂的专利，例如CN102775527A披露了一种二苯硫醚酮肟酯类光引发剂及其制备方法，CN102492059A公开了取代的二苯硫醚酮肟酯类光引发剂等等。但是大多数引发剂的紫外吸收波长在250-350nm，无法与日益发展的LED光源匹配，这就大大限制了肟酯类光引发剂的应用。
CN104817653A披露了一种适用于UV-LED光源固化的肟酯类光引发剂，该 引发剂化合物为香豆素醛肟酯类化合物，然而研究表明此类化合物的热稳定性不及OXE-01[朱桂刚，香豆素肟酯衍生物的合成及其在LED光固化中的应用，硕士论文，2016；Dietliker K，Birbaum J L，Hüsler R，et al.Photolatent catalysts[J].CHIMIA International Journal for Chemistry，2002，56(5):197-202.]。
CN1889960A披露了香豆素酮肟酯类化合物可用于药物组合物或者化妆品组合物中，用以预防和治疗疾病，包括免疫性疾病、慢性炎症、神经疾病和皮肤病、肿瘤疾病、特定病毒(特别是SARS)等。从这个意义上说，此类化合物是安全无毒的。因此，开发具有高感光性、稳定性高、且易于制备的光引发剂仍是光固化行业快速发展的需求，研究和开发具有更高性能的光引发剂一直是该领域的核心工作。
发明内容
鉴于现有技术中存在的问题，本发明的发明人在适于(UV-vis)LED光源(发射波长300-550nm、尤其365-525nm)辐射固化的光引发剂方面进行了广泛而又深入的研究，以期找到一种能够替代OXE-01和OXE-02以更适合(UV-vis)LED光源固化并且感光性能优异，具有良好热稳定性及溶解性良好的光引发剂。本发明人发现，双官能团香豆素肟酯在300-550nm、尤其365-525nm范围内具有很强的紫外吸收，吸收光能后能够迅速发生能量转移，持续引发聚合，在感光性及图案完整性方面具有明显优势并且具有良好的热稳定性和溶解性，从而适合用作(UV-vis)LED光源辐射固化的光引发剂。本发明目的正是基于前述发现得以实现。
因此，本发明的一个目的是提供一种双官能团香豆素肟酯化合物，该类化合物的吸收波长不仅适合(UV-vis)LED光源辐射固化，而且还具有很好的热稳定性。
本发明的另一目的是提供制备本发明双官能团香豆素肟酯化合物的方法。
本发明的再一目的是提供本发明双官能团香豆素肟酯化合物作为光引发剂或光敏剂的用途。
实现本发明上述目的的技术方案可以概括如下:
1.式(I)的双官能团香豆素肟酯化合物：
Figure PCTCN2021121682-appb-000001
其中：M为
Figure PCTCN2021121682-appb-000002
其中M中的两个吡喃酮环(即
Figure PCTCN2021121682-appb-000003
结构)与Ch 1稠合；
其中：Ch 1为
Figure PCTCN2021121682-appb-000004
其中A为CR 3R 4,NR 5,S或O；
或
Figure PCTCN2021121682-appb-000005
其中B为CR 9R 10、S、O或C(＝O)；
或
Figure PCTCN2021121682-appb-000006
其中D为S、C(＝O)或CR 7R 8,
或
苯环或具有2-5个苯环的稠合体系且所述苯环或稠合体系中的各苯环具有0至最大可能数目的取代基R 6(Ch 1-4)；
R 1、R 2、’R 1、’R 2相互独立地表示直链或支化的C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基，其中前述C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 6烷基、C 1-C 6烷硫基、C 1-C 6烷氧基、卤素、 硝基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基和巯基，
R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10相互独立地表示氢、卤素、硝基、羟基、巯基、羧基、C 1-C 8羧酸酯基、磺酸基、氨基、氰基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基，其中前述氨基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、C 2-C 6烯基和C 2-C 6炔基，
各R 0相互独立地表示直链或支化的C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基或C 4-C 10烷基环烷基；和
n为0至最大可能取代数目，优选0-2。
2.根据第1项的化合物，其中R 1、R 2、’R 1、’R 2相互独立地表示直链或支化的C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基，其中前述C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基，
优选的是，R 1、R 2、’R 1、’R 2彼此独立地选自直链或支化的C 1-C 8烷基、直链或支化的C 1-C 8全氟烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 4烷基、被苯基取代的C 1-C 4烷基和苯基，其中前述苯基各自任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基；
更优选的是，R 1、’R 1为直链或支化的C 1-C 6烷基、直链或支化的C 1-C 4全氟烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 2烷基或者苯基，前述苯基 任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基和巯基，以及
R 2、’R 2为直链或支化的C 1-C 7烷基或苯基，其中该苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基。
3.根据第1或2项的化合物，其中R 1、’R 1为直链或支化的C 1-C 6烷基或直链或支化的C 1-C 4全氟烷基。
4.根据第1-3项中任一项的化合物，其中R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、C 1-C 6羧酸酯基、磺酸基、氨基、氰基、C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基、C 6-C 10芳基、C 6-C 10芳氧基和C 6-C 10芳硫基，其中前述氨基、C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基、C 6-C 10芳基、C 6-C 10芳氧基和C 6-C 10芳硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基、C 2-C 4烯基和C 2-C 4炔基；
优选的是，R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢、卤素、硝基、C 1-C 4羧酸酯基、C 1-C 6烷基、C 2-C 4烯基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基；
更优选R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢和C 1-C 6烷基。
5.根据第1-4项中任一项的化合物，其中各R 0相互独立地表示直链或支化的C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基或C 4-C 8烷基环烷基，优选直链或支化的C 1-C 8烷基。
6.根据第1项的化合物，其中
R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢、卤素、硝基、C 1-C 4羧酸酯基、C 1-C 6烷基、C 2-C 4烯基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷 基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基；
