WO2018049976A1 - 芴类光引发剂、其制备方法、具有其的光固化组合物及其在光固化领域的应用 - Google Patents

芴类光引发剂、其制备方法、具有其的光固化组合物及其在光固化领域的应用 Download PDF

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WO2018049976A1
WO2018049976A1 PCT/CN2017/099294 CN2017099294W WO2018049976A1 WO 2018049976 A1 WO2018049976 A1 WO 2018049976A1 CN 2017099294 W CN2017099294 W CN 2017099294W WO 2018049976 A1 WO2018049976 A1 WO 2018049976A1
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group
photoinitiator
formula
cycloalkyl
acrylate
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PCT/CN2017/099294
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English (en)
French (fr)
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钱晓春
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常州强力先端电子材料有限公司
常州强力电子新材料股份有限公司
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Priority claimed from CN201610821992.3A external-priority patent/CN107814694B/zh
Priority claimed from CN201710530354.0A external-priority patent/CN109134712B/zh
Application filed by 常州强力先端电子材料有限公司, 常州强力电子新材料股份有限公司 filed Critical 常州强力先端电子材料有限公司
Priority to EP17850178.9A priority Critical patent/EP3514135B1/en
Priority to JP2019501481A priority patent/JP6833171B2/ja
Priority to KR1020197004737A priority patent/KR102197059B1/ko
Publication of WO2018049976A1 publication Critical patent/WO2018049976A1/zh
Priority to US16/259,779 priority patent/US10976660B2/en

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    • G—PHYSICS
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    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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Definitions

  • the present invention relates to the field of photocuring, and in particular to an anthraquinone photoinitiator, a process for the preparation thereof, a photocurable composition therewith and its use in the field of photocuring.
  • Terpenoids have large molecular weights and their use in UV curing is well known in the art. Using it as a photoinitiator can overcome the problems faced by conventional small molecule photoinitiators. However, the problem faced by large molecular weight terpenoids is that the quinone initiator has a low quantum absorption rate for long wavelengths under light irradiation.
  • the main object of the present invention is to provide a quinone photoinitiator, a preparation method thereof, a photocurable composition therewith and the use thereof in the field of photocuring to solve the problem that the photoinitiator has poor photoinitiation performance. problem.
  • an aspect of the present invention provides a quinone-based photoinitiator having a structure represented by the formula (I), or a quinone-based photoinitiator comprising the structure represented by the formula (II):
  • R 1 and R 1 ' are each independently selected from hydrogen, halogen, a linear or branched alkyl group of C 1 to C 20 , a cycloalkyl group of C 3 to C 8 , and C 3 ⁇ a cycloalkyl-substituted C 1 -C 10 alkyl group of C 8 or a C 2 -C 20 alkenyl group;
  • R 2 and R 3 are each independently selected from a C 1 - C 20 linear or branched alkyl group; a C 3 -C 8 cycloalkyl group, a C 3 -C 8 cycloalkyl group substituted C 1 -C 10 alkyl group, or a C 6 -C 20 aryl group; or R 2 and R 3 are bonded to form C a cycloalkyl group of 3 to C 8 ;
  • X is -A-(X') n , wherein A is selected from a hetero atom, the hetero atom
  • R 5 and R 6 are each independently selected from any one of a hydrogen atom, a halogen and a chain group, and the chain group is a C 1 - C 20 linear alkyl group or a C 1 - C 20 branch.
  • Ar is a substituent containing an aromatic ring or a heteroaromatic ring
  • R 1 and R 1 ' are independently selected from hydrogen, halogen, C 1 - C 10 linear or branched alkyl or C 3 - C 8 cycloalkyl, C 3 - cycloalkyl substituted C C 8 1 ⁇ C 10 alkyl group; preferably, R 1 and R 1 'are independently selected from hydrogen, C linear or branched alkyl group of 1 ⁇ C 4, C 3 ⁇ C 6 cycloalkyl substituted with C 1 -C 3 alkyl.
  • R 2 and R 3 are each independently selected from a C 1 - C 10 linear or branched alkyl group or a C 3 - C 8 cycloalkyl group, a C 3 - C 8 cycloalkyl group. a substituted C 1 -C 10 alkyl group; or R 2 and R 3 are bonded to form a C 3 -C 10 cycloalkyl group; preferably, R 2 and R 3 are each independently selected from a C 1 -C 4 linear chain Or a branched alkyl group, a C 4 -C 8 cycloalkylalkyl group; or R 2 and R 3 are bonded to form a C 3 -C 6 cycloalkyl group.
  • X' is selected from a methyl group, an ethyl group, a cyclohexyl group or a cyclopentyl group.
  • quinone photoinitiator represented by the formula (I) is selected from one or more of the following compounds:
  • Another aspect of the present application also provides a method for preparing a quinone photoinitiator having the structure represented by the formula (I), which comprises: a bromination reaction: a raw material a, a brominated reagent and a first organic solvent The bromination reaction occurs to obtain the intermediate product b, and the starting material a has the structure represented by the formula (III).
  • the intermediate product b has the structure of the formula (IV),
  • Substitution reaction a substitution reaction is carried out using an intermediate product b, a substitution reagent and a second organic solvent to obtain a quinone photoinitiator, wherein R 1 and R 1 ' are each independently selected from the group consisting of hydrogen, halogen, and C 1 to C 20 a chain or branched alkyl group, a C 3 -C 8 cycloalkyl group, a C 3 -C 8 cycloalkyl substituted C 1 -C 10 alkyl group or a C 2 -C 20 alkenyl group; R 2 and R 3 C 1 to C 10 alkyl, C 6 independently selected from C 1 to C 20 linear or branched alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl substituted An aryl group of -C 20 ; or R 2 and R 3 are bonded to form a C 3 -C 8 cycloalkyl group; R 4 is a hydroxyl group or an N-
  • the brominated reagent is selected from one or more of the group consisting of N-bromosuccinimide, hydrobromic acid, bromine and dibromohydantoin; preferably, the substitution reagent is XONa, and X is -A-(X') n , wherein A is selected from a hetero atom, the hetero atom is selected from O, N or S, and X' is selected from a linear or branched alkyl group of C 1 - C 20 , C 3 - C 8 A cycloalkyl, C 3 -C 8 cycloalkyl substituted C 1 -C 10 alkyl group, or one or more of the carbon atoms in X' is substituted by a hetero atom, n being 1 or 2.
  • the first organic solvent is a polar solvent, preferably propylene carbonate.
  • the temperature of the bromination reaction is from 10 to 60 ° C, preferably 25 ° C.
  • the second organic solvent is selected from one or more of the group consisting of dichloromethane, dichloroethane, benzene, and xylene.
  • Still another aspect of the present application provides a coating composition comprising a photoinitiator and a photopolymerizable monomer, wherein the photoinitiator is an anthraquinone photoinitiator having a structure represented by the formula (I), and the photopolymerizable monomer is an alkenyl group.
  • the photoinitiator is an anthraquinone photoinitiator having a structure represented by the formula (I)
  • the photopolymerizable monomer is an alkenyl group.
  • the photopolymerizable monomer is an acrylate compound; preferably, the photopolymerizable monomer is selected from the group consisting of an epoxy acrylate oligomer, a urethane acrylate oligomer, and a polyester acrylate oligomer. kind or more.
  • the coating composition further comprises an auxiliary agent selected from the group consisting of a solvent, a surface conditioner, a sensitizer, a sensitizer, a curing accelerator, a photocrosslinking agent, a photosensitizer, a photosensitive resin, and the like.
  • an auxiliary agent selected from the group consisting of a solvent, a surface conditioner, a sensitizer, a sensitizer, a curing accelerator, a photocrosslinking agent, a photosensitizer, a photosensitive resin, and the like.
  • a dispersing aid a filler, an adhesion promoter, an antioxidant, a UV absorber, a deflocculant, a thermal polymerization inhibitor, an antifoaming agent, a leveling agent, a surfactant, and a chain transfer agent Or a variety.
  • Still another aspect of the present application provides an ink composition
  • a photoinitiator comprising a photoinitiator, a photopolymerizable monomer and a pigment
  • the photoinitiator is an anthraquinone photoinitiator having a structure represented by the formula (I)
  • the photopolymerizable monomer is Alkenyl-containing compounds and/or epoxy compounds.
  • the photopolymerizable monomer is an acrylate compound; preferably, the photopolymerizable monomer is selected from the group consisting of an epoxy acrylate oligomer, a urethane acrylate oligomer, and a polyester acrylate oligomer. kind or more.
  • the ink composition further comprises an auxiliary agent selected from the group consisting of a solvent, a surface conditioner, a sensitizer, a curing accelerator, a photocrosslinking agent, a sensitizer, a photosensitizer, a photosensitive resin, and the like.
  • an auxiliary agent selected from the group consisting of a solvent, a surface conditioner, a sensitizer, a curing accelerator, a photocrosslinking agent, a sensitizer, a photosensitizer, a photosensitive resin, and the like.
  • a dispersing aid a filler, an adhesion promoter, an antioxidant, a UV absorber, a deflocculant, a thermal polymerization inhibitor, an antifoaming agent, a leveling agent, a surfactant, and a chain transfer agent Or a variety.
  • the chain group is a C 1 -C 10 linear alkyl group, a C 1 -C 10 branched alkyl group or a C 4 -C 10 cycloalkylalkyl group.
  • Ar is phenyl, methylphenyl, ethylphenyl, chlorophenyl, bromophenyl, methoxyphenyl, nitrophenyl, cyanophenyl, diphenyl Thioether group, pyridyl group, thienyl group, furyl group, 2-methyl-thienyl group, 3-methylthienyl group, furyl group, 2-methyl-furyl group or 3-methylfuranyl group.
  • the quinone photoinitiator has a structure represented by the following formula (V):
  • R 8 has n external linkages and is a C 1 -C 60 linear alkyl group or a branched alkyl group, or a C 1 -C 60 linear alkyl group or a branched alkyl group or any carbon or Hydrogen is replaced by oxygen, sulfur or phenyl;
  • A represents a repeating unit having a structure of -(Q-CHR 9 ) m -, R 9 is hydrogen, methyl or ethyl, and Q represents O or a linker, wherein the linker represents -(CHR 9 ) m directly linked to O m is an integer from 1 to 6;
  • n an integer of 1-20.
  • R8 is selected from any one of the following groups: *CH 2 -CH 2 *, *CH 2 -CH 2 -CH 2 *, *CH 2 CH 2 CH 2 CH 2 *,
  • A is selected from -[(Q-CHR 9 ) m ] y - wherein R 9 is hydrogen or methyl, m is an integer of 1 to 3, and y represents an integer of 1 to 9.
  • n is an integer of from 1 to 8, preferably 1, 2, 3, 4, 5 or 6.
  • Step S1 the raw material a having the structural formula A and the raw material b having the structural formula B are produced The reaction is carried out to obtain intermediate c having the structural formula C; optional step S2, intermediate c is subjected to a Friedel-Craft reaction with the starting material d having the structural formula D to obtain an intermediate e having the structural formula E; and optionally in the step S3, The transesterification reaction of the body e with an alcohol or a polyol having the structural formula F to obtain a quinone photoinitiator, wherein
  • Structural formula A is Structural formula B is Wherein X 1 is a halogen and the structural formula C is Structural formula D is Wherein X 2 is halogen and the structural formula E is The structural formula F is R 8 (AOH) n .
  • the Friedel-Crafts reaction of the step S1 and the step S2 is carried out in the presence of aluminum trichloride or zinc chloride and a solvent, and preferably the reaction temperatures of the Friedel-Crafts of the step S1 and the step S2 are each independently -10 to 40 °C.
  • step S3 undergoes a transesterification reaction under the action of a catalyst and a polymerization inhibitor
  • the catalyst is one or more titanate compounds, more preferably the catalyst is selected from the group consisting of titanyl-2-ethylhexylate and titanate
  • the catalyst is selected from the group consisting of titanyl-2-ethylhexylate and titanate
  • the molar ratio of the intermediate e to the alcohol or polyol having the structural formula F is n:1, preferably the weight of the catalyst is 3 to 10 ⁇ based on the total weight of the material, and more preferably the weight of the polymerization inhibitor is the material.
