WO2019120081A1 - 含氟芴肟酯类光引发剂、包含其的光固化组合物及其应用 - Google Patents

含氟芴肟酯类光引发剂、包含其的光固化组合物及其应用 Download PDF

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WO2019120081A1
WO2019120081A1 PCT/CN2018/119354 CN2018119354W WO2019120081A1 WO 2019120081 A1 WO2019120081 A1 WO 2019120081A1 CN 2018119354 W CN2018119354 W CN 2018119354W WO 2019120081 A1 WO2019120081 A1 WO 2019120081A1
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group
substituted
fluorine
formula
photoinitiator
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PCT/CN2018/119354
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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 CN201711415551.4A external-priority patent/CN109957046B/zh
Priority claimed from CN201810020889.8A external-priority patent/CN110016002B/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 JP2020534205A priority Critical patent/JP6999039B2/ja
Priority to KR1020207021061A priority patent/KR102361560B1/ko
Publication of WO2019120081A1 publication Critical patent/WO2019120081A1/zh

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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
    • C07C251/16—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Definitions

  • the present invention relates to the field of organic synthesis, and in particular to a fluorine-containing oxime ester photoinitiator, a photocurable composition comprising the same, and use thereof.
  • the liquid crystal display device Compared with the traditional image tube monitor, the liquid crystal display device has the advantages of low energy consumption, small volume and no radiation, but there are still defects such as a small visual corner, image smearing, poor brightness and contrast.
  • people have put forward higher requirements for liquid crystal display devices.
  • the requirements of large size, high brightness, high contrast and wide viewing angle are mentioned, which is made for liquid crystal displays.
  • the materials used in the paper put forward higher requirements.
  • Color, black photoresist and optical spacers are important components of liquid crystal flat panel displays. They are also essential materials for high-dimensional flat panel display to achieve large size and high resolution.
  • High-sensitivity oxime ester initiators are photoresist and gap. An important part of the formulation, in recent years, the research on high-sensitivity initiators is very hot, but the poor drying performance and easy migration of these disclosed photoinitiators have not been effectively solved, which affects materials to varying degrees. Application performance.
  • the main object of the present invention is to provide a fluorine-containing oxime ester photoinitiator, a photocurable composition comprising the same, and use thereof to solve the problem of poor surface dryness and easy migration of the existing oxime ester photoinitiator.
  • the present invention provides a fluorine-containing oxime ester-based photoinitiator having a structure represented by the general formula (I) or (II):
  • n represents an integer of 1 to 4
  • m represents an integer of 1 to 4
  • n R 1 are each independently selected from -G-(M') q , hydrogen, nitro, halogen, or m' represents an integer of from 1 to 4; wherein G is selected from a hetero atom or a carbonyl group, the hetero atom is O, N or S, and M' is selected from a linear or branched alkyl group of C 1 - C 20 , C 3 - C 8 cycloalkyl group, a cycloalkyl group of C 3 ⁇ C 8 alkyl group substituted with a C 1 ⁇ C 10, and C 6 ⁇ C 20 aryl group, the C 1 ⁇ C 10 alkyl group, a nitro-substituted C 6 -C 20 aryl, cyano substituted C 6 -C 20 aryl, C 4 -C 20 heteroaryl, nitro substituted C 6 -C 20 heteroaryl or cyano substituted C 6 -C 20 a heteroaryl group, or one or more carbon atoms in
  • R 2 and R 2 ' are each independently selected from a polymerizable group
  • Z and Z' independently represent an empty or a carbonyl group
  • n R 3 and m'R 5 are each independently selected from fluorine, a linear or branched alkyl group substituted by one or more fluorines, a linear or branched alkoxy group substituted by one or more fluorines;
  • R 4 and R 6 are each independently selected from a C 1 - C 20 straight or branched alkyl group, a C 3 - C 20 cycloalkyl group, a C 3 - C 8 cycloalkyl substituted C 1 - C 10 alkane, respectively. a C 3 -C 8 cycloalkyl group substituted with an alkyl group of C 1 -C 10 , an aryl group of C 6 -C 20 , a heteroaryl group of C 4 -C 20 or an alkenyl group of C 2 -C 20 ;
  • R 1 and R 1 ' each independently represent a fluorine-containing group
  • R 2 and R 3 each independently represent a C 1 to C 20 linear or branched alkyl group, a C 3 to C 12 cycloalkyl group, a C 4 to C 18 cycloalkylalkyl group, or a C 6 to C 20 group.
  • Aryl, C 7 -C 24 arylalkyl, substituted or unsubstituted C 4 -C 20 heteroaryl, or R 2 and R 3 are bonded to each other to form a C 3 -C 10 cycloalkyl;
  • R 4 represents a hydroxyl group, N-morpholinyl group, N-piperidinyl group, N-piperazinyl group, N-pyrrolyl group or N-secondary amino group;
  • A represents hydrogen, a nitro group, a -CO-CR 2 R 3 R 4 group, or -R 5 -(R 6 ) n , wherein R 5 represents O, S, N or a carbonyl group, and R 6 represents a C 1 - C 20 linear or branched alkyl, C 3 -C 12 cycloalkyl, C 4 -C 18 cycloalkylalkyl, substituted or unsubstituted C 6 -C 20 aryl, C 7 -C 24 arylalkyl, five- or six-membered unsaturated heterocyclic group, a substituted or unsubstituted heteroaryl C 4 ⁇ C 20, n is 1 or 2.
  • the photoinitiator in the fluorine-containing oxime ester photoinitiator represented by the formula (I) or (II) provided by the present application, the photoinitiator has high initiation efficiency by introducing a fluorine-containing group. advantage. Moreover, the above structural speciality makes the photoinitiator also have the advantages of good surface dryness, good surface curing effect, and difficulty in migration. On the basis of the above, the photoinitiator has the advantages of high initiation efficiency, good surface dry performance, good surface curing effect and difficulty in migration, and has broad application prospects.
  • the existing oxime ester photoinitiators have problems of poor surface dryness and easy migration.
  • the present invention provides a fluorine-containing oxime ester-based photoinitiator having a structure represented by the general formula (I) or (II):
  • n represents an integer of 1 to 4
  • m represents an integer of 1 to 4
  • n R 1 are each independently selected from -G-(M') q , hydrogen, nitro, halogen, or m' represents an integer from 1 to 4; wherein G includes, but is not limited to, a hetero atom or a carbonyl group, the hetero atom is O, N or S, and M' includes, but is not limited to, a C 1 - C 20 linear or branched alkyl group, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl substituted C 1 -C 10 alkyl group, C 6 -C 20 aryl group, C 1 -C 10 alkyl group, nitro group substitution C 6 -C 20 aryl, cyano substituted C 6 -C 20 aryl, C 4 -C 20 heteroaryl, nitro substituted C 6 -C 20 heteroaryl or cyano substituted C 6 ⁇ C 20 heteroaryl, or one or more carbon atoms in M′ are substituted by a hetero atom
  • R 1 and R 1 ' each independently represent a fluorine-containing group
  • R 2 and R 3 each independently represent a C 1 to C 20 linear or branched alkyl group, a C 3 to C 12 cycloalkyl group, a C 4 to C 18 cycloalkylalkyl group, or a C 6 to C 20 group.
  • Aryl, C 7 -C 24 arylalkyl, substituted or unsubstituted C 4 -C 20 heteroaryl, or R 2 and R 3 are bonded to each other to form a C 3 -C 10 cycloalkyl;
  • R 4 represents a hydroxyl group, N-morpholinyl group, N-piperidinyl group, N-piperazinyl group, N-pyrrolyl group or N-secondary amino group;
  • A represents hydrogen, a nitro group, a -CO-CR 2 R 3 R 4 group, or -R 5 -(R 6 ) n , wherein R 5 represents O, S, N or a carbonyl group, and R 6 represents a C 1 - C 20 linear or branched alkyl, C 3 -C 12 cycloalkyl, C 4 -C 18 cycloalkylalkyl, substituted or unsubstituted C 6 -C 20 aryl, C 7 -C 24 arylalkyl, five- or six-membered unsaturated heterocyclic group, a substituted or unsubstituted heteroaryl C 4 ⁇ C 20, n is 1 or 2.
  • the photoinitiator has an advantage of high initiating efficiency by introducing a fluorine-containing group. Moreover, the above-mentioned structural speciality makes the photoinitiator have the advantages of good surface dryness, good surface curing effect, and difficulty in migration. On the basis of the above, the photoinitiator has the advantages of high initiation efficiency, good surface dry performance, good surface curing effect and easy migration, and has broad application prospects.
  • a polymerizable group is introduced at the 9-position of the fluorene structure, which enables the photoinitiator represented by the general formula (I) to be polymerized with the substrate, thereby It is beneficial to further improve the non-migratory property of the photoinitiator.