R 1、’R 1为直链或支化的C 1-C 6烷基、卤代C 1-C 6烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 2烷基或者苯基，前述苯基任选地被一个或多个独立地选自下组的基团取代：氟、氯、溴、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基和卤代C 1-C 4烷基，以及
R 2、’R 2为直链或支化的C 1-C 7烷基或苯基，其中该苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基和二(C 1-C 4烷基)氨基，
或者
R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基；
R 1、’R 1为直链或支化的C 1-C 6烷基、卤代C 1-C 6烷基、C 5-C 6环烷基或被C 5-C 6环烷基取代的C 1-C 2烷基，以及
R 2、’R 2为直链或支化的C 1-C 6烷基或任选被硝基取代的苯基。
7.根据第1项的化合物，其中式(I)化合物选自表1所示的化合物1-64。
8.一种制备如第1-7项中任一项所定义的式(I)的双官能团香豆素肟酯化合物的方法，包括以下步骤：
(1)肟化反应：使式(II)化合物与羟胺和/或盐酸羟胺进行肟化反应，得到式(III)化合物
Figure PCTCN2021121682-appb-000007
其中：R 1、’R 1和M如权利要求1-7项中任一项所定义；
以及
(2)将式(III)化合物酯化，得到式(I)化合物。
9.根据第8项的方法，其中
所述肟化反应满足以下条件中的一个或多个：
在乙酸钠、吡啶、哌啶、三乙胺、四甲基氢氧化铵或其混合物存在下进行；
肟化反应在乙醇或含水的乙醇作为溶剂存在下进行；
肟化反应的温度为60-120℃；
肟化反应时间为0.1-20小时，优选0.5-10小时；
式(II)化合物与选自羟胺和/或盐酸羟胺的化合物的摩尔比为1:2.5-1.25:2，优选1:2.2-1.1:2。
10.根据第8或9项的方法，其中步骤(2)的酯化采用选自下式(IVa)、(IVb)和(IVc)化合物的酯化试剂进行：
Figure PCTCN2021121682-appb-000008
其中X为卤素，尤其是氯，和R 2如权利要求1-7中任一项所定义。
11.根据第8-10项中任一项的方法，其中酯化反应在选自下组的一种或多种催化剂存在下进行：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙、四甲基氢氧化铵和叔胺，例如三烷基胺，如三甲基胺和三乙胺。
12.根据第8-11项中任一项的方法，其中酯化反应在选自四氢呋喃、苯、甲苯、N,N-二甲基甲酰胺、二氯甲烷和丙酮的溶剂中进行；和/或，式(III)与选自(IVa)、(IVb)和(IVc)化合物的酯化试剂的摩尔比为1:1.6-1:2.5，优选1:1.8-1:2.2。
13.如第1-7项中任一项所要求的式(I)化合物作为光引发剂的用途，尤其是在(UV-vis)LED光固化体系中作为光引发剂的用途，特别是在辐射波长为300-550nm、优选350-525nm、尤其365-525nm，例如420-525nm的光固化体系中作为光引发剂的用途。
14.包含至少一种根据第1-7项中任一项的光引发剂的光固化性组合物。
15.可由第14项的光固化性组合物得到的固化材料。
16.一种制备光固化材料的方法，其包括用发射波长为300-550nm，尤其365-525，例如420-525nm的光源，例如(UV-vis)LED光源对第14项的光固化 性组合物进行辐照。
附图说明
图1是乌格拉(Ugra)晒版测试条的示意图，其中
1——连续密度梯尺段，
2——阴阳微米等线同心圆线圈段，
3——全阶调网点段，
4——重影控制段，和
5——高光、暗调控制段。
具体实施方式
本发明的第一个方面提供了式(I)的双官能团香豆素肟酯化合物：
Figure PCTCN2021121682-appb-000009
其中：M为
Figure PCTCN2021121682-appb-000010
其中M中的两个吡喃酮环与Ch 1稠合；
其中：Ch 1为
Figure PCTCN2021121682-appb-000011
其中A为CR 3R 4,NR 5,S或O；
或
Figure PCTCN2021121682-appb-000012
其中B为CR 9R 10、S、O或C(＝O)；
或
Figure PCTCN2021121682-appb-000013
其中D为S、C(＝O)或CR 7R 8,
或
苯环或具有2-5个苯环的稠合体系且所述苯环或稠合体系中的各苯环具有0至最大可能数目的取代基R 6(Ch 1-4)；
R 1、R 2、’R 1、’R 2相互独立地表示直链或支化的C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基，其中前述C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 6烷基、C 1-C 6烷硫基、C 1-C 6烷氧基、卤素、硝基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基和巯基，
R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10相互独立地表示氢、卤素、硝基、羟基、巯基、羧基、C 1-C 8羧酸酯基、磺酸基、氨基、氰基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基，其中前述氨基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、C 2-C 6烯基和C 2-C 6炔基，
各R 0相互独立地表示直链或支化的C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基或C 4-C 10烷基环烷基；和
n为0至最大可能取代数目，优选0-2。
式(I)化合物中既包含香豆素基结构部分，又包含肟酯类结构部分并且包含两个香豆素肟酯结构。该化合物在350-550nm范围内具有很强的紫外吸收，吸收光能后能够迅速发生能量转移，持续引发聚合，在感光性及图案完整性方面具有明显优势，非常适合于(UV-vis)LED光源且其安全无毒可被用于食品包装等领域。此外，式(I)化合物还具有良好的热稳定性。
在本发明中，前缀“C n-C m”在每种情况下表示该基团中包含的碳原子数为n-m个。
“卤素”是指氟、氯、溴和碘。在本发明中，优选的是，卤素包括F、Cl或其组合。本文所用的术语“C n-C m烷基”是指具有n-m个，例如1-20个，优选1-12个，更优选1-8个，特别优选1-6个，尤其优选1-4个碳原子的支化或未支化饱和烃基，例如甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、己基、1,1-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基、庚基、辛基、2-乙基己基、壬基、癸基、十一烷基、十二烷基及其异构体。C 1-C 8烷基可以是甲基、乙基、丙基、异丙基、正丁基、2-丁基、叔丁基、戊基、异戊基、己基、庚基、辛基及其异构体。C 1-C 6烷基可以是甲基、乙基、丙基、异丙基、正丁基、2-丁基、叔丁基、戊基、异戊基、己基及其异构体。C 1-C 4烷基可以是甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基及其异构体。
