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CN116444460A - Oxime ester compound, photoinitiator containing oxime ester compound, photo-curing resin composition containing oxime ester compound and application of photo-curing resin composition - Google Patents

Oxime ester compound, photoinitiator containing oxime ester compound, photo-curing resin composition containing oxime ester compound and application of photo-curing resin composition Download PDF

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Publication number
CN116444460A
CN116444460A CN202210017800.9A CN202210017800A CN116444460A CN 116444460 A CN116444460 A CN 116444460A CN 202210017800 A CN202210017800 A CN 202210017800A CN 116444460 A CN116444460 A CN 116444460A
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Prior art keywords
acrylate
meth
acrylic acid
alkyl
oxime ester
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Inventor
胡春青
翁云峰
于培培
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Priority to CN202210017800.9A priority Critical patent/CN116444460A/en
Publication of CN116444460A publication Critical patent/CN116444460A/en
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    • 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
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    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
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    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
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    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/61—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms not forming part of a nitro radical, attached to ring nitrogen atoms
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    • C07—ORGANIC CHEMISTRY
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    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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

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Abstract

The invention provides an oxime ester compound, a photoinitiator containing the oxime ester compound, a photo-curing resin composition and application of the oxime ester compound. The oxime ester compound has a structure shown in any one of formulas (I) to (IV): the oxime ester compound with the structures of the formulas (I) to (IV) has a stable structure, is not easy to generate small molecular fragments, has excellent anti-oxidation and polymerization inhibition performance, and is not influenced by oxygen in the environment in the photo-curing process; meanwhile, the fluorescent dye has higher photosensitivity and higher photoinitiation activity (especially suitable for photoinitiation systems under 385nm illumination). The oxime ester compound is introduced into the oxime ester photoinitiator, so that the anti-oxidation polymerization resistance of the oxime ester photoinitiator can be obviously improved; meanwhile, the generation of small molecule fragments is reduced. The oxime ester photoinitiator is particularly suitable for photocuring under 385nm illumination.

Description

Oxime ester compound, photoinitiator containing oxime ester compound, photo-curing resin composition containing oxime ester compound and application of photo-curing resin composition
Technical Field
The invention relates to the technical field of photo-curing, in particular to an oxime ester compound, a photoinitiator containing the oxime ester compound, a photo-curing resin composition and application of the oxime ester compound.
Background
Oxime ester photoinitiators are novel compounds capable of generating alkaline substances under special illumination conditions, and have the problems of large system volume shrinkage, serious oxygen inhibition and the like due to free radical photocuring, and super-strong acids which can corrode substrates are generated in cationic photocuring, so that the application of the oxime ester photoinitiators in certain aspects is limited, and the use of photobase generators can avoid the problems, so that the oxime ester photoinitiators are increasingly valued.
To meet the rapidly changing demands of the market, various novel oxime ester initiators have been developed. The prior document (publication No. CN107635960 a) discloses an oxime ester compound and a polymerization initiator containing the same, which can obtain a photoinitiator with higher transparency and has the characteristics of high sensitivity and high solubility. The prior document (publication No. CN 103998422A) discloses a cyclopentanedione oxime ester initiator which has higher activity. The prior document (publication No. CN 112876584A) likewise discloses oxime ester initiators which are relatively excellent in a variety of combinations under the current application conditions.
However, the problem of oxygen inhibition caused by the application of the oxime ester initiator is still not solved effectively. With the rise of display technologies such as OLED and quantum dot, research and development of an oxime ester compound with a novel structure are needed to solve the problem of oxygen inhibition caused by application of the oxime ester compound.
Disclosure of Invention
The invention mainly aims to provide an oxime ester compound, a photoinitiator containing the oxime ester compound, a photo-curing resin composition and application thereof, so as to solve the problems that the oxime ester photoinitiator in the prior art is easy to generate small molecular fragments under the irradiation of ultraviolet light or mercury lamps and has poor anti-oxidation polymerization resistance.
In order to achieve the above object, in one aspect, the present invention provides an oxime ester compound having a structure represented by any one of formulas (I) to (IV):
each R is 1 Are independently selected from C 1 ～C 30 Alkyl, C of (2) 6 ～C 24 Aryl substituted C 1 ～C 20 Alkyl, C 6 ～C 24 Aryloxy substituted C 1 ～C 20 Alkyl, C 1 ～C 20 Haloalkyl, C 6 ～C 24 Aryl, C of (2) 1 ～C 12 Alkyl substituted C 6 ～C 24 Aryl, C 4 ～C 24 Heterocyclic groups of (2), or C interrupted by more than 1 ether or thioether bond 2 ～C 30 Alkyl of (a); in each structure, R 3 And R is 4 Are each independently selected from hydrogen, nitro, cyano, hydroxy, halogen, C 1 ～C 30 Alkyl, C of (2) 6 ～C 24 Aryl substituted C 1 ～C 20 Alkyl, C 6 ～C 24 Aryloxy substituted C 1 ～C 20 Alkyl, C 1 ～C 20 Haloalkyl, C 2 ～C 8 Acyl group, C 6. ～C 12 Aryl, C of (2) 1 ～C 8 C interrupted by more than 1 ether or thioether bond(s) 2 ～C 30 Is, -C (=o) -O-C (=n) -C (=o) R 2 The group(s) is (are) a radical,R 5 selected from methyl, phenyl or thienyl; r is R 2 Selected from C 1 ～C 30 Alkyl, C of (2) 6 ～C 24 Aryl substituted C 1 ～C 20 Alkyl, C 6 ～C 24 Aryloxy substituted C 1 ～C 20 Alkyl, C 6 ～C 24 Aryl, C of (2) 1 ～C 12 Alkyl substituted C 6 ～C 24 Aryl, or C interrupted by more than 1 ether or thioether bond 2 ～C 30 Alkyl of (a); x is a connecting bond, C 1 ～C 10 A linear or branched alkylene group, a substituent formed by substitution of the above-mentioned group with one or more oxygen atoms, sulfur atoms or arylene groups; each P is independently selected from 0 or 1; each A is independently selected from C 1 ～C 3 Alkyl of (a); in each structure, C m And C n Identical or different, the said C m And said C n Are independently selected from C 1 ～C 3 An alkylene group of (a); each Y is independently selected from N, O, S or carbonyl.