  • M' includes, but is not limited to, a C 1 - C 10 linear or branched alkyl group, C 3 a C 6 -cycloalkyl group, a C 3 -C 6 cycloalkyl group-substituted C 1 -C 5 alkyl group, a C 6 -C 10 aryl group, a C 1 -C 5 alkyl group, or a nitro-substituted C 6 to C 10 aryl, cyano substituted C 6 -C 10 aryl, C 4 -C 10 heteroaryl, nitro substituted C 6 -C 10 heteroaryl or cyano substituted C 6 -C 10 heteroaryl.
  • R 2 and R 2 ' are each independently selected from a polymerizable group containing a double bond or an epoxy group. group.
  • R 2 and R 2 ' are each independently selected from a C 2 -C 12 alkenyl group, or one or more of R 2 and R 2 '- CH 2 - can be independently -O-, Replaced
  • R 2 and R 2 ' are each independently selected from a C 3 -C 8 alkenyl group, or one or more -CH 2 - in R 2 may be independently -O -, Replaced.
  • R 2 and R 2 ' are each independently selected from an oxiranyl-substituted C 1 -C 10 alkyl group or an oxypropylene group-substituted C 1 group.
  • -C 10 alkyl, or one or more of -C 2 - in the C 1 -C 10 alkyl group in R 2 and R 2 ' are each independently -O-, Or -O-CH 2 -CH(OH)-CH 2 -O-.
  • R 2 and R 2 ' are each independently selected from a C 1 -C 8 alkyl group having an oxiranyl group or a cyclopropyl group as a capping group.
  • one or more of -C 2 - of the C 1 -C 8 alkyl groups in R 2 and R 2 ' are each independently -O-, Or substituted with -O-CH 2 -CH(OH)-CH 2 -O-, or H in the oxiranyl or propylene oxide group may be substituted by a C 1 -C 4 alkyl group.
  • m R 3 and m' R 5 are each independently selected from F,
  • R 3 and R 5 are each independently selected from F,
  • the use of the above groups as R 3 and R 5 is advantageous for further increasing the initiation efficiency of the photoinitiator.
  • R 4 and R 6 are each independently selected from a C 1 -C 6 straight or branched alkyl group, a C 3 -C 10 cycloalkyl group, a C 3 -C 6 ring An alkyl-substituted C 1 -C 8 alkyl group, a C 1 -C 8 alkyl-substituted C 3 -C 6 cycloalkyl group or a C 6 -C 12 aryl group.
  • R 4 and R 6 are each independently selected from phenyl, C 1 -C 4 linear or branched alkyl, C 3 -C 8 cycloalkyl or C 3 a C 6 cycloalkyl substituted C 1 -C 4 alkyl group.
  • the fluorine-containing oxime ester photoinitiator represented by the general formula (I) is selected from the group consisting of
  • the present invention provides a method for producing a fluorine-containing oxime ester photoinitiator represented by the above formula (I), comprising the steps of:
  • A is empty or methylene.
  • A is a methylene group to form intermediate b, and the synthesis route is as follows:
  • Z is empty or carbon based.
  • the starting materials used in the above synthesis are all known compounds, which are commercially available or can be conveniently obtained by known synthetic methods, wherein the starting material a can be obtained according to the synthesis method disclosed in Chinese Patent Application No. 201710274018.4.
  • the synthesis process in turn comprises a Friedel acylation reaction, a deuteration reaction and an esterification reaction, all of which are conventional reaction types in the field of organic chemical synthesis.
  • the specific reaction conditions will be readily ascertainable to those skilled in the art after clarifying the reaction scheme.
  • the reaction temperature in the step (1) is usually -10 to 30 °C.
  • the type of the organic solvent to be used is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction, and is preferably one or more of the group consisting of dichloromethane, dichloroethane, benzene, toluene and xylene. kind.
  • the preparation of the intermediate b is carried out in a solvent system, and the type of the solvent to be used is not particularly limited as long as the raw material can be dissolved and the reaction is not adversely affected.
  • the solvent used may be a mixed solvent of an alcohol and water, preferably a mixed solvent of ethanol and water; the reaction is carried out under heating under reflux.
  • Z is a carbonyl group
  • the solvent used includes, but is not limited to, one or more of the group consisting of dichloromethane, benzene, toluene and tetrahydrofuran, and nitrites include, but are not limited to, ethyl nitrite, isoamyl nitrite.
  • One or more of the group consisting of isooctyl nitrite including but not limited to sodium nitrite and/or potassium nitrite.
  • the esterification reaction is carried out in an organic solvent
  • the type of the solvent is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction, and is preferably dichloromethane, dichloroethane, benzene or toluene.
  • R 1 and R 1 ' each independently represent a linear or branched C 2 -C 10 chain.
  • a fluorine-containing alkyl group optionally, wherein -CH 2 - may be substituted by -O- or a phenylene group, and H on the phenylene group may be optionally a C 1 -C 4 alkyl group Replaced.
  • R 1 and R 1 ' each independently represent a C 3 -C 8 group having a terminal group of -CF 3 , -CF 2 CF 3 , -CF 2 -CH 2 F or -CF 2 -CHF 2 a linear or branched fluoroalkyl group, optionally wherein -CH 2 - may be substituted by -O- or 1,4-phenylene, and H on 1,4-phenylene may be The ground is replaced by an alkyl group of C 1 to C 4 .
  • R 2 and R 3 each independently represent a C 1 -C 8 linear or branched alkyl group, a C 4 -C 12 cycloalkylalkyl group, or a C 7 -C 14
  • the arylalkyl group, or R 2 and R 3 are bonded to each other to form a C 3 -C 8 cycloalkyl group.
  • R 2 and R 3 each independently represent a C 1 -C 4 linear or branched alkyl group, a C 4 -C 10 cycloalkylalkyl group, a C 7 -C 10 phenylalkyl group, Or R 2 and R 3 are bonded to each other to form a C 3 - C 8 cycloalkyl group.
  • R 4 represents a hydroxyl group, an N-morpholinyl group, an N-piperidinyl group, or an amine group in which two hydrogens are substituted by a C 1 -C 4 alkyl group.
  • A represents hydrogen, a nitro group, a -CO-CR 2 R 3 R 4 group, or -R 5 -(R 6 ) n , wherein R 5 represents O, S, N Or a carbonyl group, R 6 represents a C 1 -C 8 linear or branched alkyl group, a C 6 -C 12 aryl group, a C 1 -C 5 alkyl group, a nitro group or a cyano group substituted C 6 -C 12 An aryl, five-membered unsaturated heterocyclic group, and n represents 1 or 2.
  • R 6 represents a C 1 -C 4 linear or branched alkyl group, a furyl group, a pyrrolyl group, a thienyl group, a C 6 -C 10 aryl group, a C 1 -C 4 alkyl group, a nitro group. Or a cyano substituted C 6 -C 10 aryl group.
  • fluorine-containing quinone photoinitiator represented by the general formula (II) may be selected from the following structures:
  • the present invention also relates to a process for producing a fluorine-containing anthraquinone photoinitiator represented by the above formula (II), wherein the starting materials a and b are reacted under the action of a catalyst, and the reaction formula is as follows:
  • R 0 is R 1 and R 0 ' is R 1 '
  • R 0 and R 0 ' correspond to R 1 and R 1 ', respectively, and R 1 represents OR 0 and R 1 ' represents OR 0 ',
  • X represents Cl or Br.
  • the starting materials and reagents used in the above preparation methods are all known compounds in the prior art or can be conveniently prepared by a known process, wherein the raw material a can be passed through, for example, application numbers 201510937328.0, 201710088234.X, 201710530354.0, 201710835527.X.
  • the synthetic method described in the Chinese invention patent application is prepared.
  • the reaction is carried out in an organic solvent, and the type of the solvent is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction, and is preferably a polar solvent, particularly DMF.
  • the catalyst is a basic catalyst, preferably at least one of lithium t-butoxide, sodium t-butoxide and potassium t-butoxide.
  • the reaction temperature is 10-50 °C.
  • the reaction time varies slightly depending on the type of raw material, and is usually from 1 to 6 h.
  • the present invention also provides a photocurable composition
  • a photoinitiator comprising the above formula (I) and/or formula (II) Fluorinated oxime ester photoinitiator.
  • the photoinitiator has an advantage of high initiating efficiency by introducing a fluorine-containing group. Moreover, the above-mentioned structural speciality makes the photoinitiator have the advantages of good surface dryness, good surface curing effect, and difficulty in migration. On the basis of the above, the photoinitiator has the advantages of being difficult to migrate, high initiating efficiency, good surface drying performance and good surface curing effect, and has broad application prospects.
  • the present invention also provides the use of the fluorine-containing oxime ester-based photoinitiator represented by the above formula (I) or (II) in the field of photocuring.