  • the total weight is 3 to 10 Torr, and it is more preferable that the temperature of the transesterification reaction is 70 to 130 ° C and the reaction time is 1 to 8 hours.
  • Another aspect of the present application provides a photocurable composition
  • a photoinitiator which is an anthraquinone photoinitiator comprising a structure of formula (II).
  • Another aspect of the present application provides an application of a quinone-based photoinitiator comprising the structure of the formula (II) in the field of photocuring.
  • applications include applications in coatings, inks, adhesives, color photoresists, black matrices, photo spacers, rib gates, dry films, and/or semiconductor photoresists.
  • introducing a new group on the existing ruthenium structure not only increases the molecular weight of the photoinitiator, but also improves the related performance of the photoinitiator initiation efficiency and the like.
  • the existing photoinitiator has a problem of poor performance.
  • the present invention provides a quinone type photoinitiator having a structure represented by the formula (I):
  • R 1 and R 1 ' are each independently selected from hydrogen, halogen, C 1 -C 20 linear or branched alkyl, C 3 -C 8 cycloalkyl, C 2 -C 20 alkenyl Or a C 3 -C 8 cycloalkyl-substituted C 1 -C 10 alkyl group;
  • R 2 and R 3 are each independently selected from a C 1 -C 20 linear or branched alkyl group, C 3 -C 8 a cycloalkyl group, a C 3 -C 8 cycloalkyl substituted C 1 -C 10 alkyl group or a C 6 -C 20 aryl group; or R 2 and R 3 are bonded to form a C 3 -C 8 ring Alkyl;
  • X is -A-(X') n , wherein A is selected from a hetero atom, the hetero atom is O, N or S, and X' includes, but is not limited to, a C
  • the quinone photoinitiator comprises the structure shown in formula (II):
  • R 5 and R 6 are each independently selected from any one of a hydrogen atom, a halogen and a chain group, and the chain group is a C 1 - C 20 linear alkyl group or a C 1 - C 20 branch.
  • the R 7 ' group is a group to which an alcohol or a polyol is linked by a transesterification reaction.
  • the group containing a hetero atom N, S, O
  • the hetero atom-containing substituent is advantageous for red shifting the absorption wavelength of the quinone compound, which can increase the initiation efficiency of the compound. This allows the photoinitiator to have a high quantum absorption rate under long-wavelength irradiation when a quinone compound containing a hetero atom substituent is used as a photoinitiator.
  • the quinone photoinitiator comprising a group represented by the formula (II)
  • a small molecule group is introduced into the side chain of the quinone compound, on the one hand, the molecular weight of the quinone compound is increased, and on the other hand, the initiator is
  • the problems of initiation efficiency, yellowing resistance, non-migration, low odor, solubility, etc. can be better improved and balanced, and by applying the photosensitive composition, it is found that the quinone initiator is applied to the current routine.
  • the photocurable formulation is well suited for curing UV-LED sources.
  • the anthracene photoinitiator having the above substituent has a high quantum absorption efficiency for a long wavelength.
  • R 1 and R 1 ' are independently selected from hydrogen, halogen, C 1 -C 10 linear or branched alkyl, or C 4 -C 10 cycloalkylalkyl; preferably, R 1 and R 1 ' independently includes, but is not limited to, hydrogen, a C 1 -C 4 linear or branched alkyl group, or a C 3 -C 6 cycloalkyl substituted C 1 -C 3 alkyl group.
  • R 2 and R 3 are each independently selected from a C 1 -C 10 linear or branched alkyl group or a C 4 -C 10 cycloalkylalkyl group; or R 2 and R 3 are bonded to form C 3 - C 10 cycloalkyl.
  • R 2 and R 3 are each independently selected from a C 1 -C 4 linear or branched alkyl group or a C 4 -C 8 cycloalkylalkyl group; or R 2 and R 3 are bonded to form C 3 - C 6 cycloalkyl.
  • X' includes, but is not limited to, methyl, ethyl, cyclohexyl or cyclopentyl.
  • the quinone photoinitiator of formula (I) includes, but is not limited to, one or more of the following organics;
  • Another aspect of the present application also provides a method for preparing a quinone-based photoinitiator represented by the formula (I), which comprises the steps of: bromination: bromination of a raw material a, a brominated reagent and a first organic solvent The reaction is carried out to obtain an intermediate product b, and the starting material a has a structure represented by the formula (III).
  • the intermediate product b has the structure of the formula (IV),
  • Substitution reaction a substitution reaction is carried out using an intermediate product b, a substitution reagent, and a second organic solvent to obtain a quinone photoinitiator.
  • the raw material a is obtained by a synthetic method disclosed in Patent No. 2015109373280, and other raw materials are known compounds in the prior art, which can be easily prepared by a commercially available product or by a known synthesis method. to make.
  • the quinone photoinitiator of the present application can be obtained by the above two steps, and the reactions involved in the steps (1) and (2) are all reactions which are conventionally used in the prior art, and therefore, the preparation process is easy to realize and control.
  • the reaction conditions of the bromination reaction and the substitution reaction can be carried out by referring to the conventional bromination reaction and substitution reaction of the prior art.
  • the present application is directed to the above substrate, preferably, the bromination reagent includes, but is not limited to, one or more of the group consisting of N-bromosuccinimide, hydrobromic acid, bromine, and dibromohydantoin;
  • the substitution reagent is XONa, and X is -A-(X') n , wherein A is selected from a hetero atom, the hetero atom is selected from O, N or S, and X' is selected from a linear or branched chain of C 1 - C 20
  • One or more of an alkyl group, a C 3 -C 8 cycloalkyl group, a C 3 -C 8 cycloalkyl group-substituted C 1 -C 10 alkyl group, or a carbon atom in X' is Atom
  • the reaction system is a preferred polar solvent system, and a Lewis acid is selectively added as a catalyst, and the first organic solvent is particularly preferably propylene carbonate; preferably, the temperature of the bromination reaction is 10 to 60 ° C, preferably 25 °C.
  • the second organic solvent used in the substitution reaction may be a common organic solvent that does not participate in the reaction in the prior art.
  • the second organic solvent includes, but is not limited to, dichloromethane, dichloroethane, One or more of the group consisting of benzene and xylene.
  • An aspect of the present application provides a coating composition comprising a photoinitiator and a photopolymerizable monomer, the photoinitiator is an anthracene photoinitiator represented by the formula (I), and the photopolymerizable monomer is an alkenyl group-containing compound and / or epoxy compounds.
  • the curing mechanism of the above coating composition is that the photoinitiator is activated under illumination; then the photopolymerizable monomer is polymerized by the activated initiator to form a film.
  • the coating composition containing the above photoinitiator has low curing energy and curing efficiency during photocuring. Higher advantages.
  • the photoinitiator provided by the present application may be compounded with an initiator commonly used in the art.
  • the photopolymerizable monomer is an acrylate compound; preferably, the photopolymerizable monomer includes, but is not limited to, an epoxy acrylate oligomer, a urethane acrylate oligomer, and a polyester acrylate resin. One or more of the group consisting of polymers.
  • the above photopolymerizable monomers include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( Cyclohexyl methacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy (meth) acrylate 2-hydroxypropyl ester, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, two Methylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoro (meth) acrylate
  • the coating composition further comprises an auxiliary agent including, but not limited to, a solvent, a surface conditioner, a sensitizer, a sensitizer, a curing accelerator, and a photocrosslinking agent.
  • an auxiliary agent including, but not limited to, a solvent, a surface conditioner, a sensitizer, a sensitizer, a curing accelerator, and a photocrosslinking agent.
  • photosensitizer, photosensitive resin, dispersing aid, filler, adhesion promoter, antioxidant, UV absorber, deflocculant, thermal polymerization inhibitor, defoamer, leveling agent, surfactant and chain transfer One or more of the group consisting of agents.
  • the addition of additives facilitates the improvement of the overall performance of the coating composition.
  • photoinitiator of the present invention can also be used in combination with other photoinitiators for reasons such as cost and the like.
  • Still another aspect of the present application provides an ink composition
  • a photoinitiator comprising a photoinitiator, a photopolymerizable monomer, and a pigment
  • the photoinitiator is an anthraquinone photoinitiator represented by the formula (I)
  • the photopolymerizable monomer is Alkenyl compounds and/or epoxy compounds.
  • the curing mechanism of the above ink composition is such that the photoinitiator is activated under illumination; then the photopolymerizable monomer is polymerized by the activated initiator to form a film.
  • the quinone type photoinitiator represented by the formula (I) provided by the present application has a high quantum absorption efficiency for long wavelengths
  • the ink composition containing the above photoinitiator has low curing energy and curing efficiency during photocuring. Higher advantages.
  • the photoinitiator provided by the present application may be compounded with an initiator commonly used in the art.
  • the photopolymerizable monomer is an acrylate compound; preferably, the photopolymerizable monomer includes, but is not limited to, an epoxy acrylate oligomer, a urethane acrylate oligomer, and a polyester acrylate resin. One or more of the group consisting of polymers.
  • the photopolymerizable monomer includes, but is not limited to, the above photopolymerizable monomers including, but not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid 2-ethylhexyl ester, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( 2-phenoxy-2-hydroxypropyl methacrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerol mono(meth) acrylate, (methyl) Tetrahydrofurfuryl acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, (meth) acryl
  • the ink composition further includes an auxiliary agent including, but not limited to, a solvent, a surface conditioner, a sensitizer, a sensitizer, a curing accelerator, and a photocrosslinking agent.
  • an auxiliary agent including, but not limited to, a solvent, a surface conditioner, a sensitizer, a sensitizer, a curing accelerator, and a photocrosslinking agent.
  • photosensitizer, photosensitive resin, dispersing aid, filler, adhesion promoter, antioxidant, UV absorber, deflocculant, thermal polymerization inhibitor, defoamer, leveling agent, surfactant and chain transfer One or more of the group consisting of agents.
  • the addition of the auxiliary agent is advantageous for improving the overall performance of the ink composition.
  • the chain group is a C 1 -C 10 linear alkyl group, a C 1 -C 10 branched alkyl group or a C 4 -C 10 cycloalkylalkyl group. base.
  • Ar is phenyl, methylphenyl, ethylphenyl, chlorophenyl, bromophenyl, methoxyphenyl, nitrophenyl, cyanophenyl, diphenyl Thioether group, pyridyl group, thienyl group, furyl group, 2-methyl-thienyl group, 3-methylthienyl group, furyl group, 2-methyl-furyl group or 3-methylfuranyl group.
  • the quinone photoinitiator has a structure represented by the following formula (V):
  • R 8 has n external linkages and is a C 1 -C 60 linear alkyl group or a branched alkyl group, or a C 1 -C 60 linear alkyl group or a branched alkyl group or any carbon or Hydrogen is replaced by oxygen, sulfur or phenyl;
  • A represents a repeating unit having a structure of -(Q-CHR 9 ) m -, R 9 is hydrogen, methyl or ethyl, and Q represents O or a linker, wherein the linker represents -(CHR 9 ) m directly linked to O m is an integer of 1 to 6; n represents an integer of 1 to 20.
  • the oxime-based photoinitiator having the above structural formula (V) is characterized in that its mobility is lowered not only because of its larger molecular weight, but also because it has more excellent solubility properties.
  • the photoinitiator having the group represented by the above formula (II) and the photoinitiator having the structure represented by the formula (V) have an absorption band of between 330 and 400 nm, and are almost odorless, in the (meth)acrylic resin and Vinyl ether compounds have good solubility, are not easy to migrate after application, and are resistant to yellowing.
  • A is selected from -[(Q-CHR 9 ) m ] y - wherein R 9 is hydrogen or methyl, m is an integer of from 1 to 3, and y represents an integer of from 1 to 9.