Further, R 1 、R 2 、R 3 And R is 4 Are independently selected from C 1 ～C 22 Alkyl, C of (2) 6 ～C 20 Aryl substituted C 1 ～C 12 Alkyl, C of (2) 6 ～C 20 Aryloxy substituted C 1 ～C 20 Alkyl, C 1 ～C 10 Haloalkyl, C 6 ～C 20 Aryl, C of (2) 1 ～C 8 Alkyl substituted C 6 ～C 20 Aryl, C 4 ～C 18 Or (B) a heterocyclic group, orC interrupted by more than 1 ether or thioether bond 2 ～C 20 Is a hydrocarbon group.
Further, R 1 、R 2 、R 3 And R is 4 Are independently selected from C 1 ～C 17 Alkyl of (C) is preferred 1 ～C 10 Straight-chain, branched, single-cyclic or condensed polycyclic alkyl groups; or, R 1 、R 2 、R 3 And R is 4 Are independently selected from C 6 ～C 18 Aryl substituted C 1 ～C 10 Alkyl of (C) is preferred 6 ～C 10 Aryl substituted C 1 ～C 6 Alkyl of (a); or, R 1 、R 2 、R 3 And R is 4 Are independently selected from C 6 ～C 18 Aryloxy substituted C 1 ～C 8 Alkyl, preferably C 6 ～C 10 Aryloxy substituted C 1 ～C 4 An alkyl group; or, R 1 、R 2 、R 3 And R is 4 Are independently selected from C 2 ～C 8 Haloalkyl of (C) is preferred 2 ～C 5 A linear or branched haloalkyl group; or, R 1 、R 2 、R 3 And R is 4 Are independently selected from C 6 ～C 18 Aryl of (C) is preferred 6 ～C 10 Aryl of (a); or, R 1 、R 2 、R 3 And R is 4 Are independently selected from C 1 ～C 6 Alkyl substituted C 6 ～C 18 Aryl, preferably C 1 ～C 4 Alkyl substituted C 6 ～C 10 An aryl group; or, R 1 、R 2 、R 3 And R is 4 Are independently selected from C 4 ～C 14 Heterocyclic groups of (C) are preferred 4 ～C 10 An aromatic or alicyclic heterocyclic group; or, R 1 、R 2 、R 3 And R is 4 Independently selected from C interrupted by more than 1 ether or thioether bond 2 ～C 15 Preferably C interrupted by more than 1 ether or thioether bond(s) 2 ～C 10 Is a hydrocarbon group.
Further toGround, R 1 Selected from methyl, cyclopentyl, ethyl, phenyl, thienyl, o-tolyl, cyclopentyl substituted methylene, or phenyl; r is R 2 Selected from ethyl; r is R 3 And R is 4 Independently selected from hydrogen, C m And C n Identical, and C m And C n Are all-CH 2 -CH 2 -; a is selected from ethylene; y is selected from sulfur atom or oxygen atom; x is methylene, straight-chain butylene, 1-ethylene or phenylene, and P is 0 or 1.
Further, the oxime ester compound is selected from one or more of compounds having a structure shown below:
In order to achieve the above object, another aspect of the present invention further provides an oxime ester photoinitiator, which includes the oxime ester compound provided in the present application.
In order to achieve the above object, another aspect of the present invention also provides a photocurable resin composition comprising a photoinitiator, an alkali-soluble resin, and a polymerization monomer, wherein the photoinitiator comprises the above oxime ester photoinitiator provided herein.
Further, the photo-curing resin composition comprises 1 to 5 parts by weight of oxime ester photoinitiator, 10 to 100 parts by weight of alkali-soluble resin and 10 to 50 parts by weight of polymerized monomer; preferably, the photocurable resin composition further comprises 0 to 500 parts by weight of a solvent.
Further, the alkali-soluble resin is selected from carboxyl-containing copolymer molecules; the polymeric monomer is selected from monofunctional, difunctional or polyfunctional acrylate monomers; preferably, the alkali-soluble resin is selected from the group consisting of (meth) acrylic acid/(meth) acrylic acid methyl ester copolymer, (meth) acrylic acid/(meth) acrylic acid benzyl ester copolymer, (meth) acrylic acid 2-hydroxyethyl/(meth) acrylic acid benzyl ester copolymer, (meth) acrylic acid/(meth) acrylic acid methyl ester/polystyrene macromer copolymer, (meth) acrylic acid/(meth) acrylic acid methyl ester/polymethyl methacrylate macromer copolymer, (meth) acrylic acid/(meth) acrylic acid benzyl ester/polystyrene macromer copolymer, (meth) acrylic acid/(meth) acrylic acid benzyl ester/polymethyl methacrylate macromer copolymer, (meth) acrylic acid 2-hydroxyethyl/(meth) acrylic acid benzyl ester/polystyrene macromer copolymer, (meth) acrylic acid 2-hydroxyethyl/(meth) acrylic acid benzyl ester/polymethyl methacrylate macromer copolymer, methacrylic acid/styrene/(meth) acrylic acid benzyl ester/N-phenylmaleimide copolymer, one or more of the group consisting of (meth) acrylic acid/succinic acid mono [2- (meth) acryloyloxyethyl ]/styrene/(meth) acrylic acid benzyl ester/N-phenylmaleimide copolymer, (meth) acrylic acid/succinic acid mono [2- (meth) acryloyloxyethyl ]/styrene/(meth) acrylic acid allyl ester/N-phenylmaleimide copolymer, (meth) acrylic acid/styrene/(meth) acrylic acid benzyl ester/glycerol mono (meth) acrylate/N-phenylmaleimide copolymer, and (meth) acrylic acid/ω -carboxypolycaprolactone mono (meth) acrylate/styrene/(meth) acrylic acid benzyl ester/glycerol mono (meth) acrylate/N-phenylmaleimide copolymer; preferably, the polymeric monomer is selected from one or more of the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, isobornyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-trifluoroethyl acrylate, beta-carboxyethyl acrylate, and omega-carboxypolycaprolactone monoacrylate; or, the polymeric monomer is selected from one or more of the group consisting of dicyclopentenyl acrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol a diacrylate, EO modified bisphenol a diacrylate, PO modified bisphenol a diacrylate, hydrogenated bisphenol a diacrylate, EO modified hydrogenated bisphenol a diacrylate, PO modified hydrogenated bisphenol a diacrylate, bisphenol F diacrylate, EO modified bisphenol F diacrylate, PO modified bisphenol F diacrylate, EO modified tetrabromobisphenol a diacrylate, and tricyclodecane dimethylol diacrylate; or, the polymerization monomer is selected from one or more of glycerin PO modified triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate and tetramethylolmethane tetraacrylate; or, an ethoxylated product or a propoxylated product of the acrylate monomer. Preferably, the ethoxylation or propoxylation products of the acrylate monomers include, but are not limited to, one or more of the group consisting of dicyclopentadienyloxyethyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 1, 3-butanediol methyl ether acrylate, butoxyethyl acrylate, monoacryloxyethyl succinate, trimethylsiloxyethyl acrylate, and diphenyl-2-acryloyloxyethyl phosphate.