  • the photoinitiator has an advantage of high initiating efficiency by introducing a fluorine-containing group. Moreover, the above-mentioned structural speciality makes the photoinitiator have the advantages of good surface dryness, good surface curing effect, and difficulty in migration. On the basis of the above, the photoinitiator has the advantages of being difficult to migrate, high initiating efficiency, good surface drying performance and good surface curing effect, and has broad application prospects.
  • the invention further relates to the use of the above-mentioned fluorine-containing quinone photoinitiator in the field of photocuring.
  • the photoinitiator can be applied to color resists (RGB), black matrix (BM), photo-spacers, ribs, dry films, semiconductor photoresists, inks, and the like. aspect.
  • the photoinitiator is highly efficient and provides excellent surface dryness and weatherability.
  • the above reaction system was slowly poured into 400 g of ice water and 50 mL of concentrated hydrochloric acid (37%) in diluted hydrochloric acid, and stirred while stirring, then poured into a separatory funnel, and the lower layer of methylene chloride was separated and used.
  • the aqueous layer was washed further with 50 mL of dichloromethane and the dichloromethane layer was combined.
  • the methylene chloride layer was washed with a 5 wt% aqueous solution of sodium hydrogencarbonate (150 mL each time), then the methylene chloride layer was washed with water until the pH was neutral, and the methylene chloride layer was dried over 80 g of anhydrous magnesium sulfate.
  • the above reaction system was slowly poured into 400 g of ice water and 50 mL of concentrated hydrochloric acid (37%) in diluted hydrochloric acid, and stirred while stirring, then poured into a separatory funnel, and the lower layer of methylene chloride was separated and used.
  • the aqueous layer was further washed with 50 mL of dichloromethane, and the methylene chloride layer was combined.
  • the methylene chloride layer was washed with a 5 wt% aqueous sodium hydrogencarbonate solution (150 mL each time), and then the methylene chloride layer was washed with water until the pH was neutral.
  • the methylene chloride layer was dried over 80 g of anhydrous magnesium sulfate.
  • the synthetic route is as follows:
  • the preparation of the representative photocurable resin composition is used to evaluate the curing speed, migration property, surface dryness and the like of the photoinitiator represented by the formula (I) of the present invention, and the specific steps are as follows:
  • a photocurable resin composition (parts by weight) having the following composition was prepared, as shown in Table 2.
  • D1 is butanone (solvent).
  • the above composition was stirred under a yellow light, and then the film was formed by roll coating on a PET template, and dried at 90 ° C for 2 minutes to obtain a coating film having a dry film thickness of 2 ⁇ m. Then, the above coating film was cooled to room temperature, and irradiated with a high pressure mercury lamp (exposure model: RW-UV70201, single exposure amount: 50 mJ/cm 2 ) to expose the coating film to form a film.
  • a high pressure mercury lamp exposure model: RW-UV70201, single exposure amount: 50 mJ/cm 2
  • the number of passes of the viscous exposure tape after the film was cured to form a cured film was evaluated. The more the number of passes, the less the curing speed was.
  • the cured film described above was cut into a sample.
  • a sample of 0.5 g of the cured film was weighed into a 50 mL beaker, 4.5 mL of methanol was added, and ultrasonically sonicated for 30 min.
  • the obtained solution was transferred to a 10 mL volumetric flask, and the sample was further washed twice with methanol (2 mL ⁇ 2), poured into a volumetric flask, and 0.1 mL of toluene was pipetted as an internal standard, and methanol was dissolved. Shake evenly and let stand.
  • the cotton film is not left on the surface of the film, and it is recorded as A;
  • the surface of the film is not left with cotton yarn, which means that the surface is dry, indicating that the film has excellent surface dryness.
  • the polymerizable group-containing oxime ester photoinitiator represented by the general formula (I) of the present invention is excellent in surface drying property, and the initiator is highly efficient in photocuring applications.
  • the curing speed is fast and no migration occurs, and the comprehensive performance is obviously superior to the existing oxime ester photoinitiator products.
  • the layer was neutral to pH, and the methylene chloride layer was dried over 80 g of anhydrous magnesium sulfate. After filtration, the dichloromethane product solution was evaporated, and the methanol was recrystallized and dried in an oven at 70 ° C for 2 h to obtain 41.9 g of compound 1 in a yield of 75%. The purity is 98%.
  • the layer was neutral to pH, and the methylene chloride layer was dried over 80 g of anhydrous magnesium sulfate. After filtration, the dichloromethane product solution was evaporated, and the methanol was recrystallized and dried in an oven at 70 ° C for 2 h to obtain 51.4 g of compound 2 in a yield of 68%. The purity is 98%.
  • the compound having the structure shown in Table 4 was prepared from the corresponding starting materials by the method of Example 1.
  • An exemplary photocurable resin composition was disposed to evaluate the critical application properties of the photoinitiator represented by the general formula (II) of the present invention.
  • the photocurable resin composition is composed of the following components:
  • the photoinitiator is a fluorine-containing anthraquinone photoinitiator represented by the formula (II) of the present invention or a representative anthraquinone photoinitiator known in the prior art as a comparative example.
  • the evaluation of the properties of the photocurable resin composition includes curing speed, surface drying properties, and weather resistance.
  • the photocurable resin composition was stirred under a yellow light, and the film was taken up by a roll coating on a PET template, and dried at 90 ° C for 2 minutes to obtain a coating film having a dry film thickness of 2 ⁇ m, and then cooled to room temperature, using a high-pressure mercury lamp ( Exposure machine model: RW-UV70201, single exposure amount 50 mJ/cm 2 ) The coating film was exposed to light to form a film.
  • the number of passes of the shimming exposure tape required for curing the cured film into a cured film the more the number of passes, the less satisfactory the curing speed.
  • the fully cured cured film is placed in a pre-conditioned temperature-controlled humidity control box (temperature 50 ⁇ 1°C, relative humidity 96 ⁇ 2%), and after 240 hours, the surface of the cured film is evaluated for foaming, cracking, yellowing and the like. phenomenon.
  • the cotton ball can be blown away and the cotton film is not left on the surface of the film, the surface is dry, indicating that the film has excellent surface dryness.
  • the photocurable resin composition using the fluorine-containing anthraquinone photoinitiator represented by the general formula (II) of the present invention can be sufficiently cured at a single exposure dose of 50 mJ/cm 2 . It exhibits significantly higher initiation efficiency, and weatherability and surface dryness are also significantly better than samples using existing quinone photoinitiators.