  • n is an integer of from 1 to 8, preferably 1, 2, 3, 4, 5 or 6.
  • the preparation method comprises the following steps: Step S1, the raw material a having the structural formula A and the raw material b having the structural formula B are fuk Reaction, to obtain intermediate c having the structural formula C; optional step S2, the intermediate c is subjected to a Friedel-Craft reaction with the starting material d having the structural formula D to obtain an intermediate e having the structural formula E; and optionally the step S3, an intermediate e is transesterified with an alcohol or a polyol having the structural formula F to obtain a quinone photoinitiator, wherein
  • Structural formula A is Structural formula B is Wherein X 1 is a halogen and the structural formula C is Structural formula D is Wherein X 2 is halogen and the structural formula E is The structural formula F is R 8 (AOH) n .
  • R5, R6, Ar, R7, R7' and R8 in the above respective structural formulas are the same as the corresponding groups represented by the structural formula (II) and the structural formula (V).
  • the Friedel-Crafts reaction of the aforementioned step S1 and the step S2 is carried out in the presence of aluminum trichloride or zinc chloride and a solvent, and preferably the reaction temperatures of the Friedel-Crafts of the step S1 and the step S2 are each independently -10 to 40 °C.
  • the conditions of the Friedel-Crafts in the above two steps may be the same or different, and the solvents may be the same or different, wherein the solvent may be a common organic solvent that does not participate in the reaction in the prior art, such as dichloromethane, dichloroethane, toluene, Benzene, xylene, when the same solvent is used in both steps, the completion of step S1 may be followed by the completion of the Friedel-Craft reaction of step S2 without purification.
  • the solvent may be a common organic solvent that does not participate in the reaction in the prior art, such as dichloromethane, dichloroethane, toluene, Benzene, xylene, when the same solvent is used in both steps, the completion of step S1 may be followed by the completion of the Friedel-Craft reaction of step S2 without purification.
  • the transesterification reaction of the above step S3 can be carried out directly in the system completed in the step S2 or can be carried out by re-disposing in the solvent, and the solvent of the step S3 is not particularly limited as long as the reaction reagent can be dissolved. And there is no adverse effect on the reaction, such as toluene, benzene, xylene.
  • the above step S3 undergoes a transesterification reaction under the action of the catalyst and the polymerization inhibitor
  • the catalyst is one or more titanate compounds
  • the catalyst is selected from the group consisting of 2-ethylhexyl titanate, tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetrakis(2-ethylhexyl) titanate.
  • One or more of the groups of esters, preferably the polymerization inhibitor is selected from the group consisting of p-hydroxyanisole, N,N-diethylhydroxylamine, hydroquinone, catechol, p-tert-butyl catechol, Any one of the group consisting of methylhydroquinone, p-methoxyphenol, phenothiazine, and triphenylphosphine.
  • the molar ratio of the intermediate e to the alcohol or polyol having the structural formula F is n: 1, preferably the weight of the catalyst is 3 of the total weight of the material.
  • the weight of the polymerization inhibitor is from 3 to 10 Torr based on the total weight of the material, and further preferably the temperature of the transesterification reaction is from 70 to 130 ° C and the reaction time is from 1 to 8 hours.
  • a photocurable composition comprising a photoinitiator which is an anthraquinone photoinitiator comprising a structure of formula (II).
  • the initiating efficiency and yellowing resistance, migration resistance, low odor, solubility and the like of the quinone photoinitiator comprising the structure represented by the formula (II) of the present application can be compared with the prior art benzophenone or benzene
  • the formyl initiator is better improved and balanced, and therefore, when applied to the composition, the structural properties of the composition can be more stable, and the photocurable composition can be made in a UV-LED source. It can be cured under the illumination, thus saving energy and complying with environmental requirements.
  • the oxime-based photoinitiator comprising the structure represented by the formula (II) provided by the present application allows the photocurable composition having the same to be cured under irradiation of a UV-LED source, the application containing the same saves energy more.
  • the above applications include applications in coatings, inks, adhesives, color resists, black matrices, photo spacers, rib gates, dry films, and/or semiconductor photoresists.
  • the structural characterization data of the intermediate product 1a is as follows: 1 H-NMR (CDCl 3 , 500 MHz): 0.9146 to 1.0002 (6H, t), 1.2878 to 1.3328 (8H, m), 1.4844 (6H, s), 1.8754 - 2.1045 (5H, m), 7.5801 to 8.0837 (6H, m).
  • the structural characterization data of the intermediate product 2a is as follows: 1 H-NMR (CDCl 3 , 500 MHz): 1.3629 (6H, s), 1.6578 (6H, s), 2.3899-2.3835 (4H, t), 3.6703-3.6801 ( 4H, t), 7.5481-7.8997 (6H, m).
  • the raw materials were placed in a dark room with reference to the composition shown in Tables 2 to 5.
  • the stirred raw material was placed on a PET film and coated with a coating bar to a film thickness of about 25 ⁇ m.
  • Samples 1 to 34 (corresponding to the compositions of Examples 1 to 28) and Comparative sheets 1 to 4 (corresponding to the compositions of Comparative Examples 1 to 4) were sequentially obtained according to the above method.
  • the coated PET film was placed in a crawler exposure machine (RW-UV.70201, wavelength 300-500 nm) for exposure, and the energy received for one exposure was 80 mJ/cm 2 , and the curing of each group was recorded. The minimum energy required.
  • Performance evaluation Refer to the finger-touch method in the paint film drying time test standard GB/T 1728-1979 to evaluate the curing speed of the paint film surface, that is, touch the coating with a finger to make the surface smooth, and the non-stick hand indicates that the surface is completely cured;
  • the bottom curing speed was measured by the finger licking method, that is, the coating was lightly rubbed with a nail to prevent the bottom layer from solidifying.
  • the evaluation results are shown in Table 6.
  • the anthraquinone compound and the composition thereof according to the present invention achieve the following technical effects: the anthraquinone compound and the composition thereof according to the present invention have obvious advantages in curing efficiency, and the energy required for curing is significantly low. Compositions having the same initiator structure.
  • a different raw material a, b may be used for the Friedel-Craft reaction to obtain the product a of different structures, but is not limited thereto, as shown in Table 7.
  • the product 1a85g and dichloromethane 100mL were added to a 500 mL four-necked flask, and the mixture was stirred at room temperature.
  • the mixed solution of the raw material 1c38g and 50mL of dichloromethane was continuously added to the four-necked flask, and the temperature was controlled at 30 ° C or lower, and the addition was completed in about 1 hour.
  • stirring was continued for 2 hours, and the liquid phase was traced to completion to obtain a product system containing the product 1b. Then, the product system was slowly poured into 400 g of ice water and 50 mL of concentrated hydrochloric acid (37%) in a diluted hydrochloric acid.
  • products a and c may be subjected to a Friedel-Craft reaction to obtain products b of different structures, but are not limited thereto, as shown in Table 8 (the compounds in Table 8 are numbered sequentially, but it does not mean that they are obtained in Table 8
  • the compound is prepared by using the corresponding number of the compounds in Table 7 as raw materials.
  • Those skilled in the art can carry out the Friedel-Craft reaction of the product a and the starting material c according to the above description and the prior art to obtain the corresponding product b).
  • a different product b and a raw material d may be used for transesterification to obtain a product c of a different structure, but is not limited thereto, as shown in Table 9 (the compounds in Table 9 are numbered sequentially, but do not represent the results in Table 9).
  • the compounds are prepared by using the corresponding number of the compounds in Table 8 as raw materials.
  • Those skilled in the art can carry out transesterification reaction according to the above description and the prior art by selecting suitable product b and starting material d to obtain the corresponding product c).
  • the photoinitiators of the formulas (I) and (II) of the present invention and the initiators of the conventional formulations of the conventional benzophenones and benzoylformides are prepared in the ink preparation.
  • the application performance is evaluated.
  • the radiation curable composition was prepared according to the formulation of Table 10, and the commonly used benzophenone and formyl ester initiators were compared with the photoinitiator of the present invention, and the weight % (wt%) was based on radiation. Total weight of the cured composition:
  • the photocurable composition is stirred under a yellow light, and is taken up on a PET template to form a film by a roll to form a film having a film thickness of about 20 ⁇ m.
  • the film is exposed by a crawler, and a mask is attached, respectively, using a high-pressure mercury lamp (exposure type).
  • No. RW-UV70201, wavelength 200-500nm, light intensity 100mW/cm 2 ) and LED lamps (Blue Spectrum Rick LP300w, wavelength 395nm, light intensity 100mW/cm 2 ) are irradiated to pass the track through the film. The number of times is evaluated, and the test results are shown in Table 11.
  • the cured film prepared by the above high-pressure mercury lamp was subjected to aging test by RW-UV.2BP ultraviolet aging test box, and the light source was a high-pressure mercury lamp (main wavelength 365 nm, whole machine power: about 2.2 KW), and the cured film was continuously irradiated for 6 hours.
  • the yellowing of the cured film was observed and evaluated according to the following criteria, as shown in Table 11.
  • ⁇ colorless and transparent, the surface is smooth, indicating good yellowing resistance
  • ⁇ The surface is yellow or the viscosity is increased, indicating easy yellowing.
  • the bismuth photoinitiator of the present invention has high sensitivity not only under a high pressure mercury lamp but also at a high level under a UV-LED source, in the case where the other components are the same.
  • the existing benzophenone and benzoylformate photoinitiators exhibit significant deficiencies under the UV-LED light source; and it can be seen from the yellowing resistance test and the migration test that the present invention
  • the quinone photoinitiator has the characteristics of good yellowing resistance, low solubility and low odor, and is difficult to migrate.
  • the quinone photoinitiator having a group represented by the formula (II) and the quinone photoinitiator having the structure represented by the formula (V) in the present application can be excellent in application in the field of photocuring.
  • Application performance has broad application prospects.

