WO2018149370A1 - 芴氨基酮类光引发剂、其制备方法及含芴氨基酮类光引发剂的uv光固化组合物 - Google Patents

芴氨基酮类光引发剂、其制备方法及含芴氨基酮类光引发剂的uv光固化组合物 Download PDF

Info

Publication number
WO2018149370A1
WO2018149370A1 PCT/CN2018/076209 CN2018076209W WO2018149370A1 WO 2018149370 A1 WO2018149370 A1 WO 2018149370A1 CN 2018076209 W CN2018076209 W CN 2018076209W WO 2018149370 A1 WO2018149370 A1 WO 2018149370A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
acrylate
meth
photoinitiator
Prior art date
Application number
PCT/CN2018/076209
Other languages
English (en)
French (fr)
Inventor
钱晓春
Original Assignee
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 EP18755112.2A priority Critical patent/EP3584242A4/en
Priority to KR1020197023666A priority patent/KR102252495B1/ko
Priority to JP2019544745A priority patent/JP7032416B2/ja
Priority to US16/485,724 priority patent/US11118065B2/en
Publication of WO2018149370A1 publication Critical patent/WO2018149370A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C225/14—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated
    • C07C225/16—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
    • C07C225/18—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings the carbon skeleton containing also rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/41—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/788—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with keto groups bound to a condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
    • C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/108—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
    • C07D295/112—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/135—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing 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
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/04—Polymeric products of isocyanates or isothiocyanates with vinyl compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G03F7/0295—Photolytic halogen compounds
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/357—Six-membered rings