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Abstract

本发明提供了一种含氟芴肟酯类光引发剂、包含其的光固化组合物及其应用。该光引发剂具有通式(I)或(Ⅱ)所示结构。本申请提供的通式(I)或(Ⅱ)所示的含氟芴肟酯类光引发剂中，通过引入含氟基团使得该光引发剂具有引发效率高的优点。且上述结构上的特殊性使得该光引发剂还具有表干性能好、表面固化效果好及不易迁移等的优点。在此基础上，上述光引发剂具有不易迁移、引发效率高、表干性能好及表面固化效果好等的优点，且具有广阔的应用前景。

Description

含氟芴肟酯类光引发剂、包含其的光固化组合物及其应用 技术领域
本发明涉及有机合成领域，具体而言，涉及一种含氟芴肟酯类光引发剂、包含其的光固化组合物及其应用。
背景技术
液晶显示装置较传统的映像管监视器，具有能耗低、体积小和无辐射的优点，但是仍然存在可视转角过小、影像拖尾、亮度和对比度不佳的缺陷。近年来，随着人民生活水平的不断提高，人们对液晶显示装置也提出了更高的要求，大尺寸、高辉度、高对比度以及广视角的等需求被提及，这就对液晶显示器制作中所用的材料提出了更高的要求。
彩色、黑色光阻及光间隙物是组成液晶平板显示器的重要组成部分，更是高世代平板显示实现大尺寸和高分辨率必不可少的材料，高感度的肟酯引发剂是光阻及间隙物配方的重要组成部分，近年来，有关高感度引发剂的研究非常火热，但是这些公开的光引发剂的表干性能差及易迁移的问题仍然没有得到有效解决，这不同程度上影响了材料的应用性能。
发明内容
本发明的主要目的在于提供一种含氟芴肟酯类光引发剂、包含其的光固化组合物及其应用，以解决现有的肟酯类光引发剂表干性差和易迁移的问题。
为了实现上述目的，本发明提供了一种含氟芴肟酯类光引发剂，光引发剂具有通式(I)或(Ⅱ)所示结构：
Figure PCTCN2018119354-appb-000001
其中，通式(I)中，n表示1～4的整数；m表示1～4的整数；
n个R 1分别独立地选自-G-(M’) q、氢、硝基、卤素、或
Figure PCTCN2018119354-appb-000002
m’表示1～4的整数；其中，G选自杂原子或羰基，杂原子为O、N或S，M’选自C 1～C 20的直链或支链烷基、C 3～C 8的环烷基、C 3～C 8的环烷基取代的C 1～C 10的烷基、C 6～C 20的芳基、C 1～C 10的烷基、硝基取代的C 6～C 20芳基、氰基取代的C 6～C 20芳基、C 4～C 20的杂芳基、硝基取代的C 6～C 20杂芳基或氰基取代的C 6～C 20杂芳基，或者M’中的一个或多个碳原子被杂原子取代，q为1或2；
R 2和R 2’分别独立地选自可聚合基团；
Z和Z’分别独立地表示空或羰基；
m个R 3和m’R 5分别独立地选自氟、被一个或多个氟取代的直链或支链烷基、被一个或多个氟取代的直链或支链烷氧基；
R 4和R 6分别独立地选自C 1～C 20的直链或支链烷基、C 3～C 20的环烷基、C 3～C 8环烷基取代的C 1～C 10烷基、C 1～C 10的烷基取代的C 3～C 8环烷基、C 6～C 20的芳基、C 4～C 20的杂芳基或C 2～C 20的链烯基；
通式(Ⅱ)中，R 1和R 1 ’各自独立地表示含氟基团；
R 2和R 3各自独立地表示C 1～C 20的直链或支链烷基、C 3～C 12的环烷基、C 4～C 18的环烷基烷基、C 6～C 20的芳基、C 7～C 24的芳基烷基、取代或未取代的C 4～C 20的杂芳基，或者R 2和R 3彼此相连形成C 3～C 10的环烷基；
R 4表示羟基、N-吗啉基、N-哌啶基、N-哌嗪基、N-吡咯基或N-仲胺基；
A表示氢、硝基、-CO-CR 2R 3R 4基团、或-R 5-(R 6) n，其中，R 5表示O、S、N或羰基，R 6表示C 1～C 20的直链或支链烷基、C 3～C 12的环烷基、C 4～C 18的环烷基烷基、取代或未取代的C 6～C 20的芳基、C 7～C 24的芳基烷基、五元或六元的不饱和杂环基团、取代或未取代的C 4～C 20的杂芳基，n表示1或2。
应用本发明的技术方案，本申请提供的通式(I)或(Ⅱ)所示的含氟芴肟酯类光引发剂中，通过引入含氟基团使得该光引发剂具有引发效率高的优点。且上述结构上的特殊性使得 该光引发剂还具有表干性能好、表面固化效果好及不易迁移等的优点。在此基础上，上述光引发剂具有引发效率高、表干性能好及表面固化效果好及不易迁移等的优点，且具有广阔的应用前景。
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，现有的肟酯类光引发剂存在表干性差和易迁移的问题。为了解决上述技术问题，本发明提供了一种含氟芴肟酯类光引发剂，该光引发剂具有通式(I)或(Ⅱ)所示结构：
Figure PCTCN2018119354-appb-000003
其中，n表示1～4的整数；m表示1～4的整数；
n个R 1分别独立地选自-G-(M’) q、氢、硝基、卤素、或
Figure PCTCN2018119354-appb-000004
m’表示1～4的整数；其中，G包括但不限于杂原子或羰基，杂原子为O、N或S，M’包括但不限于C 1～C 20的直链或支链烷基、C 3～C 8的环烷基、C 3～C 8的环烷基取代的C 1～C 10的烷基、C 6～C 20的芳基、C 1～C 10烷基、硝基取代的C 6～C 20芳基、氰基取代的C 6～C 20芳基、C 4～C 20的杂芳基、硝基取代的C 6～C 20杂芳基或氰基取代的C 6～C 20杂芳基，或者M’中的一个或多个碳原子被杂原子取代，q为1或2；
R 2和R 2’分别独立地选自可聚合基团；Z和Z’分别独立地表示空或羰基；m个R 3和m’个R 5分别独立地选自氟、被一个或多个氟取代的直链或支链烷基、被一个或多个氟取代的直 链或支链烷氧基；R 4和R 6分别独立地选自C 1～C 20的直链或支链烷基、C 3～C 20的环烷基、C 3～C 8环烷基取代的C 1～C 10烷基、C 1～C 10的烷基取代的C 3～C 8环烷基、C 6～C 20的芳基、C 4～C 20的杂芳基或C 2～C 20的链烯基；
通式(Ⅱ)中，R 1和R 1’各自独立地表示含氟基团；
R 2和R 3各自独立地表示C 1～C 20的直链或支链烷基、C 3～C 12的环烷基、C 4～C 18的环烷基烷基、C 6～C 20的芳基、C 7～C 24的芳基烷基、取代或未取代的C 4～C 20的杂芳基，或者R 2和R 3彼此相连形成C 3～C 10的环烷基；
R 4表示羟基、N-吗啉基、N-哌啶基、N-哌嗪基、N-吡咯基或N-仲胺基；
A表示氢、硝基、-CO-CR 2R 3R 4基团、或-R 5-(R 6) n，其中，R 5表示O、S、N或羰基，R 6表示C 1～C 20的直链或支链烷基、C 3～C 12的环烷基、C 4～C 18的环烷基烷基、取代或未取代的C 6～C 20的芳基、C 7～C 24的芳基烷基、五元或六元的不饱和杂环基团、取代或未取代的C 4～C 20的杂芳基，n表示1或2。
本申请提供的通式(I)或(Ⅱ)所示的含氟芴肟酯类光引发剂中，通过引入含氟基团使得该光引发剂具有引发效率高的优点。且上述结构上的特殊性使得该光引发剂还具有表干性能好、表面固化效果好及不易迁移等的优点。在此基础上，上述光引发剂具有引发效率高、表干性能好、表面固化效果好及不易迁移等的优点，且具有广阔的应用前景。
此外通式(I)所示的光引发剂中，还在芴结构的9位引入了可聚合基团，这使得通式(I)所示的光引发剂能够与基材发生聚合，从而有利于进一步提高该光引发剂的不易迁移性。
为了进一步提高上述含氟芴肟酯类光引发剂的结构稳定性，优选地，通式(I)中，M’包括但不限于C 1～C 10的直链或支链烷基、C 3～C 6的环烷基、C 3～C 6的环烷基取代的C 1～C 5的烷基、C 6～C 10的芳基、C 1～C 5烷基、硝基取代的C 6～C 10芳基、氰基取代的C 6～C 10芳基、C 4～C 10的杂芳基、硝基取代的C 6～C 10杂芳基或氰基取代的C 6～C 10杂芳基。
为了进一步降低上述含氟芴肟酯类光引发剂的迁移性，优选地，通式(I)中，R 2和R 2’分别独立地选自含有双键或环氧基团的可聚合基团。
在一种优选的实施例中，通式(I)中，R 2和R 2’分别独立地选自C 2～C 12的链烯基，或者R 2和R 2’中一个或多个-CH 2-可各自独立地被-O-、
Figure PCTCN2018119354-appb-000005
所取代；
优选地，通式(I)中，R 2和R 2’分别独立地选自C 3～C 8的链烯基，或者R 2中一个或多个-CH 2-可各自独立地被-O-、
Figure PCTCN2018119354-appb-000006
所取代。
在一种优选的实施例中，通式(I)中，R 2和R 2’分别独立地选自环氧乙烷基取代的C 1～C 10烷基或环氧丙烷基取代的C 1～C 10烷基，或R 2和R 2’中C 1～C 10烷基中的一个或多个-CH 2-各自独立地被-O-、