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Abstract

本发明提供了一种芴类光引发剂、其制备方法、具有其的光固化组合物及其在光固化领域的应用。该芴类光引发剂具有式(I)所示的结构，X为-A-(X')n，其中A选自杂原子，杂原子选自O、N或S，X'选自C1～C20的直链或支链烷基、C3～C8环烷基、C3～C8环烷基取代的C1～C10的烷基，或者X中的碳原子中的一个或多个被杂原子取代，n为1或2；R4为羟基或者N-吗啉基；或者该芴类光引发剂包含式(Ⅱ)所示的结构。在现有的芴结构上引入新的基团，不仅增加了光引发剂的分子量，而且还提高了光引发剂的引发效率等相关性能。

Description

芴类光引发剂、其制备方法、具有其的光固化组合物及其在光固化领域的应用 技术领域
本发明涉及光固化领域，具体而言，涉及一种芴类光引发剂、其制备方法、具有其的光固化组合物及其在光固化领域的应用。
背景技术
传统小分子光引发剂具有优异的感光性能和溶解性，但在实际应用中存在光解碎片容易迁移和挥发性大等问题。人们设法通过增加化合物分子量来解决这些不足，但是分子量增加通常会降低光引发效果。
芴类化合物分子量较大，且在紫外光固化中的应用已被本领域所熟知。将其作为光引发剂可以克服传统的小分子光引发剂所面临的问题。然而大分子量的芴类化合物所面临的问题是在光的照射下芴类化合物引发剂对长波长的量子吸收率较低。
发明内容
本发明的主要目的在于提供一种芴类光引发剂、其制备方法、具有其的光固化组合物及其在光固化领域的应用，以解决现有的光引发剂存在光引发性能较差的问题。
为了实现上述目的，本发明一个方面提供了一种芴类光引发剂，芴类光引发剂具有式(I)所示的结构，或者，芴类光引发剂包含式(II)所示结构：
Figure PCTCN2017099294-appb-000001
其中，式(I)中，R1和R1’分别独立地选自氢、卤素、C1～C20的直链或支链烷基、C3～C8的环烷基、C3～C8的环烷基取代的C1～C10的烷基或C2～C20的链烯基；R2和R3分别独立地选自C1～C20的直链或支链烷基、C3～C8的环烷基、C3～C8的环烷基取代的C1～C10的烷基、C6～C20的芳基；或者，R2和R3相连形成C3～C8的环烷基；X为-A-(X’)n，其中A选自杂原子，杂原子选自O、N或S，X’选自C1～C20的直链或支链烷基、C3～C8的环烷基、C3～C8的环烷基取代的C1～C10的烷基，或者X’中的碳原子中的一个或多个被杂原子取代，n为1或2；R4为羟基或者N-吗啉基；或者
式(Ⅱ)中：
Figure PCTCN2017099294-appb-000002
其中，R5、R6分别独立地选自氢原子、卤素和链基基团中的任意一种，链基基团为C1-C20的直链烷基、C1-C20的支链烷基或C1-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基和C2-C20的链烯基，或者R5和R6以链基基团中的任意一种或两种成环，且链基基团中的-CH2-可任选地被-O-、-C(＝O)O-、卤素、苯基所取代；
Ar为含有芳香环或杂芳香环的取代基；
以及与式(II)所示的基团的连接键相连的R7，R7为氢原子、-C(＝O)R7’或-C(＝O)C(＝O)O-R7’基团，其中，R7’表示取代或未被取代的C1-C40的直链、C1-C40的支链烷基、C1-C20的环烷基、C1-C40的链烯基、含有芳香环或杂芳香环的取代基，或者R7为-C(＝O)C(＝O)O-R7’基团，R7’基团为醇或多元醇通过酯交换反应而连接的基团。
进一步地，式(I)中，R1和R1’独立地选自氢、卤素、C1～C10的直链或支链烷基或C3～C8的环烷基、C3～C8的环烷基取代的C1～C10的烷基；优选地，R1和R1’独立地选自氢、C1～C4的直链或支链烷基、C3～C6的环烷基取代的C1-C3烷基。
进一步地，式(I)中，R2和R3分别独立地选自C1～C10的直链或支链烷基或C3～C8环烷基、C3～C8环烷基取代的C1～C10的烷基；或者R2和R3相连形成C3～C10的环烷基；优选地，R2和R3分别独立地选自C1～C4的直链或支链烷基、C4～C8的环烷基烷基；或者R2和R3相连形成C3～C6的环烷基。
进一步地，式(I)中，X’选自甲基、乙基、环己基或环戊基。
进一步地，式(I)所示的芴类光引发剂选自以下化合物中的一种或多种：
Figure PCTCN2017099294-appb-000003
Figure PCTCN2017099294-appb-000004
Figure PCTCN2017099294-appb-000005
本申请的另一方面还提供了一种具有式(I)所示结构的芴类光引发剂的制备方法，该制备方法包括：溴代反应：将原料a、溴代试剂及第一有机溶剂发生溴代反应，得到中间产物b，原料a具有式(Ⅲ)所示的结构，
Figure PCTCN2017099294-appb-000006
中间产物b具有式(Ⅳ)结构，
Figure PCTCN2017099294-appb-000007
取代反应：采用中间产物b、取代试剂及第二有机溶剂发生取代反应，得到芴类光引发剂，其中，R1和R1’分别独立地选自氢、卤素、C1～C20的直链或支链烷基、C3～C8的环烷基、C3～C8环烷基取代的C1～C10的烷基或C2～C20的链烯基；R2和R3分别独立地选自C1～C20的直链或支链烷基、C3～C8环烷基、C3～C8环烷基取代的C1～C10的烷基、C6～C20的芳基；或者，R2和R3相连形成C3～C8的环烷基；R4为羟基或者N-吗啉基。
进一步地，溴代试剂选自N-溴代丁二酰亚胺、氢溴酸、溴素和二溴海因组成的组中的一种或多种；优选地，取代试剂为XONa，X为-A-(X’)n，其中A选自杂原子，杂原子选自O、N或S，X’选自C1～C20的直链或支链烷基、C3～C8的环烷基、C3～C8环烷基取代的C1～C10的烷基，或者X’中的碳原子中的一个或多个被杂原子取代，n为1或2。
进一步地，溴代反应中，第一有机溶剂为极性溶剂，优选为碳酸丙烯酯。
进一步地，溴代反应的温度为10～60℃，优选为25℃。
进一步地，第二有机溶剂选自二氯甲烷、二氯乙烷、苯和二甲苯组成的组中的一种或多种。
本申请又一方面还提供了一种涂料组合物，包括光引发剂和光聚合单体，光引发剂为具有式(I)所示结构的芴类光引发剂，光聚合单体为含烯基的化合物和/或环氧化合物。
进一步地，光聚合单体为丙烯酸酯类化合物；优选地，光聚合单体选自环氧丙烯酸树脂低聚物、聚氨酯丙烯酸树脂低聚物和聚酯丙烯酸树脂低聚物组成的组中的一种或多种。
进一步地，按重量份计，涂料组合物还包括助剂，助剂选自溶剂、表面调节剂、增感剂、敏化剂、固化促进剂、光交联剂、光敏化剂、光敏树脂、分散助剂、填充剂、密合促进剂、抗氧化剂、紫外线吸收剂、抗絮凝剂、热聚合阻止剂、消泡剂、流平剂、表面活性剂和链转移剂组成的组中的一种或多种。
本申请又一方面还提供了一种油墨组合物，包括光引发剂、光聚合单体和颜料，光引发剂为具有式(I)所示结构的芴类光引发剂，光聚合单体为含烯基的化合物和/或环氧化合物。
进一步地，光聚合单体为丙烯酸酯类化合物；优选地，光聚合单体选自环氧丙烯酸树脂低聚物、聚氨酯丙烯酸树脂低聚物和聚酯丙烯酸树脂低聚物组成的组中的一种或多种。
进一步地，按重量份计，油墨组合物还包括助剂，助剂选自溶剂、表面调节剂、敏化剂、固化促进剂、光交联剂、增感剂、光敏化剂、光敏树脂、分散助剂、填充剂、密合促进剂、抗氧化剂、紫外线吸收剂、抗絮凝剂、热聚合阻止剂、消泡剂、流平剂、表面活性剂和链转移剂组成的组中的一种或多种。
进一步地，式(Ⅱ)中，链基基团为C1-C10的直链烷基、C1-C10的支链烷基或C4-C10的环烷基烷基。
进一步地，式(Ⅱ)中，Ar为苯基、甲基苯基、乙基苯基、氯苯基、溴苯基、甲氧基苯基、硝基苯基、氰基苯基、二苯硫醚基、吡啶基、噻吩基、呋喃基、2-甲基-噻吩基、3-甲基噻吩基、呋喃基、2-甲基-呋喃基或3-甲基呋喃基。
进一步地，R7为-C(＝O)C(＝O)O-R7’基团，芴类光引发剂具有如下式(Ⅴ)所示的结构：
Figure PCTCN2017099294-appb-000008
其中，R8具有n个对外连接键，且为C1-C60的直链烷基或支链烷基，或C1-C60的直链烷基或支链烷基中任意的碳或氢被氧、硫或苯基所取代；
A表示具有-(Q-CHR9)m-结构的重复单元，R9为氢、甲基或乙基，Q代表O或连接符，其中，连接符表示-(CHR9)m与O直接相连，m为1～6的整数；
n代表1～20的整数。
进一步地，式(Ⅴ)中，R8选自下列基团中的任意一种：
Figure PCTCN2017099294-appb-000009
Figure PCTCN2017099294-appb-000010
*CH2-CH2*、*CH2-CH2-CH2*、*CH2CH2CH2CH2*、
Figure PCTCN2017099294-appb-000011
Figure PCTCN2017099294-appb-000012
进一步地，式(Ⅴ)中，A选自-[(Q-CHR9)m]y-，其中R9为氢或甲基，m为1～3的整数，y代表1～9的整数。
进一步地，式(Ⅴ)中，n是1～8的整数，优选为1、2、3、4、5或6。
本申请的另一方面提供了一种包含式(Ⅱ)所示结构的芴类光引发剂的制备方法，制备方法包括：步骤S1，具有结构式A的原料a与具有结构式B的原料b发生傅克反应，得到具有结构式C的中间体c；可选的步骤S2，中间体c与具有结构式D的原料d发生傅克反应，得到具有结构式E的中间体e；以及可选的步骤S3，中间体e与具有结构式F的醇或多元醇发生酯交换反应，得到芴类光引发剂，其中，
结构式A为
Figure PCTCN2017099294-appb-000013
结构式B为
Figure PCTCN2017099294-appb-000014
其中X1为卤素，结构式C为
Figure PCTCN2017099294-appb-000015
结构式D为
Figure PCTCN2017099294-appb-000016
其中X2为卤素，结构式E为
Figure PCTCN2017099294-appb-000017
结构式F为R8(AOH)n。
进一步地，步骤S1和步骤S2的傅克反应在三氯化铝或氯化锌及溶剂存在下进行，优选步骤S1和步骤S2的傅克反应的反应温度各自独立地为-10～40℃。
进一步地，步骤S3在催化剂和阻聚剂的作用下发生酯交换反应，优选催化剂为一种或多种钛酸类化合物，更优选催化剂选自钛酸-2-乙基己酯、钛酸四甲酯、钛酸四异丙酯、钛酸四丁酯、钛酸四异丁酯、钛酸四(2-乙基己)酯组成的组中的一种或多种，优选阻聚剂选自对羟基苯甲醚、N,N-二乙基羟胺、对苯二酚、邻苯二酚、对叔丁基邻苯二酚、甲基氢醌、对甲氧基苯酚、吩噻嗪和三苯基膦组成的组中的任意一种。
进一步地，步骤S3中，中间体e与具有结构式F的醇或多元醇的摩尔比是n：1，优选催化剂的重量是物料总重量的3～10‰，更优选阻聚剂的重量是物料总重量的3～10‰，进一步优选酯交换反应的温度为70～130℃、反应时间为1～8h。
本申请的另一方面提供了一种光固化组合物，包括光引发剂，光引发剂为包含式(Ⅱ)所示结构的芴类光引发剂。
本申请的另一方面提供了一种包含式(Ⅱ)所示结构的芴类光引发剂在光固化领域的应用。
进一步地，应用包括涂料、油墨、粘合剂、彩色光阻、黑色矩阵、光间隔物、肋栅、干膜和/或半导体光刻胶中的应用。
应用本发明的技术方案，在现有的芴结构上引入新的基团，不仅增加了光引发剂的分子量，而且还提高了光引发剂的引发效率等相关性能。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