Definitions

  • the invention relates to the technical field of new materials for UV light radiation radical polymerization, in particular to a fluorenylaminoketone photoinitiator, a preparation method thereof and a UV light curing composition containing a fluorenylaminoketone photoinitiator.
  • Alpha-aminoalkylphenone photoinitiators are a class of highly reactive photoinitiators. Among them, commercial photoinitiators are 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone and 2-(4-methylbenzyl)-2-dimethyl Amino-1-(4-morpholinylphenyl)butanone is an ⁇ -aminoalkyl phenone photoinitiator developed by Ciba Corporation under the trade names "Irgacure 369" and "Irgacure 379", respectively. as follows:
  • photoinitiators are often combined with thioxanthone photoinitiators for photocuring in colored systems and exhibit excellent photoinitiator properties.
  • photoinitiators are widely used in ceramic inkjet technology.
  • these photoinitiators have poor compatibility with the matrix resin, and often require a large amount of organic solvent, which is disadvantageous to the health of the production operator, and also causes certain environmental pollution, and the solvent is added, the ink is easily diffused, and the pattern becomes Blurring, can not achieve high-resolution, high-precision decorative effects.
  • due to the application in the colored system there are disadvantages such as low curing speed, difficulty in curing in the deep portion, and limited thickness of the coating, thereby limiting its application.
  • the present invention aims to provide a fluorenylaminoketone photoinitiator, a preparation method thereof and a UV photocurable composition containing a fluorenylaminoketone photoinitiator, which can improve the solubility of a conventional photoinitiator and reduce the activity of a small molecule reactive diluent. use.
  • a fluorenylaminoketone photoinitiator includes a compound having a structure represented by the general formula (I) or a derivative thereof,
  • R 2 represents a C 1 -C 20 linear or branched alkyl group, a C 2 -C 20 alkenyl group, and R 3 is selected from any of the following groups:
  • R 4 represents N-morpholinyl, N-piperidinyl, N-pyrrolyl or N-dialkyl, wherein one or more of the hydrogen atoms of these groups may be substituted by a halogen or a hydroxyl group;
  • R 5 and R 5 ' independently of each other represent a C 1 -C 20 linear or branched alkyl group, a C 4 -C 20 cycloalkyl group, a C 2 -C 20 alkenyl group, a C 6 -C 20 Aryl, C 6 -C 20 alkylaryl group, wherein one or more of these groups may be independently substituted with one another by an alkyl group, a halogen, a hydroxyl group, a nitro group, and optionally, these groups -CH 2 - in the group may be substituted by -O-; or R 5 and R 5 ' may be bonded to each other or form a five- or six-membered ring through -O-, -S-, -NH-;
  • R 6 represents a C 1 -C 20 linear or branched alkyl group, a C 4 -C 20 cycloalkyl group, a C 4 -C 20 alkylcycloalkyl group, a C 2 -C 20 alkenyl group, a C 6 -C 20 aryl, C 6 -C 20 alkylaryl group, wherein -CH 2 - in these groups may be substituted by -O-, -S-, and one or more of these groups
  • the hydrogen atom may be independently substituted with an alkyl group, a halogen, a nitro group, a cyano group, SR 7 , OR 8 ;
  • R 7 and R 8 independently of each other represent hydrogen, a C 1 -C 20 linear or branched alkyl group.
  • a derivative compound having a photoinitiator having a structure represented by the general formula (I) includes a derivative compound obtained by substituting or linking each other under the premise that the main structure of the compound of the formula (I) is maintained. .
  • the derivative compound has a compound represented by the formula (II) or (III):
  • M represents a linking group formed by dimerization, which may be a null bond, a C 1 -C 10 linear or branched alkylene group, a C 6 -C 12 arylene group or a heteroarylene group,
  • -CH 2 - in M is substituted by sulfur, oxygen, NH or carbonyl, optionally, the hydrogen atom is replaced by OH or NO 2 .
  • a UV-curable composition containing a fluorenylaminoketone photoinitiator includes an ethylenically unsaturated photopolymerizable compound and a photoinitiator; wherein the photoinitiator is any of the above-described mercaptoaminoketone photoinitiators.
  • the photoinitiator is a photoinitiator having a structure represented by the general formula (I) or a derivative thereof as a mixture of two or more compounds.
  • the ethylenically unsaturated photopolymerizable compound is a compound containing one carbon-carbon double bond, preferably an acrylate compound or a methacrylate compound; or the ethylenically unsaturated photopolymerizable compound contains two or more a compound having a carbon-carbon double bond, preferably an alkyl diol, an acrylate or methacrylate of a polyhydric alcohol or a polyester polyol, a polyether polyol, an epoxy resin polyol, an acrylate of a polyurethane polyol, or ethylene An unsaturated polyester of a base ether and an unsaturated dicarboxylic acid polyol.
  • the UV-curable composition when used as a UV resist ink or a UV solder resist ink, at least one of the ethylenically unsaturated photopolymerizable compounds used contains an alkali-soluble group, preferably a carboxyl group-containing resin.
  • the carboxyl group-containing resin is a (meth) acrylate, an ethylenically unsaturated carboxylic acid or a (meth) acrylate type polymer; preferably, the (meth) acrylate is selected from methyl (meth) acrylate , ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, diethylaminoethyl (meth)acrylate, (methyl) a group consisting of acrylate dimethylaminoethyl ester, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, decyl (meth) acrylate, glycidyl (meth) acrylate
  • the ethylenically unsaturated carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, vinyl
  • the UV-curable composition further includes other photoinitiators.
  • other photoinitiators are selected from the group consisting of benzophenone, benzil dimethyl ketal, 2-hydroxy-2-methyl-1-benzene.
  • the UV-curable composition further includes a sensitizer; preferably, the sensitizer is a pyrazoline compound, an acridine compound, an anthraquinone compound, a coumarin compound or a tertiary amine compound.
  • the sensitizer is a pyrazoline compound, an acridine compound, an anthraquinone compound, a coumarin compound or a tertiary amine compound.
  • the UV-curable composition further includes a colorant, which is an inorganic pigment or an organic pigment.
  • the UV-curable composition further includes an additive including one or more of a surfactant, a wetting agent, a dispersing agent, a rheology modifier, an antifoaming agent, or a storage enhancer.
  • an additive including one or more of a surfactant, a wetting agent, a dispersing agent, a rheology modifier, an antifoaming agent, or a storage enhancer.
  • the intermediate a and the raw material are subjected to a Friedel-Craft reaction under a catalyst condition to form an intermediate b, and the raw material b is
  • the intermediate a and the raw material c are subjected to a substitution reaction in an organic solvent to form an intermediate b, and the raw material c is thionyl chloride or liquid bromine.
  • the intermediate b and the raw material d are subjected to a substitution reaction in an organic solvent to form an intermediate c, wherein the raw material d is HX.
  • the intermediate c and the starting material e undergo a Stevens rearrangement reaction in an organic solvent under basic conditions to form an intermediate d, wherein the starting material e is R 3 -Br.
  • the product, in the raw material a, B F, the intermediate d and the starting material f are substituted under basic conditions in an organic solvent to form a compound of the formula (I), the raw material f is HA;
  • the product, then B H in the starting material a, the intermediate d and the starting material g undergo a Friedel-Craft reaction under the catalyst conditions to form a compound of the formula (I), and the starting material g is ACl or ABr.
  • a UV-curable composition containing a fluorenylaminoketone photoinitiator includes: an ethylenically unsaturated photopolymerizable compound and a photoinitiator; wherein the photoinitiator comprises a compound having a structure represented by the formula (I) or a derivative thereof,
  • R 4 represents N-morpholinyl, N-piperidinyl, N-pyrrolyl or N-dialkyl, wherein one or more of the hydrogen atoms of these groups may be substituted by a halogen or a hydroxyl group;
  • R 5 and R 5 ' independently of each other represent a C 1 -C 20 linear or branched alkyl group, a C 4 -C 20 cycloalkyl group, a C 2 -C 20 alkenyl group, a C 6 -C 20 Aryl, C 6 -C 20 alkylaryl group, wherein one or more of these groups may be independently substituted with one another by an alkyl group, a halogen, a hydroxyl group, a nitro group, and optionally, these groups -CH 2 - in the group may be substituted by -O-; or R 5 and R 5 ' may be bonded to each other or form a five- or six-membered ring through -O-, -S-, -NH-;
  • R 6 represents a phenyl group which is unsubstituted or substituted by one or more C 1 -C 20 alkyl groups, halogen, cyano group, SR 7 , OR 8 ;
  • R 7 and R 8 independently of each other represent hydrogen, a C 1 -C 20 linear or branched alkyl group.
  • the ethylenically unsaturated photopolymerizable compound is used in an amount of 5 to 95 parts by mass, and the photoinitiator is used in an amount of 0.05 to 15 parts by mass.
  • the ethylenically unsaturated photopolymerizable compound is used in an amount of 10 to 90 parts by mass, and the photoinitiator is used in an amount of 1 to 10 parts by mass.
  • photoinitiator having a structure represented by the general formula (I) is selected from
  • a derivative compound having a photoinitiator having a structure represented by the general formula (I) includes a derivative compound obtained by substituting or linking each other under the premise that the main structure of the compound of the formula (I) is maintained. .
  • the derivative compound has a compound represented by the formula (II) or (III):
  • M represents a linking group formed by dimerization, which may be a null bond, a C 1 -C 10 linear or branched alkylene group, a C 6 -C 12 arylene group or a heteroarylene group,
  • -CH 2 - in M is substituted by sulfur, oxygen, NH or carbonyl, optionally, the hydrogen atom is replaced by OH or NO 2 .
  • a photoinitiator having a structure represented by the general formula (I) or a derivative thereof is a mixture of two or more compounds.
  • the ethylenically unsaturated photopolymerizable compound is a monomer compound or oligomer.
  • the ethylenically unsaturated photopolymerizable compound is a compound containing one carbon-carbon double bond, preferably an acrylate compound or a methacrylate compound; or the ethylenically unsaturated photopolymerizable compound contains two or more a compound having a carbon-carbon double bond, preferably an alkyl diol, an acrylate or methacrylate of a polyhydric alcohol or a polyester polyol, a polyether polyol, an epoxy resin polyol, an acrylate of a polyurethane polyol, or ethylene An unsaturated polyester of a base ether and an unsaturated dicarboxylic acid polyol.
  • the UV-curable composition when used as a UV resist ink or a UV solder resist ink, at least one of the ethylenically unsaturated photopolymerizable compounds used contains an alkali-soluble group, preferably a carboxyl group-containing resin.
  • the carboxyl group-containing resin is a (meth) acrylate, an ethylenically unsaturated carboxylic acid or a (meth) acrylate based polymer;
  • the (meth) acrylate is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate.
  • Base ester diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (methyl)
  • the ethylenically unsaturated carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, vinyl benzoic acid, maleic acid, alkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid One or more of a group consisting of a polymer, an addition product of a hydroxyl group-containing monomer and a cyclic acid anhydride, and an ⁇ -carboxy-polycaprolactone-(meth) acrylate, more preferably (meth) acrylic acid;
  • the (meth) acrylate-based polymer is selected from the group consisting of (meth)acrylamide, n-butyl (meth)acrylate, styrene, vinyl naphthalene, (meth) acrylonitrile, vinyl acetate, ethylene One or more of the group consisting of cyclohexane.
  • the UV-curable composition further includes other photoinitiators.
  • other photoinitiators are selected from the group consisting of benzophenone, benzil dimethyl ketal, 2-hydroxy-2-methyl-1-benzene.
  • the UV-curable composition further includes a sensitizer; preferably, the sensitizer is a pyrazoline compound, an acridine compound, an anthraquinone compound, a coumarin compound or a tertiary amine compound; more preferably The sensitizer is used in an amount of 0 to 5 parts by mass, and more preferably, the amount of the sensitizer is 0 to 2 parts by mass.
  • a sensitizer is a pyrazoline compound, an acridine compound, an anthraquinone compound, a coumarin compound or a tertiary amine compound; more preferably The sensitizer is used in an amount of 0 to 5 parts by mass, and more preferably, the amount of the sensitizer is 0 to 2 parts by mass.
  • the UV-curable composition further includes a colorant which is an inorganic pigment or an organic pigment, and the colorant is used in an amount of 0 to 50 parts by mass.
  • the colorant is used in an amount of 0 to 20 parts by mass.
  • the UV-curable composition further comprises: the additive comprises one or more of a surfactant, a wetting agent, a dispersing agent, a rheology modifier, an antifoaming agent or a storage reinforcing agent; preferably, the additive The amount is 0 to 5 parts by mass, and more preferably, the amount of the additive is 0 to 3 parts by mass.
  • the UV ink includes a UV resist ink, a UV solder resist ink, a flexo ink, an offset ink, and the like.
  • the fluorenylaminoketone-containing photoinitiator provided by the invention can effectively improve the solubility of the traditional photoinitiator, reduce the use of the small molecule reactive diluent, and has high sensitivity, good deep curing effect, and light curing combination in the field of photocuring.
  • the promotion and application of materials, especially colored ink systems, have a good driving effect.
  • the raw materials used are all known compounds in the prior art, and can be easily prepared by a commercially available product or by a known synthesis method, and the preparation method is simple and the product purity is high. Very suitable for industrial production.
  • the UV-curable composition containing the mercaptoaminoketone photoinitiator of the invention has high sensitivity, no residue after development, good pattern integrity, and the coating has no odor or low odor after curing, and the yellowing resistance is excellent. .
  • a fluorenylaminoketone photoinitiator includes a compound having a structure represented by the general formula (I) or a derivative thereof,
  • R 2 represents a C 1 -C 20 linear or branched alkyl group, a C 2 -C 20 alkenyl group, and R 3 is selected from any of the following groups:
  • R 4 represents N-morpholinyl, N-piperidinyl, N-pyrrolyl or N-dialkyl, wherein one or more of the hydrogen atoms of these groups may be substituted by a halogen or a hydroxyl group;
  • R 5 and R 5 ' independently of each other represent a C 1 -C 20 linear or branched alkyl group, a C 4 -C 20 cycloalkyl group, a C 2 -C 20 alkenyl group, a C 6 -C 20 Aryl, C 6 -C 20 alkylaryl group, wherein one or more of these groups may be independently substituted with one another by an alkyl group, a halogen, a hydroxyl group, a nitro group, and optionally, these groups -CH 2 - in the group may be substituted by -O-; or R 5 and R 5 ' may be bonded to each other or form a five- or six-membered ring through -O-, -S-, -NH-;
  • R 6 represents a C 1 -C 20 linear or branched alkyl group, a C 4 -C 20 cycloalkyl group, a C 4 -C 20 alkylcycloalkyl group, a C 2 -C 20 alkenyl group, a C 6 -C 20 aryl, C 6 -C 20 alkylaryl group, wherein -CH 2 - in these groups may be substituted by -O-, -S-, and one or more of these groups
  • the hydrogen atom may be independently substituted with an alkyl group, a halogen, a nitro group, a cyano group, SR 7 , OR 8 ;
  • R 7 and R 8 independently of each other represent hydrogen, a C 1 -C 20 linear or branched alkyl group.
  • the fluorenylaminoketone-containing photoinitiator provided by the invention can effectively improve the solubility of the traditional photoinitiator, reduce the use of the small molecule reactive diluent, and has high sensitivity, good deep curing effect, and light curing combination in the field of photocuring.
  • the promotion and application of materials, especially colored ink systems, have a good driving effect.
  • a derivative compound having a photoinitiator having a structure represented by the general formula (I) includes, by maintaining the main structure of the compound of the formula (I), substituted by its branch or each other A derivative compound obtained by ligation.
  • the derivative compound has a compound as shown in the formula (II) or (III):
  • M represents a linking group formed by dimerization, which may be a null bond, a C 1 -C 10 linear or branched alkylene group, a C 6 -C 12 arylene group or a heteroarylene group,
  • -CH 2 - in M is substituted by sulfur, oxygen, NH or carbonyl, optionally, the hydrogen atom is replaced by OH or NO 2 .
  • the above derivative compound may be a compound of the following structure:
  • a photoinitiator having a structure as shown in the general formula (I) can also be used in combination with other known photoinitiators.
  • the preparation method comprises the following steps:
  • the intermediate a and the raw material are subjected to a Friedel-Craft reaction under the catalyst condition to form an intermediate b, and the raw material b is
  • the intermediate a and the starting material c are substituted in an organic solvent to form the intermediate b, and the raw material c is thionyl chloride or liquid bromine.
  • the intermediate b and the raw material d are substituted in an organic solvent to form an intermediate c, wherein the raw material d is HX.
  • the intermediate c and the starting material e undergo a Stevens rearrangement reaction in an organic solvent under basic conditions to form an intermediate d, wherein the starting material e is R 3 -Br.
  • the intermediate d is the compound of the general formula (I);
  • the product, in the raw material a, B F, the intermediate d and the starting material f are substituted in an organic solvent under basic conditions to form a compound of the formula (I), the raw material f is HA;
  • the product, then B H in the starting material a, the intermediate d and the starting material g undergo a Friedel-Craft reaction under the catalyst conditions to form a compound of the formula (I), and the starting material g is ACl or ABr.
  • the raw materials used are all known compounds in the prior art, and are commercially available or can be easily prepared by a known synthesis method.
  • the reactions involved in the steps (1) to (5) are conventional reactions for synthesizing similar compounds in the art, and the specific reaction conditions are easily determined by those skilled in the art on the basis of knowing the synthetic idea disclosed in the present invention.
  • the preparation method of the invention is simple, the product has high purity and is suitable for industrial production.
  • a UV-curable composition containing a fluorenylaminoketone photoinitiator includes: an ethylenically unsaturated photopolymerizable compound and a photoinitiator; wherein the photoinitiator comprises a compound having a structure represented by the formula (I) or a derivative thereof,
  • R 2 represents a C 1 -C 20 linear or branched alkyl group, a C 2 -C 20 alkenyl group, and R 3 is selected from any of the following groups:
  • R 4 represents N-morpholinyl, N-piperidinyl, N-pyrrolyl or N-dialkyl, wherein one or more of the hydrogen atoms of these groups may be substituted by a halogen or a hydroxyl group;
  • R 5 and R 5 ' independently of each other represent a C 1 -C 20 linear or branched alkyl group, a C 4 -C 20 cycloalkyl group, a C 2 -C 20 alkenyl group, a C 6 -C 20 Aryl, C 6 -C 20 alkylaryl group, wherein one or more of these groups may be independently substituted with one another by an alkyl group, a halogen, a hydroxyl group, a nitro group, and optionally, these groups -CH 2 - in the group may be substituted by -O-; or R 5 and R 5 ' may be bonded to each other or form a five- or six-membered ring through -O-, -S-, -NH-;