本文所用术语“C 2-C m烯基”是指具有2-m个，例如2-20个，优选2-6个，更优选2-4个碳原子并且具有一个或多个位于任何位置的双键的支化或未支化不饱和开链烃基，如乙烯基、1-丙烯基、2-丙烯基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基、1-甲基-1-丁烯基、2-甲基-1-丁烯基、3-甲基-1-丁烯基、1-甲基-2-丁烯基、2-甲基-2-丁烯基、3-甲基-2-丁烯基、1-甲基-3-丁烯基、2-甲基-3-丁烯基、3-甲基-3-丁烯基、1,1-二甲基-2-丙烯基、1,2-二甲基-1-丙烯基、1,2-二甲基-2-丙烯基、1-乙基-1-丙烯基、1-乙基-2-丙烯基、1-己烯基、2-己烯基、3-己烯基、4-己烯基、5-己烯基、1-甲基-1-戊烯基、2-甲基-1-戊烯基、3-甲基-1-戊烯基、4-甲基-1-戊烯基、1-甲基-2-戊烯基、2-甲基-2-戊烯基、3-甲基-2-戊烯基、4-甲基-2-戊烯基、1-甲基-3-戊烯基、2-甲基-3-戊烯基、3-甲基-3-戊烯基、4-甲基-3-戊烯基、1-甲基-4-戊烯基、2-甲基-4-戊烯基、3-甲基-4-戊烯基、4-甲基-4-戊烯基、1,1-二甲基-2-丁烯基、1,1-二甲基-3-丁烯基、1,2-二甲基-1-丁烯基、1,2-二甲基-2-丁烯基、1,2-二甲基-3-丁烯基、1,3- 二甲基-1-丁烯基、1,3-二甲基-2-丁烯基、1,3-二甲基-3-丁烯基、2,2-二甲基-3-丁烯基、2,3-二甲基-1-丁烯基、2,3-二甲基-2-丁烯基、2,3-二甲基-3-丁烯基、3,3-二甲基-1-丁烯基、3,3-二甲基-2-丁烯基、1-乙基-1-丁烯基、1-乙基-2-丁烯基、1-乙基-3-丁烯基、2-乙基-1-丁烯基、2-乙基-2-丁烯基、2-乙基-3-丁烯基、1,1,2-三甲基-2-丙烯基、1-乙基-1-甲基-2-丙烯基、1-乙基-2-甲基-1-丙烯基、1-乙基-2-甲基-2-丙烯基及其异构体。C 2-C 6烯基可以是乙烯基、丙烯基、1-丁烯基、2-丁烯基、异丁烯基、1-戊烯基、2-戊烯基、新戊烯基、1-己烯基、2-己烯基、3-己烯基、异己烯基、新己烯基及其异构体。C 2-C 4烯基可以是乙烯基、1-丙烯基、2-丙烯基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基及其异构体。
本文所用术语“C 2-C m炔基”是指具有2-m个，例如2-20个，优选2-6个，更优选2-4个碳原子并且具有一个或多个位于任何位置的叁键的支化或未支化不饱和开链烃基，如乙炔基、丙炔基、1-丁炔基、2-丁炔基及其异构体。C 2-C 6炔基可以是乙炔基、丙炔基、1-丁炔基、2-丁炔基、1-戊炔基、2-戊炔基、3-戊炔基、4-戊炔基、1-己炔基、2-己炔基、3-己炔基、4-己炔基、5-己炔基及其异构体。C 2-C 4炔基可以是乙炔基、丙炔基、1-丁炔基、2-丁炔基及其异构体。
本文所用术语“C 3-C m环烷基”是指具有3-m个，例如3-20个，优选3-8个，更优选5-6个环碳原子的饱和脂环族单环基团，例如环丙基、环丁基、环戊基、环己基、环庚基、环辛基和环癸基。
术语“C 4-C m环烷基烷基”表示被环烷基取代的烷基并且总共含有4-m个碳原子，例如4-20个碳原子，优选4-10个碳原子，更优选4-6个碳原子，其中烷基和环烷基适用本文所定义，例如环丙基甲基、环丙基乙基、环丙基丙基、环丙基丁基、环丁基甲基、环丁基乙基、环丁基丙基、环丁基丁基、环戊基甲基、环戊基乙基、环戊基丙基、环戊基丁基、环己基甲基、环己基乙基、环己基丙基、环己基丁基等。
术语“C 4-C 10烷基环烷基”表示被烷基取代的环烷基并且总共含有4-m个碳原子，例如4-10个碳原子，优选4-8个碳原子，更优选4-6个碳原子，其中烷基和环烷基适用本文所定义，例如甲基环丙基、乙基环丙基、丙基环丙基、丁基环丙基、甲基环丁基、乙基环丁基、丙基环丁基、丁基环丁基、甲基环戊基、乙基环戊基、丙基环戊基、丁基环戊基、甲基环己基、乙基环己基、丙基环己基、丁基环己基等。
本文所用术语“C 6-C m芳基”是指含有6-m个碳原子，例如6-18个，优选6-10个碳原子的单环、双环或三环芳族烃基。作为C 6-C m芳基的实例，可提及苯基、甲苯基、乙苯基、丙苯基、丁苯基、二甲苯基、甲基乙基苯基、二乙基苯基、甲基.丙基苯基和萘基等；优选苯基或萘基，尤其是苯基(作为取代基也表示为C 6H 5)。
术语“C 7-C 20芳烷基”表示被芳基取代的烷基并且总共含有7-20个碳原子，例如7-12个，优选7-10个碳原子，更优选7-8个碳原子，其中烷基和芳基适用本文所定义，例如苯甲基、苯乙基、萘甲基、萘乙基等。
术语“C 7-C 20烷基芳基”表示被烷基取代的芳基并且总共含有7-20个碳原子，例如7-12个，优选7-10个碳原子，更优选7-8个碳原子，其中烷基和芳基适用本文所定义，例如甲基苯基、二甲基苯基、三甲基苯基、乙基苯基、二乙基苯基、三乙基苯基、甲基萘基、乙基萘基等。
术语“C n-C m烷氧基”和“C n-C m烷硫基”是指在C n-C m烷基对应的开链C n-C m烷烃的任何碳原子上键合有一个氧原子或一个硫原子作为连接基团的C n-C m烷基，例如C 1-C 20烷氧(或硫)基，优选C 1-C 12烷氧(或硫)基，更优选C 1-C 8烷氧(或硫)基，特别优选C 1-C 6烷氧(或硫)基，尤其优选C 1-C 4烷氧(或硫)基。C 1-C 8烷氧基可以是甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、2-丁氧基、叔丁氧基、戊氧基、异戊氧基、己氧基、庚氧基、辛氧基、异辛氧基及其异构体。C 1-C 4烷氧基可以是甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基、叔丁氧基及其异构体。C 1-C 8烷硫基可以是甲硫基、乙硫基、丙硫基、异丙硫基、正丁硫基、2-丁硫基、叔丁硫基、戊硫基、异戊硫基、己硫基、庚硫基、辛硫基、异辛硫基及其异构体。C 1-C 4烷硫基可以是甲硫基、乙硫基、丙硫基、异丙硫基、正丁硫基及其异构体。
术语“C 2-C m烯氧基”和“C 2-C m烯硫基”是指在C 2-C m烯基对应的C 2-C m链烯烃中的任何饱和碳原子上键合有一个氧原子或一个硫原子作为连接基团的C 2-C m烯基，例如C 2-C 20烯氧(或硫)基，优选C 2-C 12烯氧(或硫)基，更优选C 2-C 8烯氧(或硫)基，特别优选C 2-C 6烯氧(或硫)基，尤其优选C 2-C 4烯氧(或硫)基，例如乙烯氧基、丙烯氧基、异丙烯氧基、正丁烯氧基、仲丁烯氧基、异丁烯氧基、叔丁烯氧基及其异构体、乙烯硫基、丙烯硫基、异丙烯硫基、正丁烯硫基及其异构体。
术语“C 2-C m炔氧基”和“C 2-C m炔硫基”是指在C 2-C m炔基对应的C 2-C m链 炔烃中的任何饱和碳原子上键合有一个氧原子或一个硫原子作为连接基团的C 2-C m炔基，例如C 2-C 20炔氧(或硫)基，优选C 2-C 12炔氧(或硫)基，更优选C 2-C 8炔氧(或硫)基，特别优选C 2-C 6炔氧(或硫)基，尤其优选C 2-C 4炔氧(或硫)基，例如乙炔氧基、丙炔氧基、正丁炔氧基、仲丁炔氧基及其异构体、乙炔硫基、丙炔硫基、丙炔硫基、正丁炔硫基、仲丁炔硫基及其异构体。
术语“C 3-C m环烷氧基”和“C 3-C m环烷硫基”是指在C 3-C m环烷基对应的C 3-C m环烷烃中的任何环碳原子上键合有一个氧原子或一个硫原子作为连接基团的C 3-C m环烷基，例如C 3-C 20环烷氧(或硫)基，优选C 3-C 8环烷氧(或硫)基，更优选C 5-C 6环烷氧(或硫)基，例如环丙基氧基、环丁基氧基、环戊基氧基、环己基氧基、环庚基氧基、环辛基氧基、环癸基氧基及其异构体、环丙基硫基、环丁基硫基、环戊基硫基、环己基硫基、环庚基硫基、环辛基硫基、环癸基硫基及其异构体。
术语“C 4-C m环烷基烷氧基”和“C 4-C m环烷基烷硫基”是指被环烷基取代的烷氧(硫)基并且总共含有4-m个碳原子，例如4-20个碳原子，优选4-8个碳原子，其中环烷基和烷氧(硫)基适用本文所定义，例如环丙基甲氧基、环丙基乙氧基、环丙基丙氧基、环丙基丁氧基、环丁基甲氧基、环丁基乙氧基、环丁基丙氧基、环丁基丁氧基、环戊基甲氧基、环戊基乙氧基、环戊基丙氧基、环戊基丁氧基、环己基甲氧基、环己基乙氧基、环己基丙氧基、环己基丁氧基、环丙基甲硫基、环丙基乙硫基、环丙基丙硫基、环丙基丁硫基、环丁基甲硫基、环丁基乙硫基、环丁基丙硫基、环丁基丁硫基、环戊基甲硫基、环戊基乙硫基、环戊基丙硫基、环戊基丁硫基、环己基甲硫基、环己基乙硫基、环己基丙硫基、环己基丁硫基等。