正如背景技术所描述的，现有的光引发剂存的性能较差的问题。为了解决上述技术问题，本发明提供了一种芴类光引发剂，芴类光引发剂具有式(I)所示的结构：
Figure PCTCN2017099294-appb-000018
其中，R1和R1’分别独立地选自氢、卤素、C1～C20的直链或支链烷基、C3～C8的环烷基、C2～C20的链烯基或C3～C8的环烷基取代的C1～C10的烷基；R2和R3分别独立地选自C1～C20的直链或支链烷基、C3～C8的环烷基、C3～C8的环烷基取代的C1～C10的烷基或C6～C20的芳基；或者，R2和R3相连形成C3～C8的环烷基；X为-A-(X’)n，其中A选自杂原子，杂原子为O、N或S，X’包括但不限于C1～C20的直链或支链烷基、C3～C20的环烷基、C3～C20的环烷基烷基或C4～C20的环烷基烷基，且X’中的碳原子中的一个或多个被杂原子取代，n为1或2；R4为羟基或者N-吗啉基；或者
芴类光引发剂包含式(Ⅱ)所示的结构：
Figure PCTCN2017099294-appb-000019
其中，R5、R6分别独立地选自氢原子、卤素和链基基团中的任意一种，链基基团为C1-C20的直链烷基、C1-C20的支链烷基或C1-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基和C2-C20的链烯基，或者所R5和R6以链基基团中的任意一种或两种成环，且链基基团中的-CH2-可任选地被-O-、-C(＝O)O-、卤素、苯基所取代；
Ar为含有芳香环或杂芳香环的取代基；以及与式(I)所示的基团的连接键相连的R7，所述R7为氢原子、-C(＝O)R7’或-C(＝O)C(＝O)O-R7’基团，其中，R7’表示取代或未被取代的C1-C40的直链、C1-C40的支链烷基、C1-C20的环烷基、C1-C40的链烯基、含有芳香环或杂芳香环的取代基，或者R7为-C(＝O)C(＝O)O-R7’基团，R7’基团为醇或多元醇通过酯交换反应而连接的基团。
上述两种芴类光引发剂均是在现有的芴结构上引入新的基团，不仅增加了光引发剂的分子量，而且还提高了光引发剂的引发效率等相关性能。
在具有式(I)所示的结构的芴类光引发剂中，由于含有杂原子(N、S、O)的基团在长波长下具有吸收峰，因而在芴类化合物的侧链上引入含杂原子的取代基，有利于使芴类化合物的吸收波长发生红移，这能够提高该类化合物的引发效率。这使得将含有杂原子取代基的芴类化合物作为光引发剂时，光引发剂在长波长的照射下具有较高的量子吸收率。进一步地，当基团X中的碳原子中的一个或多个被杂原子取代或者和其他取代基中含有杂原子时，有利于进一步提高芴类化合物光引发剂对长波长的量子吸收效率。
在包含式(Ⅱ)所示的基团的芴类光引发剂中，芴类化合物的侧链上引入小分子基团，一方面提高了芴类化合物的分子量，另一方面还使得引发剂的引发效率与耐黄变、不易迁移、气味性低、溶解性等问题能够得到较好的改善和均衡，并且通过对其感光性组合物进行应用研究，发现将该芴类引发剂应用于目前常规的光固化配方就能够很好的适用于UV-LED光源的固化。
以下将与式(I)所示的芴类光引发剂有关的技术方案作为第一实施方式，将与包含式(Ⅱ)所示结构的芴类光引发剂相关的技术方案称为第二实施方式
在第一实施方式中，式(I)中，具有上述取代基的芴类光引发剂对长波长具有较高的量子吸收效率。优选地，R1和R1’独立地选自氢、卤素、C1～C10的直链或支链烷基、或C4～C10的环烷基烷基；优选地，R1和R1’独立地包括但不限于氢、C1～C4的直链或支链烷基、或C3～C6的环烷基取代的C1～C3的烷基。
优选地，R2和R3分别独立地选自C1～C10的直链或支链烷基或C4～C10的环烷基烷基；或者R2和R3相连形成C3～C10的环烷基。优选地，R2和R3分别独立地选自C1～C4的直链或支链烷基或C4～C8的环烷基烷基；或者R2和R3相连形成C3～C6的环烷基。
优选地，X’包括但不限于甲基、乙基、环己基或环戊基。
上述式(I)中，当基团R1、R2和R3及X中的碳原子数较少时，有利于提高光引发剂的结构稳定性，同时具有上述取代基团的芴类多官能团化合物也更易合成。
在一种优选的实施例中，式(I)所示的芴类光引发剂包括但不限于以下有机物中的一种或几种
Figure PCTCN2017099294-appb-000020
Figure PCTCN2017099294-appb-000021
Figure PCTCN2017099294-appb-000022
本申请的另一方面还提供了一种式(I)所示的芴类光引发剂的制备方法，制备方法包括：溴代反应：将原料a、溴代试剂及第一有机溶剂发生溴代反应，得到中间产物b，原料a具有式(Ⅲ)所示的结构，
Figure PCTCN2017099294-appb-000023
中间产物b具有式(Ⅳ)结构，
Figure PCTCN2017099294-appb-000024
取代反应：采用中间产物b、取代试剂及第二有机溶剂发生取代反应，得到芴类光引发剂。
按照本领域技术人员常规所理解的，式(Ⅲ)和式(Ⅳ)所示的结构式中的取代基团R1、R2、R3、R4及X与式(I)中相应基团的结构相同。上述制备方法的化学反应过程如下：
(1)溴代反应：
Figure PCTCN2017099294-appb-000025
(2)取代反应：
Figure PCTCN2017099294-appb-000026
上述制备方法中，原料a通过专利号为2015109373280的专利公开的合成方法制得，其它原料均是现有技术中的已知化合物，可通过商业购得或者经已知的合成方法简便地制备而成。并且，通过上述两个步骤可得到本申请的芴类光引发剂，步骤(1)和(2)中涉及的反应都是现有技术中成熟常用的反应，因此，制备过程易于实现和控制。
本申请提供的制备方法中，溴代反应和取代反应的反应条件可以参考现有技术常规的溴代反应和取代反应实施。本申请针对上述底物，优选地，溴代试剂包括但不限于N-溴代丁二酰亚胺、氢溴酸、溴素.和二溴海因组成的组中的一种或多种；优选地，取代试剂为XONa，X为-A-(X’)n，其中A选自杂原子，杂原子选自O、N或S，X’选自C1～C20的直链或支链烷基、C3～C8的环烷基、C3～C8的环烷基取代的C1～C10的烷基，或者X’中的碳原子中的一个或多个被上述杂原子取代，n为1或2。
优选地，反应体系为优选极性溶剂体系，反应可选择性地加入路易斯酸作为催化剂，第一有机溶剂特别优选碳酸丙烯酯；优选地，溴代反应的温度为10～60℃，优选为25℃。
取代反应中使用的第二有机溶剂常可以采用现有技术中不参与反应的常用有机溶剂，在一种优选的实施方式中，第二有机溶剂包括但不限于二氯甲烷、二氯乙烷、苯和二甲苯组成的组中的一种或多种。
为了更好地，理解本申请提供的芴类光引发剂的性能，本申请对其应用进行进一步地介绍。
本申请的一方面提供了一种涂料组合物，包括光引发剂和光聚合单体，光引发剂为式(I)所示的芴类光引发剂，光聚合单体为含烯基的化合物和/或环氧化合物。
上述涂料组合物的固化机理为：在光照下，光引发剂被激活；然后通过被激活的引发剂使光聚合单体进行聚合，进而固化成膜。
由于本申请提供的式(I)所示的芴类光引发剂对长波长的量子吸收效率较高，因而在光固化过程中，含有上述光引发剂的涂料组合物具有固化能量低，固化效率高等优点。
需要说明的是，上述涂料组合物在实际的使用过程中，可以将本申请提供的光引发剂与本领域常用的引发剂进行复配使用。
在一种优选的实施例中，光聚合单体为丙烯酸酯类化合物；优选地，光聚合单体包括但不限于环氧丙烯酸树脂低聚物、聚氨酯丙烯酸树脂低聚物和聚酯丙烯酸树脂低聚物组成的组中的一种或多种。
更优选地，上述光聚合单体包括但不限于(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸2-羟基丁酯、(甲基)丙烯酸2-苯氧基-2-羟基丙酯、邻苯二甲酸2-(甲基)丙烯酰基氧基-2-羟基丙酯、甘油单(甲基)丙烯酸酯、(甲基)丙烯酸四氢糠基酯、二甲基氨基(甲基)丙烯酸酯、(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、邻苯二甲酸衍生物的(甲基)丙烯酸半酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、1,12-十二烷二醇二(甲基)丙烯酸酯、乙氧基化己二醇二(甲基)丙烯酸酯、三环癸烷二甲醇二(甲基)丙烯酸酯、(甲基)丙烯酸2-羟基-3-(甲基)丙烯酰氧基丙酯、二季戊四醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、乙氧基化新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚(乙烯-丙烯)二醇二(甲基)丙烯酸酯、聚1,4-丁二醇二(甲基)丙烯酸酯、乙氧基化双酚A二(甲基)丙烯酸酯、丙氧基化双酚A二(甲基)丙烯酸酯、丙氧基化乙氧基化双酚A二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、2,2-双(4-(甲基)丙烯酰氧基二乙氧基苯基)丙烷、2,2-双(4-(甲基)丙烯酰氧基聚乙氧基苯基)丙烷、(甲基)丙烯酸2-羟基-3-(甲基)丙烯酰基氧基丙酯、乙二醇二缩水甘油醚二(甲基)丙烯酸酯、二乙二醇二缩水甘油醚二(甲基)丙烯酸酯、邻苯二甲酸二缩水甘油酯二(甲基)丙烯酸酯、甘油三丙烯酸酯、甘油聚缩水甘油醚聚(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯(即，甲苯二异氰酸酯)、三甲基-1,6-己二异氰酸酯和1,6-己二异氰酸酯等与(甲基)丙烯酸2-羟基乙酯的反应物、亚甲基双(甲基)丙烯酰胺、(甲基)丙烯酰胺亚甲基醚、多元醇与N-羟甲基(甲基)丙烯酰胺的缩合物、1,3,5-三丙烯酰基六氢-1,3,5-三嗪、2,4,6-三氧代六氢-1,3,5-三嗪-1,3,5-三乙醇三丙烯酸酯和2,4,6-三氧代六氢-1,3,5-三嗪-1,3,5-三乙醇二丙烯酸酯，组成的组中的一种或多种。
在一种优选的实施例中，按重量份计，涂料组合物还包括助剂，助剂包括但不限于溶剂、表面调节剂、增感剂、敏化剂、固化促进剂、光交联剂、光敏化剂、光敏树脂、分散助剂、填充剂、密合促进剂、抗氧化剂、紫外线吸收剂、抗絮凝剂、热聚合阻止剂、消泡剂、流平剂、表面活性剂和链转移剂组成的组中的一种或多种。助剂的添加有利于提高涂料组合物的综合性能。
进一步的，出于成本等因素的考虑，本发明所述的光引发剂还可与其他光引发剂配合使用。
本申请的又一方面还提供了一种油墨组合物，包括光引发剂、光聚合单体和颜料，光引发剂为式(I)所示的芴类光引发剂，光聚合单体为含烯基的化合物和/或环氧化合物。
上述油墨组合物的固化机理为：在光照下，光引发剂被激活；然后通过被激活的引发剂使光聚合单体进行聚合，进而固化成膜。
由于本申请提供的式(I)所示的芴类光引发剂对长波长的量子吸收效率较高，因而在光固化过程中，含有上述光引发剂的油墨组合物具有固化能量低，固化效率高等优点。
需要说明的是，上述油墨组合物在实际的使用过程中，可以将本申请提供的光引发剂与本领域常用的引发剂进行复配使用。
在一种优选的实施例中，光聚合单体为丙烯酸酯类化合物；优选地，光聚合单体包括但不限于环氧丙烯酸树脂低聚物、聚氨酯丙烯酸树脂低聚物和聚酯丙烯酸树脂低聚物组成的组中的一种或多种。