  • R 6 represents a C 1 -C 20 linear or branched alkyl group, a C 4 -C 20 cycloalkyl group, a C 4 -C 20 alkylcycloalkyl group, a C 2 -C 20 alkenyl group, a C 6 -C 20 aryl, C 6 -C 20 alkylaryl group, wherein -CH 2 - in these groups may be substituted by -O-, -S-, and one or more of these groups
  • the hydrogen atom may be independently substituted with an alkyl group, a halogen, a nitro group, a cyano group, SR 7 , OR 8 ;
  • R 7 and R 8 independently of each other represent hydrogen, a C 1 -C 20 linear or branched alkyl group.
  • the UV-curable composition containing the mercaptoaminoketone photoinitiator of the invention has high sensitivity, no residue after development, good pattern integrity, and the coating has no odor or low odor after curing, and the yellowing resistance is excellent. .
  • the preparation process of the UV light curing composition of the invention is simple. According to an exemplary embodiment of the invention, the above components can be stirred and mixed uniformly in a dark room or a yellow light environment.
  • the UV-curable composition further includes other photoinitiators.
  • the other photoinitiators are selected from the group consisting of benzophenone, benzil dimethyl ketal, 2-hydroxy-2. -Methyl-1-phenyl-acetone, 1-hydroxy-cyclohexyl-phenyl-one, isopropyl thiazepine, (2,4,6-trimethyl-benzoyl)diphenylphosphine oxide And one or more of the group consisting of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
  • the UV-curable composition further comprises a colorant, the colorant being an inorganic pigment or an organic pigment, and the colorant is used in an amount of 0 to 50 parts by mass, preferably, the amount of the colorant is 0- 20 parts by mass.
  • the UV-curable composition further includes an additive including one of a surfactant, a wetting agent, a dispersing agent, a rheology modifier, an antifoaming agent or a storage reinforcing agent or A variety.
  • Ethylenically unsaturated photopolymerizable compound A compound having a radically polymerizable ethylenically unsaturated bond, which may be a monomeric compound (low molecular weight) or an oligomer (higher molecular weight).
  • a compound containing a carbon-carbon double bond preferably an acrylate compound, a methacrylate compound, for example, an acrylate or methacrylate of a monohydric alcohol: methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid Cyclohexyl ester, isobornyl acrylate, hydroxyethyl acrylate, methyl methacrylate and acrylonitrile, N-dialkyl acrylamide, N-vinyl pyrrolidone, vinyl benzene, vinyl acetate, vinyl ether .
  • a compound containing two or more carbon-carbon double bonds including: an alkyl diol, an acrylate or methacrylate of a polyhydric alcohol or a polyester polyol, a polyether polyol, an epoxy resin polyol, a polyurethane
  • An acrylate of a polyol, a vinyl ether, and an unsaturated polyester of an unsaturated dicarboxylic acid polyol for example, polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate , polyethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, polyester oligomer acrylate, urethane oligomer acrylate, aromatic epoxy acrylate, horse Ethylene glycol polyester.
  • the UV-curable composition When the UV-curable composition is used as a UV resist ink or a UV solder resist ink, at least one of the ethylenically unsaturated photopolymerizable compounds used contains an alkali-soluble group, and such a compound can be initiated by cross-linking polymerization. Further, it is also possible to have solubility in a developing solution (usually an alkaline developing solution) used in the developing treatment step when forming an image pattern, and a carboxyl group-containing resin is preferable. In particular, a (meth) acrylate-based polymer obtained by copolymerizing a (meth) acrylate, an ethylenically unsaturated carboxylic acid, and another copolymerizable monomer.
  • the (meth) acrylate may be methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate.
  • the decyl acrylate and the glycidyl (meth) acrylate may be used singly or in combination of two or more.
  • the ethylenically unsaturated carboxylic acid is preferably acrylic acid, methacrylic acid, vinyl benzoic acid, maleic acid, alkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid Addition of a polymer, a monomer having a hydroxyl group (for example, 2-hydroxyethyl (meth)acrylate, etc.) and a cyclic acid anhydride (for example, maleic anhydride or phthalic anhydride, cyclohexane dicarboxylic anhydride) Product, ⁇ -carboxy-polycaprolactone-(meth)acrylate, and the like.
  • a polymer a monomer having a hydroxyl group (for example, 2-hydroxyethyl (meth)acrylate, etc.) and a cyclic acid anhydride (for example, maleic anhydride or phthalic anhydride, cyclohexane dicarboxy
  • (meth)acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
  • These ethylenically unsaturated carboxylic acids may be used singly or in combination of two or more.
  • the other copolymerizable monomers are preferably (meth)acrylamide, n-butyl (meth)acrylate, styrene, vinyl naphthalene, (meth)acrylonitrile, vinyl acetate, vinyl cyclohexane. These monomers may be used singly or in combination of two or more.
  • These carbon-carbon double bond compounds may be used alone or in combination of two or more, or may be pre-copolymerized to form an oligomer for use in the formulation.
  • the radical polymerizable resin is used in the photocurable composition in an amount of 5 to 95 parts by mass, preferably about 10 to 90 parts by mass.
  • the photoinitiator used in the photocurable composition of the present invention contains at least one of a compound having a quinone compound represented by the general formula (I) as a main structure or a derivative thereof:
  • R 2 represents a C 1 -C 20 linear or branched alkyl group, a C 2 -C 20 alkenyl group, and R 3 is selected from any of the following groups:
  • R 4 represents N-morpholinyl, N-piperidinyl, N-pyrrolyl or N-dialkyl, wherein one or more of the hydrogen atoms of these groups may be substituted by a halogen or a hydroxyl group;
  • R 5 and R 5 ' independently of each other represent a C 1 -C 20 linear or branched alkyl group, a C 4 -C 20 cycloalkyl group, a C 2 -C 20 alkenyl group, a C 6 -C 20 Aryl, C 6 -C 20 alkylaryl group, wherein one or more of these groups may be independently substituted with one another by an alkyl group, a halogen, a hydroxyl group, a nitro group, and optionally, these groups -CH 2 - in the group may be substituted by -O-; or R 5 and R 5 ' may be bonded to each other or form a five- or six-membered ring through -O-, -S-, -NH-;
  • R 6 represents a C 1 -C 20 linear or branched alkyl group, a C 4 -C 20 cycloalkyl group, a C 4 -C 20 alkylcycloalkyl group, a C 2 -C 20 alkenyl group, a C 6 -C 20 aryl, C 6 -C 20 alkylaryl group, wherein -CH 2 - in these groups may be substituted by -O-, -S-, and one or more of these groups
  • the hydrogen atom may be independently substituted with an alkyl group, a halogen, a nitro group, a cyano group, SR 7 , OR 8 ;
  • R 7 and R 8 independently of each other represent hydrogen, a C 1 -C 20 linear or branched alkyl group.
  • the indole amino ketone compound of the formula (I) comprises a compound represented by the following structure:
  • the derivative compound having a compound represented by the formula (I) as a main structure means a derivative obtained by substituting or linking each other while maintaining the main structure of the compound of the formula (I).
  • the derivative compound having a compound represented by the formula (I) as a main structure is a compound represented by the following formulas (II) and (III):
  • Formula (II) and formula (III) are dimers of formula (I), and M represents a linking group formed by dimerization, which may be a null bond, a linear or branched chain of C 1 -C 10 Alkyl, C 6 -C 12 arylene or heteroarylene, -CH 2 - in M is optionally substituted by sulfur, oxygen, NH or carbonyl, the hydrogen atom optionally being OH or NO 2 Replace.
  • M represents a linking group formed by dimerization, which may be a null bond, a linear or branched chain of C 1 -C 10 Alkyl, C 6 -C 12 arylene or heteroarylene, -CH 2 - in M is optionally substituted by sulfur, oxygen, NH or carbonyl, the hydrogen atom optionally being OH or NO 2 Replace.
  • the above derivative compound may be a compound of the following structure:
  • a photoinitiator having a structure as shown in the general formula (I) can also be used in combination with other known photoinitiators.
  • camphorquinone benzophenone (BP), benzophenone derivatives such as 2,4,6-trimethylbenzophenone, 2-methylbenzophenone, 2-methyldiphenyl Ketone, 3-methylbenzophenone, 4-methylbenzophenone, 2-methylcarbonylbenzophenone, 4,4'-bis(chloromethyl)benzophenone, 4- Chlorobenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxy-benzophenone, [4-(4-methylphenylthio)phenyl] -Phenyl ketone, methyl 2-benzoylbenzoate, 3-methyl-4'-phenylbenzophenone, 2,4,6-trimethyl-4'-phenylbenzophenone , 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, ketal compounds, such as benzil dimethyl ketal (651 Acetophenone,
  • a photoinitiator having a structure represented by the general formula (I) is particularly suitable for addition to the compounds of the formula (I), the formula (II) and the formula (III), and BP, 651, 1173, 184, One or more of ITX, TPO, and 819 are used in combination.
  • the photoinitiator i.e., a photoinitiator having a structure represented by the formula (I) and other photoinitiators, is used in the photocurable composition in an amount of from 0.05 to 15 parts by mass, preferably from 1 to 10 parts by mass.
  • the photocurable composition of the present invention may further contain a sensitizer in order to obtain higher sensitivity or to match the LED light source.
  • the type of the sensitizer may be a pyrazoline compound, an acridine compound, an anthraquinone compound, a coumarin compound or a tertiary amine compound.
  • a pyrazoline compound 1-phenyl-3-(4-tert-butylstyryl)-5-(4-tert-butylphenyl)pyrazoline, 1-phenyl-3-linked Phenyl-5-(4-tert-butylphenyl)pyrazoline; 9-phenyl acridine, 9-p-methylphenyl acridine, 9-m-methylphenyl acridine, 9-o-chlorobenzene Acridine; 2-ethylhydrazine-9,10-bis(methyl 4-chlorobutyrate), 1,2,3-trimethylhydrazine-9,10-dioctyl ester, 2-ethylhydrazine- 9,10-diethyl ester, 2-e
  • the sensitizer is used in the photocurable composition in an amount of from 0 to 5 parts by mass, preferably from 0 to 2 parts by mass.
  • One or more pigments may be included as a colorant in the UV photocurable composition.
  • the pigment can be of any color including, but not limited to, black, blue, brown, cyan, green, white, purple, magenta, red, orange, and yellow, as well as spot colors of their mixtures.
  • the pigment may be an inorganic pigment or an organic pigment.
  • the organic pigments present in the UV-curable composition may be perylene, phthalocyanine fuels (eg, phthalocyanine green, phthalocyanine blue), cyanine pigments (Cy3, Cy5, and Cy7), naphthalocyanine pigments, nitroso pigments.
  • phthalocyanine fuels eg, phthalocyanine green, phthalocyanine blue
  • cyanine pigments Cy3, Cy5, and Cy7
  • naphthalocyanine pigments nitroso pigments.
  • azo pigment, diazo pigment, diazo condensation pigment basic dye pigment, basic blue pigment, blue anthraquinone pigment, root red pigment, quinacridone pigment, isoindolinone pigment, dioxazine pigment, Carbazole dioxazine violet pigment, alizarin lake pigment, phthalamide pigment, carmine red lake pigment, tetrachloroisoindolinone pigment, picone pigment, anthraquinone pigment and quinophthalone pigment, and A mixture of two or more of the above or a derivative of the above.
  • Inorganic pigments in the photocurable composition include, for example, metal oxides (e.g., titanium dioxide, conductive titanium dioxide), iron oxides (e.g., red iron oxide, yellow iron oxide, black iron oxide, and transparent iron oxide), aluminum oxide, silicon oxide. , carbon black pigment, metal sulfide, metal chloride and a mixture of two or more thereof.
  • metal oxides e.g., titanium dioxide, conductive titanium dioxide
  • iron oxides e.g., red iron oxide, yellow iron oxide, black iron oxide, and transparent iron oxide
  • aluminum oxide silicon oxide.
  • carbon black pigment e.g., carbon black pigment, metal sulfide, metal chloride and a mixture of two or more thereof.
  • the colorant is used in the photocurable composition in an amount of from 0 to 50 parts by mass, preferably from 0 to 20 parts by mass.
  • Additives include, but are not limited to, one or more of a surfactant, a wetting agent, a dispersing agent, a rheology modifier, an antifoaming agent, or a storage enhancer.
  • the additive is used in the photocurable composition in an amount of from 0 to 5 parts by mass, preferably from 0 to 3 parts by mass.
  • the photocurable composition of the present invention is polymerized by imparting energy such as ultraviolet rays, visible rays, near-infrared rays, or the like to an electron beam during the polymerization reaction, whereby a target polymer can be obtained.
  • a light source for imparting energy a light source having a dominant wavelength that emits light in a wavelength region of 250 nm to 450 nm is preferable.
  • the light source having a dominant wavelength of light emitted in a wavelength region of 250 nm to 450 nm include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, and a high power metal halide lamp.
  • xenon lamp pulsed xenon lamp, xenon lamp, Led lamp, fluorescent lamp, Nd-YAG3 double-wave laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser, semiconductor excited solid laser, etc.
  • kind of light source
  • the structure of the product was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry.
  • the structure of the product was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry.
  • the method is the same as the preparation method of 38a, MS (m/z): 349 (M+1) + .
  • the method is the same as the preparation method of 38b, MS (m/z): 383 (M+1) + .
  • the method is the same as the preparation method of 38c, MS (m/z): 392 (M+1) + .
  • the method is the same as the preparation method of 38d.
  • the structure of the product was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry.
  • the structure of the product was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry.
  • the photoinitiator of the present invention and the solubility properties of Irgacure 369 and Irgacure 379 mentioned in the background are exemplified by the widely used diluents 1,6-hexanediol diacrylate (HDDA) and acetone solvent.
  • HDDA 1,6-hexanediol diacrylate
  • acetone solvent a widely used diluent for diluents 1,6-hexanediol diacrylate (HDDA) and acetone solvent.
  • the test the maximum weight which can be dissolved in 100 g of solvent at 20 ° C is used as an evaluation standard.
  • the test results are shown in Table 2.
  • the ⁇ -aminoketone photoinitiator containing the fluorene structure of the present invention has greatly improved solubility compared with the commercial Irgacure 369 and Irgacure 379 photoinitiators, and can be greatly reduced in use. Use of small molecule reactive diluents.
  • the ⁇ -aminoketone photoinitiator has high photoinitiator activity in photocurable color system, and is especially suitable for photocuring paints and inks. Therefore, the curing performance is evaluated by applying the initiator to the ink system. .
  • Step 1 Prepare a color paste.
  • the weight percentage of each component in the color paste is as follows:
  • the above raw material components were ground to a particle size of ⁇ 1 ⁇ m using a sitting sand mill, and filtered to obtain the color paste.
  • Step 2 preparing an ink for UV curing, the weight of each component in the ink is as follows:
  • the photoinitiator in the above ink components is the photoinitiator of the invention or the commercial Irgacure 369 and 907. Since the solubility of 369 is relatively poor, it is necessary to add about 10% of methyl ethyl ketone solvent to the above formulation to dissolve it completely.
  • the above formulation was stirred in a four-necked flask at room temperature for 3 hours in the dark, and filtered to obtain an ink for curing.
  • the ink is sprayed on the ceramic tile, the thickness of the spray is 60-80 ⁇ m, and then the ultraviolet light source is used for ultraviolet light for 80 mw/cm 2 for 50 s, and then the ultraviolet-cured ceramic tile is sintered at 80 ° C for 50 min, and cooled. After the detection of the ink coating effect on the ceramic tile.
  • the adhesion test refers to the GB/T 9286-1998 test standard, and is tested by the 100-grid method and evaluated according to the 0-5 standard; the deep curing degree is measured by the finger-point method, that is, coated with nail file, Shedding, no bottoming phenomenon means that the bottom layer is completely cured; the pattern effect is observed by the naked eye, and the pattern is clear and fine, and the edge is smooth and rough without roughness.
  • the specific test results are shown in Tables 3, 4, 5 and 6.
  • the fluorenylaminoketone-containing photoinitiator provided by the present invention can effectively improve the solubility of a conventional photoinitiator and reduce the activity of small molecules.
  • the use of thinner, and high sensitivity, deep curing effect, has a good role in promoting the promotion and application of colored ink systems in the field of light curing.
  • the residual odor of the cured film is evaluated by the nose, and the test results are divided into three levels: 1 (no odor), 2 (taste), and 3 (irritating odor);
  • the yellowing is subjected to full transmission scanning by using a color difference meter (X-Rite Color i7).
  • the scanning wavelength is 400-700 nm, and the ⁇ b value is read to evaluate the yellowing. The smaller the ⁇ b is, the less obvious the yellowing is. On the contrary, the yellower is more serious;
  • the adhesion evaluation refers to GB9286-88 "color paint and varnish paint film cross-cut test", through the cross-cut test method to evaluate the adhesion of the film.
  • the degree of damage it is divided into 0-5 grades (6 grades in total), of which 0 is preferred, and none of the membrane faces fall off; 5 grades are extremely poor, and the membrane surface is severely peeled off.
  • UV-curable compositions were formulated to measure the components in weight percent with Irgacure 907 and APi-307 as the reference compounds under equivalent conditions.
  • Coating conditions Refer to "GB/T 9271-2008 Paint and varnish standard test plate" to pre-treat the substrate horse mouth patch, and then mix the uniform formula in the dark room with 25# wire rod coating and Makou On the patch, the coating thickness is about 25 ⁇ m, exposure conditions: RW-UV.70201 crawler exposure machine, radiation wavelength is 250-450nm, aging conditions: after exposure, placed in an oven at 80 ° C for 24h, the test results are shown in Table 7 below Shown as follows:
  • the components A and B were uniformly mixed at 3:1 and allowed to stand for half an hour.
  • Printing conditions 36-43T silk screen, dry film thickness 12-15 ⁇ m, pre-baking conditions: 75 °C first side 20 minutes, second side 25 minutes; exposure conditions: RW-UV.70201 crawler exposure machine, radiation wavelength 250 -450 nm; development conditions: 0.5% sodium hydroxide solution, developed at 30 ⁇ 2 ° C for 60 s, the test results are shown in Table 9 below:
  • Example 24 UV flexo ink
  • the above raw materials were uniformly mixed in a dark room, and coated on a white paperboard at a thickness of 5 ⁇ m.
  • the exposure conditions were: RW-UV.70201 crawler type exposure machine, and the radiation wavelength was 250-450 nm.
  • the test results are shown in Table 10 below:
  • the above materials were uniformly mixed in a dark room and applied to a plastic substrate at a thickness of 2 ⁇ m.
  • the exposure conditions were: RW-UV.70201 crawler type exposure machine, and the radiation wavelength was 250-450 nm.
  • the test results are shown in Table 11 below:
  • the photocurable composition containing the mercaptoaminoketone photoinitiator of the present invention is applied to a photocurable coating and an ink, has good photocuring properties, good yellowing resistance, and no odor after curing. Residue, excellent overall performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Polymerisation Methods In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一种芴氨基酮类光引发剂、其制备方法及含芴氨基酮类光引发剂的UV光固化组合物。该光引发剂包括具有如通式（Ⅰ）所示结构的化合物或其衍生化合物（Ⅰ）。本发明提供的芴氨基酮类光引发剂可以有效的改善传统光引发剂的溶解性，降低小分子活性稀释剂的使用，而且感度高，深层固化效果好，对光固化领域的光固化组合物、特别是有色油墨体系的推广应用有很好的推动作用，本发明的含芴氨基酮光引发剂的UV光固化组合物，具有高感度，显影后无残留，图案完整性好，并且固化后涂层无气味或低气味，另外耐黄变性能也很优异。