In a further aspect, the present invention provides an oxime ester photoinitiator as provided herein, or an application of the above photocurable resin composition as provided herein in the field of photocuring.
By applying the technical scheme of the invention, the oxime ester compound with the structures of the formulas (I) to (IV) has a stable structure, small molecular fragments are not easy to generate, the anti-oxidation polymerization inhibition performance is excellent, and the photocuring process is not influenced by oxygen in the environment; meanwhile, the fluorescent dye has higher photosensitivity and higher photoinitiation activity (especially suitable for photoinitiation systems under 385nm illumination). The oxime ester compound is introduced into the oxime ester photoinitiator, so that the anti-oxidation polymerization resistance of the oxime ester photoinitiator can be obviously improved; meanwhile, the generation of small molecule fragments is reduced. The oxime ester photoinitiator is particularly suitable for photocuring under 385nm illumination.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As described in the background art, the existing oxime ester photoinitiator has the problems that small molecular fragments are easy to generate under the irradiation of ultraviolet light or mercury lamps, and the anti-oxidation polymerization inhibition performance is poor. In order to solve the technical problems, a first aspect of the present application provides an oxime ester compound having a structure shown in any one of formulas (I) to (IV):
Each R is 1 Each independently include but are not limited to C 1 ～C 30 Alkyl, C of (2) 6 ～C 24 Aryl substituted C 1 ～C 20 Alkyl, C 6 ～C 24 Aryloxy substituted C 1 ～C 20 Alkyl, C 1 ～C 20 Is an alkyl halide of (2)Radical, C 6 ～C 24 Aryl, C of (2) 1 ～C 12 Alkyl substituted C 6 ～C 24 Aryl, C 4 ～C 24 Heterocyclic groups of (2), or C interrupted by more than 1 ether or thioether bond 2 ～C 30 Alkyl of (a); in each structure, R 3 And R is 4 Each independently includes but is not limited to hydrogen, nitro, cyano, hydroxy, halogen, C 1 ～C 30 Alkyl, C of (2) 6 ～C 24 Aryl substituted C 1 ～C 20 Alkyl, C 6 ～C 24 Aryloxy substituted C 1 ～C 20 Alkyl, C 1 ～C 20 Haloalkyl, C 2 ～C 8 Acyl group, C 6. ～C 12 Aryl, C of (2) 1 ～C 8 C interrupted by more than 1 ether or thioether bond(s) 2 ～C 30 Is, -C (=o) -O-C (=n) -C (=o) R 2 The group(s) is (are) a radical,R 5 including but not limited to methyl, phenyl or thienyl; r is R 2 Including but not limited to C 1 ～C 30 Alkyl, C of (2) 6 ～C 24 Aryl substituted C 1 ～C 20 Alkyl, C 6 ～C 24 Aryloxy substituted C 1 ～C 20 Alkyl, C 6 ～C 24 Aryl, C of (2) 1 ～C 12 Alkyl substituted C 6 ～C 24 Aryl, or C interrupted by more than 1 ether or thioether bond 2 ～C 30 Alkyl of (a); x is a connecting bond, C 1 ～C 10 A linear or branched alkylene group, a substituent formed by substitution of the above-mentioned group with one or more oxygen atoms, sulfur atoms or arylene groups; each P independently includes, but is not limited to, 0 or 1; each A independently includes but is not limited to C 1 ～C 3 Alkyl of (a); in each structure, C m And C n Identical or different, C m And C n Each independently include but are not limited to C 1 ～C 3 An alkylene group of (a); each Y independently includes but is notLimited to N, O, S or carbonyl.
The oxime ester compound with the structures of the formulas (I) to (IV) has a stable structure, is not easy to generate small molecular fragments, has excellent anti-oxidation and polymerization inhibition performance, and is not influenced by oxygen in the environment in the photo-curing process; meanwhile, the fluorescent dye has higher photosensitivity and higher photoinitiation activity (especially suitable for photoinitiation systems under 385nm illumination). The oxime ester compound is introduced into the oxime ester photoinitiator, so that the anti-oxidation polymerization resistance of the oxime ester photoinitiator can be obviously improved; meanwhile, the generation of small molecule fragments is reduced. The oxime ester photoinitiator is particularly suitable for photocuring under 385nm illumination.
In a preferred embodiment, R 1 、R 2 、R 3 And R is 4 Each independently include but are not limited to C 1 ～C 22 Alkyl, C of (2) 6 ～C 20 Aryl substituted C 1 ～C 12 Alkyl, C of (2) 6 ～C 20 Aryloxy substituted C 1 ～C 20 Alkyl, C 1 ～C 10 Haloalkyl, C 6 ～C 20 Aryl, C of (2) 1 ～C 8 Alkyl substituted C 6 ～C 20 Aryl, C 4 ～C 18 Heterocyclic groups of (2), or C interrupted by more than 1 ether or thioether bond 2 ～C 20 Is a hydrocarbon group.
R 1 、R 2 、R 3 And R is 4 The oxime ester compound is beneficial to improving the photosensitivity of the oxime ester compound, improving the photocuring performance of the oxime ester compound under 385nm illumination condition, reducing the possibility of generating small molecular fragments and improving the anti-oxidation polymerization inhibition performance.