更优选地，光聚合单体包括但不限于上述光聚合单体包括但不限于(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸2-羟基丁酯、(甲基)丙烯酸2-苯氧基-2-羟基丙酯、邻苯二甲酸2-(甲基)丙烯酰基氧基-2-羟基丙酯、甘油单(甲基)丙烯酸酯、(甲基)丙烯酸四氢糠基酯、二甲基氨基(甲基)丙烯酸酯、(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、邻苯二甲酸衍生物的(甲基)丙烯酸半酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、1,12-十二烷二醇二(甲基)丙烯酸酯、乙氧基化己二醇二(甲基)丙烯酸酯、三环癸烷二甲醇二(甲基)丙烯酸酯、(甲基)丙烯酸2-羟基-3-(甲基)丙烯酰氧基丙酯、二季戊四醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、乙氧基化新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚(乙烯-丙烯)二醇二(甲基)丙烯酸酯、聚1,4-丁二醇二(甲基)丙烯酸酯、乙氧基化双酚A二(甲基)丙烯酸酯、丙氧基化双酚A二(甲基)丙烯酸酯、丙氧基化乙氧基化双酚A二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、2,2-双(4-(甲基)丙烯酰氧基二乙氧基苯基)丙烷、2,2-双(4-(甲基)丙烯酰氧基聚乙氧基苯基)丙烷、(甲基)丙烯酸2-羟基-3-(甲基)丙烯酰基氧基丙酯、乙二醇二缩水甘油醚二(甲基)丙烯酸酯、二乙二醇二缩水甘油醚二(甲基)丙烯酸酯、邻苯二甲 酸二缩水甘油酯二(甲基)丙烯酸酯、甘油三丙烯酸酯、甘油聚缩水甘油醚聚(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯(即，甲苯二异氰酸酯)、三甲基-1,6-己二异氰酸酯和1,6-己二异氰酸酯等与(甲基)丙烯酸2-羟基乙酯的反应物、亚甲基双(甲基)丙烯酰胺、(甲基)丙烯酰胺亚甲基醚、多元醇与N-羟甲基(甲基)丙烯酰胺的缩合物、1,3,5-三丙烯酰基六氢-1,3,5-三嗪、2,4,6-三氧代六氢-1,3,5-三嗪-1,3,5-三乙醇三丙烯酸酯和2,4,6-三氧代六氢-1,3,5-三嗪-1,3,5-三乙醇二丙烯酸酯，组成的组中的一种或多种。
在一种优选的实施例中，按重量份计，油墨组合物还包括助剂，助剂包括但不限于溶剂、表面调节剂、增感剂、敏化剂、固化促进剂、光交联剂、光敏化剂、光敏树脂、分散助剂、填充剂、密合促进剂、抗氧化剂、紫外线吸收剂、抗絮凝剂、热聚合阻止剂、消泡剂、流平剂、表面活性剂和链转移剂组成的组中的一种或多种。助剂的添加有利于提高油墨组合物的综合性能。
在第二实施方式中，式(Ⅱ)中，链基基团为C1-C10的直链烷基、C1-C10的支链烷基或C4-C10的环烷基烷基。
优选地，式(Ⅱ)中，Ar为苯基、甲基苯基、乙基苯基、氯苯基、溴苯基、甲氧基苯基、硝基苯基、氰基苯基、二苯硫醚基、吡啶基、噻吩基、呋喃基、2-甲基-噻吩基、3-甲基噻吩基、呋喃基、2-甲基-呋喃基或3-甲基呋喃基。
优选地，R7为-C(＝O)C(＝O)O-R7’基团，芴类光引发剂具有如下式(Ⅴ)所示的结构：
Figure PCTCN2017099294-appb-000027
其中，R8具有n个对外连接键，且为C1-C60的直链烷基或支链烷基，或C1-C60的直链烷基或支链烷基中任意的碳或氢被氧、硫或苯基所取代；
A表示具有-(Q-CHR9)m-结构的重复单元，R9为氢、甲基或乙基，Q代表O或连接符，其中，连接符表示-(CHR9)m与O直接相连，m为1～6的整数；n代表1～20的整数。
具有上述结构式(Ⅴ)的芴类光引发剂不仅由于其分子量更大，使得其迁移性降低，而且其还具有溶解性能更为优异的特点。
此外，具有上述式(Ⅱ)所示基团的光引发剂和式(Ⅴ)所示结构的光引发剂的吸收波段在330-400nm之间，几乎无气味，在(甲基)丙烯酸树脂及乙烯基醚类化合物均有很好的溶解性，应用后不易迁移，耐黄变。
此外，式(Ⅴ)中，R8选自下列基团中的任意一种时，结构更稳定：
Figure PCTCN2017099294-appb-000028
Figure PCTCN2017099294-appb-000029
*CH2-CH2*、*CH2-CH2-CH2*、*CH2CH2CH2CH2*、
Figure PCTCN2017099294-appb-000030
优选地，式(Ⅴ)中，A选自-[(Q-CHR9)m]y-，其中R9为氢或甲基，m为1～3的整数，y代表1～9的整数。
优选地，式(Ⅴ)中，n是1～8的整数，优选为1、2、3、4、5或6。
在一种优选的实施例中，具有上述式(Ⅱ)所示基团的光引发剂的制备方法，制备方法包括：步骤S1，具有结构式A的原料a与具有结构式B的原料b发生傅克反应，得到具有结构式C的中间体c；可选的步骤S2，中间体c与具有结构式D的原料d发生傅克反应，得到具有结构式E的中间体e；以及可选的步骤S3，中间体e与具有结构式F的醇或多元醇发生酯交换反应，得到芴类光引发剂，其中，
结构式A为
Figure PCTCN2017099294-appb-000031
结构式B为
Figure PCTCN2017099294-appb-000032
其中X1为卤素，结构式C为
Figure PCTCN2017099294-appb-000033
结构式D为
Figure PCTCN2017099294-appb-000034
其中X2为卤素，结构式E为
Figure PCTCN2017099294-appb-000035
结构式F为R8(AOH)n。
按照本领域技术人员常规所理解的，前述各结构式中的R5、R6、Ar、R7、R7’和R8均和结构式(Ⅱ)及结构式(Ⅴ)中所表示的相应基团相同。
上述制备方法的化学反应过程如下：
Figure PCTCN2017099294-appb-000036
通过上述一个步骤或两个步骤或三个步骤均可得到不同的本申请的芴类光引发剂，且各步骤采用的反应均为现有技术中成熟常用的反应，因此，制备过程易于实现和控制。其中，当R8(AOH)n中的n为大于1的整数时，多个中间体E和R8(AOH)n同时发生酯交换反应，进而得到上述产物。
前述步骤S1和步骤S2的傅克反应在三氯化铝或氯化锌及溶剂存在下进行，优选步骤S1和步骤S2的傅克反应的反应温度各自独立地为-10～40℃。前述两个步骤中的傅克反应条件可以相同也可以不同，溶剂可以相同或者不同，其中溶剂可以采用现有技术中不参与反应的常用有机溶剂，比如二氯甲烷、二氯乙烷、甲苯、苯、二甲苯，当两个步骤采用相同的溶剂时，步骤S1完成后可不进行提纯而继续进行步骤S2的傅克反应。
前述的步骤S3的酯交换反应可以在步骤S2完成的体系中直接进行或者提纯后重新置于溶剂中进行均可实现，且本申请对步骤S3的溶剂没有特别的限定，只要能够溶解各反应试剂且对反应无不良影响即可，比如甲苯、苯、二甲苯。
为了加快反应，并尽可能多地得到目标产物减少副产物的产生，优选上述步骤S3在催化剂和阻聚剂的作用下发生酯交换反应，优选催化剂为一种或多种钛酸类化合物，更优选催化剂选自钛酸-2-乙基己酯、钛酸四甲酯、钛酸四异丙酯、钛酸四丁酯、钛酸四异丁酯、钛酸四(2-乙基己)酯组成的组中的一种或多种，优选阻聚剂选自对羟基苯甲醚、N,N-二乙基羟胺、对苯二酚、邻苯二酚、对叔丁基邻苯二酚、甲基氢醌、对甲氧基苯酚、吩噻嗪和三苯基膦组成的组中的任意一种。
此外，为了在保证目标产物产量的基础上节约原料，优选上述步骤S3中，中间体e与具有结构式F的醇或多元醇的摩尔比是n：1，优选催化剂的重量是物料总重量的3～10‰，更优选阻聚剂的重量是物料总重量的3～10‰，进一步优选酯交换反应的温度为70～130℃、反应时间为1～8h。
在本申请另一种典型的实施方式中，提供了一种光固化组合物，包括光引发剂，该光引发剂为包含式(Ⅱ)所示结构的芴类光引发剂。
由于本申请的包含式(Ⅱ)所示结构的芴类光引发剂的引发效率与耐黄变、不易迁移、气味性低、溶解性等问题能够相对于现有技术的二苯甲酮或苯甲酰甲酸酯类引发剂得到较好的改善和均衡，因此，其应用在组合物中时能够使组合物形成的结构各项性能更稳定，且可以使该光固化组合物在UV-LED光源的照射下即可固化，因此节约了能源更符合环保要求。
在本申请另一种典型的实施方式中，提供了一种包含式(Ⅱ)所示结构的芴类光引发剂在光固化领域的应用。
由于本申请提供的包含式(Ⅱ)所示结构的芴类光引发剂使具有其的光固化组合物在UV-LED光源的照射下即可固化，因此使含有其的应用节约了能源更符合环保要求。优选上述应用包括涂料、油墨、粘合剂、彩色光阻、黑色矩阵、光间隔物、肋栅、干膜和/或半导体光刻胶中的应用。
以下结合具体实施例对本发明作进一步详细描述，这些实施例不能理解为限制本发明所要求保护的范围。
具体实施方式
以下将结合具体实施例对本发明作进一步详细说明，但不应将其理解为对本发明保护范围的限制。
(一)与具有式(I)所示的芴类光引发剂相关的制备方案及性能评价。
1、光引发剂的制备。
制备实施例1
(1)取代反应：中间体1a的制备。
向500mL的四口烧瓶中加入36.5g原料1a、N-溴代琥珀酰亚胺18g、碳酸丙烯酯100mL，室温搅拌，液相跟踪反应至原料不再发生变化，接着将物料缓慢倒入1000g去离子水中，边加边搅拌，大量固体析出，抽滤，水洗，无水乙醇得37.2g中间体1a。合成路线如下：
Figure PCTCN2017099294-appb-000037
该中间产物1a的结构表征数据如下所示：1H-NMR(CDCl3，500MHz)：0.9146～1.0002(6H，t)，1.2878～1.3328(8H，m)，1.4844(6H，s)，1.8754～2.1045(5H,m)，7.5801～8.0837(6H,m)。
MS(m/z):444(M+1)+。
(2)取代反应：化合物1的制备。
向500mL四口烧瓶中加入中间体1a 22.2g、甲醇50mL，甲醇钠14.0g，室温搅拌，液相跟踪反应至原料量不再发生变化，接着将反应液倒入500mL去离子水中，产物析出，水洗，甲醇重结晶，得白色固体15.5g，即化合物1。合成路线如下：
Figure PCTCN2017099294-appb-000038
化合物1的结构表征数据如下所示：1H-NMR(CDCl3，500MHz)：1.6642(6H,s)，2.0629(6H，s)，7.3080～7.8346(7H，m)；MS(m/z):3:95(M+1)+。
制备实施例2
步骤取代反应：中间体2a的制备。
向500mL的四口烧瓶中加入35.0g原料2a、N-溴代琥珀酰亚胺18g、碳酸丙烯酯100mL，室温搅拌，液相跟踪反应至原料不再发生变化，接着将物料缓慢倒入1000g去离子水中，边加边搅拌，大量固体析出，抽滤，水洗，无水乙醇得36.8g中间体2a。合成路线如下：
Figure PCTCN2017099294-appb-000039
该中间产物2a的结构表征数据如下所示：1H-NMR(CDCl3，500MHz)：1.3629(6H，s)，1.6578(6H，s)，2.3899-2.3835(4H，t)，3.6703-3.6801(4H,t)，7.5481-7.8997(6H,m)。
MS(m/z):429(M+1)+。
(2)取代反应：化合物2的制备。
向500mL四口烧瓶中加入中间体2a 21.4g、二甲苯50mL，甲醇钠14.0g，100℃加热回流，减压条件下反应(1Mpa)，液相跟踪反应至原料量不再发生变化，接着将反应液倒入500mL去离子水中，产物析出，水洗，甲醇重结晶，得白色固体16.7g，即化合物2。合成路线如下：
Figure PCTCN2017099294-appb-000040
化合物2的结构表征数据如下所示：
1H-NMR(CDCl3，500MHz)：1.3702(6H，s)，1.6695(6H,s)，2.3693～2.3742(4H，t)，2.8994～2.9347(4H，m)，3.6548～3.6775(8H，m)，6.8303～7.9403(6H，m)；
MS(m/z):435(M+1)+。
制备实施例3至20