Description

芴氨基酮类光引发剂、其制备方法及含芴氨基酮类光引发剂的UV光固化组合物 技术领域
本发明涉及UV光辐射自由基聚合新材料技术领域，具体而言，涉及一种芴氨基酮类光引发剂、其制备方法及含芴氨基酮类光引发剂的UV光固化组合物。
背景技术
α-氨烷基苯酮类光引发剂是一类反应活性很高的光引发剂。其中，商品化的光引发剂有2-苄基-2-二甲基氨基-1-(4-吗啉苯基)丁酮和2-(4-甲基苄基)-2-二甲基氨基-1-(4-吗啉苯基)丁酮，是Ciba公司研制成的α-氨烷基苯酮类光引发剂，商品名分别为“Irgacure 369”和“Irgacure 379”，其结构是如下：
Figure PCTCN2018076209-appb-000001
这类光引发剂常与硫杂蒽酮类光引发剂配合，应用于有色体系的光固化，表现出优异的光引发剂性能，例如，在陶瓷喷墨技术中这类光引发剂被广泛应用。然而，这些光引发剂与基体树脂的相容性差，常常需要添大量的有机溶剂，不利于生产操作者的健康，同时还会造成一定的环境污染，而且添加溶剂，墨水容易扩散，图案变得模糊，无法达到高分辨率、高精度的装饰效果。另一方面，由于应用在有色体系中，在性能上还存在固化速度低，深层部位难以固化完全、涂层厚度受限等缺点，从而限制其应用。
2001年，专利文件JP2001348412A中公开了2-甲基-1-[4-(甲基硫代)苯基]-2-(4-吗啉基)-1-丙酮(商品名Irgacure 907)作为光引发剂组分的液态硬化性树脂组合物。但是，该化合物结构中芳香环体系含有甲硫基，因此不可避免地存在光照裂解后产生不良气味，固化产品出现严重的黄变等问题，这在食品包装、清漆涂料、白色油墨等领域是不能被应用的。
针对上述缺陷，近年来，对于Irgacure 907光引发剂替代品的研究也有相关报道，例如专利申请号CN101724099中披露了一系列联苯基衍生物的α-氨基酮类化合物，其中1-([1，1-联苯基]-4-基)-2-甲基-2-吗啉基丙烷-1-酮是Irgacure 907的有效替代品。该化合物不含硫元素，应用于UV自由基光聚合固化体系中体现了优异的耐黄变性、光照分解后不会产生不良气味。但是在实际应用中发现，该类光引发剂溶解性差，易升华，会对生产设备和光源造成污染，所以并非是一个完美的替代品。
这些问题已在业内引起广泛关注，因光引发剂的气味性、黄变性、毒性等问题大大限制了UV涂料、UV油墨在家具、电器、汽车内饰、香烟、食品、医药以及化妆品等众多领域的应用。开发可以有效解决上述问题且在经济和环境友好性上具备优势竞争力的光固化组合物是当前该产业领域面临的重要课题之一。
发明内容
本发明旨在提供一种芴氨基酮类光引发剂、其制备方法及含芴氨基酮类光引发剂的UV光固化组合物，改善传统光引发剂的溶解性，降低小分子活性稀释剂的使用。
为了实现上述目的，根据本发明的一个方面，提供了一种芴氨基酮类光引发剂。该光引发剂包括具有如通式(Ⅰ)所示结构的化合物或其衍生化合物，
Figure PCTCN2018076209-appb-000002
其中，
A代表氢、卤素、硝基、C 1-C 20的直链或支链烷基、C 3-C 10的烷基环烷基、C 4-C 10的烷基环烷基或环烷基烷基、
Figure PCTCN2018076209-appb-000003
-COR 6、或-CO-CR 2R 3R 4基团，其中，可选的，-CH 2-被O、N、S或C(＝O)所取代；
R 1代表氢、卤素、C 1-C 20的直链或支链烷基、C 4-C 20的环烷基烷基或C 2-C 20的链烯基，可选的，R 1中的-CH 2-被O、N、S或C(＝O)所取代，R 1之间可成环；
R 2和R 3分别独立地代表C 1-C 20的直链或支链烷基、C 3-C 20的环烷基、C 4-C 20的环烷基烷基、C 4-C 20的烷基环烷基、C 6-C 20芳基、C 6-C 20的烷基芳基，其中这些基团中的一个或多个氢可彼此独立地被烷基、卤素、羟基、硝基所取代，并且可选的，R 2和R 3中的-CH 2-被O、N、S或C(＝O)所取代，且R 2和R 3可相互成环；
或R 2代表C 1-C 20的直链或支链的烷基、C 2-C 20的链烯基，R 3选自下列任一种基团：
a)化学式如下的基团：
Figure PCTCN2018076209-appb-000004
其中m是0或1，R 9代表氢、C 1-C 8烷基或苯基，R 10、R 11和R 12彼此独立地表示氢、C 1-C 4烷基；或
b)化学式如下的基团：
Figure PCTCN2018076209-appb-000005
其中n是0，1，2或3；或
c)化学式如下的基团：
Figure PCTCN2018076209-appb-000006
其中Ar是取代或未被取代的苯基、萘基、呋喃基、噻吩基或吡啶基；
R 4代表N-吗啉基、N-哌啶基、N-吡咯基或N-二烷基，其中这些基团中的一个或多个氢原子可被卤素、羟基所取代；
R 5、R 5’彼此独立地代表C 1-C 20的直链或支链的烷基、C 4-C 20的环烷基、C 2-C 20的链烯基、C 6-C 20的芳基、C 6-C 20的烷基芳基，其中这些基团中的一个或多个氢可彼此独立地被烷基、卤素、羟基、硝基所取代，并且任选地，这些基团中的-CH 2-可被-O-取代；或者R 5和R 5’可以彼此相连或通过-O-、-S-、-NH-形成五元或六元环；
R 6代表C 1-C 20的直链或支链的烷基、C 4-C 20的环烷基、C 4-C 20的烷基环烷基、C 2-C 20的链烯基、C 6-C 20的芳基、C 6-C 20的烷基芳基，其中这些基团中的-CH 2-可被-O-、-S-取代，并且这些基团的一个或多个氢原子可以独立地被选自烷基、卤素、硝基、氰基、SR 7、OR 8所取代；
R 7和R 8相互独立地代表氢、C 1-C 20的直链或支链烷基。
进一步地，具有如通式(Ⅰ)所示结构的光引发剂的衍生化合物包括在保持式(I)化合物主体结构不变的前提下，通过其支链取代或彼此连接而得到的衍生物化合物。
进一步地，衍生物化合物具有如通式(II)或(III)所示的化合物：
Figure PCTCN2018076209-appb-000007
Figure PCTCN2018076209-appb-000008
其中，M代表二聚化而形成的连接基团，其可为空键、C 1-C 10的直链或支链亚烷基、C 6-C 12的亚芳基或亚杂芳基，任选地，M中的-CH 2-被硫、氧、NH或羰基所取代，任选地，氢原子被OH或NO 2所取代。
根据本发明的另一个方面，提供了一种含芴氨基酮类光引发剂的UV光固化组合物。该UV光固化组合物包括：烯属不饱和可光聚合化合物和光引发剂；其中，光引发剂为上述任一种的芴氨基酮类光引发剂。
进一步地，光引发剂为具有如通式(Ⅰ)所示结构的光引发剂或其衍生化合物为两种或多种化合物的混合物。
进一步地，烯属不饱和可光聚合化合物为包含一个碳碳双键的化合物，优选为丙烯酸酯化合物或甲基丙烯酸酯化合物；或烯属不饱和可光聚合化合物为包含两个及两个以上碳碳双键的化合物，优选为烷基二元醇、多元醇的丙烯酸酯或甲基丙烯酸酯或者聚酯多元醇、聚醚多元醇、环氧树脂多元醇、聚氨酯多元醇的丙烯酸酯、乙烯基醚以及不饱和二元羧酸多元醇的不饱和聚酯。
进一步地，当UV光固化组合物作为UV抗蚀油墨或UV阻焊油墨用途时，使用的烯属不饱和可光聚合化合物中至少一种化合物含有碱溶性基团，优选为含羧基的树脂。
进一步地，含羧基的树脂为(甲基)丙烯酸酯、乙烯性不饱和羧酸或(甲基)丙烯酸酯系聚合物；优选的，(甲基)丙烯酸酯选自由(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸酯二甲胺基乙酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸糠基酯、(甲基)丙烯酸缩水甘油酯组成的组中的一种或多种；优选的，乙烯性不饱和羧酸选自由丙烯酸、甲基丙烯酸、乙烯基安息酸、马来酸、马来酸烷基酯、富马酸、衣康酸、丁烯酸、肉桂酸、丙烯酸二聚体、具有羟基的单体和环状酸酐的加成产物、ω-羧基-聚己内酯-(甲基)丙烯酸酯组成的组中的一种或多种，更优选为(甲基)丙烯酸；优选的，(甲基)丙烯酸酯系聚合物选自由(甲基)丙烯酰胺、(甲基)丙烯酸正丁酯、苯乙烯、乙烯基萘、(甲基)丙烯晴、乙酸乙烯基酯、乙烯基环己烷组成的组中的一种或多种。
进一步地，UV光固化组合物还包括其他光引发剂，优选的，其他光引发剂选自由二苯甲酮、苯偶酰二甲基缩酮、2-羟基-2-甲基-1-苯基-丙酮、1-羟基-环己基-苯基-酮、异丙基硫杂蒽、(2,4,6-三甲基-苯甲酰基)二苯基氧化膦和双(2,4,6-三甲基苯甲酰基)-苯基氧化膦组成的组中的一种或多种。
进一步地，UV光固化组合物还包括增感剂；优选的，增感剂为吡唑啉类化合物、吖啶类化合物、蒽类化合物、香豆素类化合物或叔胺类化合物。
进一步地，UV光固化组合物还包括着色剂，着色剂为无机颜料或有机颜料。
进一步地，UV光固化组合物还包括添加剂，添加剂包括表面活性剂、润湿剂、分散剂、流变改性剂、消泡剂或储存增强剂中的一种或多种。
根据本发明的再一个方面，提供了一种上述芴氨基酮类光引发剂的制备方法，包括以下步骤：
(1)原料a与原料b发生傅克反应生成中间体a，反应式如下：
Figure PCTCN2018076209-appb-000009
(2)中间体a发生取代反应生成中间体b：
Figure PCTCN2018076209-appb-000010
(3)中间体b发生取代反应生成中间体c：
Figure PCTCN2018076209-appb-000011
(4)中间体c发生Stevens重排反应生成中间体d：
Figure PCTCN2018076209-appb-000012
(5)当预得到A＝H的产物，则原料a中B＝H，中间体d即为通式(I)化合物；
当预得到
Figure PCTCN2018076209-appb-000013
的产物，则原料a中B＝F，中间体d发生取代反应生成具有如下通式(I)化合物；
Figure PCTCN2018076209-appb-000014
当预得到
Figure PCTCN2018076209-appb-000015
的产物，则原料a中B＝H，中间体d发生傅克反应生成具有如下通式(I)化合物；
Figure PCTCN2018076209-appb-000016
进一步地，步骤(1)中，中间体a与原料在催化剂条件下发生傅克反应生成中间体b，原料b为
Figure PCTCN2018076209-appb-000017
进一步地，步骤(2)中，中间体a与原料c于有机溶剂中发生取代反应生成中间体b，原料c为二氯亚砜或液溴。
进一步地，步骤(3)中，中间体b与原料d于有机溶剂中发生取代反应生成中间体c，其中，原料d为HX。
进一步地，步骤(4)中，中间体c与原料e在碱性条件下于有机溶剂中发生Stevens重排反应生成中间体d其中，原料e为R 3-Br。
进一步地，步骤(5)中，当预得到A＝H的产物，则原料a中B＝H，中间体d即为通式(I)化合物；当预得到
Figure PCTCN2018076209-appb-000018
的产物，则原料a中B＝F，中间体d与原料f在碱性条件下于有机溶剂中发生取代反应生成通式(I)所示化合物，原料f为HA；当预得到
Figure PCTCN2018076209-appb-000019
的产物，则原料a中B＝H，中间体d与原料g在催化剂条件下发生傅克反应生成通式(I)所示化合物，原料g为ACl或ABr。
根据本发明的又一个方面，提供了一种上述UV光固化组合物在UV涂料和UV油墨方面的应用。
为了实现上述目的，根据本发明的一个方面，提供了一种含芴氨基酮类光引发剂的UV光固化组合物。该UV光固化组合物包括：烯属不饱和可光聚合化合物和光引发剂；其中，光引发剂包括具有如通式(Ⅰ)所示结构的化合物或其衍生化合物，
Figure PCTCN2018076209-appb-000020
其中，
A代表氢、卤素、硝基、C 1-C 20的直链或支链烷基、C 3-C 10的烷基环烷基、C 4-C 10的烷基环烷基或环烷基烷基、
Figure PCTCN2018076209-appb-000021
-COR 6、或-CO-CR 2R 3R 4基团，其中，可选的，-CH 2-被O、N、S或C(＝O)所取代；
R 1代表氢、卤素、C 1-C 20的直链或支链烷基、C 4-C 20的环烷基烷基或C 2-C 20的链烯基，可选的，R 1中的-CH 2-被O、N、S或C(＝O)所取代，R 1之间可成环；
R 2和R 3分别独立地代表C 1-C 20的直链或支链烷基、C 3-C 20的环烷基、C 4-C 20的环烷基烷基、C 4-C 20的烷基环烷基、C 6-C 20芳基、C 6-C 20的烷基芳基，其中这些基团中的一个或多个氢可彼此独立地被烷基、卤素、羟基、硝基所取代，并且可选的，R 2和R 3中的-CH 2-被O、N、S或C(＝O)所取代，且R 2和R 3可相互成环；
R 4代表N-吗啉基、N-哌啶基、N-吡咯基或N-二烷基，其中这些基团中的一个或多个氢原子可被卤素、羟基所取代；
R 5、R 5’彼此独立地代表C 1-C 20的直链或支链的烷基、C 4-C 20的环烷基、C 2-C 20的链烯基、C 6-C 20的芳基、C 6-C 20的烷基芳基，其中这些基团中的一个或多个氢可彼此独立地被烷基、卤素、羟基、硝基所取代，并且任选地，这些基团中的-CH 2-可被-O-取代；或者R 5和R 5’可以彼此相连或通过-O-、-S-、-NH-形成五元或六元环；
R 6代表未取代的或被一个或多个C 1-C 20烷基、卤素、氰基、SR 7、OR 8取代的苯基；
R 7和R 8相互独立地代表氢、C 1-C 20的直链或支链烷基。
进一步地，烯属不饱和可光聚合化合物的用量为5-95质量份，光引发剂的用量为0.05-15质量份。
进一步地，烯属不饱和可光聚合化合物的用量为10-90质量份，光引发剂的用量为1-10 质量份。
进一步地，具有如通式(Ⅰ)所示结构的光引发剂选自由
Figure PCTCN2018076209-appb-000022
Figure PCTCN2018076209-appb-000023
Figure PCTCN2018076209-appb-000024
Figure PCTCN2018076209-appb-000025
组成的组中的一种或多种。
进一步地，具有如通式(Ⅰ)所示结构的光引发剂的衍生化合物包括在保持式(I)化合物主体结构不变的前提下，通过其支链取代或彼此连接而得到的衍生物化合物。
进一步地，衍生物化合物具有如通式(II)或(III)所示的化合物：
Figure PCTCN2018076209-appb-000026
Figure PCTCN2018076209-appb-000027
其中，M代表二聚化而形成的连接基团，其可为空键、C 1-C 10的直链或支链亚烷基、C 6-C 12的亚芳基或亚杂芳基，任选地，M中的-CH 2-被硫、氧、NH或羰基所取代，任选地，氢原子被OH或NO 2所取代。
进一步地，衍生物化合物为
Figure PCTCN2018076209-appb-000028
Figure PCTCN2018076209-appb-000029
进一步地，具有如通式(Ⅰ)所示结构的光引发剂或其衍生化合物为两种或多种化合物的混合物。
进一步地，烯属不饱和可光聚合化合物为单体化合物或低聚物。
进一步地，烯属不饱和可光聚合化合物为包含一个碳碳双键的化合物，优选为丙烯酸酯化合物或甲基丙烯酸酯化合物；或烯属不饱和可光聚合化合物为包含两个及两个以上碳碳双键的化合物，优选为烷基二元醇、多元醇的丙烯酸酯或甲基丙烯酸酯或者聚酯多元醇、聚醚多元醇、环氧树脂多元醇、聚氨酯多元醇的丙烯酸酯、乙烯基醚以及不饱和二元羧酸多元醇的不饱和聚酯。
进一步地，当UV光固化组合物作为UV抗蚀油墨或UV阻焊油墨用途时，使用的烯属不饱和可光聚合化合物中至少一种化合物含有碱溶性基团，优选为含羧基的树脂。
进一步地，含羧基的树脂为(甲基)丙烯酸酯、乙烯性不饱和羧酸或(甲基)丙烯酸酯系聚合物；
优选的，(甲基)丙烯酸酯选自由(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙 烯酸丁酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸酯二甲胺基乙酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸糠基酯、(甲基)丙烯酸缩水甘油酯组成的组中的一种或多种；
优选的，乙烯性不饱和羧酸选自由丙烯酸、甲基丙烯酸、乙烯基安息酸、马来酸、马来酸烷基酯、富马酸、衣康酸、丁烯酸、肉桂酸、丙烯酸二聚体、具有羟基的单体和环状酸酐的加成产物、ω-羧基-聚己内酯-(甲基)丙烯酸酯组成的组中的一种或多种，更优选为(甲基)丙烯酸；
优选的，(甲基)丙烯酸酯系聚合物选自由(甲基)丙烯酰胺、(甲基)丙烯酸正丁酯、苯乙烯、乙烯基萘、(甲基)丙烯晴、乙酸乙烯基酯、乙烯基环己烷组成的组中的一种或多种。
进一步地，UV光固化组合物还包括其他光引发剂，优选的，其他光引发剂选自由二苯甲酮、苯偶酰二甲基缩酮、2-羟基-2-甲基-1-苯基-丙酮、1-羟基-环己基-苯基-酮、异丙基硫杂蒽、(2,4,6-三甲基-苯甲酰基)二苯基氧化膦和双(2,4,6-三甲基苯甲酰基)-苯基氧化膦组成的组中的一种或多种。
进一步地，UV光固化组合物还包括增感剂；优选的，增感剂为吡唑啉类化合物、吖啶类化合物、蒽类化合物、香豆素类化合物或叔胺类化合物；更优选的，增感剂的用量为0-5质量份，进一步优选的，增感剂的用量为0-2质量份。
进一步地，UV光固化组合物还包括着色剂，着色剂为无机颜料或有机颜料，着色剂的用量为0-50质量份，优选的，着色剂的用量为0-20质量份。
进一步地，UV光固化组合物还包括，添加剂包括表面活性剂、润湿剂、分散剂、流变改性剂、消泡剂或储存增强剂中的一种或多种；优选的，添加剂的用量为0-5质量份，更优选的，添加剂的用量为0-3质量份。
根据本发明的另一方面，提供了一种上述任一种UV光固化组合物在UV涂料和UV油墨方面的应用。
进一步地，UV油墨包括UV抗蚀油墨、UV阻焊油墨、柔印油墨和胶印油墨等。
本发明提供的含芴氨基酮类光引发剂可以有效的改善传统光引发剂的溶解性，降低小分子活性稀释剂的使用，而且感度高，深层固化效果好，对光固化领域的光固化组合物、特别是有色油墨体系的推广应用有很好的推动作用。
而且，在本发明的制备方法中，使用的原料均是现有技术中的已知化合物，可通过商业购得或者通过已知的合成方法简便地制备而成，制备方法简单，产品纯度高，非常适合工业化生产。
本发明的含芴氨基酮光引发剂的UV光固化组合物，具有高感度，显影后无残留，图案完整性好，并且固化后涂层无气味或低气味，另外耐黄变性能也很优异。
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。
针对现有技术的不足，本发明提出了如下技术方案：
根据本发明一种典型的实施方式，提供了一种芴氨基酮类光引发剂。该光引发剂包括具有如通式(Ⅰ)所示结构的化合物或其衍生化合物，
Figure PCTCN2018076209-appb-000030
其中，
A代表氢、卤素、硝基、C 1-C 20的直链或支链烷基、C 3-C 10的烷基环烷基、C 4-C 10的烷基环烷基或环烷基烷基、
Figure PCTCN2018076209-appb-000031
-COR 6、或-CO-CR 2R 3R 4基团，其中，可选的，-CH 2-被O、N、S或C(＝O)所取代；