Figure PCTCN2018119354-appb-000007
或-O-CH 2-CH(OH)-CH 2-O-取代。
在一种优选的实施例中，通式(I)中，R 2和R 2’分别独立地选自环氧乙烷基或环丙烷基为封端基团的C 1～C 8的烷基，或者，R 2和R 2’中C 1～C 8的烷基中的一个或多个-CH 2-各自独立地被-O-、
Figure PCTCN2018119354-appb-000008
或-O-CH 2-CH(OH)-CH 2-O-所取代，或者环氧乙烷基或环氧丙烷基中的H可被C 1～C 4的烷基所取代。
优选地，通式(I)中，m个R 3和m’个R 5分别独立地选自F、
Figure PCTCN2018119354-appb-000009
Figure PCTCN2018119354-appb-000010
Figure PCTCN2018119354-appb-000011
选用上述基团作为R 3和R 5有利于进一步提高光引发剂的引发效率。
优选地，通式(I)中，R 4和R 6分别独立地选自C 1～C 6的直链或支链烷基、C 3～C 10的环烷基、C 3～C 6环烷基取代的C 1～C 8烷基、C 1～C 8烷基取代的C 3～C 6环烷基或C 6～C 12的芳基。
更优选地，通式(I)中，R 4和R 6分别独立地选自苯基、C 1～C 4的直链或支链烷基、C 3～C 8的环烷基或C 3～C 6环烷基取代的C 1～C 4烷基。
更优选地，通式(I)所示的含氟芴肟酯类光引发剂选自
Figure PCTCN2018119354-appb-000012
Figure PCTCN2018119354-appb-000013
Figure PCTCN2018119354-appb-000014
Figure PCTCN2018119354-appb-000015
Figure PCTCN2018119354-appb-000016
Figure PCTCN2018119354-appb-000017
Figure PCTCN2018119354-appb-000018
组成的组中的一种或多种。
根据本发明的另一个方面，本发明还提供上述通式(I)所示的含氟芴肟酯类光引发剂的制备方法，包括下列步骤：
(1)中间体a的制备
在三氯化铝或氯化锌的催化作用下，原料a与原料b在有机溶剂中发生傅克酰基化反应，得到中间体a；合成路线如下：
Figure PCTCN2018119354-appb-000019
A为空或亚甲基。
(2)中间体b的制备
当中间体a在盐酸羟胺和醋酸钠的作用下进行肟化反应时，A为空，生成中间体b，合成路线如下：
Figure PCTCN2018119354-appb-000020
当在浓盐酸存在下，中间体a与亚硝酸酯或亚硝酸盐于常温下进行肟化反应时，A为亚甲基，生成中间体b，合成路线如下：
Figure PCTCN2018119354-appb-000021
(3)产物的制备
中间体b与酸酐
Figure PCTCN2018119354-appb-000022
或酰氯化合物
Figure PCTCN2018119354-appb-000023
进行酯化反应，得到目标产物，合成路线如下：
Figure PCTCN2018119354-appb-000024
，Z为空或碳基。
上述合成中所用原料均为已知化合物，可通过商购获得或通过已知合成方法方便地制得，其中原料a可根据中国专利申请号为201710274018.4中公开的合成方法而得到。该合成过程依次包含傅克酰基化反应、肟化反应和酯化反应，这些均为有机化学合成领域的常规反应类型。在明晰了反应流程后，具体反应条件对本领域技术人员而言是容易确定的。
步骤(1)中的反应温度通常为-10～30℃。对使用的有机溶剂种类并没有特别限定，只要能够溶解原料且对反应无不良影响即可，优选为二氯甲烷、二氯乙烷、苯、甲苯和二甲苯组成的组中的一种或多种。
步骤(2)中，中间体b的制备在溶剂体系中进行，对使用的溶剂种类并没有特别限定，只要能够溶解原料且对反应无不良影响即可。当Z为空时，使用的溶剂可以是醇和水的混合溶剂，优选乙醇和水的混合溶剂；该反应在加热回流状态下进行。当Z为羰基时，使用的溶剂包括但不限于二氯甲烷、苯、甲苯和四氢呋喃组成的组中的一种或多种，亚硝酸酯包括但不限于亚硝酸乙酯、亚硝酸异戊酯和亚硝酸异辛酯组成的组中的一种或多种，亚硝酸盐包括但不限于亚硝酸钠和/或亚硝酸钾。
步骤(3)中，酯化反应在有机溶剂中进行，对溶剂种类并没有特别限定，只要能够溶解原料且对反应无不良影响即可，优选为二氯甲烷、二氯乙烷、苯、甲苯和二甲苯组成的组中的一种或多种。
在另一种优选的实施方式中，上述通式(Ⅱ)所示的含氟芴类光引发剂中，R 1和R 1 ’各自独立地表示C 2～C 10的直链或支链的含氟烷基，任选地(optionally)，其中的-CH 2-可被-O-或亚苯基所取代，且亚苯基上的H可任选地被C 1～C 4的烷基所取代。进一步优选地，R 1和R 1 ’各自独立地表示以-CF 3、-CF 2CF 3、-CF 2-CH 2F或-CF 2-CHF 2为端基的、C 3～C 8的直链或支链的含氟烷基，任选地，其中的-CH 2-可被-O-或1,4-亚苯基所取代，且1,4-亚苯基上的H可任选地被C 1～C 4的烷基所取代。
优选地，通式(Ⅱ)中，R 2和R 3各自独立地表示C 1～C 8的直链或支链烷基、C 4～C 12的环烷基烷基、C 7～C 14的芳基烷基，或者R 2和R 3彼此相连形成C 3～C 8的环烷基。进一步优选地，R 2和R 3各自独立地表示C 1-C 4的直链或支链烷基、C 4～C 10的环烷基烷基、C 7～C 10的苯基烷基，或者R 2和R 3彼此相连形成C 3～C 8的环烷基。
优选地，通式(Ⅱ)中，R 4表示羟基、N-吗啉基、N-哌啶基、或两个氢被C 1～C 4烷基取代的胺基。
优选地，通式(Ⅱ)中，A表示氢、硝基、-CO-CR 2R 3R 4基团、或-R 5-(R 6) n，其中，R 5表示O、S、N或羰基，R 6表示C 1～C 8的直链或支链烷基、C 6～C 12的芳基、被C 1～C 5烷基、硝基或氰基取代的C 6～C 12的芳基、五元不饱和杂环基团，n表示1或2。进一步优选地，R 6表示C 1～C 4的直链或支链烷基、呋喃基、吡咯基、噻吩基、C 6～C 10的芳基、被C 1～C 4烷基、硝基或氰基取代的C 6～C 10的芳基。
非限制性地，通式(Ⅱ)所示的含氟芴类光引发剂可选自如下结构：
Figure PCTCN2018119354-appb-000025
Figure PCTCN2018119354-appb-000026
Figure PCTCN2018119354-appb-000027
Figure PCTCN2018119354-appb-000028
相应地，本发明还涉及上述通式(Ⅱ)所示的含氟芴类光引发剂的制备方法，将原料a和b在催化剂作用下反应，反应式如下所示：
Figure PCTCN2018119354-appb-000029
其中，M表示H或OH，
当M表示H时，R 0即为R 1、R 0’即为R 1’，
当M表示OH时，R 0、R 0’分别对应于R 1、R 1’，且R 1表示OR 0、R 1’表示OR 0’，
X表示Cl或Br。
上述制备方法中使用的原料和试剂均为现有技术中的已知化合物或可通过已知工艺方便地制得，其中原料a可通过如申请号为201510937328.0、201710088234.X、201710530354.0、201710835527.X等的中国发明专利申请中记载的合成方法制备而成。
反应在有机溶剂中进行，对溶剂种类并无特别的限定，只要能够溶解原料且对反应无不良影响即可，优选极性溶剂，特别是DMF。所述的催化剂是碱性催化剂，优选叔丁醇锂、叔丁醇钠和叔丁醇钾中的至少一种。反应温度为10-50℃。反应时间根据原料种类略有差异，通常为1-6h。
根据本发明的又一个方面，本发明还提供一种光固化组合物，该光固化组合物包含光引发剂，光引发剂包括上述通式(I)和/或通式(Ⅱ)所示的含氟芴肟酯类光引发剂。
本申请提供的通式(I)或(Ⅱ)所示的含氟芴肟酯类光引发剂中，通过引入含氟基团使得该光引发剂具有引发效率高的优点。且上述结构上的特殊性使得该光引发剂还具有表干性能好、表面固化效果好及不易迁移等的优点。在此基础上，上述光引发剂具有不易迁移、引发效率高、表干性能好及表面固化效果好等的优点，且具有广阔的应用前景。
根据本发明的又一个方面，本发明还提供上述通式(I)或(Ⅱ)所示的含氟芴肟酯类光引发剂在光固化领域中的应用。
本申请提供的通式(I)或(Ⅱ)所示的含氟芴肟酯类光引发剂中，通过引入含氟基团使得该光引发剂具有引发效率高的优点。且上述结构上的特殊性使得该光引发剂还具有表干性能好、表面固化效果好及不易迁移等的优点。在此基础上，上述光引发剂具有不易迁移、引发效率高、表干性能好及表面固化效果好等的优点，且具有广阔的应用前景。