In a preferred embodiment, R 1 、R 2 、R 3 And R is 4 Each independently include but are not limited to C 1 ～C 17 Alkyl of (C) is preferred 1 ～C 10 Straight-chain, branched, single-cyclic or condensed polycyclic alkyl groups; or, R 1 、R 2 、R 3 And R is 4 Each independently include but are not limited to C 6 ～C 18 Aryl substituted C 1 ～C 10 Alkyl of (C) is preferred 6 ～C 10 Aryl substituted C 1 ～C 6 Alkyl of (a); or, R 1 、R 2 、R 3 And R is 4 Each independently include but are not limited to C 6 ～C 18 Aryloxy substituted C 1 ～C 8 Alkyl, preferably C 6 ～C 10 Aryloxy substituted C 1 ～C 4 An alkyl group; or, R 1 、R 2 、R 3 And R is 4 Each independently include but are not limited to C 2 ～C 8 Haloalkyl of (C) is preferred 2 ～C 5 A linear or branched haloalkyl group; or, R 1 、R 2 、R 3 And R is 4 Each independently include but are not limited to C 6 ～C 18 Aryl of (C) is preferred 6 ～C 10 Aryl of (a); or, R 1 、R 2 、R 3 And R is 4 Each independently include but are not limited to C 1 ～C 6 Alkyl substituted C 6 ～C 18 Aryl, preferably C 1 ～C 4 Alkyl substituted C 6 ～C 10 An aryl group; or, R 1 、R 2 、R 3 And R is 4 Each independently include but are not limited to C 4 ～C 14 Heterocyclic groups of (C) are preferred 4 ～C 10 An aromatic or alicyclic heterocyclic group; or, R 1 、R 2 、R 3 And R is 4 Each independently includes, but is not limited to, C interrupted by more than 1 ether linkage or thioether linkage 2 ～C 15 Preferably C interrupted by more than 1 ether or thioether bond(s) 2 ～C 10 Is a hydrocarbon group.
R 1 、R 2 、R 3 And R is 4 The oxime ester compounds of the above species are adopted to further improve the stability of the structure, further inhibit the generation of small molecular fragments and further improve the anti-oxidation polymerization inhibition performance; at the same time, the sensitivity of the oxime ester compound is further improved, and furtherHigh photocuring performance under 385nm illumination condition; meanwhile, the possibility of generating small molecular fragments is further reduced, and the anti-oxidation polymerization inhibition performance is further improved.
In a preferred embodiment, R 1 、R 2 、R 3 And R is 4 Each independently includes, but is not limited to, methyl, ethyl, propyl, n-butyl, hexyl, isopentyl, cyclohexyl, 2-chloroethyl, 4-chlorobutyl, 2-chlorobutyl, 5-bromopentyl, methoxymethyl, ethoxymethyl, butoxymethyl, or (2-butoxyethoxy) methyl; or, phenylmethyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl; or, phenoxymethyl, 1-phenoxyethyl, 2-phenoxyethyl, 3-phenoxypropyl, or 4-phenoxybutyl; or, phenyl, o-tolyl, m-tolyl, p-tolyl, chloromethylphenyl, 3, 5-dimethylphenyl, 4-cyanophenyl, 4-nitrophenyl, 4-methoxybenzyl, phenylmethyl, 1-phenylethyl, chlorophenyl methyl, 3-phenylpropyl, nitrophenylmethyl, phenoxymethyl, 1-phenoxyethyl, chlorophenoxymethyl, nitrophenoxymethyl, 1-naphthyl, or 2-ethoxy-1-naphthyl; or thienyl, thiophene-2-methyl, pyridyl, 2-furyl, quinolinyl, pyranyl, imidazolyl, piperidinyl, morpholinyl, thioxanthyl, or indolyl.
In a preferred embodiment, R 1 、R 2 、R 3 And R is 4 Each independently includes, but is not limited to, methyl, ethyl, propyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, sec-butyl, tert-butyl, sec-pentyl, tert-octyl, neopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, bornyl, 2-chloroethyl, 4-chlorobutyl, 2-chlorobutyl, 5-bromopentyl, 3-chloro-2-methylpropyl, 3-chloropropyl, 4-chlorobutyl, 5-chloropentyl, 6-chlorohexyl, methoxymethyl, ethoxymethyl, butoxymethyl, (2-butoxyethoxy) methyl, ethoxyethyl, methoxy-ethoxy-ethyl, ethoxypropylA group, methoxyethyl, methoxypropyl, methoxypropoxypropyl, or ethoxyisopropyl.
In order to further improve the photosensitivity of the oxime ester compound, and further improve the photocuring performance of the oxime ester compound under 385nm illumination condition; meanwhile, the possibility of generating small molecular fragments is further reduced, and the anti-oxidation polymerization inhibition performance is further improved. In a preferred embodiment, R 1 Including but not limited to methyl, cyclopentyl, ethyl, phenyl, thienyl, o-tolyl, cyclopentyl substituted methylene, or phenyl; r is R 2 Including but not limited to ethyl; r is R 3 And R is 4 Each independently includes but is not limited to hydrogen, C m And C n Identical, and C m And C n Are all-CH 2 -CH 2 -; a includes, but is not limited to, ethylene; y includes, but is not limited to, a sulfur atom or an oxygen atom; x is methylene, straight-chain butylene, 1-ethylene or phenylene, and P is 0 or 1.
In a preferred embodiment, oxime ester compounds include, but are not limited to, one or more of the compounds having the structure shown below:
the chemical structure of the compound is more stable, the possibility of generating small molecular fragments is smaller, and the anti-oxidation polymerization inhibition performance is more excellent; meanwhile, the compound with the structure has higher photosensitivity and higher photoinitiation activity, and is particularly suitable for photocuring under 385nm illumination condition.
In a second aspect, the present application provides an oxime ester photoinitiator, which includes the oxime ester compound provided in the present application.
The oxime ester compound provided by the application has a stable structure, is not easy to generate small molecular fragments, and has excellent anti-oxidation polymerization resistance; meanwhile, the fluorescent dye has higher photosensitivity and higher photoinitiation activity (especially suitable for photoinitiation systems under 385nm illumination). The oxime ester compound is introduced into the oxime ester photoinitiator, so that the anti-oxidation polymerization resistance of the oxime ester photoinitiator can be obviously improved; meanwhile, the generation of small molecule fragments is reduced. The oxime ester photoinitiator provided by the application is particularly suitable for photocuring under 385nm illumination condition.
The third aspect of the present application provides a synthesis method of a preferred oxime ester compound, wherein the synthesis route of the synthesis method is as follows: when the value of P is 1, the number of the elements,
when P is a value of 0, the number of times,
when P is 1, the method for synthesizing the oxime ester compound comprises the following steps:
s1, under alkaline or acidic conditions, carrying out oximation reaction on a first reactant and a first oximation reagent to obtain a first intermediate; the first intermediate isWherein Y is 1 Y has the same definition as Y in the structures shown in the general formulas (I) to (IV), R 1 X has the same definition as the above, B is +.>Preferably, the temperature of the oximation reaction is-15 to 50 ℃, more preferably 0 to 25 ℃;
s2, in a second solvent, enabling the first intermediate and the first acylating reagent to perform esterification reaction under the action of alkali to obtain the oxime ester photoinitiator.