本文所用术语“C 6-C m芳氧基”和“C 6-C m芳硫基”是指在C 6-C m芳基对应的C 6-C m芳烃中的任何芳族碳原子上键合有一个氧原子或一个硫原子作为连接基团的C 6-C m芳基，例如苯硫基、苯氧基、甲苯氧基、甲苯硫基、萘硫基、萘氧基等。
在本发明中，R 1、R 2、’R 1、’R 2相互独立地表示直链或支化的C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基，其中前述C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 6烷硫基、C 1-C 6烷氧基、C 1-C 6 烷基、卤素、硝基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基和巯基。
优选的是，R 1、R 2、’R 1、’R 2相互独立地表示直链或支化的C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基，其中前述C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基。
特别优选的是，R 1、R 2、’R 1、’R 2彼此独立地选自直链或支化的C 1-C 8烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 4烷基、被苯基取代的C 1-C 4烷基和苯基，其中前述苯基各自任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基。
更优选的是，R 1、’R 1为直链或支化的C 1-C 6烷基、直链或支化的C 1-C 4全氟烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 2烷基或者苯基，前述苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基和巯基，以及
R 2、’R 2为直链或支化的C 1-C 7烷基或苯基，其中该苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基。
根据一个优选实施方案，R 1、’R 1为直链或支化的C 1-C 6烷基或直链或支化的C 1-C 4全氟烷基。
在一个实施方案中，R 1和’R 1可以具有相同或不同的含义，优选具有相同含义，即’R 1具有对R 1所提及的定义。在一个实施方案中，R 2和’R 2可以具有相同或不同的含义，优选具有相同含义，即’R 2具有对R 2所提及的定义。
在本发明中，R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、C 1-C 8羧酸酯基、磺酸基、氨基、氰基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基，其中前述氨基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧 基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、C 2-C 6烯基和C 2-C 6炔基。
优选的是，R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、C 1-C 6羧酸酯基、磺酸基、氨基、氰基、C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基、C 6-C 10芳基、C 6-C 10芳氧基和C 6-C 10芳硫基，其中前述氨基、C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基、C 6-C 10芳基、C 6-C 10芳氧基和C 6-C 10芳硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基、C 2-C 4烯基和C 2-C 4炔基。
特别优选的是，R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢、卤素、硝基、C 1-C 4羧酸酯基、C 1-C 6烷基、C 2-C 4烯基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基。
根据本发明的一个优选实施方案，R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢和C 1-C 6烷基。
根据本发明的一个优选实施方案，各R 0相互独立地表示直链或支化的C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基或C 4-C 8烷基环烷基，优选直链或支化的C 1-C 8烷基。n各自独立地为0-2，如0、1或2。
在本发明的一个优选实施方案中：R 1、’R 1为直链或支化的C 1-C 6烷基、卤代C 1-C 6烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 2烷基或者苯基，前述苯基任选地被一个或多个独立地选自下组的基团取代：氟、氯、溴、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基和卤代C 1-C 4烷基，以及
R 2、’R 2为直链或支化的C 1-C 7烷基或苯基，其中该苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、卤素、硝基、氨基、单(C 1-C 4烷基 )氨基和二(C 1-C 4烷基)氨基，
R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢、卤素、硝基、C 1-C 4羧酸酯基、C 1-C 6烷基、C 2-C 4烯基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基。
在(Ch 1-4)结构中，所述具有2-5个苯环的稠合体系可以是萘环、蒽环、菲环、苯并(a)蒽、并四苯或并五苯结构。
在(Ch 1-4)结构中，所述苯环或稠合体系中的各苯环优选具有0-2个，如0、1或2个取代基R 6。在一个实施方案中，所述稠合体系中仅有1或2个苯环具有1或2个取代基R 6。
根据本发明优选的是，(Ch 1-4)结构为苯环或具有2-4苯环的稠合体系，例如萘环、蒽环、菲环、苯并(a)蒽或并四苯结构。
在本发明的一个特别优选的实施方案中，式(I)化合物选自下文表1的化合物1-64。化合物1-64分别在实施例1-64中制备。
根据本发明的第二个方面，提供了一种制备本发明式(I)化合物的方法，包括以下步骤：
(1)肟化反应：使式(II)化合物与羟胺和/或盐酸羟胺进行肟化反应，得到式(III)化合物
Figure PCTCN2021121682-appb-000014
其中：R 1、’R 1和M如上所定义，
(2)将式(III)化合物酯化，得到式(I)化合物。
为了制备本发明的式(I)化合物，可以先进行肟化反应，以引入肟基，然后肟基中的羟基经酯化反应转变成相应的酯基，从而获得本发明的双官能团香豆素肟酯化合物。
肟化反应
肟化反应通常从羰基化合物开始。为此，使式(II)化合物与羟胺和/或盐酸羟胺进行肟化反应，得到式(III)化合物
Figure PCTCN2021121682-appb-000015
式(II)和(III)中的R 1、’R 1和M如上所定义。为了将式(II)中的非环羰基转变为肟基，通常需要使用盐酸羟胺(NH 2OH.HCl)、羟胺(NH 2OH)或其混合物作为肟化试剂。该肟化反应通常在有机溶剂中进行，优选在有机极性溶剂中进行。可采用的溶剂例如有乙醇或含水的乙醇。如果使用含水乙醇，乙醇与水的体积比可以为10:1-1:10，优选5:1-1:5，例如3:1,1:1或1:2。为了促进肟化反应进行完全，一般需加入乙酸钠、吡啶、哌啶、三乙胺之类的碱。这当中，吡啶、哌啶、三乙胺也可用作碱和/或溶剂或助溶剂。肟化反应的温度一般为溶剂的回流温度，温度范围通常在60-120℃，例如60-90℃。肟化反应时间也没有特别的限制，通常进行0.1-20小时，优选0.3-10小时。式(II)化合物与选自羟胺和/或盐酸羟胺的化合物的相对用量没有特别的限制，例如二者的摩尔比为1:2.5-1.25:2，优选1:2.2-1.1:2，例如约1:2。