本发明还涉及上述含氟芴类光引发剂在光固化领域中的应用。非限制性地，该光引发剂可应用在彩色光阻(RGB)、黑色矩阵(BM)、光间隔物(photo-spacer)、肋栅(rib)、干膜、半导体光刻胶及油墨等方面。该光引发剂引发效率高，可带来优异的表干性能和耐候性能。
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。
通式(I)所示含氟芴肟酯类光引发剂的制备实施例如下：
实施例1
(1)中间体1a的合成
向500mL的四口烧瓶中加入66.1g中间体1a、三氯化铝27.0g及二氯甲烷100mL，使用冰水浴将四口烧瓶中原料的温度降至0℃。然后在搅拌下，向上述原料中滴加57.0g原料1b与50mL二氯甲烷的混合溶液，同时将反应体系的温度控制在10℃以下，2h滴加完毕。滴加完毕后，继续搅拌2h，液相跟踪反应至完全。接着将上述反应体系缓慢倒入400g冰水与50mL浓盐酸(37％)配成的稀盐酸中，边加边搅拌，随后将其倒入分液漏斗中，分出下层二氯甲烷层，并用50mL二氯甲烷继续清洗水层，合并二氯甲烷层。用5wt％的碳酸氢钠水溶液(每次150mL，共3次)清洗二氯甲烷层，接着水洗二氯甲烷层至pH呈中性，用80g无水硫酸镁干燥二氯甲烷层，过滤后旋蒸二氯甲烷产物溶液，以甲醇为溶剂进行重结晶，然后在80℃烘箱中干燥2h，得97.2g中间体1a，收率84wt％，纯度98wt％。合成路线如下：
Figure PCTCN2018119354-appb-000030
中间体1a通过核磁共振氢谱和质谱得到确认:
1H-NMR(CDCl 3，500MHz)：1.2885-1.3307(8H，m)，1.8654-1.9975(8H,m)，2.3506(3H，s)，3.8098(2H，s)，4.9657-5.0342(4H，m)，5.6786-5.7153(2H，t)，6.1976(1H，s)，6.4672-6.8400(3H,m),7.2813-7.9503(7H，m)。
MS(m/z)：579(M+1) +。
(2)中间体1b的合成
向500mL四口烧瓶中加入57.9g中间体1a、盐酸羟胺7.0g、醋酸钠8.2g、100mL乙醇、50mL水，85℃加热回流搅拌5h后停止反应，将物料倒入1000mL大烧杯中，加入500mL水搅拌，使用100mL二氯甲烷萃取，在萃取液中加入30g无水MgSO 4干燥，抽滤，将滤液减压旋蒸除去溶剂，旋转瓶中得到油状粘稠物，将粘稠物倒入100mL石油醚中搅拌析出，抽滤，得白色粉末状固体，70℃烘5h，得中间体1b 43.7g，收率72wt％，纯度98wt％，MS(m/z):608(M+1) +。合成路线为：
Figure PCTCN2018119354-appb-000031
(3)化合物1的合成
向250mL四口烧瓶中加入30.4g中间体1b、100mL二氯甲烷，室温下搅拌5min，然后滴加5g丙酰氯，约30min滴加完毕，继续搅拌2h，然后加入5％NaHCO 3水溶液调pH值至中性，分液漏斗分出有机层，再用100mL水洗2遍，20g无水MgSO 4干燥，过滤后旋蒸出溶剂，得粘稠状液体，甲醇重结晶得到白色固体粉末，过滤，得化合物1共27.2g，收率82％，纯度99％。合成路线如下：
Figure PCTCN2018119354-appb-000032
化合物1结构通过核磁共振氢谱和质谱得到确认:
1H-NMR(CDCl 3，500MHz)：0.9869-1.0045(3H，t)，1.2895-1.3347(8H,m)，1.8678-1.9668(8H，m)，2.2678-2.3567(5H，m)，4.9678-5.0546(4H，m)，5.6695-5.7206(2H，m)，6.1996(1H，s)，6.7846-8.0331(10H，m)。
MS(m/z)：664(M+1) +。
实施例2
(1)中间体2a的合成
向500mL的四口烧瓶中加入72.5g中间体2a、三氯化铝27.0g、二氯甲烷100mL，使用冰水浴将四口烧瓶中原料的温度降至0℃。然后在搅拌下，向上述原料中滴加54.5g原料2b与50mL二氯甲烷的混合溶液，同时将反应体系的温度控制10℃以下，2h滴加完毕。滴加完毕后，继续搅拌2h，液相跟踪反应至完全。接着将上述反应体系缓慢倒入400g冰水与50mL浓盐酸(37％)配成的稀盐酸中，边加边搅拌，随后将其倒入分液漏斗中，分出下层二氯甲烷层，并用50mL二氯甲烷继续清洗水层，合并二氯甲烷层，用5wt％的碳酸氢钠水溶液(每次150mL，共3次)清洗二氯甲烷层，接着水洗二氯甲烷层至pH呈中性，用80g无水硫酸镁干燥二氯甲烷层，过滤后旋蒸二氯甲烷产物溶液，以甲醇为溶剂进行重结晶，然后在80℃烘箱干燥2h，得101.8g中间体2a，收率85wt％，纯度98wt％。合成路线如下：
Figure PCTCN2018119354-appb-000033
中间体2a通过核磁共振氢谱和质谱得到确认：
1H-NMR(CDCl 3，500MHz)：2.1489-2.1673(4H，t)，2.3507(3H，s)，4.1043-4.1554(4H，t)，5.7986-6.0521(4H，m)，6.4207-6.4332(2H，d)，7.1105-7.8023(10H，m)。
MS(m/z)：599(M+1) +。
(2)中间体2b的合成
向250mL四口烧瓶中加入59.8g中间体2a、37wt％的盐酸10.0g、亚硝酸异戊酯11.8g、100mL四氢呋喃，在常温下搅拌5h，停止反应。将物料倒入1000mL大烧杯中，加入500mL水搅拌，使用100mL二氯甲烷萃取，在萃取液中加30g无水MgSO 4干燥，抽滤，将滤液减压旋蒸除去溶剂，旋转瓶中得到油状粘稠物，将粘稠物倒入100mL石油醚中搅拌析出，抽滤，得白色粉末状固体，70℃烘5h，得中间体2b44.8g，收率75％，纯度98％，MS(m/z)：614(M+1) +。合成路线如下：
Figure PCTCN2018119354-appb-000034
(3)化合物2的合成
向250mL四口烧瓶中加入30.7g中间体2b、100mL二氯甲烷，室温下搅拌5min，然后滴加6.5g丙酸酐，约30min滴加完毕，继续搅拌2h，然后加入5％NaHCO 3水溶液调pH值至中性，分液漏斗分出有机层，再用200mL水洗2遍，50g无水MgSO 4干燥，过滤后旋蒸出溶剂，得粘稠状液体，甲醇重结晶得到白色固体粉末，过滤，得产品28.5g，收率85％，纯度99％。
合成路线如下：
Figure PCTCN2018119354-appb-000035
化合物2结构通过核磁共振氢谱和质谱得到确认：
1H-NMR(CDCl 3，500MHz)：1.0004-1.1049(3H，t)，2.1497-2.2732(6H,m)，4.1003-4.1666(4H,t)，5.8006-6.1056(4H，m)，6.4275-6.4365(2H，d)，7.2809-8.0603(7H，m)。
MS(m/z)：670(M+1) +。
实施例3
参照实施例1和2的方法，由相应原料制备具有表1中所示结构的化合物3～13。
表1
Figure PCTCN2018119354-appb-000036
Figure PCTCN2018119354-appb-000037
Figure PCTCN2018119354-appb-000038
光引发剂性能评价
通过配制代表性光固化树脂组合物，对本发明式(I)所示光引发剂的固化速度、迁移性、表干等应用性能进行评价，具体步骤如下：
(1)配制如下组成的光固化树脂组合物(重量份)，见表2。
表2
Figure PCTCN2018119354-appb-000039
其中，表2中A：1，6-己二醇二丙烯酸酯。
B:丙烯酸酯共聚物[甲基丙烯酸苄酯/甲基丙烯酸/甲基丙烯酸羟乙酯(摩尔比70/10/20)共聚物(Mv:10000)]。
C1：化合物1，C2：化合物2，C3：化合物4，C4：化合物7，C5：化合物11，C6：化合物12。
C7为
Figure PCTCN2018119354-appb-000040
C8为
Figure PCTCN2018119354-appb-000041
C9为
Figure PCTCN2018119354-appb-000042
C10为
Figure PCTCN2018119354-appb-000043
D1为丁酮(溶剂)。
(2)固化速度。
将上述组合物在黄光灯下搅拌，然后取料在PET模板上利用滚涂成膜，在90℃下干燥2min，得到干膜厚度为2μm的涂膜。然后将上述涂膜冷却至室温，用高压汞灯(曝光机型号：RW-UV70201，单次曝光量50mJ/cm 2)照射，以对上述涂膜进行曝光，使其固化成膜。
以涂膜固化成固化膜所经过履式曝光带的次数评价，经过次数越多，表明固化速度越不理想。
(3)迁移性。