In the general formula (I), R 1 、R 3 、R 4 、C m 、C n Y, P and A have the same meanings as defined above, respectively, wherein P is 1 and R 3 、R 4 May be further varied depending on the amount of the first oximating agent or the first reactant.
When P is 0, the method for synthesizing the oxime ester compound comprises the following steps:
s1, under alkaline or acidic conditions, carrying out oximation reaction on a second reactant and a second oximation reagent to obtain a second intermediate; the second intermediate is Wherein Y is 1 Y has the same definition as Y in the structures shown in the general formulas (I) to (IV), R 1 X has the same definition as the above, B is +.>Preferably, the temperature of the oximation reaction is-15 to 50 ℃, more preferably 0 to 25 ℃;
s2, in a second solvent, enabling the first intermediate and the first acylating reagent to perform esterification reaction under the action of alkali to obtain the oxime ester photoinitiator.
In the general formula (I), R 1 、R 3 、R 4 、C m 、C n Y, P and A have the same meanings as defined above, respectively, wherein P is 0 and R 3 、R 4 May be further varied depending on the amount of the first oximating agent or the first reactant.
In an alternative embodiment, when R 3 、R 4 In the case of a compound containing an oxime ester group, the indole group may be subjected to Friedel-crafts reaction, and then to hydroxylation and oximation reactions, the reaction amounts of which differ depending on the amounts of the raw materials, R 3 Substitution bit priority R 4 Substitution reaction.
In a preferred embodiment, the first oximating reagent and the second oximating reagent each independently include, but are not limited to, one or more of the group consisting of methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, and isoamyl nitrite.
In a preferred embodiment, the first acylating agent and the second acylating agent each independently include, but are not limited to, cyclohexanoyl chloride, 2-propylpentanoyl chloride, 3, 5-trimethylhexanoyl chloride, 3-chloropropionyl chloride, 5-chloropentanoyl chloride, 3-chlorotivaloyl chloride, 6-bromohexanoyl chloride, methoxyacetyl chloride, ethoxyacetyl chloride, butoxyacetyl chloride, 3- (methylthio) propionyl chloride, (2-butoxyethoxy) acetyl chloride, benzoyl chloride, toluoyl chloride, 3, 5-dimethylbenzoyl chloride, 4-methoxybenzoyl chloride, 4-cyanobenzoyl chloride, 4-nitrobenzoyl chloride, 4-phenylbenzoyl chloride, chlorobenzoyl chloride, phenylacetyl chloride, phenylpropionyl chloride, chlorobenzoyl acetyl chloride, 4-phenylbutyryl chloride, 6-phenylhexanoyl chloride, nitrophenyl acetyl chloride, phenoxyacetyl chloride, phenoxypropionyl chloride, nitrophenyl acetyl chloride, 2-thiophenyl chloride, 2-acetyl chloride, nicotinyl chloride, 2-furanyl chloride, naphthalene-benzoyl chloride, 2-naphthoyl chloride, naphthalene-1-naphthoyl chloride, naphthalene-carbonyl chloride, and the like, or acetic anhydride, propionic anhydride, decanoic anhydride, stearic anhydride, isobutyric anhydride, t-valeric anhydride, 4-methoxyphenylacetic anhydride, and the like. The inert solvent of (a) is one or more of diethyl ether, acetonitrile, tert-butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, methyl ethyl ketone, methylene chloride, chloroform, chlorobenzene, dimethylacetamide, and dimethylformamide.
In a preferred embodiment, the base includes, but is not limited to, one or more of the group consisting of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide, and sodium hydride.
A fourth aspect of the present application provides a photocurable resin composition comprising a photoinitiator, an alkali-soluble resin, and a polymeric monomer, wherein the photoinitiator comprises the above oxime ester photoinitiator provided herein.
Under the irradiation of a light source, compared with other types of photoinitiators, the oxime ester photoinitiator provided by the application can absorb energy from the light source more efficiently and generate free radicals with higher activity, so that a polymerization monomer is initiated to generate photopolymerization reaction more rapidly, and the photocuring resin can be obtained after further curing reaction. The oxime ester photoinitiator provided by the application has excellent anti-oxidation polymerization performance; meanwhile, small molecule fragments are not easy to generate. The oxime ester photoinitiator is particularly suitable for photocuring under 385nm and 405nm illumination conditions.
In a preferred embodiment, the photocurable resin composition comprises 1 to 5 parts by weight of an oxime ester photoinitiator, 10 to 100 parts by weight of an alkali-soluble resin, and 10 to 50 parts by weight of a polymeric monomer. Compared with other dosages, the dosages of the oxime ester photoinitiator, the alkali-soluble resin and the polymerization monomer are respectively limited in the above ranges, which is beneficial to improving the compatibility of the oxime ester photoinitiator, the alkali-soluble resin and the polymerization monomer; meanwhile, the light curing effect of the light curing resin composition is further improved, and especially the light curing effect under the illumination condition of 385nm is improved; meanwhile, the generation of small molecule fragments is restrained, and the occurrence of faults of the light-emitting equipment is greatly reduced.
In order to further improve the compatibility of the oxime ester photoinitiator, the alkali-soluble resin, and the polymerization monomer and further to exert the photo-curing effect of the photo-curable resin composition, it is preferable that the photo-curable resin composition further includes 0 to 500 parts by weight of a solvent.
In a preferred embodiment, the alkali soluble resin includes, but is not limited to, carboxyl-containing copolymer molecules; the polymeric monomers include, but are not limited to, monofunctional, difunctional, or multifunctional acrylate monomers. The use of the above-described kind of alkali-soluble resin is advantageous in improving the solvent resistance and heat resistance of the photocurable resin composition as compared with other kinds of alkali-soluble resins.