可选用不同的原料，参照实施例1或2的合成方法，制备结构不同的化合物3至20，且化合物3至20的结构见表1。
表1
Figure PCTCN2017099294-appb-000041
Figure PCTCN2017099294-appb-000042
Figure PCTCN2017099294-appb-000043
Figure PCTCN2017099294-appb-000044
2、光固化组合物的制备
为了进一步验证上述芴类光引发剂的性能，将其制成涂料组合物或油墨组合物后进行性能评价，涂料组合物的组成见表2和3，油墨组合物的组成见表4和5。
表2
Figure PCTCN2017099294-appb-000045
Figure PCTCN2017099294-appb-000046
表3
Figure PCTCN2017099294-appb-000047
表4
Figure PCTCN2017099294-appb-000048
Figure PCTCN2017099294-appb-000049
表5
Figure PCTCN2017099294-appb-000050
实施例1至28及对比例1至4中使用的原料：
EA为环氧丙烯酸树脂，型号FB9801；PUA为聚氨酯丙烯酸树脂，型号MR-1305；PEA为聚酯丙烯酸树脂，型号TSG-2305；TPGDA为二缩三丙二醇二丙烯酸酯；TMPTA为三丙烯酸丙烷三甲醇酯；黄颜料为联苯胺黄YH1200；化合物A具有式(Ⅵ)所示的结构：
Figure PCTCN2017099294-appb-000051
3、性能评价
成膜：参照表2至5中所示的组成配置原料，将上述原料在暗室中搅拌均匀。将搅拌好的原料置于PET膜上，采用涂布棒涂布成膜，膜厚约25μm。根据上述方法依次获得样片1至34(对应实施例1至28的组合物)及对比片1至4(对应对比例1至4的组合物)。将涂有涂层的PET膜置于履带式曝光机(RW-UV.70201，波长300～500nm)中进行曝光，曝光单次所接受的能量为80mJ/cm2，记录各组配方固化完全所需的最低能量。
性能评价：参照漆膜干燥时间测试标准GB/T 1728-1979中的指触法来评价漆膜表面的固化速度，即用手指轻触涂层，以表面滑爽，不粘手表示表面固化完全；采用指抠法测量底部固化速度，即用指甲轻抠涂层，以无脱落，无露底现象表示底层固化完全。评价结果见表6。
表6
Figure PCTCN2017099294-appb-000052
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：本发明所述的芴类化合物及其组合物在固化效率方面具有明显优势，固化完全所需的能量明显低于具有相同引发剂结构的组合物。
(二)与包含式(Ⅱ)所示基团的芴类光引发剂相关的制备方案及性能评价。
制备实施例
(1)产物1a的制备：
Figure PCTCN2017099294-appb-000053
向1000mL四口烧瓶中加入原料1a83g、二氯甲烷300mL、三氯化铝67g后搅拌形成第一混合体系，冰水浴将该第一混合体系降至0℃，并向该第一混合体系中滴加77g原料1b与50mL二氯甲烷的形成的混合溶液，控温10℃以下，约2h滴加完，液相跟踪反应至不再发生变化，得到中间体1a的产物溶液，接着将该产物溶液缓慢倒入400g冰水与50mL浓盐酸(37％)配成的稀盐酸中，边加边搅拌，产物溶液加入完毕后倒入分液漏斗中，利用分液漏斗分出下层二氯甲烷层，并用50mL二氯甲烷继续清洗水层后再次分出下层二氯甲烷层，合并两次得到的二氯甲烷层，用5％的碳酸氢钠水溶液(每次150mL，共3次)清洗合并后的二氯甲烷层，接着水洗二氯甲烷层至pH呈中性，用50g无水硫酸镁干燥二氯甲烷层，并过滤干燥后的二氯甲烷层，旋蒸过滤得到的二氯甲烷产物溶液后利用甲醇重结晶，所得结晶在80℃烘箱干燥2h，得135g产物1a，纯度98％，MS(m/z):285(M+1)+，1H-NMR(CDCl3，500MHz)：2.3540(3H，s)，3.8721(2H，s)，7.1701-7.8411(11H，m)。
进一步的，可选用不同的原料a、b进行傅克反应，从而得到不同结构的产物a，但不限于如此，见表7。
表7
Figure PCTCN2017099294-appb-000054
Figure PCTCN2017099294-appb-000055
Figure PCTCN2017099294-appb-000056
(2)产物1b的制备：
Figure PCTCN2017099294-appb-000057
向500mL四口烧瓶中加入产物1a85g、二氯甲烷100mL后室温搅拌，继续向该四口烧瓶滴加原料1c38g与50mL二氯甲烷形成的混合溶液，控温30℃以下，约1h滴加完，滴加完继续搅拌2h，液相跟踪反应至完全，得到含有产物1b的产物体系，接着将该产物体系缓慢倒入400g冰水与50mL浓盐酸(37％)配成的稀盐酸中，边加边搅拌，产物体系完全加入后倒入分液漏斗中，利用分液漏斗分出下层二氯甲烷层，并用50mL二氯甲烷继续清洗水层再次分出下层二氯甲烷层，合并两次得到的二氯甲烷层，用5％的碳酸氢钠水溶液(每次100mL，共3次)清洗合并后二氯甲烷层，接着水洗二氯甲烷层至pH呈中性，用50g无水硫酸镁干燥二氯甲烷层，并过滤干燥后的二氯甲烷层，旋蒸过滤得到的二氯甲烷产物溶液后利用甲醇重结晶，所得结晶在80℃烘箱干燥2h，得98g产物1b，纯度98％，MS(m/z):385(M+1)+，1H-NMR(CDCl3，500MHz)：1.2996-1.3025(3H,m)，2.3535(3H，s)，3.8757(2H，s)，4.19543-4.2103(2H，m)7.1686-8.0943(10H，m)。
进一步的，可选用不同的产物a、原料c进行傅克反应，从而得到不同结构的产物b，但不限于如此，见表8(表8中的化合物按照顺序编号，但是不代表得到表8中的化合物是以对应编号的表7中的化合物为原料制备而成的，本领域技术人员可以根据前述说明和现有技术选用合适的产物a和原料c进行傅克反应得到相应的产物b)。
表8
Figure PCTCN2017099294-appb-000058
Figure PCTCN2017099294-appb-000059
Figure PCTCN2017099294-appb-000060
(3)化合物1c的制备：
Figure PCTCN2017099294-appb-000061
向500mL的四口烧瓶中加入中间体1b 77g、原料1d100mL、钛酸四异丙酯0.1g、对羟基苯甲醚0.1g，加热四口烧瓶并控制其温度在90～100℃下同时搅拌该四口烧瓶内加入的物质形成反应液，随后对反应液进行减压蒸馏，蒸出反应产生的乙醇，直至无乙醇蒸出，趁热过滤，得淡黄色固体93g，即为产物1c，MS(m/z):483(M+1)+，1H-NMR(CDCl3，500MHz)：0.9655-0.97231(3H，t)，1.2897-1.3305(12H,m)，1.5677-1.5708(2H,m)，2.3546(3H，s)，3.8777(2H，s)，4.1607-4.1702(2H，t)7.1659-8.0902(10H，m)。
进一步的，可选用不同的产物b、原料d进行酯交换反应，从而得到不同结构的产物c，但不限于如此，见表9(表9中的化合物按照顺序编号，但是不代表得到表9中的化合物是以对应编号的表8中的化合物为原料制备而成的，本领域技术人员可以根据前述说明和现有技术选用合适的产物b和原料d进行酯交换反应得到相应的产物c)。
表9
Figure PCTCN2017099294-appb-000062
Figure PCTCN2017099294-appb-000063
Figure PCTCN2017099294-appb-000064
Figure PCTCN2017099294-appb-000065
Figure PCTCN2017099294-appb-000066
Figure PCTCN2017099294-appb-000067
Figure PCTCN2017099294-appb-000068
Figure PCTCN2017099294-appb-000069
Figure PCTCN2017099294-appb-000070
Figure PCTCN2017099294-appb-000071
性能评价
通过配制示例性可辐射固化组合物，对本发明式(I)及式(Ⅱ)所示光引发剂及同样配方下传统二苯甲酮类及苯甲酰甲酸酯类的引发剂在油墨制备中的应用性能进行评价。
选用不同的可自由基固化所需的单体或低聚物，根据需要添加适当比例的增感剂、着色剂、分散剂、分散增效剂、表面活性剂或阻聚剂等，制备可固化墨水。
可辐射固化组合物的制备：
根据表10的配方制备可辐射固化组合物，选用常用的二苯甲酮类及甲酰甲酸酯类的引发剂和本发明所述的光引发剂进行对比，重量％(wt％)基于可辐射固化组合物的总重量：
表10
Figure PCTCN2017099294-appb-000072
Figure PCTCN2017099294-appb-000073
评价方法：
<感度测试>
将光固化组合物在黄光灯下搅拌，取料于PET模板上滚涂成膜,形成膜厚约20μm的涂膜，采用履带式曝光，附上掩膜板，分别采用高压汞灯(曝光机型号RW-UV70201，波长200-500nm，光强100mW/cm2)及LED灯(蓝谱里克LP300w，波长395nm、光强100mW/cm2)进行辐射，以涂膜完全固化所需通过履带的次数来评价，测试结果见表11。
<耐黄变性评价>
将上述高压汞灯下制得的固化膜采用RW-UV.2BP紫外老化试验箱进行老化实验，光源为高压汞灯(主波长365nm，整机功率：约2.2KW)，连续照射固化膜6h，观察固化膜的黄变情况，按照以下标准进行评价，见表11。
◇：无色透明，表面光滑，表示具有很好的耐黄变性能；
□：微黄或表面有发粘，表示耐黄变性能不理想；
◆：表面发黄或粘度增大，表示易黄变。
<气味性及迁移性评价>
称取同样质量上述光固化组合物高压汞灯下制得的固化膜，通过扇闻法对其气味性进行评价，接着剪碎后放入同样体积的甲醇溶液中，室温密封浸泡24h，液相(流动相甲醇/水＝80/20)检测甲醇溶液中是否有引发剂的存在，按照以下标准进行评价：
①气味性：
◇没有气味；
◆有气味。
②迁移性：
◇：未检测到引发剂的存在，表明不易迁移；
◆：检测到有引发剂存在，表明迁移性有待改善。
表11
Figure PCTCN2017099294-appb-000074
从表11的评价结果可以看出，在其他组分相同的情况下，本发明的芴类光引发剂不仅在高压汞灯下具有较高的感度，在UV-LED光源下高度也比较理想，而现有的二苯甲酮类及苯甲酰甲酸酯类光引发剂在UV-LED光源下感度则表现出明显的不足；并且通过耐黄变实验及迁移性实验可以看出，本发明所述的芴类光引发剂，具有很好的耐黄变性能、溶解性及气味低、不易迁移的特点。
综上所述，本申请中具有式(Ⅱ)所示基团的芴类光引发剂及式(Ⅴ)所示结构的芴类光引发剂在应用在光固化领域，能够表现出非常优异的应用性能，具有广阔的应用前景。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有光引发剂或增感剂配合使用、树脂的替换等各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (29)

  1. 一种芴类光引发剂，其特征在于，所述芴类光引发剂具有式(I)所示的结构，或者，所述芴类光引发剂包含式(II)所示结构；
    Figure PCTCN2017099294-appb-100001
    其中，所述式(I)中，
    所述R1和所述R1’分别独立地选自氢、卤素、C1～C20的直链或支链烷基、C3～C8的环烷基、C2～C20的链烯基或C3～C8的环烷基取代的C1～C10的烷基；