将上述固化膜剪碎，作为样品。称取0.5g固化膜样品置于50mL烧杯中，加入4.5mL甲醇，并利用超声波超声溶解30min。将所得的溶液移至10mL容量瓶中，并将样品继续用甲醇清洗两次(2mL×2)，倒入容量瓶中，用移液管移取0.1mL甲苯为内标物，加入甲醇定溶，摇晃均匀，静置。
采用日本岛津LC-20A液相色谱(shim pack柱，150×6.0nm，检测器SPD-20A，检测限20ppm，检测波长254nm)，在25℃下使用，流速1.0mL/min，流动相(体积比甲醇/水＝90/10)，观察是否能检测到光引发剂的存在。以相对甲苯的液相出峰面积比的百分量计，液相中引发剂含量越高，说明迁移性越大。
(4)表干测定
采用吹棉球法(GB/T 1728-1979(1989))，在固化膜表面轻放1个1cm 2的疏松脱脂棉球，用嘴距棉球15cm沿水平方向轻吹棉球。
如能吹走棉球，膜表面不留棉丝，记为A；
如能吹走棉球，但膜表面留有棉丝，记为B；
如能不能吹走棉球，记为C；
如能吹走棉球，膜表面不留棉丝，即为表面干燥，说明膜的表干性能优异。
表征结果如表3中所示。
表3
Figure PCTCN2018119354-appb-000044
从表3的测试结果可以看出，本发明的通式(I)所示的含有可聚合基团的芴肟酯类光引发剂的表干性能优异，在光固化应用中引发剂效率高、固化速度快，且不发生迁移，综合性能明显优于现有的肟酯类光引发剂产品。
通式(Ⅱ)所示含氟芴肟酯类光引发剂的制备实施例如下：
实施例1
化合物1的合成
Figure PCTCN2018119354-appb-000045
向250mL的四口烧瓶中加入36.8g原料1a、叔丁醇钠10.6g和DMF 50mL，室温(约25℃)搅拌，滴加26.6g原料1b，约1h滴加完，滴加完后继续搅拌3h，液相跟踪反应至完全。将物料缓慢倒入200g水中，二氯甲烷(每次50mL，共2次)萃取，用5％的碳酸氢钠水溶液(每次100mL，共3次)清洗二氯甲烷层，接着水洗二氯甲烷层至pH呈中性，用80g无水硫酸镁干燥二氯甲烷层，过滤后旋蒸二氯甲烷产物溶液，甲醇重结晶，70℃烘箱干燥2h，得41.9g化合物1，收率75％，纯度98％。
化合物1的结构通过核磁共振氢谱和质谱得到确认:
1H-NMR(CDCl 3，500MHz)：1.3662-1.3772(6H，s)，1.8068-1.8925(8H,m)，2.3675-2.4704(7H，m)，3.6523-3.6744(4H，t)，7.3027-8.1823(6H，m)。
MS(m/z)：560(M+1) +。
实施例2
化合物2的合成
Figure PCTCN2018119354-appb-000046
向250mL的四口烧瓶中加入50.5g原料2a、叔丁醇钾10.6g和DMF 50mL，室温(约25℃)搅拌，滴加27,3g原料2b，约1h滴加完，滴加完后继续搅拌3h，液相跟踪反应至完全。将物料缓慢倒入200g水中，二氯甲烷(每次50mL，共2次)萃取，用5％的碳酸氢钠水溶液(每次100mL，共3次)清洗二氯甲烷层，接着水洗二氯甲烷层至pH呈中性，用80g无水硫酸镁干燥二氯甲烷层，过滤后旋蒸二氯甲烷产物溶液，甲醇重结晶，70℃烘箱干燥2h，得51.4g化合物2，收率68％，纯度98％。
化合物1的结构通过核磁共振氢谱和质谱得到确认:
1H-NMR(CDCl 3，500MHz)：0.9556-0.9918(3H,t)，1.5208-1.5476(2H，m)，2.2675-2.2807(6H,s)，2.7598-2.7604(2H,s)，5.9989-6.0387(2H，d)，7.1225-8.1783(16H，m)。
MS(m/z)：706(M+1) +。
实施例3-20
参照实施例1的方法，由相应原料制备具有表4中所示结构的化合物。
表4
Figure PCTCN2018119354-appb-000047
Figure PCTCN2018119354-appb-000048
Figure PCTCN2018119354-appb-000049
Figure PCTCN2018119354-appb-000050
Figure PCTCN2018119354-appb-000051
性能表征
配置示例性的光固化树脂组合物，对本发明通式(Ⅱ)所示光引发剂的关键应用性能进行评价。
1.光固化树脂组合物的配制
光固化树脂组合物由下列组分组成：
1,6-己二醇二丙烯酸酯            20重量份
丙烯酸酯共聚物[甲基丙烯酸苄酯/甲基丙烯酸/甲基丙烯酸羟乙酯(摩尔比70/10/20)共聚物，Mv＝10000]            57重量份
光引发剂                                   3重量份
丁酮(溶剂)                                 20重量份。
将各组分混合均匀，即可得到用于性能评价的光固化树脂组合物。其中，所述的光引发剂是本发明通式(Ⅱ)所示的含氟芴类光引发剂或作为对比的现有技术中已知的代表性芴类光引发剂。
2.性能评价
对光固化树脂组合物的性能评价包括固化速度、表干性能和耐候性。
(1)固化速度
将光固化树脂组合物在黄光灯下搅拌，取料于PET模板上利用滚涂成膜，在90℃下干燥2min，得到干膜厚为2μm的涂膜，然后冷却至室温，用高压汞灯(曝光机型号：RW-UV70201，单次曝光量50mJ/cm 2)照射对涂膜进行曝光，使其固化成膜。
以涂膜固化成固化膜所需经过履式曝光带的次数评价，经过次数越多，表明固化速度越不理想。
(2)耐候性
参照GB/T-1740-2007，采用漆膜耐湿热性测定方法。将充分固化的固化膜放入预先调节好的调温调湿箱中(温度50±1℃，相对湿度96±2％)，放置240h后，评定固化膜表面起泡、开裂、黄变等破坏现象。
如果没有变化，记为A；
如果有气泡、开裂或黄变等破坏现象，记为B。
(3)表干性能
参照GB/T 1728-1979(1989)，采用吹棉球法进行测定。在固化膜表面轻放1个约1cm 2的疏松脱脂棉球，用嘴距棉球15cm沿水平方向轻吹棉球。
如能吹走棉球，且膜表面不留棉丝，记为A；
如能吹走棉球，但膜表面留有棉丝，记为B；
如不能吹走棉球，记为C。
若能吹走棉球且膜表面不留棉丝，即为表面干燥，说明膜的表干性能优异。
性能评价结果如表5中所示。
表5
Figure PCTCN2018119354-appb-000052
Figure PCTCN2018119354-appb-000053
表5中，比较化合物1和2的结构如下所示：
Figure PCTCN2018119354-appb-000054
从表5的测试结果可以看出，使用本发明通式(Ⅱ)所示的含氟芴类光引发剂的光固化树脂组合物，在单次50mJ/cm 2曝光剂量下就能充分固化，展现出了明显更高的引发效率，且耐候性和表干性能也明显优于采用现有芴类光引发剂的样品。
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 (22)

  1. 一种含氟芴肟酯类光引发剂，其特征在于，所述光引发剂具有通式(I)或(Ⅱ)所示结构：
    Figure PCTCN2018119354-appb-100001
    其中，所述通式(I)中，所述n表示1～4的整数；所述m表示1～4的整数；
    n个所述R 1分别独立地选自-G-(M’)q、氢、硝基、卤素、或
    Figure PCTCN2018119354-appb-100002
    所述m’表示1～4的整数；其中，所述G选自杂原子或羰基，所述杂原子为O、N或S，所述M’选自C 1～C 20的直链或支链烷基、C 3～C 8的环烷基、C 3～C 8的环烷基取代的C 1～C 10的烷基、C 6～C 20的芳基、C 1～C 10的烷基、硝基取代的C 6～C 20芳基、氰基取代的C 6～C 20芳基、C 4～C 20的杂芳基、硝基取代的C 6～C 20杂芳基或氰基取代的C 6～C 20杂芳基，或者所述M’中的一个或多个碳原子被所述杂原子取代，q为1或2；
    所述R 2和所述R 2’分别独立地选自可聚合基团；
    所述Z和所述Z’分别独立地表示空或羰基；
    m个所述R 3和m’所述R 5分别独立地选自氟、被一个或多个氟取代的直链或支链烷基、被一个或多个氟取代的直链或支链烷氧基；
    所述R 4和所述R 6分别独立地选自C 1～C 20的直链或支链烷基、C 3～C 20的环烷基、C 3～C 8环烷基取代的C 1～C 10烷基、C 1～C 10的烷基取代的C 3～C 8环烷基、C 6～C 20的芳基、C 4～C 20的杂芳基或C 2～C 20的链烯基；
    所述通式(Ⅱ)中，所述R 1和所述R 1’各自独立地表示含氟基团；
    所述R 2和所述R 3各自独立地表示C 1～C 20的直链或支链烷基、C 3～C 12的环烷基、C 4～C 18的环烷基烷基、C 6～C 20的芳基、C 7～C 24的芳基烷基、取代或未取代的C 4～C 20的杂芳基，或者R 2和R 3彼此相连形成C 3～C 10的环烷基；