每个肟酯基可能存在两种构型，(Z)型或(E)型。可通过常规方法分离异构体，但也可使用异构体混合物作为光引发物质。因此，本发明还涉及式(I)化合物的构型异构体的混合物。
酯化反应
式(III)化合物的酯化是常规的，通过该反应，肟基中的羟基转变为酯基，从而获得式(I)化合物。作为酯化试剂，没有特别的限制，只要能将式(III)化合物肟基中的羟基转变为酯基即可。作为酯化试剂，可以使用相应的酰卤，如酰氯，也可使用相应的羧酸，还可使用相应的酸酐。这些化合物可分别表示为式(IVa)、 (IVb)和(IVc):
Figure PCTCN2021121682-appb-000016
其中X为卤素，尤其是氯，和R 2如上所定义。
为了加速酯化反应，上述酯化反应通常在适于酯化反应的催化剂存在下进行。作为催化剂，既可以使用酸性催化剂，也可以使用碱性催化剂。作为催化剂，可以使用选自下组的一种或多种：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙、四甲基氢氧化铵和叔胺，例如三烷基胺，如三甲基胺和三乙胺。催化剂的用量是常规的，可以通过本领域的常识确定，或者通过几个例行的预备实验来确定。
为了提高式(I)化合物的产率，有利的是，在酯化反应过程中移除酯化反应产生的水。这例如可以通过蒸馏冷凝来进行。
上述酯化反应通常在溶剂中，优选在有机溶剂中进行。作为溶剂的类型的选择，没有特别的限制，只要能够将式(III)化合物和酯化试剂溶解并且对酯化反应呈化学惰性即可，即不参与该酯化反应即可。作为溶剂的实例，可以提及四氢呋喃、苯、甲苯、N,N-二甲基甲酰胺、二氯甲烷和丙酮。溶剂可以使用单一种，也可以使用两种或更多种溶剂的混合物。
式(III)化合物与式(IVa)、(IVb)和(IVc)化合物的酯化试剂的相对用量没有特别的限制，二者的摩尔比为1:1.6-1:2.5，优选1:1.8-1:2.2，例如约1:2。
酯化反应可以在非常宽的温度范围内进行。根据本发明有利的是，酯化反应在-10℃至150℃，优选0℃至100℃的温度下进行，优选常温下进行。酯化反应时间也没有特别的限制，通常进行0.5-24小时，优选0.8-12小时。
在酯化反应完成之后，获得包含式(I)化合物的反应混合物。因此，可以对该反应混合物进行后处理，以得到提纯的式(I)化合物。通常而言，首先过滤酯化反应得到的反应混合物，取出滤液部分。然后，将滤液进行洗涤，以除去催化剂和未反应的原料。作为洗液，没有特别的限制，只要能除去催化剂和未反应的原料即可。作为洗液的实例，可以提及稀盐酸(水溶液)、饱和碳酸氢钠水溶液和水。稀盐酸的浓度没有特别的限制，通常而言使用浓度为5-12％的稀盐酸。用 洗液洗涤可以进行一次，也可进行多次；在进行多次的情况下，可使用单一种洗液，也可依次使用不同的洗液。根据本发明有利的是，将对酯化反应得到的反应混合物过滤得到的滤液依次用稀盐酸、饱和碳酸氢钠水溶液和水进行洗涤。当然，每一次用洗液洗涤后，都需要倒掉水相之后再用下一种洗液对有机相进行洗涤。洗涤之后，需要干燥以除去残留的水。为此，通常可使用无水硫酸钠进行干燥。干燥之后，再除去残留的有机溶剂。作为这里除去有机溶剂的手段，没有特别的限制，通常可通过减压蒸馏来除去有机溶剂。除去残留有机溶剂之后，得到了式(I)化合物的粗产物。如果想要进一步提高式(I)化合物的纯度，还可对该化合物进行进一步提纯，这例如可通过重结晶的方式来进行。重结晶溶剂的选择是常规的，没有特别的限制。根据本发明，有利的是，采用甲醇对式(I)化合物的粗产物进行重结晶。
本发明式(I)化合物，在300-550nm、特别是350-525nm、尤其是在365-525nm，例如420-525nm的波长范围内有较强吸收，故可应用于(UV-vis)LED光固化体系中。本发明式(I)化合物的制备原料都是毒性较小的香豆素酮类化合物，相比传统的光引发剂，对人体和环境的危害程度降低。
因此，根据本发明的第三个方面，提供了本发明式(I)化合物作为光引发剂的用途。本发明式(I)化合物在(UV-vis)LED光固化体系中作为光引发剂，可以有效地引发固化反应。
式(I)化合物可在涂料、油墨、微电子、印刷等领域用作光引发剂或光敏剂。当式(I)化合物用作光引发剂或光敏剂时，其用量是常规的，或者通过例行的预备试验即可确定。
本发明的另一方面涉及包含至少一种本发明的光引发剂的光固化性组合物。
本发明光引发剂的量通常为0.01-10重量％，例如0.02重量％，0.05重量％，0.08重量％，0.1重量％，0.2重量％，0.5重量％，0.8重量％，1重量％，1.2重量％，1.5重量％，1.8重量％，2重量％，2.2重量％，2.5重量％，2.8重量％，3重量％，3.2重量％，3.5重量％，3.8重量％，4重量％，4.5重量％，5重量％，5.5重量％，6重量％，6.5重量％，7重量％，7.5重量％，8重量％，8.5重量％，9重量％，9.5重量％，优选0.1-6重量％，如0.2-5重量％，基于光固化性组合物的活性成分量。
在公开的上下文中，活性成分是指光固化性组合物中除去溶剂之外的成分。
除了本发明的光引发剂之外，所述光固化性组合物还包含光固化树脂。
在本发明中，作为光固化树脂，它指的是含有不饱和碳碳双键的低聚物或预聚物。该低聚物或预聚物经光线照射后，能由光引发剂引发聚合反应，进而发生交联固化。光固化树脂是光固化产品(例如UV涂料、UV油墨、UV胶粘剂等)的主体组成。
作为光固化树脂，可以提及环氧(甲基)丙烯酸酯树脂、聚酯类(甲基)丙烯酸酯、聚氨酯(甲基)丙烯酸酯、烯属不饱和聚酯、氨基(甲基)丙烯酸酯树脂、光成像碱溶性树脂等。根据本发明有利的是，采用环氧(甲基)丙烯酸酯树脂、聚酯类(甲基)丙烯酸酯、聚氨酯(甲基)丙烯酸酯或它们的组合。
环氧(甲基)丙烯酸酯树脂优选双酚A环氧(甲基)丙烯酸酯，三缩丙二醇二(甲基)丙烯酸酯稀释的双酚A环氧丙烯酸酯或其组合，例如无锡树脂厂的双酚A环氧丙烯酸酯WSR-U125，台湾长兴化学公司的20％三缩丙二醇二丙烯酸酯稀释的双酚A环氧丙烯酸酯621A-80，台湾长兴化学公司的改性双酚A环氧丙烯酸酯623-100，台湾长兴化学公司20％三缩丙二醇二丙烯酸酯稀释的改性双酚A环氧丙烯酸酯6231A-80。
聚酯类(甲基)丙烯酸酯优选的是高官能度的超支化聚酯丙烯酸树脂，尤其是官能度为5-30的超支化聚酯丙烯酸树脂，例如含6-20官能度的超支化聚酯丙烯酸酯预聚体。对此，可以提及如无锡诺克斯公司的超支化聚酯丙烯酸酯预聚体932-100(6官能度)，美国沙多玛公司的超支化聚酯丙烯酸酯预聚体CN2300(8官能度)，CN2301(9官能度)、CN2302(16官能度)等。
聚氨酯(甲基)丙烯酸酯优选脂肪族聚氨酯丙烯酸树酯。对此，可以提及如台湾长兴化学公司的脂肪族聚氨酯六丙烯酸酯6145-100、6161-100、15％1,6-己二醇二丙烯酸酯(HDDA)稀释的脂肪族聚氨酯二丙烯酸酯611B-85，20％乙氧化三羟甲基丙烷三丙烯酸酯稀释的聚酯多元醇丙烯酸树脂，脂肪族聚氨酯二丙烯酸酯6141H-80；美国沙多玛公司的脂肪族聚氨酯丙烯酸酯CN9013(9官能度)，美国沙多玛公司15％1,6-己二醇二丙烯酸酯(HDDA)稀释的脂肪族聚氨酯丙烯酸酯CN966B85(2官能度)，脂肪族聚氨酯丙烯酸酯CN962(2官度)。
光固化树脂在光固化性组合物中的用量通常为10-90重量％，例如15重量％，20重量％，25重量％，30重量％，40重量％，50重量％，60重量％，70重量％，80重量％，85重量％，优选55-80重量％，基于光固化性组合物的活性成分量。在公开的上下文中，活性成分是指光固化性组合物中除去溶剂之外的成分。
所述光固化性组合物可以进一步包含多官能活性稀释剂。
在本发明中，作为多官能活性稀释剂，它指含有两个或两个以上的可光聚合基团的单体。多官能活性稀释剂粘度较低，溶解能力较强。多官能活性稀释剂经光源辐照后可以被活性自由基引发聚合形成交联的网络结构。