R 1代表氢、卤素、C 1-C 20的直链或支链烷基、C 4-C 20的环烷基烷基或C 2-C 20的链烯基，可选的，R 1中的-CH 2-被O、N、S或C(＝O)所取代，R 1之间可成环；
R 2和R 3分别独立地代表C 1-C 20的直链或支链烷基、C 3-C 20的环烷基、C 4-C 20的环烷基烷基、C 4-C 20的烷基环烷基、C 6-C 20芳基、C 6-C 20的烷基芳基，其中这些基团中的一个或多个氢可彼此独立地被烷基、卤素、羟基、硝基所取代，并且可选的，R 2和R 3中的-CH 2-被O、N、S或C(＝O)所取代，且R 2和R 3可相互成环；
或R 2代表C 1-C 20的直链或支链的烷基、C 2-C 20的链烯基，R 3选自下列任一种基团：
a)化学式如下的基团：
Figure PCTCN2018076209-appb-000032
其中m是0或1，R 9代表氢、C 1-C 8烷基或苯基，R 10、R 11和R 12彼此独立地表示氢、C 1-C 4烷基；或
b)化学式如下的基团：
Figure PCTCN2018076209-appb-000033
其中n是0，1，2或3；或
c)化学式如下的基团：
Figure PCTCN2018076209-appb-000034
其中Ar是取代或未被取代的苯基、萘基、呋喃基、噻吩基或吡啶基；
R 4代表N-吗啉基、N-哌啶基、N-吡咯基或N-二烷基，其中这些基团中的一个或多个氢原子可被卤素、羟基所取代；
R 5、R 5’彼此独立地代表C 1-C 20的直链或支链的烷基、C 4-C 20的环烷基、C 2-C 20的链烯基、C 6-C 20的芳基、C 6-C 20的烷基芳基，其中这些基团中的一个或多个氢可彼此独立地被烷基、卤素、羟基、硝基所取代，并且任选地，这些基团中的-CH 2-可被-O-取代；或者R 5和R 5’可以彼此相连或通过-O-、-S-、-NH-形成五元或六元环；
R 6代表C 1-C 20的直链或支链的烷基、C 4-C 20的环烷基、C 4-C 20的烷基环烷基、C 2-C 20的链烯基、C 6-C 20的芳基、C 6-C 20的烷基芳基，其中这些基团中的-CH 2-可被-O-、-S-取代，并且这些基团的一个或多个氢原子可以独立地被选自烷基、卤素、硝基、氰基、SR 7、OR 8所取代；
R 7和R 8相互独立地代表氢、C 1-C 20的直链或支链烷基。
本发明提供的含芴氨基酮类光引发剂可以有效的改善传统光引发剂的溶解性，降低小分子活性稀释剂的使用，而且感度高，深层固化效果好，对光固化领域的光固化组合物、特别是有色油墨体系的推广应用有很好的推动作用。
根据本发明一种典型的实施方式，具有如通式(Ⅰ)所示结构的光引发剂的衍生化合物包括在保持式(I)化合物主体结构不变的前提下，通过其支链取代或彼此连接而得到的衍生物化合物。
优选的，衍生物化合物具有如通式(II)或(III)所示的化合物：
Figure PCTCN2018076209-appb-000035
Figure PCTCN2018076209-appb-000036
其中，M代表二聚化而形成的连接基团，其可为空键、C 1-C 10的直链或支链亚烷基、C 6-C 12的亚芳基或亚杂芳基，任选地，M中的-CH 2-被硫、氧、NH或羰基所取代，任选地，氢原子被OH或NO 2所取代。
示例性地，上述衍生化合物可以是下列结构的化合物：
Figure PCTCN2018076209-appb-000037
在某些情况下，使用两种或更多种以上所述引发剂的混合物是有利的。
当然，具有如通式(Ⅰ)所示结构的光引发剂也可以与已知的其他光引发剂混合使用。
根据本发明一种典型的实施方式，提供了一种上述芴氨基酮类光引发剂的制备方法。该制备方法包括以下步骤：
(1)原料a与原料b发生傅克反应生成中间体a，反应式如下：
Figure PCTCN2018076209-appb-000038
(2)中间体a发生取代反应生成中间体b：
Figure PCTCN2018076209-appb-000039
(3)中间体b发生取代反应生成中间体c：
Figure PCTCN2018076209-appb-000040
(4)中间体c发生Stevens重排反应生成中间体d：
Figure PCTCN2018076209-appb-000041
(5)当预得到A＝H的产物，则原料a中B＝H，中间体d即为通式(I)化合物；
当预得到
Figure PCTCN2018076209-appb-000042
的产物，则原料a中B＝F，中间体d发生取代反应生成具有如下通式(I)化合物；
Figure PCTCN2018076209-appb-000043
当预得到
Figure PCTCN2018076209-appb-000044
的产物，则原料a中B＝H，中间体d发生傅克反应生成具有如下通式(I)化合物；
Figure PCTCN2018076209-appb-000045
优选的，步骤(1)中，中间体a与原料在催化剂条件下发生傅克反应生成中间体b，原 料b为
Figure PCTCN2018076209-appb-000046
优选的，步骤(2)中，中间体a与原料c于有机溶剂中发生取代反应生成中间体b，原料c为二氯亚砜或液溴。
优选的，步骤(3)中，中间体b与原料d于有机溶剂中发生取代反应生成中间体c，其中，原料d为HX。
优选的，步骤(4)中，中间体c与原料e在碱性条件下于有机溶剂中发生Stevens重排反应生成中间体d其中，原料e为R 3-Br。
优选的，步骤(5)中，当预得到A＝H的产物，则原料a中B＝H，中间体d即为通式(I)化合物；当预得到
Figure PCTCN2018076209-appb-000047
的产物，则原料a中B＝F，中间体d与原料f在碱性条件下于有机溶剂中发生取代反应生成通式(I)所示化合物，原料f为HA；当预得到
Figure PCTCN2018076209-appb-000048
的产物，则原料a中B＝H，中间体d与原料g在催化剂条件下发生傅克反应生成通式(I)所示化合物，原料g为ACl或ABr。
在本发明的制备方法中，使用的原料均是现有技术中的已知化合物，可通过商业购得或者通过已知的合成方法简便地制备而成。步骤(1)-(5)中涉及的反应都是本领域合成类似化合物的常规反应，在知晓了本发明公开的合成思路的基础上，具体反应条件对本领域技术人员而言是容易确定的。本发明的制备方法简单，产品纯度高，适合工业化生产。
根据本发明的又一个方面，提供了一种上述UV光固化组合物在UV涂料和UV油墨方面的应用。
根据本发明一种典型的实施方式，提供一种含芴氨基酮类光引发剂的UV光固化组合物。该UV光固化组合物包括：烯属不饱和可光聚合化合物和光引发剂；其中，光引发剂包括具有如通式(Ⅰ)所示结构的化合物或其衍生化合物，
Figure PCTCN2018076209-appb-000049
其中，
A代表氢、卤素、硝基、C 1-C 20的直链或支链烷基、C 3-C 10的烷基环烷基、C 4-C 10的烷基 环烷基或环烷基烷基、
Figure PCTCN2018076209-appb-000050
-COR 6、或-CO-CR 2R 3R 4基团，其中，可选的，-CH 2-被O、N、S或C(＝O)所取代；
R 1代表氢、卤素、C 1-C 20的直链或支链烷基、C 4-C 20的环烷基烷基或C 2-C 20的链烯基，可选的，R 1中的-CH 2-被O、N、S或C(＝O)所取代，R 1之间可成环；
R 2和R 3分别独立地代表C 1-C 20的直链或支链烷基、C 3-C 20的环烷基、C 4-C 20的环烷基烷基、C 4-C 20的烷基环烷基、C 6-C 20芳基、C 6-C 20的烷基芳基，其中这些基团中的一个或多个氢可彼此独立地被烷基、卤素、羟基、硝基所取代，并且可选的，R 2和R 3中的-CH 2-被O、N、S或C(＝O)所取代，且R 2和R 3可相互成环；
或R 2代表C 1-C 20的直链或支链的烷基、C 2-C 20的链烯基，R 3选自下列任一种基团：
a)化学式如下的基团：
Figure PCTCN2018076209-appb-000051
其中m是0或1，R 9代表氢、C 1-C 8烷基或苯基，R 10、R 11和R 12彼此独立地表示氢、C 1-C 4烷基；或
b)化学式如下的基团：
Figure PCTCN2018076209-appb-000052
其中n是0，1，2或3；或
c)化学式如下的基团：
Figure PCTCN2018076209-appb-000053
其中Ar是取代或未被取代的苯基、萘基、呋喃基、噻吩基或吡啶基；
R 4代表N-吗啉基、N-哌啶基、N-吡咯基或N-二烷基，其中这些基团中的一个或多个氢原子可被卤素、羟基所取代；
R 5、R 5’彼此独立地代表C 1-C 20的直链或支链的烷基、C 4-C 20的环烷基、C 2-C 20的链烯基、C 6-C 20的芳基、C 6-C 20的烷基芳基，其中这些基团中的一个或多个氢可彼此独立地被烷基、卤素、羟基、硝基所取代，并且任选地，这些基团中的-CH 2-可被-O-取代；或者R 5和R 5’可以彼此相连或通过-O-、-S-、-NH-形成五元或六元环；
R 6代表C 1-C 20的直链或支链的烷基、C 4-C 20的环烷基、C 4-C 20的烷基环烷基、C 2-C 20的链烯基、C 6-C 20的芳基、C 6-C 20的烷基芳基，其中这些基团中的-CH 2-可被-O-、-S-取代，并且这些基团的一个或多个氢原子可以独立地被选自烷基、卤素、硝基、氰基、SR 7、OR 8所取代；
R 7和R 8相互独立地代表氢、C 1-C 20的直链或支链烷基。
本发明的含芴氨基酮光引发剂的UV光固化组合物，具有高感度，显影后无残留，图案完整性好，并且固化后涂层无气味或低气味，另外耐黄变性能也很优异。
本发明的UV光固化组合物制备工艺简单，根据本发明一种典型的实施方式，上述组分于暗室或黄光灯环境中搅拌混合均匀即可。
根据本发明一种典型的实施方式，UV光固化组合物还包括其他光引发剂，优选的，其他光引发剂选自由二苯甲酮、苯偶酰二甲基缩酮、2-羟基-2-甲基-1-苯基-丙酮、1-羟基-环己基-苯基-酮、异丙基硫杂蒽、(2,4,6-三甲基-苯甲酰基)二苯基氧化膦和双(2,4,6-三甲基苯甲酰基)-苯基氧化膦组成的组中的一种或多种。
根据本发明一种典型的实施方式，UV光固化组合物还包括着色剂，着色剂为无机颜料或有机颜料，着色剂的用量为0-50质量份，优选的，着色剂的用量为0-20质量份。
根据本发明一种典型的实施方式，UV光固化组合物还包括添加剂，添加剂包括表面活性剂、润湿剂、分散剂、流变改性剂、消泡剂或储存增强剂中的一种或多种。
以下将对本发明的UV光固化组合物各组分进行更加详细的说明。
1)烯属不饱和可光聚合化合物
烯属不饱和可光聚合化合物：具有可自由基聚合的烯属不饱和键的化合物，可以为单体化合物(低分子量)或低聚物(较高分子量)。
包含一个碳碳双键的化合物，优选丙烯酸酯化合物、甲基丙烯酸酯化合物，例如：一元醇的丙烯酸酯或甲基丙烯酸酯：丙烯酸甲酯、丙烯酸丁酯、丙烯酸2‐乙基己酯、丙烯酸环己酯、丙烯酸异冰片酯、丙烯酸羟乙酯、甲基丙烯酸甲酯以及丙烯腈、N‐二烷基丙烯酰胺、N‐乙烯基吡咯烷酮、乙烯基苯、乙烯基乙酸酯、乙烯基醚。
包含两个及两个以上碳碳双键的化合物，包括：烷基二元醇、多元醇的丙烯酸酯或甲基丙烯酸酯或者聚酯多元醇、聚醚多元醇、环氧树脂多元醇、聚氨酯多元醇的丙烯酸酯、乙烯基醚以及不饱和二元羧酸多元醇的不饱和聚酯，例如，聚乙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、多乙氧基化三羟甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯、聚酯低聚物丙烯酸酯、聚氨酯低聚物丙烯酸酯、芳香族环氧树脂丙烯酸酯、马来酸乙二醇聚酯。
当UV光固化组合物作为UV抗蚀油墨或UV阻焊油墨用途时，使用的烯属不饱和可光聚合化合物中至少一种化合物含有碱溶性基团，这类化合物除了能够被引发交联聚合外，还要能够在形成图像图案时对显影处理工序中使用的显影液(常用碱性显影液)具有可溶解性，优选含羧基的树脂。特别是由(甲基)丙烯酸酯、乙烯性不饱和羧酸和其他可共聚单体共聚而成的(甲基)丙烯酸酯系聚合物。所述的(甲基)丙烯酸酯可以是(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸酯二甲胺基乙酯、(甲基)丙烯酸羟乙酯、(甲基) 丙烯酸羟丙酯、(甲基)丙烯酸糠基酯、(甲基)丙烯酸缩水甘油酯，这些(甲基)丙烯酸酯可以单独使用，也可以两种以上组合使用。所述的乙烯性不饱和羧酸优选是丙烯酸、甲基丙烯酸、乙烯基安息酸、马来酸、马来酸烷基酯、富马酸、衣康酸、丁烯酸、肉桂酸、丙烯酸二聚体、具有羟基的单体(例如(甲基)丙烯酸-2-羟乙酯等)和环状酸酐(例如：马来酸酐或邻苯二甲酸酐、环己烷二缩酸酐)的加成产物、ω-羧基-聚己内酯-(甲基)丙烯酸酯等。其中从共聚性或成本、溶解性等观点考虑，特别优选(甲基)丙烯酸。这些乙烯性不饱和羧酸可以单独使用，也可以两种以上组合使用。所述的其他可共聚单体优选是(甲基)丙烯酰胺、(甲基)丙烯酸正丁酯、苯乙烯、乙烯基萘、(甲基)丙烯晴、乙酸乙烯基酯、乙烯基环己烷，这些单体可以单独使用，也可以两种以上组合使用。
这些碳碳双键化合物不仅可以单独使用，还可以两种以上混合使用或混合物之间可以进行预共聚形成低聚物供配制组合物使用。存在于光固化组合物中自由基聚合性树脂的用量为5-95质量份，优选约10-90质量份。
2)具有如通式(Ⅰ)所示结构的光引发剂
作为本发明光固化组合物中所使用的光引发剂，至少包含具有通式(I)所示的芴类化合物为主体结构的化合物或其衍生物化合物中的一种：
Figure PCTCN2018076209-appb-000054
其中，
A代表氢、卤素、硝基、C 1-C 20的直链或支链烷基、C 3-C 10的烷基环烷基、C 4-C 10的烷基环烷基或环烷基烷基、
Figure PCTCN2018076209-appb-000055
-COR 6、或-CO-CR 2R 3R 4基团，其中，可选的，-CH 2-被O、N、S或C(＝O)所取代；
R 1代表氢、卤素、C 1-C 20的直链或支链烷基、C 4-C 20的环烷基烷基或C 2-C 20的链烯基，可选的，R 1中的-CH 2-被O、N、S或C(＝O)所取代，R 1之间可成环；
R 2和R 3分别独立地代表C 1-C 20的直链或支链烷基、C 3-C 20的环烷基、C 4-C 20的环烷基烷基、C 4-C 20的烷基环烷基、C 6-C 20芳基、C 6-C 20的烷基芳基，其中这些基团中的一个或多个氢可彼此独立地被烷基、卤素、羟基、硝基所取代，并且可选的，R 2和R 3中的-CH 2-被O、N、S或C(＝O)所取代，且R 2和R 3可相互成环；
或R 2代表C 1-C 20的直链或支链的烷基、C 2-C 20的链烯基，R 3选自下列任一种基团：
a)化学式如下的基团：
Figure PCTCN2018076209-appb-000056
其中m是0或1，R 9代表氢、C 1-C 8烷基或苯基，R 10、R 11和R 12彼此独立地表示氢、C 1-C 4烷基；或
b)化学式如下的基团：
Figure PCTCN2018076209-appb-000057
其中n是0，1，2或3；或
c)化学式如下的基团：
Figure PCTCN2018076209-appb-000058
其中Ar是取代或未被取代的苯基、萘基、呋喃基、噻吩基或吡啶基；
R 4代表N-吗啉基、N-哌啶基、N-吡咯基或N-二烷基，其中这些基团中的一个或多个氢原子可被卤素、羟基所取代；
R 5、R 5’彼此独立地代表C 1-C 20的直链或支链的烷基、C 4-C 20的环烷基、C 2-C 20的链烯基、C 6-C 20的芳基、C 6-C 20的烷基芳基，其中这些基团中的一个或多个氢可彼此独立地被烷基、卤素、羟基、硝基所取代，并且任选地，这些基团中的-CH 2-可被-O-取代；或者R 5和R 5’可以彼此相连或通过-O-、-S-、-NH-形成五元或六元环；
R 6代表C 1-C 20的直链或支链的烷基、C 4-C 20的环烷基、C 4-C 20的烷基环烷基、C 2-C 20的链烯基、C 6-C 20的芳基、C 6-C 20的烷基芳基，其中这些基团中的-CH 2-可被-O-、-S-取代，并且这些基团的一个或多个氢原子可以独立地被选自烷基、卤素、硝基、氰基、SR 7、OR 8所取代；
R 7和R 8相互独立地代表氢、C 1-C 20的直链或支链烷基。
作为优选方案，式(I)所示芴氨基酮类化合物包括以下结构所示化合物：
Figure PCTCN2018076209-appb-000059
Figure PCTCN2018076209-appb-000060
Figure PCTCN2018076209-appb-000061
Figure PCTCN2018076209-appb-000062
Figure PCTCN2018076209-appb-000063
以式(I)所示化合物为主体结构的衍生化合物是指在保持式(I)化合物主体结构不变的前提下，通过其支链取代或彼此连接而得到的衍生物。在本发明中作为光引发剂使用时，所述以式(I)所示化合物为主体结构的衍生化合物是如下式(II)、(III)所示的化合物：
Figure PCTCN2018076209-appb-000064
式(II)和式(III)即为式(I)的二聚物，M表示二聚化而形成的连接基团，其可为空键、C 1-C 10的直链或支链亚烷基、C 6-C 12的亚芳基或亚杂芳基，M中的-CH 2-任选地被硫、氧、NH或羰基所取代，氢原子任选地被OH或NO 2所取代。
示例性地，上述衍生化合物可以是下列结构的化合物：
Figure PCTCN2018076209-appb-000065
Figure PCTCN2018076209-appb-000066
在某些情况下，使用两种或更多种以上所述引发剂的混合物是有利的。
当然，具有如通式(Ⅰ)所示结构的光引发剂也可以与已知的其他光引发剂混合使用。
3)其他光引发剂
例如：樟脑醌、二苯甲酮(BP)、二苯甲酮衍生物，例如2,4,6-三甲基二苯甲酮、2-甲基二苯甲酮、2-甲基二苯甲酮、3-甲基二苯甲酮、4-甲基二苯甲酮、2-甲基基羰基二苯甲酮、4,4’-双(氯甲基)二苯甲酮、4-氯二苯甲酮、4-苯基二苯甲酮、3,3’-二甲基-4-甲氧基-二苯甲酮、[4-(4-甲基苯硫基)苯基]-苯基甲酮、2-苯甲酰基苯甲酸甲酯、3-甲基-4’-苯基二苯甲酮、2,4,6-三甲基-4’-苯基二苯甲酮、4,4’-双(二甲基氨基)二苯甲酮、4,4’-双(二乙基氨基)二苯甲酮、缩酮化合物，例如苯偶酰二甲基缩酮(651)；苯乙酮、苯乙酮衍生物，例如α-羟基环烷基苯基酮，例如2-羟基-2-甲基-1-苯基-丙酮(1173)、1-羟基-环己基-苯基-酮(184)；1-[4-(2-羟基乙氧基)-苯基]-2-羟基-2-甲基-1-丙-1-酮(2959)；2-羟基-1-{4-[4-(2-羟基-2-甲基-丙酰基)-苄基]-苯基}-2-甲基-丙-1-酮(127)；2-羟基-1-{4-[4-(2-羟基-2-甲基-丙酰基)-苯氧基]-基}-2-甲基-丙-1-酮；二烷氧基苯乙酮、α-羟基-或α-氨基苯乙酮，例如(4-甲硫基苯甲酰基)-1-甲基-1-吗啉代乙烷(907)、(4-吗啉代苯甲酰基)-1-苄基-1-二甲基氨基丙烷(369)、(4-吗啉代苯甲酰基)-1-(4-甲基苄基)-1-二甲基氨基丙烷(379)、(4-(2-羟基乙基)氨基苯甲酰基)-1-苄基-1-二甲基氨基丙烷)、2-苄基-2-二甲基氨基-1-(3,4-二甲氧基苯基)-1-丁酮；硫杂蒽酮及其衍生物，例如异丙基硫杂蒽(ITX)、2-氯硫杂蒽酮(CTX)、1-氯-4-丙氧基硫杂蒽酮(CPTX)、2,4-二乙基硫杂蒽酮(DETX)；苯偶姻烷基醚和苯偶酰缩酮，苯基乙醛酸酯及其衍生物，例如氧代-苯基-乙酸2-(2-羟基-乙氧基)-乙基酯，二聚的苯基乙醛酸酯，例如氧代-苯基-乙酸1-甲基-2-[2-(2-氧代-苯基乙酰氧基)-丙氧基]-乙基酯(754)；其它肟酯，例如1,2-辛二酮-1-[4-(苯硫基)苯基]-2-(4-苯甲酰基肟)(OXE01)、乙酮1-[9-乙基-6-(2-甲基苯甲酰基)-9H-咔唑-3-基]-1-(4-乙酰基肟)(OXE02)、9H-噻吨-2-甲醛9-氧代-2-(O-乙酰基肟)；单酰基氧化膦，例如(2,4,6-三甲基-苯甲酰基)二苯基氧化膦(TPO)；二酰基氧化膦，例如双-(2，6-二甲氧基-苯甲酰基)-(2,4,4-三甲基-戊基)氧化膦、双(2,4,6-三甲基苯甲酰基)-苯基氧化膦(819)、双(2,4,6-三甲基苯甲酰基)-2,4-二戊氧基苯基-氧化膦；六芳基双咪唑/共引发剂体系，例如与2-巯基苯并噻唑结合的邻氯六苯基-双咪唑等。