    所述R 4表示羟基、N-吗啉基、N-哌啶基、N-哌嗪基、N-吡咯基或N-仲胺基；
    所述A表示氢、硝基、-CO-CR 2R 3R 4基团、或-R 5-(R 6) n，其中，所述R 5表示O、S、N或羰基，所述R 6表示C 1～C 20的直链或支链烷基、C 3～C 12的环烷基、C 4～C 18的环烷基烷基、取代或未取代的C 6～C 20的芳基、C 7～C 24的芳基烷基、五元或六元的不饱和杂环基团、取代或未取代的C 4～C 20的杂芳基，n表示1或2。
  2. 根据权利要求1所述的含氟芴肟酯类光引发剂，其特征在于，所述通式(I)中，所述M’选自C 1～C 10的直链或支链烷基、C 3～C 6的环烷基、C 3～C 6的环烷基取代的C 1～C 5的烷基、C 6～C 10的芳基、C 1～C 5烷基、硝基取代的C 6～C 10芳基、氰基取代的C 6～C 10芳基、C 4～C 10的杂芳基、硝基取代的C 6～C 10杂芳基或氰基取代的C 6～C 10杂芳基。
  3. 根据权利要求1所述的含氟芴肟酯类光引发剂，其特征在于，所述通式(I)中，所述R 2和所述R 2’分别独立地选自含有双键或环氧基团的可聚合基团。
  4. 根据权利要求3所述的含氟芴肟酯类光引发剂，其特征在于，所述通式(I)中，所述R 2和所述R 2’分别独立地选自C 2～C 12的链烯基，或者，所述R 2和所述R 2’中一个或多个-CH 2-分别独立地被-O-、
    Figure PCTCN2018119354-appb-100003
    所取代；
    优选地，所述通式(I)中，所述R 2和所述R 2’分别独立地选自C 3～C 8的链烯基，或者，所述R 2和所述R 2’中一个或多个-CH 2-分别独立地被-O-、
    Figure PCTCN2018119354-appb-100004
    Figure PCTCN2018119354-appb-100005
    所取代。
  5. 根据权利要求3所述的含氟芴肟酯类光引发剂，其特征在于，所述通式(I)中，所述R 2和所述R 2’分别独立地选自环氧乙烷基取代的C 1～C 10烷基或环氧丙烷基取代的C 1～C 10 烷基，或者所述R 2和所述R 2’中C 1～C 10烷基中的一个或多个-CH 2-各自独立地被-O-、
    Figure PCTCN2018119354-appb-100006
    或-O-CH 2-CH(OH)-CH 2-O-取代。
  6. 根据权利要求5所述的含氟芴肟酯类光引发剂，其特征在于，所述通式(I)中，所述R 2和所述R 2’分别独立地选自以环氧乙烷基或环丙烷基为封端基团的C 1～C 8的烷基，或者所述R 2和所述R 2’中C 1～C 8的烷基中的一个或多个-CH 2-各自独立地被-O-、
    Figure PCTCN2018119354-appb-100007
    Figure PCTCN2018119354-appb-100008
    或-O-CH 2-CH(OH)-CH 2-O-所取代，或者所述环氧乙烷基或所述环氧丙烷基中的H被C 1～C 4的烷基所取代。
  7. 根据权利要求1至4中任一项所述的含氟芴肟酯类光引发剂，其特征在于，所述通式(I)中，m个所述R 3和m’个所述R 5分别独立地选自F、
    Figure PCTCN2018119354-appb-100009
    Figure PCTCN2018119354-appb-100010
  8. 根据权利要求1至4中任一项所述的含氟芴肟酯类光引发剂，其特征在于，所述通式(I)中，所述R 4和所述R 6分别独立地选自C 1～C 6的直链或支链烷基、C 3～C 10的环烷基、C 3～C 6环烷基取代的C 1～C 8烷基、C 1～C 8烷基取代的C 3～C 6环烷基或C 6～C 12的芳基。
  9. 根据权利要求8所述的含氟芴肟酯类光引发剂，其特征在于，所述通式(I)中，所述R 4和所述R 6分别独立地选自苯基、C 1～C 4的直链或支链烷基、C 3～C 8的环烷基或C 3～C 6环烷基取代的C 1～C 4烷基。
  10. 根据权利要求1至9中任一项所述的含氟芴肟酯类光引发剂，其特征在于，所述通式(I)所示的含氟芴肟酯类光引发剂选自
    Figure PCTCN2018119354-appb-100011
    Figure PCTCN2018119354-appb-100012
    Figure PCTCN2018119354-appb-100013
    Figure PCTCN2018119354-appb-100014
    Figure PCTCN2018119354-appb-100015
    Figure PCTCN2018119354-appb-100016
    Figure PCTCN2018119354-appb-100017
    组成的组中的一种或多种。
  11. 根据权利要求1所述的含氟芴类光引发剂，其特征在于：所述通式(Ⅱ)中，所述R 1和所述R 1’各自独立地表示C 2～C 10的直链或支链的含氟烷基，任选地，其中的-CH 2-可被-O-或亚苯基所取代，且亚苯基上的H可任选地被C 1～C 4的烷基所取代。
  12. 根据权利要求1或11所述的含氟芴类光引发剂，其特征在于：所述通式(Ⅱ)中，所述R 1和所述R 1’各自独立地表示以-CF 3、-CF 2CF 3、-CF 2-CH 2F或-CF 2-CHF 2为端基的、C 3～ C 8的直链或支链的含氟烷基，任选地，其中的-CH 2-可被-O-或1,4-亚苯基所取代，且1,4-亚苯基上的H可任选地被C 1～C 4的烷基所取代。
  13. 根据权利要求1所述的含氟芴类光引发剂，其特征在于：所述通式(Ⅱ)中，所述R 2和所述R 3各自独立地表示C 1～C 8的直链或支链烷基、C 4～C 12的环烷基烷基、C 7～C 14的芳基烷基，或者R 2和R 3彼此相连形成C 3～C 8的环烷基。
  14. 根据权利要求1或13所述的含氟芴类光引发剂，其特征在于：所述通式(Ⅱ)中，所述R 2和所述R 3各自独立地表示C 1～C 4的直链或支链烷基、C 4～C 10的环烷基烷基、C 7～C 10的苯基烷基，或者R 2和R 3彼此相连形成C 3～C 8的环烷基。
  15. 根据权利要求1所述的含氟芴类光引发剂，其特征在于：所述通式(Ⅱ)中，所述R 4表示羟基、N-吗啉基、N-哌啶基、或两个氢被C 1～C 4烷基取代的胺基。
  16. 根据权利要求1所述的含氟芴类光引发剂，其特征在于：所述通式(Ⅱ)中，所述A表示氢、硝基、-CO-CR 2R 3R 4基团、或-R 5-(R 6) n，其中，R 5表示O、S、N或羰基，R 6表示C 1～C 8的直链或支链烷基、C 6～C 12的芳基、被C 1～C 5烷基、硝基或氰基取代的C 6～C 12的芳基、五元不饱和杂环基团，n表示1或2。
  17. 根据权利要求1或16所述的含氟芴类光引发剂，其特征在于：所述通式(Ⅱ)中，所述R 6表示C 1～C 4的直链或支链烷基、呋喃基、吡咯基、噻吩基、C 6～C 10的芳基、被C 1～C 4烷基、硝基或氰基取代的C 6～C 10的芳基。
  18. 权利要求1至17中任一项所述的通式(Ⅱ)所示的含氟芴类光引发剂的制备方法，将原料a和b在催化剂作用下反应，反应式如下所示：
    Figure PCTCN2018119354-appb-100018
    其中，所述通式(Ⅱ)中，所述M表示H或OH，
    当所述M表示H时，R 0即为R 1，R 0’即为R 1’，
    当所述M表示OH时，所述R 0、所述R 0’分别对应于R 1、R 1’，且所述R 1表示OR 0、所述R 1’表示OR 0’，
    所述X表示Cl或Br。
  19. 根据权利要求18所述的制备方法，其特征在于：所述的催化剂是碱性催化剂，优选叔丁醇锂、叔丁醇钠和叔丁醇钾中的至少一种。
  20. 一种光固化组合物，其特征在于，所述光固化组合物包括光引发剂，所述光引发剂包括权利要求1至19中任一项所述的含氟芴肟酯类光引发剂。
  21. 一种权利要求1至19中任一项所述的含氟芴肟酯类光引发剂在光固化领域中的应用。
  22. 根据权利要求21所述的应用，其特征在于：所述的光引发剂被用于制备彩色光阻、黑色矩阵、光间隔物、肋栅、干膜、半导体光刻胶及油墨。
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JP2021507058A (ja) 2021-02-22
KR20200101429A (ko) 2020-08-27

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