根据本发明，优选多官能活性稀释剂为多官能(甲基)丙烯酸酯活性稀释剂。它指含有两个或两个以上的(甲基)丙烯酸酯可聚合基团的单体。作为多官能(甲基)丙烯酸酯交联剂，可以提及三羟甲基丙烷三丙烯酸酯(TMPTA)，季戊四醇四丙烯酸酯(PETTA)、丙氧化三羟甲基丙烷三丙烯酸酯(PO-TMPTA)或乙氧基三羟甲基丙烷三丙烯酸酯(EO-TMPTA)，季戊四醇三丙烯酸酯(PETA)，季戊四醇四丙烯酸酯(PETTA)，二季戊四醇五丙烯酸酯(DPEPA)，二季戊四醇六丙烯酸酯(DPHA)，二醇类双丙烯酸酯如二缩三丙二醇双丙烯酸酯(TPGDA)，1,6-己二醇二丙烯酸酯(HDDA)，1,9-壬二醇二甲基丙烯酸酯，乙二醇双丙烯酸酯，三乙二醇二甲基丙烯酸酯，二乙二醇二甲基丙烯酸酯，丙二醇双丙烯酸酯，乙二醇双丙烯酸酯，丙三醇双丙烯酸酯，一缩乙二醇双丙烯酸酯，二缩乙二醇双丙烯酸酯，乙二醇双丙烯酸酯及二甲基丙烯酸氨基甲酸酯(UDMA)等。
多官能活性稀释剂在光固化性组合物中的用量通常为8-60重量％，例如10重量％，20重量％，25重量％，30重量％，40重量％，50重量％，60重量％，优选15-45重量％，基于光固化性组合物的活性成分量。
根据本发明，所述光固化性组合物可以进一步包含单官能活性稀释剂。
在本发明中，作为单官能活性稀释剂，它指的是含有一个可光聚合基团的单体。其粘度较低，溶解能力较强，可充当部分有机溶剂的作用。该单官能活性稀释剂经光源辐照后，可被活性自由基引发聚合反应。单官能活性稀释剂主要有(甲基)丙烯酸酯类化合物和乙烯基类化合物。作为(甲基)丙烯酸酯类单官能活性稀释剂，可以提及甲基丙烯酸甲酯(MMA)、丙烯酸正丁酯(BA)、丙烯酸异辛酯(2-EHA)、丙烯酸异癸酯(IDA)、丙烯酸月桂酯(LA)、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯，以及一些带有环状结构的(甲基)丙烯酸酯。另外，作为乙烯类单官能活性稀释剂，可以提及苯乙烯(St)、醋酸乙烯酯(VA)、N-乙烯基吡咯烷酮(NVP)等。
单官能活性稀释剂在光固化性组合物中的用量通常为5-50重量％，例如10重量％，20重量％，25重量％，30重量％，40重量％，50重量％，优选8-40重量％，基于光固化性组合物的活性成分量。
本发明的光固化性组合物还可任选地包含有机溶剂。有机溶剂的选择是常规的。作为有机溶剂，可以提及芳烃类如苯、甲苯，卤代烷烃类如三氯甲烷、二 氯甲烷、氯乙烷，酮类如丙酮、丁酮、戊酮等，醇类如甲醇、乙醇、丙醇、异丙醇、乙二醇，及乙二醇醚类，乙二醇醚醋酸酯类，丙二醇醚类，丙二醇醚醋酸酯类等。
本发明的光固化性组合物还可任选地包含其他添加剂，比如流平剂、抗氧化剂、抗沉降剂、着色剂、杀微生物剂，比如抗菌剂及保温材料添加剂。在本发明的一个优选实施方案中，流平剂选自优卡化学的
Figure PCTCN2021121682-appb-000017
系列流平剂，特别优选360S、361S、362S、372S、375S、376S、380S、384S、392S、400U、415U等。
本发明光固化性组合物的制备是常规的，将本发明光固化性组合物的每个组分均匀混合在一起即可。
根据本发明的一个方面，提供了可由本发明光固化性组合物得到的固化材料。
得到的固化材料可以是光固化涂层，这包括包含功能性材料的涂层，UV光和/或可见光的滤色器的涂层；密封剂；光刻材料；全息记录材料；3D打印材料；平版印刷材料；光学器件的制备材料及改善机械性能的材料，例如碳纤维复合材料和/或无机纳米颗粒和/或有机纳米颗粒等。
根据本发明的一个方面，提供了一种由本发明光固化性组合物制备光固化材料的方法，包括采用发射波长为300-550nm，尤其365-525nm，例如420-525nm的光源，例如(UV-vis)LED光源对本发明光固化性组合物进行辐照。
实施例
以下将结合具体实施例对本发明作进一步说明，但不应将其理解为对本发明保护范围的限制。以下将结合具体实施例对本发明作进一步说明，但不应将其理解为对本发明保护范围的限制。
实施例1：化合物1的制备
Figure PCTCN2021121682-appb-000018
化合物1的合成路线如下：
Figure PCTCN2021121682-appb-000019
中间产物1a的合成
将2,3-二丁基-5,6-二羟基-1,4-苯二甲醛(0.05mol，13.92g)加入盛有50mL乙醇的250mL三口圆底烧瓶中，搅拌均匀后，将混合液加热至35℃使反应物全部溶于乙醇中。然后加入六氢吡啶(0.02mol，2mL)和乙酰乙酸乙酯(0.12mol，15.6g)，再将反应混合物加热至回流，搅拌反应1h。待反应完全后，将混合物冷却至室温，过滤得黄色固体，然后用乙醇重结晶，得18.68g产品，产率91％，经鉴定为化合物1a。1H-NMR(400MHz,CDCl 3)δ0.50(t，6H)，1.30(m，4H)，1.53(m，4H)，2.63(t，4H)，3.11(s，6H)，7.54(s，2H)。
中间产物1b的合成
将中间产物1a(16.41g，0.04mol)和50mL乙醇和水的混合溶液(V 乙醇：V 水＝2:1)倒入100mL三口圆底烧瓶中，再加入盐酸羟胺(5.56g，0.08mol)和醋酸钠(6.56g，0.08mol)。70℃下搅拌反应0.5h后，过滤反应液，然后将滤液真空旋蒸后得淡黄色固体，乙醇重结晶，得16.38g产品，产率为93％，经鉴定为化合物1b。1H-NMR(400MHz,DMSO-d6)δ0.85(t，6H)，1.25(m，4H)，1.49(m，4H)，2.60(t，4H)，3.0(s，6H)，7.44(s，2H)，8.30(s,2H)。
目标产物1的合成
将上述中间产物1b(13.2g，0.03mol)和30ml四氢呋喃加入到100mL三口圆底烧瓶中，然后加入乙酰氯(5.62g，0.072mol)和三乙胺(9.34g，0.090mol)，常温搅拌反应1h。终止反应，将反应液过滤后，滤液倒入水中，用乙酸乙酯萃取，收集有机相后依次用稀盐酸溶液、饱和碳酸钠溶液、蒸馏水洗涤，然后收集有机相，并用MgSO 4干燥过夜。过滤后减压蒸馏蒸掉有机相后得黄色粉末状固体14.8g，产率94.0％，经鉴定为化合物1。化合物1的核磁数据见表1。
实施例2-64
重复实施例1的方法，适当改变反应原料，分别获得下表化合物2-64及其核磁数据。
表1
Figure PCTCN2021121682-appb-000020
Figure PCTCN2021121682-appb-000021
Figure PCTCN2021121682-appb-000022
Figure PCTCN2021121682-appb-000023
Figure PCTCN2021121682-appb-000024
Figure PCTCN2021121682-appb-000025
Figure PCTCN2021121682-appb-000026
Figure PCTCN2021121682-appb-000027
Figure PCTCN2021121682-appb-000028
Figure PCTCN2021121682-appb-000029
Figure PCTCN2021121682-appb-000030
Figure PCTCN2021121682-appb-000031
感光性能测试：
采用乌格拉(Ugra)晒版测试条作掩膜来测试光引发剂的感光性能。乌格拉晒版测试条的各段见图1。乌格拉晒版测试条分为5个控制段，从左到右分别是：连续密度梯尺段(1)；阴阳微米等线同心圆段(2)；全阶调网点段(3)；重影控制段(4)；高光、暗调控制段(5)。第一段：连续密度梯尺段共分为13个梯度用来控制曝光量和显影。第二段：阴阳微米等线同心圆段：由12个阴阳微米等线组成的同心圆线图，分别为4、6、8、10、12、15、20、25、30、40、55、70，用于检测晒PS版时的曝光和显影情况。第三段：全阶调网点段：由10％-100％、极差为10％的评网组成，分为上下两行排列，用于测量晒版、打样和印刷的网点转移情况，并可测制出胶片网点与晒版、打样和印刷网店变化曲线图。第四段：重 影控制段：由线宽60线/厘米、面积率为60％的细线条组成，它分为4小块，0°、45°、90°三个角度排列线条和有1/4的D小块中以两边90°、中间小方块45°、上下90°的小短线排列。第五段：高光、暗调控制段，精细网点段由高光小网点与暗调深网点对应排列，用于精细控制晒版曝光和显影的准确性。将包含光引发剂的光固化性组合物涂敷于铝基板上，然后曝光显影，从得到的图像的连续调梯尺评价感度，从微线条测试块区域评价精度，从而评价光固化性组合物配方的优劣。