值得关注的是，具有如通式(Ⅰ)所示结构的光引发剂除式(I)、式(II)和式(III)的化合物之外，特别适合与BP、651、1173、184、ITX、TPO和819等其中的一个或多个组合使用。光引发剂即具有如通式(Ⅰ)所示结构的光引发剂和其他光引发剂在光固化组合物中 的用量为0.05-15质量份，优选1-10质量份。
4)增感剂
另外，本发明的光固化组合物中，为了得到更高的感度或为了与LED光源相匹配，也可进一步包含增感剂。
增感剂的种类可以是吡唑啉类化合物、吖啶类化合物、蒽类化合物、香豆素类化合物、叔胺类化合物等。具体而言可示例性地列举：1-苯基-3-(4-叔丁基苯乙烯基)-5-(4-叔丁基苯基)吡唑啉、1-苯基-3-联苯基-5-(4-叔丁基苯基)吡唑啉；9-苯基吖啶、9-对甲基苯基吖啶、9-间甲基苯基吖啶、9-邻氯苯基吖啶；2-乙基蒽-9,10-二(4-氯丁酸甲酯)、1,2,3-三甲基蒽-9,10-二辛酯、2-乙基蒽-9,10-二乙酯、2-乙基蒽-9,10-二(3-环己基丙酸酯)；3,3'-羰基双(7-二乙胺香豆素)、3-苯甲酰基-7-二乙胺香豆素、3,3'-羰基双(7-甲氧基香豆素)、7-(二乙氨基)-4-甲基香豆素；N,N-双-[4-(2-苯乙烯基-1-基)-苯基]-N,N-双(2-乙基-6甲基苯基)-1,1-双苯基-4,4-二胺、N,N-双-[4-(2-苯乙烯基-1-基)-4′-甲基苯基]-N,N-双(2-乙基-6甲基苯基)-1,1-双苯基-4,4-二胺等。
增感剂在光固化组合物中的用量为0-5质量份，优选0-2质量份。
5)着色剂
UV光固化组合物中可包含一种或多种颜料作为着色剂。颜料可为任何颜色，包括但不限于黑色、蓝色、棕色、青色、绿色、白色、紫色、品红、红色、橙色和黄色，以及他们混合物的专色。颜料可以为无机颜料或有机颜料。
UV光固化组合物中存在的有机颜料可以是二萘嵌苯、酞菁燃料(例如酞菁绿、酞菁蓝)、菁颜料(Cy3、Cy5和Cy7)、萘酞菁颜料、亚硝基颜料、偶氮颜料、重氮颜料、重氮缩合颜料、碱性染料颜料、碱性蓝颜料、蓝靛颜料、根皮红颜料、奎吖啶酮颜料、异吲哚啉酮颜料、二噁嗪颜料、咔唑二噁嗪紫颜料、茜素色淀颜料、邻苯二甲酰胺颜料、胭脂红色淀颜料、四氯异吲哚啉酮颜料、紫环酮颜料、蒽醌颜料和喹酞酮颜料，及以上两种或更多种的混合物或以上的衍生物。
光固化组合物中无机颜料包括，例如金属氧化物(例如二氧化钛、导电性二氧化钛)、铁氧化物(例如红色氧化铁、黄色氧化铁、黑色氧化铁和透明氧化铁)、铝氧化物、硅氧化物、碳黑颜料、金属硫化物、金属氯化物和它们两种或更多种的混合物。
着色剂在光固化组合物中的用量为0-50质量份，优选0-20质量份。
6)添加剂
根据不同应用的需求，光固化组合物中可任选地存在其它组分或添加剂，以改善涂料或油墨的性质和性能。添加剂包括但不限于表面活性剂、润湿剂、分散剂、流变改性剂、消泡剂或储存增强剂中的一种或多种。
添加剂在光固化组合物中的用量为0-5质量份，优选为0-3质量份。
本发明的光固化组合物在聚合反应时通过赋予紫外线、可见光线、近红外线等、电子束等产生的能量而聚合，可以得到作为目标的聚合物。作为赋予能量的光源，优选具有在250nm至450nm的波长区域中发光的主波长的光源。作为具有在250nm至450nm的波长区域中发光的主波长的光源的例子，可以举出超高压汞灯、高压汞灯、中压汞灯、汞氙灯、金属卤化物灯、大功率金属卤化物灯、氙灯、脉冲发光氙灯、氘灯、Led灯、荧光灯、Nd-YAG3倍波激光、He-Cd激光、氮激光、Xe-Cl准分子激光、Xe-F准分子激光、半导体激发固体激光等各种光源。
以下通过实施例具体说明本发明，但能够理解的是，不应将其理解为对本发明的限制，本领域的技术人员完全有能力在本发明的框架内对所示实施例进行修改，以获得相同或类似的效果。
实施例1
(1)9,9-二甲基-7-氟芴-2-丁酮(中间体38a)的制备
Figure PCTCN2018076209-appb-000067
向500ml四口烧瓶中加入80g无水三氯化铝、106g 9,9-二甲基-7-氟芴和150ml二氯甲烷溶剂，控制温度于10℃以下，缓慢滴加53g正丁酰氯，加毕升温至35-45℃搅拌4-6h，反应物冷却后倒入盐酸-冰水中，分出有机层，洗至中性，干燥、减压蒸馏得到中间体38a 109g，收率为78％，纯度99％，MS(m/z)：283(M+1) +。
(2)2-氯-9,9-二甲基-7-氟芴-1-丁酮(中间体38b)的制备
Figure PCTCN2018076209-appb-000068
在四口烧瓶中加入141g中间体38a和100ml二氯甲烷溶剂，控制温度在30-40℃下滴加59g二氯亚砜，通氮气出去氯化氢。水洗分出有机层，干燥，回收溶剂，得到147g中间体38b，收率93％，纯度98％，MS(m/z)：317(M+1) +。
(3)2-二甲氨基-9,9-二甲基-7-氟芴-1-丁酮(中间体38c)的制备
Figure PCTCN2018076209-appb-000069
在四口烧瓶中加入含75g二甲胺的乙醚溶液，置于冰浴中，搅拌下滴加158g中间体38b，控温在0℃左右搅拌反应。通氮气除去过量的二甲胺，将反应液倒入水中，分出有几层，水洗至中性，干燥，蒸出乙醚，减压蒸馏得到133g中间体38c，收率82％，纯度99％，MS(m/z)：326(M+1) +。
(4)2-苄基-2-二甲氨基-9,9-二甲基-7-氟芴-1-丁酮(中间体38d)的制备
Figure PCTCN2018076209-appb-000070
将162g中间体38c和150ml甲苯溶剂加到四口烧瓶中，搅拌下缓慢滴加63g氯苄，升温搅拌12h，蒸馏回收溶剂，加水升温至50-70℃，加入碱液回流反应0.5-1h，冷却后分离有机层，经提取、干燥后得到黄色粘稠物，用乙醇进行重结晶，得到193g中间体38d，收率93％，纯度97％，MS(m/z)：416(M+1) +。
(5)2-苄基-2-二甲氨基-9,9-二甲基-1-(7-吗啉芴基)丁酮(化合物38)的制备
Figure PCTCN2018076209-appb-000071
在四口烧瓶中依次加入103g中间体38d、45g吗啉、100mlDMSO溶剂及5g碳酸钾，升温到120-160℃反应30h。冷却后经萃取、洗涤、干燥、得到红褐色糊状物，用乙醇重结晶，烘干得到89g化合物38，收率75％，纯度99.5％。
产物结构通过核磁共振氢谱和质谱得到确认。
1H-NMR(CDCl 3，500MHz)：0.96-1.54(5H,m)，1.67(6H，s)，2.27(6H，s)，2.76(2H，s)，2.92(4H，m)，3.67(4H,m)，6.71-7.66(8H，m)，7.92-8.18(3H，m)。
MS(m/z)：483(M+1) +。
实施例2
(1)2-烯丙基-2-二甲氨基-9,9-二甲基-7-氟芴-1-丁酮(中间体39d)的制备
Figure PCTCN2018076209-appb-000072
以实施例1中的中间体38c为原料，将162g 38c和适量甲苯溶剂加到四口烧瓶中，搅拌下缓慢滴加39g烯丙基氯，升温搅拌12h，蒸馏回收溶剂，加水升温至50-70℃，加入碱液回流反应0.5-1h，冷却后分离有机层，经提取、干燥后得到黄色粘稠物，用乙醇进行重结晶，得到167g中间体39d，收率92％，纯度98％，MS(m/z):366(M+1) +。
(2)2-烯丙基-2-二甲氨基-9,9-二甲基-2-(7-哌啶芴基)丁酮(化合物39)的制备
Figure PCTCN2018076209-appb-000073
在四口烧瓶中依次加入92g中间体39d、45g哌啶、适量DMSO溶剂及少量碳酸钾，升温到120-160℃反应30h。冷却后经萃取、洗涤、干燥、得到红褐色糊状物，用乙醇重结晶，烘干得到83g化合物39，收率73％，纯度99％。
产物结构通过核磁共振氢谱和质谱得到确认。
1H-NMR(CDCl 3，500MHz)：0.96-1.54(11H,m)，1.67(6H，s)，2.17(2H，s)，2.27(6H，s)，2.72(4H，m)，4.97-5.71(3H,m)，6.71-8.18(6H，m)。
MS(m/z):431(M+1) +。
实施例3
(1)9,9-二丁基芴-1-丁酮(中间体40a)的制备
Figure PCTCN2018076209-appb-000074
方法同38a的制备方法，MS(m/z)：349(M+1) +。
(2)2-氯-9,9-二丁基芴-1-丁酮(中间体40b)的制备
Figure PCTCN2018076209-appb-000075
方法同38b的制备方法，MS(m/z)：383(M+1) +。
(3)2-二甲氨基-9,9-二丁基芴-1-丁酮(中间体40c)的制备
Figure PCTCN2018076209-appb-000076
方法同38c的制备方法，MS(m/z)：392(M+1) +。
(4)2-苄基-2-二甲氨基-9,9-二丁基芴-1-丁酮(化合物40)的制备
Figure PCTCN2018076209-appb-000077
方法同38d的制备方法。
产物结构通过核磁共振氢谱和质谱得到确认。
1H-NMR(CDCl 3，500MHz)：0.96-1.87(23H,m)，2.27(6H，s)，2.76(2H，s)，7.08-8.18(12H，m)。
MS(m/z):482(M+1) +。
实施例4
(1)2-苄基-2-二甲氨基-9,9-二丁基-1-(7-苯甲酰基)丁酮(化合物41)的制备
Figure PCTCN2018076209-appb-000078
向1000ml四口烧瓶中加入80g无水三氯化铝、240.5g化合物3和200ml二氯甲烷溶剂，控制温度于10℃以下，缓慢滴加70g苯甲酰氯，加毕升温至35-45℃搅拌4-6h，反应物冷却后倒入盐酸-冰水中，分出有机层，洗至中性，干燥、减压蒸馏得到中间体化合物39 237g，收率为81％，纯度98％。
产物结构通过核磁共振氢谱和质谱得到确认。
1H-NMR(CDCl 3，500MHz)：0.96-1.87(23H,m)，2.27(6H，s)，2.76(2H，s)，7.08-8.18(16H，m)。
MS(m/z)：586(M+1) +。
实施例5-20
参照实施例1-4的合成方法，制备了实施例5-20的化合物42-57(即实施例5制备的化合物为化合物42，实施例6制备的化合物为化合物43，以此类推)。目标化合物及其LC-MS数据列于表1。
表1
Figure PCTCN2018076209-appb-000079
Figure PCTCN2018076209-appb-000080
Figure PCTCN2018076209-appb-000081
性能评价
1、溶解性能测试
以本领域应用较为广泛的稀释剂1,6-己二醇二丙烯酸酯(HDDA)和丙酮溶剂为例，对本发明的光引发剂及背景技术中提到的Irgacure 369和Irgacure 379的溶解性能进行测试，以20℃条件下100g溶剂中能溶解的最大重量为评价标准。测试结果示于表2中。
表2
Figure PCTCN2018076209-appb-000082
Figure PCTCN2018076209-appb-000083
由表2可以看出，本发明的含芴结构的α-氨基酮类光引发剂与商品化的Irgacure 369和Irgacure 379光引发剂相比，溶解性大大提高，使用时可以很大程度上减少小分子活性稀释剂的使用。
2、固化性能测试
α-氨基酮类光引发剂在光固化有色体系中有很高的光引发剂活性，特别适用于光固化色漆和油墨中，因此通过将该类引发剂应用于油墨体系来进行固化性能评价。
步骤1、制备色浆，该色浆中各组分重量百分比如下所示：
Figure PCTCN2018076209-appb-000084
Figure PCTCN2018076209-appb-000085
将上述原料组分利用坐式砂磨机研磨至粒径<1μm，并过滤得到该色浆。
步骤2、制备UV固化用油墨，该油墨中各组分重量比如下所示：
Figure PCTCN2018076209-appb-000086
上述油墨组分中的光引发剂为本发明的光引发剂或商品化的Irgacure 369和907。由于369的溶解性相对较差，添加到上述配方中需要添加10％左右的丁酮溶剂使其溶解完全。
将上述配方于四口烧瓶中，室温避光搅拌3h，过滤得到固化用油墨。将油墨在陶瓷砖上进行喷涂，喷涂厚度为60-80μm，然后利用紫外光源线功率80mw/cm 2的紫外光进行光照50s，再将紫外固化后的陶瓷砖置于80℃下烧结50min，冷却后检测陶瓷砖上油墨涂层效果。
其中附着性测试参照GB/T 9286-1998测试标准，采用百格划格法进行测试，并按0-5级标准进行评价；深层固化度采用指抠法，即用指甲抠涂层，以无脱落，无露底现象表示底层固化完全；图案效果通过肉眼观察，以图案清晰细腻，边缘光滑无毛糙为图案效果佳的标准。具体测试结果示于表3、表4、表5和表6中。
表3黄色油墨测试结果
Figure PCTCN2018076209-appb-000087
Figure PCTCN2018076209-appb-000088
Figure PCTCN2018076209-appb-000089
表4红色油墨测试结果
Figure PCTCN2018076209-appb-000090
Figure PCTCN2018076209-appb-000091
表5蓝色油墨测试结果
Figure PCTCN2018076209-appb-000092
Figure PCTCN2018076209-appb-000093
表6黑色油墨测试结果
Figure PCTCN2018076209-appb-000094
Figure PCTCN2018076209-appb-000095
从表3、表4、表5、表6可以看到，本发明的含芴结构的α-氨基酮类光引发剂具有更高的感度，在有色体系中具有更好的深层固化性能，而且成膜后力学性能更优异。
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：本发明提供的含芴氨基酮类光引发剂可以有效的改善传统光引发剂的溶解性，降低小分子活性稀释剂的使用，而且感度高，深层固化效果好，对光固化领域的有色油墨体系的推广应用有很好的推动作用。
下面结合具体实施例进一步阐述含芴氨基酮类光引发剂的UV光固化组合物的应用体系，评价方法及标准如下：
一、显影性用扫描电子显微镜(SEM)观察基板上图案，在未曝光部分未观察到残留物(○)、在未曝光部分观察到少量残留物，但残留量可以接受(◎)、在未曝光部分观察到明显残留物(●)，图案完整性根据观察图案有没有缺陷，没有缺陷(△)、小部分缺陷(□)、严重缺陷(▲)；
二、固化膜的残余气味通过鼻子闻来评价，测试结果分成1(无气味)、2(有味道)、3 (刺激性气味)三个等级；
三、黄变性通过使用色差仪(美国爱色丽X-Rite Color i7)进行全透射扫描，扫描波长400-700nm，读取△b值评价黄变性，△b越小代表黄变越不明显，反之黄变越严重；
四、附着力评价参照GB9286-88《色漆和清漆漆膜的划格试验》，通过划格实验方法评价涂膜附着力好坏。根据破坏程度分为0-5级(共6个等级),其中最好为0级,膜面没有任一个小格脱落；5级为极差,膜面产生了严重的剥落。
在下述论述中，UV光固化组合物的配制均以重量百分数计量各组分，并以Irgacure 907和APi-307作为同等条件下的参比例化合物。
其中907和307的结构式如下所示：
Figure PCTCN2018076209-appb-000096
实施例21：UV涂料
Figure PCTCN2018076209-appb-000097
涂布条件：参照《GB/T 9271-2008色漆和清漆标准试板》将基材马口贴片进行前处理，然后将于暗室中搅拌均匀的配方用25#线棒涂布与马口贴片上，涂层厚度约为25μm，曝光条件：RW-UV.70201履带式曝光机，辐射波长为250-450nm，老化条件：曝光后置于80℃烘箱烘烤24h，测试结果如下表7所示：
表7
Figure PCTCN2018076209-appb-000098
实施例22：UV抗蚀油墨
Figure PCTCN2018076209-appb-000099
印刷条件：100T丝网，干膜厚度8-10μm，烘烤条件：75℃烘烤20分钟，曝光条件：RW-UV.70201履带式曝光机，辐射波长为250-450nm，显影条件：1％碳酸钠溶液，30±2℃显影40s，测试结果如下表8所示：
表8
Figure PCTCN2018076209-appb-000100
实施例23：UV阻焊油墨
Figure PCTCN2018076209-appb-000101
Figure PCTCN2018076209-appb-000102
A、B组分按3:1混合均匀，放置半小时。印刷条件：36-43T丝印，干膜厚度12-15μm，预烘条件：75℃第一面20分钟，第二面25分钟；曝光条件：RW-UV.70201履带式曝光机，辐射波长为250-450nm；显影条件：0.5％氢氧化钠溶液，30±2℃显影60s，测试结果如下表9所示：
表9
Figure PCTCN2018076209-appb-000103
实施例24：UV柔印油墨
Figure PCTCN2018076209-appb-000104
Figure PCTCN2018076209-appb-000105
以上原料于暗室中混合均匀，以5μm的厚度涂于白色纸板上，曝光条件：RW-UV.70201履带式曝光机，辐射波长为250-450nm，测试结果如下表10所示：
表10
Figure PCTCN2018076209-appb-000106
实施例25：UV胶印油墨
Figure PCTCN2018076209-appb-000107
Figure PCTCN2018076209-appb-000108
以上原料于暗室中混合均匀，以2μm的厚度涂于塑料基材，曝光条件：RW-UV.70201履带式曝光机，辐射波长为250-450nm，测试结果如下表11所示：
表11
Figure PCTCN2018076209-appb-000109
由实施例21-25实验结果可以看出，本发明的含芴氨基酮光引发剂的光固化组合物应用于光固化涂料及油墨中，光固化性能佳，耐黄变性好，固化后无气味残留，综合性能优异。
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 (14)