    所述R2和所述R3分别独立地选自C1～C20的直链或支链烷基、C3～C8的环烷基、C3～C8的环烷基取代的C1～C10的烷基、C6～C20的芳基；或者，所述R2和所述R3相连形成C3～C8的环烷基；
    所述X为-A-(X’)n，其中A选自杂原子，所述杂原子选自O、N或S，X’选自C1～C20的直链或支链烷基、C3～C8的环烷基、C3～C8的环烷基取代的C1～C10的烷基，或者所述X’中的碳原子中的一个或多个被所述杂原子取代，n为1或2；
    所述R4为羟基或者N-吗啉基；
    或者
    所述式(II)中，
    所述R5、所述R6分别独立地选自氢原子、卤素和链基基团中的任意一种，所述链基基团为C1-C20的直链烷基、C1-C20的支链烷基或C1-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基和C2-C20的链烯基，或者所述R5和R6以所述链基基团中的任意一种或两种成环，且所述链基基团中的-CH2-可任选地被-O-、-C(＝O)O-、卤素、苯基所取代；
    Ar为含有芳香环或杂芳香环的取代基；
    以及与所述式(II)所示的基团的连接键相连的R7，所述R7为氢原子、-C(＝O)R7’或-C(＝O)C(＝O)O-R7’基团，其中，所述R7’表示取代或未被取代的C1-C40的直链、C1-C40的支链烷基、C1-C20的环烷基、C1-C40的链烯基、含有芳香环或杂芳香环的取代基，或者所述R7为-C(＝O)C(＝O)O-R7’基团，所述R7’基团为醇或多元醇通过酯交换反应而连接的基团。
  2. 根据权利要求1所述的芴类光引发剂，其特征在于，所述式(I)中，所述R1和所述R1’分别独立地选自氢、卤素、C1～C10的直链或支链烷基、C3～C8的环烷基、或C3～C8的环烷基取代的C1～C10的烷基；
    优选地，所述R1和所述R1’分别独立地选自氢、C1～C4的直链或支链烷基、或C3～C6环烷基取代的C1～C3烷基。
  3. 根据权利要求1所述的芴类光引发剂，其特征在于，所述式(I)中，所述R2和所述R3分别独立地选自C1～C10的直链或支链烷基、C3～C8环烷基、或C3～C8环烷基取代的C1～C10的烷基；或者R2和所述R3相连形成C3～C10的环烷基；
    优选地，所述R2和所述R3分别独立地选自C1～C4的直链或支链烷基或C4～C8的环烷基烷基；或者所述R2和所述R3相连形成C3～C6的环烷基。
  4. 根据权利要求1所述的芴类光引发剂，其特征在于，所述式(I)中，所述X’选自甲基、乙基、环己基或环戊基。
  5. 根据权利要求1所述的芴类光引发剂，其特征在于，所述式(I)所示的芴类光引发剂选自以下化合物中的一种或多种：
    Figure PCTCN2017099294-appb-100002
    Figure PCTCN2017099294-appb-100003
    Figure PCTCN2017099294-appb-100004
  6. 一种权利要求1至5中任一项所述的具有式(I)所示结构的芴类光引发剂的制备方法，其特征在于，所述制备方法包括：
    溴代反应:将原料a、溴代试剂及第一有机溶剂发生溴代反应，得到中间产物b，所述原料a具有式(Ⅲ)所示的结构，
    Figure PCTCN2017099294-appb-100005
    所述中间产物b具有式(Ⅳ)结构，
    Figure PCTCN2017099294-appb-100006
    取代反应：采用所述中间产物b、取代试剂及第二有机溶剂发生取代反应，得到所述芴类光引发剂，
    其中所述R1和所述R1’分别独立地选自氢、卤素、C1～C20的直链或支链烷基、C3～C8的环烷基、C2～C20的链烯基或C3～C8环烷基取代的C1～C10的烷基；所述R2和所述R3分别独立地选自C1～C20的直链或支链烷基、C3～C8环烷基、C3～C8环烷基取代的C1～C10的烷基、C6～C20的芳基；或者，所述R2和所述R3相连形成C3～C8的环烷基；所述R4为羟基或者N-吗啉基。
  7. 根据权利要求6所述的制备方法，其特征在于，所述溴代试剂选自N-溴代丁二酰亚胺、氢溴酸、溴素和二溴海因组成的组中的一种或多种；优选地，所述取代试剂为XONa，所述X为-A-(X’)n，其中A选自杂原子，所述杂原子选自O、N或S，所述X’选自C1～C20的直链或支链烷基、C3～C8环烷基、C3～C8环烷基取代的C1～C10的烷基，或者所述X’中的碳原子中的一个或多个被所述杂原子取代，n为1或2。
  8. 根据权利要求6所述的制备方法，其特征在于，所述溴代反应中，所述第一有机溶剂为极性溶剂，优选为碳酸丙烯酯。
  9. 根据权利要求8所述的制备方法，其特征在于，所述溴代反应的温度为10～60℃，优选为25℃。
  10. 根据权利要求6至9中任一项所述的制备方法，其特征在于，所述第二有机溶剂选自二氯甲烷、二氯乙烷、苯和二甲苯组成的组中的一种或多种。
  11. 一种涂料组合物，其特征在于，包括光引发剂和光聚合单体，所述光引发剂为权利要求1至5中任一项所述的具有式(I)所示结构的芴类光引发剂，所述光聚合单体为含烯基的化合物和/或环氧化合物。
  12. 根据权利要求11所述的涂料组合物，其特征在于，所述光聚合单体为丙烯酸酯类化合物；优选地，所述光聚合单体选自环氧丙烯酸树脂低聚物、聚氨酯丙烯酸树脂低聚物和聚酯丙烯酸树脂低聚物组成的组中的一种或多种。
  13. 根据权利要求11或12所述的涂料组合物，其特征在于，按重量份计，所述涂料组合物还包括助剂，所述助剂选自溶剂、表面调节剂、增感剂、敏化剂、固化促进剂、光交联剂、光敏化剂、光敏树脂、分散助剂、填充剂、密合促进剂、抗氧化剂、紫外线吸收剂、抗絮凝剂、热聚合阻止剂、消泡剂、流平剂、表面活性剂和链转移剂组成的组中的一种或多种。
  14. 一种油墨组合物，其特征在于，包括光引发剂、光聚合单体和颜料，所述光引发剂为权利要求1至5中任一项所述的具有式(I)所示结构的芴类光引发剂，所述光聚合单体为含烯基的化合物和/或环氧化合物。
  15. 根据权利要求14所述的油墨组合物，其特征在于，所述光聚合单体为丙烯酸酯类化合物；优选地，所述光聚合单体选自环氧丙烯酸树脂低聚物、聚氨酯丙烯酸树脂低聚物和聚酯丙烯酸树脂低聚物组成的组中的一种或多种。
  16. 根据权利要求14或15所述的油墨组合物，其特征在于，按重量份计，所述油墨组合物还包括助剂，所述助剂选自溶剂、表面调节剂、增感剂、敏化剂、固化促进剂、光交联剂、光敏化剂、光敏树脂、分散助剂、填充剂、密合促进剂、抗氧化剂、紫外线吸收剂、抗絮凝剂、热聚合阻止剂、消泡剂、流平剂、表面活性剂和链转移剂组成的组中的一种或多种。
  17. 根据权利要求1所述的芴类光引发剂，其特征在于，所述式(Ⅱ)中，所述链基基团为C1-C10的直链烷基、C1-C10的支链烷基或C4-C10的环烷基烷基。
  18. 根据权利要求1所述的芴类光引发剂，其特征在于，所述式(Ⅱ)中，所述Ar为苯基、甲基苯基、乙基苯基、氯苯基、溴苯基、甲氧基苯基、硝基苯基、氰基苯基、二苯硫醚基、吡啶基、噻吩基、呋喃基、2-甲基-噻吩基、3-甲基噻吩基、呋喃基、2-甲基-呋喃基或3-甲基呋喃基。
  19. 根据权利要求1、17和18中任一项所述的芴类光引发剂，其特征在于，所述R7为-C(＝O)C(＝O)O-R7’基团，所述芴类光引发剂具有如下式(Ⅴ)所示的结构：
    Figure PCTCN2017099294-appb-100007
    其中，所述R8具有n个对外连接键，且为C1-C60的直链烷基或支链烷基，或所述C1-C60的直链烷基或支链烷基中任意的碳或氢被氧、硫或苯基所取代；
    所述A表示具有-(Q-CHR9)m-结构的重复单元，所述R9为氢、甲基或乙基，所述Q代表O或连接符，其中，所述连接符表示-(CHR9)m与O直接相连，m为1～6的整数；
    所述n代表1～20的整数。
  20. 根据权利要求19所述的芴类光引发剂，其特征在于，式(Ⅴ)中，所述R8选自下列基团中的任意一种：
    Figure PCTCN2017099294-appb-100008
    *CH2-CH2*、*CH2-CH2-CH2*、*CH2CH2CH2CH2*、
    Figure PCTCN2017099294-appb-100009
    Figure PCTCN2017099294-appb-100010
  21. 根据权利要求19所述的芴类光引发剂，其特征在于，式(Ⅴ)中，所述A选自-[(Q-CHR9)m]y-，其中所述R9为氢或甲基，m为1～3的整数，y代表1～9的整数。
  22. 根据权利要求19所述的芴类光引发剂，其特征在于，式(Ⅴ)中，所述n是1～8的整数，优选为1、2、3、4、5或6。
  23. 一种权利要求1、17至22中任一项所述的包含式(Ⅱ)所示结构的芴类光引发剂的制备方法，其特征在于，所述制备方法包括：
    步骤S1，具有结构式A的原料a与具有结构式B的原料b发生傅克反应，得到具有结构式C的中间体c；
    可选的步骤S2，所述中间体c与具有结构式D的原料d发生傅克反应，得到具有结构式E的中间体e；以及
    可选的步骤S3，所述中间体e与具有结构式F的醇或多元醇发生酯交换反应，得到所述芴类光引发剂，其中，
    所述结构式A为
    Figure PCTCN2017099294-appb-100011
    所述结构式B为
    Figure PCTCN2017099294-appb-100012
    其中X1为卤素，所述结构式C为
    Figure PCTCN2017099294-appb-100013
    所述结构式D为
    Figure PCTCN2017099294-appb-100014
    其中所述X2为卤素，所述结构式E为
    Figure PCTCN2017099294-appb-100015
    所述结构式F为R8(AOH)n。
  24. 根据权利要求23所述的制备方法，其特征在于，所述步骤S1和所述步骤S2的傅克反应在三氯化铝或氯化锌及溶剂存在下进行，优选所述步骤S1和所述步骤S2的傅克反应的反应温度各自独立地为-10～40℃。
  25. 根据权利要求23所述的制备方法，其特征在于，所述步骤S3在催化剂和阻聚剂的作用下发生所述酯交换反应，优选所述催化剂为一种或多种钛酸类化合物，更优选所述催化剂选自钛酸-2-乙基己酯、钛酸四甲酯、钛酸四异丙酯、钛酸四丁酯、钛酸四异丁酯、钛酸四(2-乙基己)酯组成的组中的一种或多种，优选所述阻聚剂选自对羟基苯甲醚、N,N-二乙基羟胺、对苯二酚、邻苯二酚、对叔丁基邻苯二酚、甲基氢醌、对甲氧基苯酚、吩噻嗪和三苯基膦组成的组中的任意一种。
  26. 根据权利要求25所述的制备方法，其特征在于，所述步骤S3中，所述中间体e与具有结构式F的醇或多元醇的摩尔比是n：1，优选催化剂的重量是物料总重量的3～10‰，更 优选所述阻聚剂的重量是所述物料总重量的3～10‰，进一步优选所述酯交换反应的温度为70～130℃、反应时间为1～8h。
  27. 一种光固化组合物，包括光引发剂，其特征在于，所述光引发剂为权利要求1、17至27中任一项所述的包含式(Ⅱ)所示结构的芴类光引发剂。
  28. 一种权利要求1、17至27中任一项所述的包含式(Ⅱ)所示结构的芴类光引发剂在光固化领域的应用。
  29. 根据权利要求28所述的应用，其特征在于，所述应用包括涂料、油墨、粘合剂、彩色光阻、黑色矩阵、光间隔物、肋栅、干膜和/或半导体光刻胶中的应用。
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