具体地，按照以下步骤对式(I)化合物的感光性能进行测试。
(1)按照如下组成配制含有光引发剂的光固化性组合物：
Figure PCTCN2021121682-appb-000032
上述组合物中光引发剂本发明的式(I)的双官能团香豆素酮肟酯类化合物或现有技术已知的光引发剂(作对比)(具体见表2)。丙烯酸酯树脂为从上海釜顺国际贸易有限公司购买的商品名为FS2600K的树脂，官能度为2，数均分子量1400。二季戊四醇六丙烯酸酯为从上海釜顺国际贸易有限公司购买的商品名为GM66G0C的产品。结晶紫染料为从上海国药购买的商品名为六甲基玫苯胺盐酸盐的产品。
感光性能测试
(2)将上述各组合物在黄光下搅拌混合均匀，利用离心机旋涂在预先处理好的并满足下列条件的PS铝版基上：
铝板基尺寸：1030mm×800mm
铝板基厚度：0.28-0.3mm
砂目规格：Ra＝0.5-0.6μm
Rh＝0.3-0.35μm
阳极氧化膜重量：3-3.5g/m 2
控制离心涂布机的转速，使涂在铝版基上的涂布量(以固含量计)为1.0-2.5g/m 2，在离心涂布机上初步干燥后，转移到100℃的鼓风干燥机中干燥3分钟，得紫激光CTP原版。然后，用Ugra测试条做掩膜测试版材的感光性能，曝光 一段时间后用1％NaOH水溶液显影。
在曝光区，可光聚合化合物在引发剂存在下发生聚合反应，显影液中不溶，而非曝光区是可溶的，于是得到阴图。通过曝光显影，从得到的图像的连续调梯尺评价光引发剂的感度。引发剂体系感光度特征为显影后保留了(即聚合的)最高灰阶数。灰阶数越高，表明测试体系灵敏度越高。结果示于表2中。
表2
Figure PCTCN2021121682-appb-000033
Figure PCTCN2021121682-appb-000034
表2中，OXE-01表示1-[4-(苯硫基)苯基]-1,2-辛烷二酮2-(O-苯甲酰肟)，OXE-02表示1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-乙酮)-1-肟乙酸酯，COXE-15表示单官能团的香豆素肟酯化合物。OXE-01、OXE-02和COXE-15结构式分别如下：
Figure PCTCN2021121682-appb-000035
由表2中的实验结果可以明显看出，本发明光引发剂1-64在365nm、385nm、395nm、405nm、420nm、470nm和525nm处灰阶数均高于商购的光引发剂OXE-01和OXE-02。也就是说，本发明的双官能团香豆素肟酯类光引发剂，其在365nm、385nm、395nm、405nm、420nm、470nm和525nm波长处感光性能更为优异，适合用于365nm、385nm、395nm、405nm、420nm、470nm和525nm的紫外可见(UV-Vis)LED光源。此外，本发明的双官能团香豆素肟酯类光引发剂在420nm、470nm和525nm波长处感光性能明显优于单官能团香豆素肟酯类光引发剂。
综上所述，本发明式(I)所示的双官能团香豆素肟酯类光引发剂在365nm、385nm、395nm、405nm、420nm、470nm和525nm波长处具有较好的感光性能，优于现阶段可商购的OXE-01和OXE-02等酮肟酯类光引发剂，在420nm、470nm和525nm波长处感光性能明显优于单官能团香豆素肟酯类光引发剂。另外本发明公开的化合物生产工艺简单，产率高，非常适合于工业生产。此类化合物与365nm、385nm、395nm、405nm、420nm、470nm和525nm的(UV-vis)LED光源匹配性良好，且可广泛应用于(UV-vis)LED光固化所涉及的领域例如涂料、油墨、微电子、印刷等领域用作光引发剂。此类物质具有很好的市场前景。鉴于目前可应用于(UV-vis)LED的光引发剂品种较少，从一定程度上限制了(UV-vis)LED光源在紫外光固化领域的推广应用，故本发明光引发剂可为推动绿色环保的(UV-vis)LED光源在UV光固化行业的广泛应用做出贡献。

Claims (16)

  1. 式(I)的双官能团香豆素肟酯化合物：
    Figure PCTCN2021121682-appb-100001
    其中：M为
    Figure PCTCN2021121682-appb-100002
    其中M中的两个吡喃酮环与Ch 1稠合；
    其中：Ch 1为
    Figure PCTCN2021121682-appb-100003
    其中A为CR 3R 4,NR 5,S或O；
    或
    Figure PCTCN2021121682-appb-100004
    其中B为CR 9R 10、S、O或C(＝O)；
    或
    Figure PCTCN2021121682-appb-100005
    其中D为S、C(＝O)或CR 7R 8,
    或
    苯环或具有2-5个苯环的稠合体系且所述苯环或稠合体系中的各苯环具有0至最大可能数目的取代基R 6(Ch 1-4)；
    R 1、R 2、’R 1、’R 2相互独立地表示直链或支化的C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基，其中前述C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基、C 4-C 10 烷基环烷基、C 6-C 20芳基、C 7-C 20芳烷基和C 7-C 20烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 6烷基、C 1-C 6烷硫基、C 1-C 6烷氧基、卤素、硝基、氨基、单(C 1-C 6烷基)氨基、二(C 1-C 6烷基)氨基和巯基，
    R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10相互独立地表示氢、卤素、硝基、羟基、巯基、羧基、C 1-C 8羧酸酯基、磺酸基、氨基、氰基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基，其中前述氨基、C 1-C 20烷基、C 2-C 20烯基、C 2-C 20炔基、C 3-C 20环烷基、C 4-C 20环烷基烷基、C 1-C 20烷氧基、C 2-C 20烯氧基、C 2-C 20炔氧基、C 3-C 20环烷氧基、C 4-C 20环烷基烷氧基、C 1-C 20烷硫基、C 2-C 20烯硫基、C 2-C 20炔硫基、C 3-C 20环烷硫基、C 4-C 20环烷基烷硫基、C 6-C 18芳基、C 6-C 18芳氧基和C 6-C 18芳硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 6烷基、C 1-C 6烷氧基、C 1-C 6烷硫基、C 2-C 6烯基和C 2-C 6炔基，
    各R 0相互独立地表示直链或支化的C 1-C 20烷基、C 3-C 10环烷基、C 4-C 10环烷基烷基或C 4-C 10烷基环烷基；和
    n为0至最大可能取代数目，优选0-2。
  2. 根据权利要求1的式(I)的双官能团香豆素肟酯化合物，其中R 1、R 2、’R 1、’R 2相互独立地表示直链或支化的C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基，其中前述C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 4-C 8烷基环烷基、C 6-C 10芳基、C 7-C 11芳烷基和C 7-C 11烷基芳基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基，
    优选的是，R 1、R 2、’R 1、’R 2彼此独立地选自直链或支化的C 1-C 8烷基、直链或支化的C 1-C 8全氟烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 4烷基、被苯基取代的C 1-C 4烷基和苯基，其中前述苯基各自任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基；