In order to further improve the heat resistance and solvent resistance of the photocurable resin composition, it is preferable, the alkali-soluble resin includes, but is not limited to, a (meth) acrylic acid/(meth) acrylic acid methyl ester copolymer, a (meth) acrylic acid/(meth) acrylic acid benzyl ester copolymer, a (meth) acrylic acid/(meth) acrylic acid-2-hydroxyethyl/(meth) acrylic acid benzyl ester copolymer (meth) acrylic acid/(meth) acrylic acid methyl ester/polystyrene macromer copolymer, (meth) acrylic acid/(meth) acrylic acid methyl ester/polymethyl methacrylate macromer copolymer, (meth) acrylic acid/(meth) acrylic acid benzyl ester/polystyrene macromer copolymer (meth) acrylic acid/(meth) acrylic acid benzyl/polymethyl methacrylate macromer copolymer, (meth) acrylic acid/(meth) acrylic acid 2-hydroxyethyl/(meth) acrylic acid benzyl/polystyrene macromer copolymer, (meth) acrylic acid 2-hydroxyethyl/(meth) acrylic acid benzyl/polymethyl methacrylate macromer copolymer, methacrylic acid styrene/(meth) acrylic acid benzyl/N-phenylmaleimide copolymer, one or more of the group consisting of (meth) acrylic acid/succinic acid mono [2- (meth) acryloyloxyethyl ]/styrene/(meth) acrylic acid benzyl ester/N-phenylmaleimide copolymer, (meth) acrylic acid/succinic acid mono [2- (meth) acryloyloxyethyl ]/styrene/(meth) acrylic acid allyl ester/N-phenylmaleimide copolymer, (meth) acrylic acid/styrene/(meth) acrylic acid benzyl ester/glycerol mono (meth) acrylate/N-phenylmaleimide copolymer, and (meth) acrylic acid/ω -carboxypolycaprolactone mono (meth) acrylate/styrene/(meth) acrylic acid benzyl ester/glycerol mono (meth) acrylate/N-phenylmaleimide copolymer;
In a preferred embodiment, the polymeric monomers include, but are not limited to, one or more of the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, isobornyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-trifluoroethyl acrylate, beta-carboxyethyl acrylate, and omega-carboxypolycaprolactone monoacrylate; or, polymerized monomers including, but not limited to, one or more of the group consisting of dicyclopentenyl acrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol a diacrylate, EO modified bisphenol a diacrylate, PO modified bisphenol a diacrylate, hydrogenated bisphenol a diacrylate, EO modified hydrogenated bisphenol a diacrylate, PO modified hydrogenated bisphenol a diacrylate, bisphenol F diacrylate, EO modified bisphenol F diacrylate, PO modified bisphenol F diacrylate, EO modified tetrabromobisphenol a diacrylate, and tricyclodecane dihydroxymethyl diacrylate; or, the polymerized monomers include, but are not limited to, one or more of the group consisting of glycerol PO modified triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, and tetramethylolmethane tetraacrylate; or, an ethoxylation product or a propoxylation product of the acrylate monomer; or, an ethoxylation product or a propoxylation product of an acrylate monomer; preferably, the ethoxylation or propoxylation products of the acrylate monomers include, but are not limited to, one or more of the group consisting of dicyclopentadienyloxyethyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 1, 3-butanediol methyl ether acrylate, butoxyethyl acrylate, monoacryloxyethyl succinate, trimethylsiloxyethyl acrylate, and diphenyl-2-acryloyloxyethyl phosphate.
The kind of the suitable solvent is not particularly limited as long as other components of the composition can be effectively dissolved. The solvent may be exemplified by those commonly used in photosensitive resin compositions, such as ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides.
In a preferred embodiment, the solvent in the photocurable resin composition includes, but is not limited to, one or more of the group consisting of ether compounds, aromatic hydrocarbon compounds, ketone compounds, alcohol compounds and ester compounds.
When the solvent is an ether compound, the ether compound includes, but is not limited to, one or more of the group consisting of ethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, and alkylene glycol alkyl ether acetate. For example, one or more of the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and the like, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; when the solvent is an aromatic hydrocarbon solvent, the aromatic hydrocarbon compound includes, but is not limited to, one or more of the group consisting of benzene, toluene, and xylene; when the solvent is a ketone solvent, the ketone compounds include, but are not limited to, one or more of the group consisting of methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; when the solvent is an alcoholic solvent, the alcoholic compound includes, but is not limited to, one or more of the group consisting of ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; when the solvent is an ester solvent, the ester compound includes, but is not limited to, one or more of the group consisting of ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate.
In order to facilitate the coating process of the photocurable resin composition and to facilitate the volatilization of the solvent and thereby promote the volatilization of the solvent during the coating process, an organic solvent having a boiling point of 100 to 200 ℃ is preferable. Such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.
In an alternative embodiment, the photocurable resin composition further comprises a pigment. Such as carbon black, c.i. pigment yellow 3, c.i. pigment red 7, c.i. pigment blue 15, c.i. pigment green 7, and the like.
In an alternative embodiment, the photocurable resin composition further comprises a sensitizer and/or a surfactant.
A fifth aspect of the present application provides an application of the above oxime ester photoinitiator provided herein, or the above photocurable resin composition provided herein in the field of photocuring.
Compared with the existing oxime ester photoinitiator, the oxime ester compound with the structures of the formulas (I) to (IV) has a stable structure, so that small molecular fragments are difficult to generate under the irradiation of ultraviolet light, and almost no overflow gas is generated after curing; meanwhile, the fluorescent dye has higher photosensitivity and higher photoinitiation activity (especially suitable for photoinitiation systems under 385nm illumination). The oxime ester compound is introduced into the oxime ester photoinitiator, so that the anti-oxidation polymerization resistance of the oxime ester photoinitiator can be obviously improved; meanwhile, the generation of small molecule fragments is reduced. When the modified ultraviolet light-curable resin composition is applied to the field of light curing, small molecular fragments are not generated, and the curing effect of the light-curable resin composition can be improved. The oxime ester photoinitiator with the specific structure is particularly suitable for photo-curing under 385nm illumination.
The photo-curing resin composition provided by the application can be applied to the fields of color photoresists (RGB), black Matrixes (BM), photo-spacers (photo-spacers), semiconductor photoresists, printing inks and the like.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
A preparation method of an oxime ester compound (compound A-1), which comprises the following steps:
(1) Preparation of intermediate A-1-1:
into a four-necked flask, 10.6g of indole, 36.8g of morpholine and 9g of water were charged, followed by stirring, heating to 140℃and reaction for 15 hours. Cooling, adding dichloromethane, washing to remove morpholine. Toluene was distilled off under reduced pressure, methanol was added thereto, stirred and cooled, and suction filtration was conducted to obtain a brown yellow solid powder (intermediate A-1-1), and the yield of intermediate A-1-1 was found to be 9.4g, and the purity was found to be 98.8%.
The structure of the product in the step (1) is confirmed by mass spectrometry, the structure of the intermediate A-1-1 is confirmed by high performance liquid chromatography-mass spectrometry (LCMS), molecular fragment peaks of 218 and 219 are obtained by means of instrument incidental software through mass spectrometry, and the molecular weight of the intermediate A-1-1 is 217 and is matched with T+1 and T+2.