  1. 一种芴氨基酮类光引发剂，其特征在于，所述光引发剂包括具有如通式(Ⅰ)所示结构的化合物或其衍生化合物，
    Figure PCTCN2018076209-appb-100001
    其中，
    A代表氢、卤素、硝基、C 1-C 20的直链或支链烷基、C 3-C 10的烷基环烷基、C 4-C 10的烷基环烷基或环烷基烷基、
    Figure PCTCN2018076209-appb-100002
    -COR 6、或-CO-CR 2R 3R 4基团，其中，可选的，-CH 2-被O、N、S或C(＝O)所取代；
    R 1代表氢、卤素、C 1-C 20的直链或支链烷基、C 4-C 20的环烷基烷基或C 2-C 20的链烯基，可选的，R 1中的-CH 2-被O、N、S或C(＝O)所取代，R 1之间可成环；
    R 2和R 3分别独立地代表C 1-C 20的直链或支链烷基、C 3-C 20的环烷基、C 4-C 20的环烷基烷基、C 4-C 20的烷基环烷基、C 6-C 20芳基、C 6-C 20的烷基芳基，其中这些基团中的一个或多个氢可彼此独立地被烷基、卤素、羟基、硝基所取代，并且可选的，R 2和R 3中的-CH 2-被O、N、S或C(＝O)所取代，且R 2和R 3可相互成环；
    或R 2代表C 1-C 20的直链或支链的烷基、C 2-C 20的链烯基，R 3选自下列任一种基团：
    a)化学式如下的基团：
    Figure PCTCN2018076209-appb-100003
    其中m是0或1，R 9代表氢、C 1-C 8烷基或苯基，R 10、R 11和R 12彼此独立地表示氢、C 1-C 4烷基；或
    b)化学式如下的基团：
    Figure PCTCN2018076209-appb-100004
    其中n是0，1，2或3；或
    c)化学式如下的基团：
    Figure PCTCN2018076209-appb-100005
    其中Ar是取代或未被取代的苯基、萘基、呋喃基、噻吩基或吡啶基；
    R 4代表N-吗啉基、N-哌啶基、N-吡咯基或N-二烷基，其中这些基团中的一个或多个氢原子可被卤素、羟基所取代；
    R 5、R 5’彼此独立地代表C 1-C 20的直链或支链的烷基、C 4-C 20的环烷基、C 2-C 20的链烯基、C 6-C 20的芳基、C 6-C 20的烷基芳基，其中这些基团中的一个或多个氢可彼此独立地被 烷基、卤素、羟基、硝基所取代，并且任选地，这些基团中的-CH 2-可被-O-取代；或者R 5和R 5’可以彼此相连或通过-O-、-S-、-NH-形成五元或六元环；
    R 6代表C 1-C 20的直链或支链的烷基、C 4-C 20的环烷基、C 4-C 20的烷基环烷基、C 2-C 20的链烯基、C 6-C 20的芳基、C 6-C 20的烷基芳基，其中这些基团中的-CH 2-可被-O-、-S-取代，并且这些基团的一个或多个氢原子可以独立地被选自烷基、卤素、硝基、氰基、SR 7、OR 8所取代；
    R 7和R 8相互独立地代表氢、C 1-C 20的直链或支链烷基。
  2. 根据权利要求1所述的芴氨基酮类光引发剂，其特征在于，所述具有如通式(Ⅰ)所示结构的光引发剂的衍生化合物包括在保持式(I)化合物主体结构不变的前提下，通过其支链取代或彼此连接而得到的衍生物化合物。
  3. 根据权利要求2所述的芴氨基酮类光引发剂，其特征在于，所述衍生物化合物具有如通式(II)或(III)所示的化合物：
    Figure PCTCN2018076209-appb-100006
    Figure PCTCN2018076209-appb-100007
    其中，M代表二聚化而形成的连接基团，其可为空键、C 1-C 10的直链或支链亚烷基、C 6-C 12的亚芳基或亚杂芳基，任选地，M中的-CH 2-被硫、氧、NH或羰基所取代，任选地，氢原子被OH或NO 2所取代。
  4. 一种含芴氨基酮类光引发剂的UV光固化组合物，其特征在于，包括：烯属不饱和可光聚合化合物和光引发剂；其中，所述光引发剂为如权利要求1至3中任一项所述的芴氨基酮类光引发剂。
  5. 根据权利要求4所述的UV光固化组合物，其特征在于，所述光引发剂为具有如通式(Ⅰ)所示结构的光引发剂或其衍生化合物为两种或多种化合物的混合物。
  6. 根据权利要求4所述的UV光固化组合物，其特征在于，所述烯属不饱和可光聚合化合物为包含一个碳碳双键的化合物，优选为丙烯酸酯化合物或甲基丙烯酸酯化合物；或
    所述烯属不饱和可光聚合化合物为包含两个及两个以上碳碳双键的化合物，优选为烷基二元醇、多元醇的丙烯酸酯或甲基丙烯酸酯或者聚酯多元醇、聚醚多元醇、环氧树 脂多元醇、聚氨酯多元醇的丙烯酸酯、乙烯基醚以及不饱和二元羧酸多元醇的不饱和聚酯。
  7. 根据权利要求4所述的UV光固化组合物，其特征在于，当所述UV光固化组合物作为UV抗蚀油墨或UV阻焊油墨用途时，使用的所述烯属不饱和可光聚合化合物中至少一种化合物含有碱溶性基团，优选为含羧基的树脂。
  8. 根据权利要求7所述的UV光固化组合物，其特征在于，所述含羧基的树脂为(甲基)丙烯酸酯、乙烯性不饱和羧酸或(甲基)丙烯酸酯系聚合物；
    优选的，所述(甲基)丙烯酸酯选自由(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸酯二甲胺基乙酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸糠基酯、(甲基)丙烯酸缩水甘油酯组成的组中的一种或多种；
    优选的，所述乙烯性不饱和羧酸选自由丙烯酸、甲基丙烯酸、乙烯基安息酸、马来酸、马来酸烷基酯、富马酸、衣康酸、丁烯酸、肉桂酸、丙烯酸二聚体、具有羟基的单体和环状酸酐的加成产物、ω-羧基-聚己内酯-(甲基)丙烯酸酯组成的组中的一种或多种，更优选为(甲基)丙烯酸；
    优选的，所述(甲基)丙烯酸酯系聚合物选自由(甲基)丙烯酰胺、(甲基)丙烯酸正丁酯、苯乙烯、乙烯基萘、(甲基)丙烯晴、乙酸乙烯基酯、乙烯基环己烷组成的组中的一种或多种。
  9. 根据权利要求4所述的UV光固化组合物，其特征在于，所述UV光固化组合物还包括其他光引发剂，优选的，所述其他光引发剂选自由二苯甲酮、苯偶酰二甲基缩酮、2-羟基-2-甲基-1-苯基-丙酮、1-羟基-环己基-苯基-酮、异丙基硫杂蒽、(2,4,6-三甲基-苯甲酰基)二苯基氧化膦和双(2,4,6-三甲基苯甲酰基)-苯基氧化膦组成的组中的一种或多种。
  10. 根据权利要求4所述的UV光固化组合物，其特征在于，所述UV光固化组合物还包括增感剂；
    优选的，所述增感剂为吡唑啉类化合物、吖啶类化合物、蒽类化合物、香豆素类化合物或叔胺类化合物。
  11. 根据权利要求4所述的UV光固化组合物，其特征在于，所述UV光固化组合物还包括着色剂，所述着色剂为无机颜料或有机颜料。
  12. 根据权利要求4所述的UV光固化组合物，其特征在于，所述UV光固化组合物还包括添加剂，所述添加剂包括表面活性剂、润湿剂、分散剂、流变改性剂、消泡剂或储存增强剂中的一种或多种。
  13. 一种如权利要求1至3中任一项所述的芴氨基酮类光引发剂的制备方法，其特征在于，包括以下步骤：
    (1)原料a与原料b发生傅克反应生成中间体a，反应式如下：
    Figure PCTCN2018076209-appb-100008
    (2)所述中间体a发生取代反应生成中间体b：
    Figure PCTCN2018076209-appb-100009
    (3)所述中间体b发生取代反应生成中间体c：
    Figure PCTCN2018076209-appb-100010
    (4)所述中间体c发生Stevens重排反应生成中间体d：
    Figure PCTCN2018076209-appb-100011
    (5)当预得到A＝H的产物，则原料a中B＝H，中间体d即为通式(I)化合物；
    当预得到
    Figure PCTCN2018076209-appb-100012
    的产物，则原料a中B＝F，中间体d发生取代反应生成具有如下通式(I)化合物；
    Figure PCTCN2018076209-appb-100013
    当预得到
    Figure PCTCN2018076209-appb-100014
    的产物，则原料a中B＝H，中间体d发生傅克反应生成具有如下通式(I)化合物；
    Figure PCTCN2018076209-appb-100015
  14. 一种如权利要求4至12中任一项所述的UV光固化组合物在UV涂料和UV油墨方面的应用。
PCT/CN2018/076209 2017-02-17 2018-02-11 芴氨基酮类光引发剂、其制备方法及含芴氨基酮类光引发剂的uv光固化组合物 WO2018149370A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP18755112.2A EP3584242A4 (en) 2017-02-17 2018-02-11 FLUORENYLAMINOCETONE PHOTOINITIATOR, ITS PREPARATION PROCESS AND UV PHOTOSETTING COMPOSITION CONTAINING IT
KR1020197023666A KR102252495B1 (ko) 2017-02-17 2018-02-11 플루오레닐아미노케톤 광개시제, 이의 제조 방법 및 이를 함유하는 uv 광경화성 조성물
JP2019544745A JP7032416B2 (ja) 2017-02-17 2018-02-11 フルオレニルアミノケトン類光開始剤、その調製方法及びフルオレニルアミノケトン類光開始剤を含有するｕｖ光硬化性組成物
US16/485,724 US11118065B2 (en) 2017-02-17 2018-02-11 Fluorenylaminoketone photoinitiator, preparation method thereof, and UV photocurable composition containing same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201710088234 2017-02-17
CN201710088234.X 2017-02-17
CN201710353951.0 2017-05-18
CN201710353951 2017-05-18