    更优选的是，R 1、’R 1为直链或支化的C 1-C 6烷基、直链或支化的C 1-C 4全氟烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 2烷基或者苯基，前述苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、C 1-C 4烷硫基、C 1-C 4烷氧基、卤素、硝基、氨基和巯基，以及
    R 2、’R 2为直链或支化的C 1-C 7烷基或苯基，其中该苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基和巯基。
  3. 根据权利要求1或2的式(I)的双官能团香豆素肟酯化合物，其中R 1、’R 1为直链或支化的C 1-C 6烷基或直链或支化的C 1-C 4全氟烷基。
  4. 根据权利要求1-3中任一项的式(I)的双官能团香豆素肟酯化合物，其中R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢、卤素、硝基、羟基、巯基、羧基、C 1-C 6羧酸酯基、磺酸基、氨基、氰基、C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基、C 6-C 10芳基、C 6-C 10芳氧基和C 6-C 10芳硫基，其中前述氨基、C 1-C 6烷基、C 2-C 6烯基、C 2-C 6炔基、C 3-C 8环烷基、C 4-C 8环烷基烷基、C 1-C 6烷氧基、C 2-C 6烯氧基、C 2-C 6炔氧基、C 3-C 8环烷氧基、C 4-C 8环烷基烷氧基、C 1-C 6烷硫基、C 2-C 6烯硫基、C 2-C 6炔硫基、C 3-C 8环烷硫基、C 4-C 8环烷基烷硫基、C 6-C 10芳基、C 6-C 10芳氧基和C 6-C 10芳硫基基团可任选地被一个或多个独立地选自下组的基团取代：卤素、硝基、羟基、巯基、羧基、磺酸基、氨基、氰基、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基、C 2-C 4烯基和C 2-C 4炔基；
    优选的是，R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢、卤素、硝基、C 1-C 4羧酸酯基、C 1-C 6烷基、C 2-C 4烯基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基；
    更优选R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢和C 1-C 6烷基。
  5. 根据权利要求1-4中任一项的式(I)的双官能团香豆素肟酯化合物，其中各R 0相互独立地表示直链或支化的C 1-C 8烷基、C 3-C 8环烷基、C 4-C 8环烷基烷基或C 4-C 8烷基环烷基，优选直链或支化的C 1-C 8烷基。
  6. 根据权利要求1的式(I)的双官能团香豆素肟酯化合物，其中
    R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢、卤素、硝基、C 1-C 4羧酸酯基、C 1-C 6烷基、C 2-C 4烯基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基；
    R 1、’R 1为直链或支化的C 1-C 6烷基、卤代C 1-C 6烷基、C 5-C 6环烷基、被C 5-C 6环烷基取代的C 1-C 2烷基或者苯基，前述苯基任选地被一个或多个独立地选自下组的基团取代：氟、氯、溴、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基和卤代C 1-C 4烷基，以及
    R 2、’R 2为直链或支化的C 1-C 7烷基或苯基，其中该苯基任选地被一个或多个独立地选自下组的基团取代：C 1-C 4烷基、卤素、硝基、氨基、单(C 1-C 4烷基)氨基和二(C 1-C 4烷基)氨基，
    或者
    R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10彼此独立地选自氢、C 1-C 4烷基、C 1-C 4烷氧基、C 1-C 4烷硫基、单(C 1-C 4烷基)氨基、二(C 1-C 4烷基)氨基、苯氧基和苯硫基；
    R 1、’R 1为直链或支化的C 1-C 6烷基、卤代C 1-C 6烷基、C 5-C 6环烷基或被C 5-C 6环烷基取代的C 1-C 2烷基，以及
    R 2、’R 2为直链或支化的C 1-C 6烷基或任选被硝基取代的苯基。
  7. 根据权利要求1的化合物，其中式(I)化合物选自下述化合物1-64:
    Figure PCTCN2021121682-appb-100006
    Figure PCTCN2021121682-appb-100007
    Figure PCTCN2021121682-appb-100008
    Figure PCTCN2021121682-appb-100009
    Figure PCTCN2021121682-appb-100010
    Figure PCTCN2021121682-appb-100011
    Figure PCTCN2021121682-appb-100012
  8. 一种制备如权利要求1-7中任一项所定义的式(I)的双官能团香豆素肟酯化合物的方法，包括以下步骤：
    (1)肟化反应：使式(II)化合物与羟胺和/或盐酸羟胺进行肟化反应，得到式(III)化合物
    Figure PCTCN2021121682-appb-100013
    其中：R 1、’R 1和M如权利要求1-7中任一项所定义；
    以及
    (2)将式(III)化合物酯化，得到式(I)化合物。
  9. 根据权利要求8的方法，其中
    所述肟化反应满足以下条件中的一个或多个：
    在乙酸钠、吡啶、哌啶、三乙胺、四甲基氢氧化铵或其混合物存在下进行；
    肟化反应在乙醇或含水的乙醇作为溶剂存在下进行；
    肟化反应的温度为60-120℃；
    肟化反应时间为0.1-20小时，优选0.5-10小时；
    式(II)化合物与选自羟胺和/或盐酸羟胺的化合物的摩尔比为1:2.5-1.25:2，优选1:2.2-1.1:2。
  10. 根据权利要求8或9的方法，其中步骤(2)的酯化采用选自下式(IVa)、(IVb)和(IVc)化合物的酯化试剂进行：
    Figure PCTCN2021121682-appb-100014
    其中X为卤素，尤其是氯，和R 2如权利要求1-7中任一项所定义。
  11. 根据权利要求8-10中任一项的方法，其中酯化反应在选自下组的一种或多种催化剂存在下进行：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙、四甲基氢氧化铵和叔胺，例如三烷基胺，如三甲基胺和三乙胺。
  12. 根据权利要求8-11中任一项的方法，其中酯化反应在选自四氢呋喃、苯、甲苯、N,N-二甲基甲酰胺、二氯甲烷和丙酮的溶剂中进行；和/或，式(III)与选自(IVa)、(IVb)和(IVc)化合物的酯化试剂的摩尔比为1:1.6-1:2.5，优选1:1.8-1:2.2。
  13. 如权利要求1-7中任一项所要求的式(I)化合物作为光引发剂的用途，尤其是在(UV-vis)LED光固化体系中作为光引发剂的用途，特别是在辐射波长为300-550nm、优选350-525nm、尤其365-525nm的光固化体系中作为光引发剂的用途。
  14. 包含至少一种根据权利要求1-7中任一项的式(I)的双官能团香豆素肟酯的光固化性组合物。
  15. 可由权利要求14的光固化性组合物得到的固化材料。
  16. 一种制备光固化材料的方法，其包括用发射波长为300-550nm，尤其365-525的光源，例如(UV-vis)LED光源对权利要求14的光固化性组合物进行辐照。
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