(2) The preparation of intermediate B-1-2 is carried out according to the following synthetic route:
22g of the intermediate A-1-1 prepared above was added to a reaction flask, mixed with 105g of ethyl acetate and 2.9g of hydrochloric acid, stirred, cooled to 10 ℃, 14g of isoamyl nitrite was added dropwise, stirred at room temperature for 5 hours after the completion of the dropwise addition, pH was adjusted to 7 with 10wt% of liquid alkali (NaOH), stirred, the aqueous layer was separated, washed with water three times, ethyl acetate was distilled off, stirred and precipitated in petroleum ether, and suction filtration was performed to obtain a yellow powdery solid (intermediate B-1-2). The yield of intermediate B-1-2 was 17g, the yield was 75% and the purity was 98.2%.
The structure of the product of step (2) was confirmed by mass spectrometry, and the structure of B-1-2 was confirmed by LCMS, and mass spectrometry analysis gave 247 and 248 molecular fragment peaks by means of instrumental incidental software, the molecular weight of the product was 246, which was consistent with T+1 and T+2, indicating that intermediate B-1-2 had the structure shown in the above synthetic route.
(3) The preparation of compound A-1 is carried out by the following synthetic route:
into a flask, 12.3g of the above-prepared intermediate B-1-2 was charged, and mixed with 40g of methylene chloride and 6.0g of acetic anhydride (acetic anhydride), stirred at room temperature for 3 hours, washed with water 3 more times, and dried over anhydrous MgSO 4 Drying and spin-removing the solvent to give a viscous liquid. Recrystallizing with methanol to obtain pale yellow solid powder, and filtering to obtain the product compound A-1. The yield of this compound A-1 was 12.5g and the purity was 99%.
The final product structure was confirmed by mass spectrometry and LCMS was used to confirm the chemical structure of compound a-1. Mass spectrometry gave 289 and 290 molecular fragment peaks by means of instrumentation software, the molecular weight of product compound a-1 being 288, consistent with t+1 and t+2.
Example 2
A preparation method of an oxime ester compound (compound B-1), which comprises the following steps:
(1) Preparation of intermediate B-1-1:
into a flask, 22.4g of indole, 42.2g of 5-bromoindenone, 114g of potassium phosphate, 1.2g of dibenzylidene acetone palladium (Pd (dba)) were charged 2 ) 52g of tri-tert-butylphosphorus (TTBP), 750g of toluene were refluxed for 19 hours. Filtering while hot to obtain a brownish red filtrate, and washing the filter cake with boiling toluene. After pumping, the organic phases are combined, washed three times by water, toluene is distilled off under reduced pressure, methanol is added, stirring and cooling are carried out, and a brown yellow solid powder is obtained through pumping filtration. The yield of this intermediate B-1-1 was 56g and the purity was 98.5%.
The structure of the product in the step (1) is confirmed by mass spectrometry, the structure of B-1-1 is confirmed by LCMS, 248 and 249 molecular fragment peaks are obtained by mass spectrometry through additional software of an instrument, and the molecular weight of the product intermediate B-1-1 is 247 and is matched with T+1 and T+2.
(2) Preparation of intermediate B-1-2:
adding 12g of an intermediate B-1-1 into a reaction bottle, adding 50g of tetrahydrofuran, adding 3.8 equivalents (calculated by the intermediate B-1-1) of concentrated hydrochloric acid, mixing, cooling to-4 ℃ by adopting an alcohol bath, dropwise adding 2.4 equivalents of isoamyl nitrite, reacting at the temperature of-4 to-8 ℃ after the dropwise adding is finished, reacting for 16 hours, filtering to obtain a product, dissolving the product in dichloromethane, washing the product to be neutral, steaming to remove dichloromethane, adding methanol, cooling to 5-10 ℃, stirring for crystallization, and filtering to obtain yellow powder. The yield of this intermediate B-1-2 was 9.8g, the yield was 71%, and the purity was 98.1%.
Step (2) is confirmed by mass spectrometry, the structure of the intermediate B-1-2 is confirmed by LCMS, mass spectrometry analysis is carried out by means of instrument incidental software to obtain 277 and 278 molecular fragment peaks, and the molecular weight of the product intermediate B-1-2 is 276 and is consistent with T+1 and T+2.
(3) Preparation of Compound B-1:
into a flask, 27.6g of Compound B-1-2, 100g of dichloromethane and 10.6g of acetic anhydride were put, mixed, stirred at room temperature for 3 hours, washed with water 3 times, and dried over anhydrous MgSO 20g 4 Drying, and rotary evaporating solvent to obtain viscous liquid. Recrystallizing with methanol to obtain pale yellow solid powder, and filtering to obtain the product compound B-1. The yield of this compound B-1 was 29g and the purity was 99.3%.
The final product structure was confirmed by mass spectrometry, and the structure of compound B-1 was confirmed by LCMS, and mass spectrometry gave 319 and 320 molecular fragment peaks by means of instrumental incidental software, compound B-1 having a molecular weight of 318, fitting t+1 and t+2.
Example 3
A preparation method of an oxime ester compound (compound B-2), which comprises the following steps:
(1) Preparation of intermediate B-2-1: the preparation method of intermediate B-2-1 is the same as that of intermediate B-1-1 in example 2.
(2) Preparation of intermediate B-2-2:
28.6g of intermediate B-2-1, 18.8g of n-octanoyl chloride and 100g of methylene dichloride serving as a solvent are added into a reaction bottle, stirred, cooled to minus 6 ℃, 17 g (1.1 equivalent) of aluminum trichloride is added in portions, and the mixture is reacted at minus 4 ℃ to minus 6 ℃ after the addition is finished, so that oily sticky substance is obtained. Pouring the sticky substance into water, stirring, separating a water layer, washing an organic layer for three times until the organic layer is neutral, steaming to remove dichloromethane, adding petroleum ether, stirring and separating out, filtering by suction to obtain yellow powdery solid, and drying at 60 ℃ for 5 hours to obtain a product intermediate B-2-2. The yield of intermediate B-2-2 was 36.7g, the yield was 85% and the purity was 97.4%.
Step (2) was confirmed by mass spectrometry, using LCMS to confirm the structure of intermediate B-2-2, mass spectrometry analysis by means of instrumental incidental software gave 734 and 475 molecular fragment peaks, the molecular weight of product intermediate B-2-2 being 373, coincident with t+1 and t+2.