Publications (1)

Publication Number Publication Date
WO2018149370A1 true WO2018149370A1 (zh) 2018-08-23

Family

ID=63170084

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/076209 WO2018149370A1 (zh) 2017-02-17 2018-02-11 芴氨基酮类光引发剂、其制备方法及含芴氨基酮类光引发剂的uv光固化组合物

Country Status (5)

Country Link
US (1) US11118065B2 (zh)
EP (1) EP3584242A4 (zh)
JP (1) JP7032416B2 (zh)
KR (1) KR102252495B1 (zh)
WO (1) WO2018149370A1 (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110591633A (zh) * 2019-09-09 2019-12-20 深圳日高胶带新材料有限公司 一种聚氨酯改性丙烯酸酯uv固化压敏胶
EP3715381A4 (en) * 2017-11-22 2020-09-30 Huizhou Huahong New Material Co. Ltd. DIBUTYLFLUORENE DERIVATIVES AND THEIR USE AS A PHOTOINITIATOR
JP6817503B1 (ja) * 2019-05-29 2021-01-20 株式会社Ｄｎｐファインケミカル カラーフィルタ用感光性着色樹脂組成物、硬化物、カラーフィルタ、及び表示装置
JP2021507058A (ja) * 2017-12-22 2021-02-22 常州強力先端電子材料有限公司Ｃｈａｎｇｚｈｏｕ Ｔｒｏｎｌｙ Ａｄｖａｎｃｅｄ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． フッ素含有フルオレンオキシムエステル系光開始剤、それを含む光硬化組成物およびその適用
CN113549167A (zh) * 2021-07-22 2021-10-26 浙江东海新材料科技股份有限公司 一种高效通用型紫外光引发剂的制备工艺
TWI747600B (zh) * 2020-11-09 2021-11-21 立大化工股份有限公司 紫外光硬化性樹脂組成物

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK3392232T3 (da) * 2015-12-15 2021-04-12 Changzhou Tronly Advanced Electronic Mat Co Ltd Multifunktionel fluorenfotoinitiator og fremstilling og anvendelse deraf, og fotosensitiv resinsammensætning indeholdende fluorenfotoinitiator og anvendelse deraf
WO2018049976A1 (zh) 2016-09-13 2018-03-22 常州强力先端电子材料有限公司 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
CN113698563A (zh) * 2021-08-05 2021-11-26 明光科迪新材料有限公司 一种硫杂蒽酮聚氨酯改性环氧丙烯酸酯led光固化树脂
JP6998490B1 (ja) * 2021-08-30 2022-01-18 サカタインクス株式会社 光硬化型インクジェット印刷用インク組成物
CN114394990B (zh) * 2022-03-14 2024-02-13 内蒙古扬帆新材料有限公司 一种同时含有α-氨基酮和有机硅的不对称大分子光引发剂及其制备方法和应用
CN115850206B (zh) * 2022-12-06 2024-05-28 天津久日新材料股份有限公司 一种芴衍生物光引发剂及其制备方法和应用
JP7298109B1 (ja) * 2022-12-21 2023-06-27 東洋インキＳｃホールディングス株式会社 活性エネルギー線硬化型組成物及び印刷物

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB928688A (en) 1960-02-03 1963-06-12 Ernest Walter Greenwood Improvements in or relating to anti-glare or anti-dazzle devices
US4950581A (en) * 1987-07-06 1990-08-21 Fuji Photo Film Co., Ltd. Photopolymerizable composition
JP2001348412A (ja) 2000-04-03 2001-12-18 Jsr Corp 液状硬化性樹脂組成物および二層フィルム
JP2009029859A (ja) * 2007-07-25 2009-02-12 Toyo Ink Mfg Co Ltd 重合性組成物、および重合物の製造方法
CN101724099A (zh) 2009-12-18 2010-06-09 深圳市东方信维科技有限公司 芳香酮类化合物及含有该化合物的光引发剂
KR20140144809A (ko) * 2013-06-11 2014-12-22 애경화학 주식회사 플루오렌 구조를 갖는 신규한 광개시제 및 이를 포함하는 반응성 액정 조성물 및 감광성 조성물
CN105916837A (zh) * 2014-01-17 2016-08-31 三养社 新型β-肟酯芴化合物、包含其的光聚合引发剂和光致抗蚀剂组合物
WO2017101553A1 (zh) * 2015-12-15 2017-06-22 常州强力先端电子材料有限公司 一种芴类多官能度光引发剂及其制备和应用、含芴类光引发剂的感光性树脂组合物及其应用
WO2018049976A1 (zh) * 2016-09-13 2018-03-22 常州强力先端电子材料有限公司 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

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH491848A (de) 1966-07-22 1970-06-15 Sandoz Ag Verfahren zur Herstellung neuer Arylketone
DE3008411A1 (de) 1980-03-05 1981-09-10 Merck Patent Gmbh, 6100 Darmstadt Neue aromatisch-aliphatische ketone, ihre verwendung als photoinitiatoren sowie photopolymerisierbare systeme enthaltend solche ketone
US4533670A (en) 1983-09-21 1985-08-06 Eli Lilly And Company Anti-convulsant fluorenylalkylimidazole derivatives, compositions, and method of use
JPS60118975U (ja) 1984-01-17 1985-08-12 富士通株式会社 プリント板試験治具
US4666824A (en) 1984-04-23 1987-05-19 Hercules Incorporated Photopolymer process and composition employing a photooxidizable component capable of forming endoperoxides
DE3880868D1 (en) 1987-03-26 1993-06-17 Ciba Geigy Ag Neue alpha-aminoacetophenone als photoinitiatoren.
TW328535B (en) 1993-07-02 1998-03-21 Novartis Ag Functional photoinitiators and their manufacture
TW353086B (en) 1994-12-30 1999-02-21 Novartis Ag Method for multistep coating of a surface
TW434456B (en) 1994-12-30 2001-05-16 Novartis Ag A compound as functionalized photoinitiator, its production process, its corresponding oligomers or polymers and its application in coating a substrate
KR987001001A (ko) 1994-12-30 1998-04-30 발덱 베르너, 케르커 니콜레 실록산 함유 네트워크(Siloxane-Containing Networks)
IT1303775B1 (it) 1998-11-19 2001-02-23 Lamberti Spa Fotoiniziatori impiegabili nella fotopolimerizzazione, e relativeformulazioni.
ITVA20030028A1 (it) 2003-08-07 2005-02-08 Lamberti Spa Sistemi fotopolimerizzabili trasparenti per la preparazione di rivestimenti ad elevato spessore.
KR100596364B1 (ko) 2004-05-31 2006-07-03 주식회사 엘지화학 감광성 수지 조성물 및 이를 이용하여 제조된 액정표시소자
JP2009019142A (ja) 2007-07-13 2009-01-29 Toyo Ink Mfg Co Ltd 光硬化型インキ
JP5334477B2 (ja) 2008-07-16 2013-11-06 富士フイルム株式会社 光硬化性組成物、インク組成物及びそれを用いたインクジェット記録方法
CN102267887A (zh) 2011-07-18 2011-12-07 连云港升南化学有限公司 1-羟基环己基苯基甲酮的合成工艺
CN103857750A (zh) 2011-10-12 2014-06-11 东洋油墨Sc控股株式会社 树脂组合物、涂膜及触控面板用绝缘膜
CN104661997B (zh) 2012-05-03 2018-06-26 韩国化学研究院 新型芴类肟酯化合物，及含有该芴类肟酯化合物的光聚合引发剂和光阻剂组合物
CN107266334B (zh) 2012-09-28 2020-04-24 大东凯米克斯株式会社 芴系化合物、含有该芴系化合物的光聚合引发剂、以及含有该光聚合引发剂的光敏性组合物
TWI646075B (zh) 2013-03-29 2019-01-01 日商東京應化工業股份有限公司 含乙烯基之茀系化合物
KR101939552B1 (ko) 2013-12-06 2019-01-17 롬엔드하스전자재료코리아유한회사 유기 전계 발광 화합물 및 이를 포함하는 유기 전계 발광 소자
KR101888799B1 (ko) 2014-07-15 2018-08-14 도쿄 오카 고교 가부시키가이샤 감광성 조성물 및 화합물
WO2016034963A1 (en) 2014-09-04 2016-03-10 Basf Se Polycyclic photoinitiators
CN107001927B (zh) 2014-11-21 2019-09-17 香港科技大学 用于细菌成像、杀灭、光动力疗法和抗生素筛选的aie发光团及其生产方法
KR101824429B1 (ko) * 2015-01-26 2018-02-06 주식회사 삼양사 신규한 디옥심에스테르 화합물 및 이를 포함하는 광중합 개시제 및 포토레지스트 조성물
JP6408715B2 (ja) * 2015-02-06 2018-10-17 コリア リサーチ インスティテュート オブ ケミカル テクノロジー 新規のオキシムエステル誘導体化合物およびこれを含む光重合開始剤、ならびにフォトレジスト組成物
CN104892512B (zh) 2015-05-21 2018-01-05 常州强力先端电子材料有限公司 一种吡唑啉类增感剂及其制备方法和应用
CN108137443B (zh) * 2015-07-31 2021-06-08 克美 芴衍生物、包含其的光聚合引发剂及光致抗蚀剂组合物
CN106883114B (zh) 2015-12-15 2019-11-19 常州强力先端电子材料有限公司 一种芴类多官能度光引发剂及其制备和应用

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB928688A (en) 1960-02-03 1963-06-12 Ernest Walter Greenwood Improvements in or relating to anti-glare or anti-dazzle devices
US4950581A (en) * 1987-07-06 1990-08-21 Fuji Photo Film Co., Ltd. Photopolymerizable composition
JP2001348412A (ja) 2000-04-03 2001-12-18 Jsr Corp 液状硬化性樹脂組成物および二層フィルム
JP2009029859A (ja) * 2007-07-25 2009-02-12 Toyo Ink Mfg Co Ltd 重合性組成物、および重合物の製造方法
CN101724099A (zh) 2009-12-18 2010-06-09 深圳市东方信维科技有限公司 芳香酮类化合物及含有该化合物的光引发剂
KR20140144809A (ko) * 2013-06-11 2014-12-22 애경화학 주식회사 플루오렌 구조를 갖는 신규한 광개시제 및 이를 포함하는 반응성 액정 조성물 및 감광성 조성물
CN105916837A (zh) * 2014-01-17 2016-08-31 三养社 新型β-肟酯芴化合物、包含其的光聚合引发剂和光致抗蚀剂组合物
WO2017101553A1 (zh) * 2015-12-15 2017-06-22 常州强力先端电子材料有限公司 一种芴类多官能度光引发剂及其制备和应用、含芴类光引发剂的感光性树脂组合物及其应用
WO2018049976A1 (zh) * 2016-09-13 2018-03-22 常州强力先端电子材料有限公司 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

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE CAS [o] 27 October 2016 (2016-10-27), retrieved from STN Database accession no. 2020359-04-8 *
See also references of EP3584242A4

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3715381A4 (en) * 2017-11-22 2020-09-30 Huizhou Huahong New Material Co. Ltd. DIBUTYLFLUORENE DERIVATIVES AND THEIR USE AS A PHOTOINITIATOR
JP2021504555A (ja) * 2017-11-22 2021-02-15 惠州市華泓新材料股▲ふん▼有限公司Ｈｕｉｚｈｏｕ Ｈｕａｈｏｎｇ Ｎｅｗ Ｍａｔｅｒｉａｌ Ｃｏ．， Ｌｔｄ． ジブチルフルオレニル誘導体及びその光開始剤としての使用
JP7059384B2 (ja) 2017-11-22 2022-04-25 惠州市華泓新材料股▲ふん▼有限公司 ジブチルフルオレニル誘導体及びその光開始剤としての使用
JP2021507058A (ja) * 2017-12-22 2021-02-22 常州強力先端電子材料有限公司Ｃｈａｎｇｚｈｏｕ Ｔｒｏｎｌｙ Ａｄｖａｎｃｅｄ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． フッ素含有フルオレンオキシムエステル系光開始剤、それを含む光硬化組成物およびその適用
JP6999039B2 (ja) 2017-12-22 2022-02-04 常州強力先端電子材料有限公司 フッ素含有フルオレンオキシムエステル系光開始剤、それを含む光硬化組成物およびその適用
JP6817503B1 (ja) * 2019-05-29 2021-01-20 株式会社Ｄｎｐファインケミカル カラーフィルタ用感光性着色樹脂組成物、硬化物、カラーフィルタ、及び表示装置
CN110591633A (zh) * 2019-09-09 2019-12-20 深圳日高胶带新材料有限公司 一种聚氨酯改性丙烯酸酯uv固化压敏胶
TWI747600B (zh) * 2020-11-09 2021-11-21 立大化工股份有限公司 紫外光硬化性樹脂組成物
CN113549167A (zh) * 2021-07-22 2021-10-26 浙江东海新材料科技股份有限公司 一种高效通用型紫外光引发剂的制备工艺
CN113549167B (zh) * 2021-07-22 2022-12-09 浙江东海新材料科技股份有限公司 一种高效通用型紫外光引发剂的制备工艺

Also Published As

Publication number Publication date
JP7032416B2 (ja) 2022-03-08
KR102252495B1 (ko) 2021-05-14
US20200002544A1 (en) 2020-01-02
EP3584242A1 (en) 2019-12-25
JP2020507664A (ja) 2020-03-12
EP3584242A4 (en) 2020-12-23
US11118065B2 (en) 2021-09-14
KR20190103370A (ko) 2019-09-04

Similar Documents

Publication Publication Date Title
WO2018149370A1 (zh) 芴氨基酮类光引发剂、其制备方法及含芴氨基酮类光引发剂的uv光固化组合物
CN108957950B (zh) 含芴氨基酮类光引发剂的uv光固化组合物
JP4975449B2 (ja) 官能化光開始剤
JP4344400B1 (ja) オキシムエステル化合物及びこれらを用いた感光性樹脂組成物
BE1014009A5 (fr) Compose photo-initiateur, composition le contenant, et leurs utilisations.
CN102093282B (zh) 肟酯光敏引发剂
TWI495631B (zh) 不對稱二肟酯化合物及其中間體與其製造方法及應用
TW200422296A (en) Oxime ester photoinitiators with heteroaromatic groups
JP2011524436A (ja) 光開始剤混合物
TW201516568A (zh) 液態雙醯基氧化膦光引發劑
WO2018196619A1 (zh) 含有可聚合基团的芴肟酯类光引发剂、制备方法及其应用
TW200403260A (en) New difunctional photoinitiators
TW201509888A (zh) 環戊二酮肟酯及其中間體與其製造方法及應用
JP5705371B2 (ja) 染料を含む高分子化合物及びこれを含む硬化性樹脂組成物
JP2013500303A (ja) 高分子光開始剤
JP2012051927A (ja) 粉末の形態での白色固体光開始剤およびその製造
JP2014505115A (ja) 染料を含む高分子化合物およびそれを含む硬化性樹脂組成物
JP2010189280A (ja) オキシムエステル化合物及びこれらを用いた感光性樹脂組成物
WO2014094658A1 (zh) 烷基苯基衍生物和其作为光引发剂的应用
JP2020537681A (ja) トランス−トランス・ジケトキシム・エステル異性体、その製造方法および適用
TW202100510A (zh) 一種新的二芳醯基哢唑化合物及其作為增感劑的應用
JP5290272B2 (ja) α−ヒドロキシケトン
JP2002534488A (ja) ベンゾフェノンおよび光重合開始剤としてのその使用
JP2022078550A (ja) 新規な光重合開始剤及びこれらを用いた感光性樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18755112

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20197023666

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2019544745

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018755112

Country of ref document: EP

Effective date: 20190917