(3) Preparation of intermediate B-2-3:
to the reaction flask was added 31.9g of Compound B-2-2, 100g of tetrahydrofuran, and 3.8 equivalents of concentrated hydrochloric acid. The mixture was cooled to-4℃using an alcohol bath, and 2.4 equivalents of isoamyl nitrite were added dropwise. And after the dripping is finished, carrying out reaction at the temperature of-4 to-8 ℃ for 16 hours. Filtering out the product, adding dichloromethane for dissolution, washing to be neutral, steaming off dichloromethane, adding methanol, cooling to 5-10 ℃, stirring for crystallization, and filtering to obtain yellow powder. The yield of intermediate B-2-3 was 29.4g, the yield was 80% and the purity was 97.7%.
Step (3) is confirmed by mass spectrometry, the structure of the intermediate B-2-3 is confirmed by LCMS, mass spectrometry analysis is carried out by means of instrument incidental software to obtain 432 and 433 molecular fragment peaks, and the molecular weight of the product intermediate B-2-3 is 431 and is consistent with T+1 and T+2.
(4) Preparation of Compound B-2:
21.6g of the product obtained in the step (3), 100g of dichloromethane and 30.6g of acetic anhydride are put into a flask, stirred for 3 hours at room temperature, washed with 100mL of water for 3 times, dried with 20g of anhydrous MgSO4, and the solvent is distilled off in a rotating way, so as to obtain a viscous liquid, methanol is recrystallized to obtain pale yellow solid powder, and the pale yellow solid powder is filtered to obtain 28g of the product with the purity of 99%.
The final product structure was confirmed by mass spectrometry, and the structure of compound B-2 was confirmed by LCMS, and mass spectrometry analysis gave peaks of fragments 516 and 517 by means of instrumental incidental software, and the molecular weight of product compound B-2 was 515, consistent with t+1 and t+2.
Example 4
A preparation method of an oxime ester compound (compound B-3), which comprises the following steps:
the production method of this example 4 was referred to the production method of the compound B-2 in example 3, except that 18.8g of n-octanoyl chloride was replaced with 24.6g of n-butyryl chloride in step (2), and accordingly, concentrated hydrochloric acid was changed to 4.2 equivalents in step (3), isoamyl nitrite was changed to 3.5 equivalents, acetic anhydride was changed to 42g in step (4), and finally, a yellow solid (compound B-3) was obtained in 99.3% purity.
Example 5
A preparation method of an oxime ester compound (compound C-1), which comprises the following steps:
the production method of this example 5 was referred to the production method of the compound B-2 in example 3, except that 6g of acetic anhydride in step (3) was replaced with 4.1g of succinyl chloride, and finally yellow solid powder was obtained with a purity of 99.0%.
Example 6
A preparation method of an oxime ester compound (compound C-2), which comprises the following steps:
(1) Preparation of intermediate C-2-1: the same procedure as in example 1 for the preparation of intermediate A-1-1 gave intermediate C-2-1.
(2) Preparation of intermediate C-2-2:
22g of intermediate C-2-1, 65g of methanol, 7.8g of hydroxylamine hydrochloride and 12g of ammonium acetate are added into a reaction bottle, stirred, heated to 65 ℃, refluxed and stirred for 5 hours, slowly cooled to 10 ℃ and filtered, methanol is added into a filter cake, heated to 10 ℃ and pulped for 30 minutes, cooled to 10 ℃, and suction filtered, thus obtaining a yellowish powdery solid, and obtaining the intermediate C-2-2. The yield of intermediate C-2-2 was 20.5g and the purity was 98.8%.
The structure of the product in the step (2) is confirmed by mass spectrometry, the structure of an intermediate C-2-2 is confirmed by LCMS, molecular fragment peaks of 233 and 234 are obtained by means of instrument incidental software through mass spectrometry, and the molecular weight of the intermediate C-2-2 is 232 and is consistent with T+1 and T+2.
(3) Preparation of Compound C-2:
into a flask, 11.6g of intermediate C-2-2, 40g of methylene chloride and 4.0g of succinyl chloride were put, stirred at room temperature for 3 hours, then washed with water 3 times, 20g of anhydrous MgSO 4 Drying, and rotary evaporating solvent to obtain viscous liquid. Recrystallizing with methanol to obtain pale yellow solid powder, and filtering to obtain the product compound C-2. The yield of this compound C-2 was 12.4g and the purity was 99%.
The final product structure was confirmed by mass spectrometry, and the structure of compound C-2 was confirmed by LCMS, mass spectrometry gave peaks of 547 and 548 molecular fragments by means of instrumental incidental software, compound C-2 having a molecular weight of 546, consistent with T+1 and T+2.
Example 7
A preparation method of an oxime ester compound (compound D-1), which comprises the following steps:
(1) Preparation of intermediate D-1-1: the intermediate D-1-1 was obtained in the same manner as in the preparation of intermediate B-1-1 in example 2.
(2) Preparation of Compound D-1-2:
into a flask, 37.5g of intermediate D-1-1, 120g of dichloromethane and 9.8g of acetic anhydride were put, stirred at room temperature for 3 hours, then washed with water for 3 times, 20g of anhydrous MgSO 4 Drying, rotary evaporating solvent to obtain viscous liquid, recrystallizing with methanol to obtain yellowish solid powder, and filtering to obtain the product compound D-1-2. The yield of this compound D-1-2 was 35.4g and the purity was 98.2%.
The final product structure was confirmed by mass spectrometry, and the structure of compound D-1-2 was confirmed using LCMS, which gave 418 and 419 molecular fragment peaks by means of instrumental side software, compound D-1-2 having a molecular weight of 417, matching T+1 and T+2.
(3) Preparation of Compound D-1:
into a 250mL four-necked flask, 20.5g of intermediate D-1-2, 100g of dichloromethane and 5.1g of terephthaloyl chloride are put, stirred for 3 hours at room temperature, then 100mL of water is used for washing for 3 times, 20g of anhydrous MgSO4 is dried, the solvent is distilled off in a rotating way, a viscous liquid is obtained, methanol is recrystallized to obtain pale yellow solid powder, and the pale yellow solid powder is filtered to obtain 17.3.4g of product with the purity of 98.8%.
The final product structure was confirmed by mass spectrometry, C-2 structure was confirmed using LCMS, mass spectrometry analysis gave 965 and 966 molecular fragment peaks by means of instrumental side software, and the molecular weight of product C-2 was 964, consistent with T+1 and T+2.
Example 8
A preparation method of oxime ester compound (compound D-2) by replacing corresponding raw materials according to the methods of examples 3, 5 and 6 gives compound D-2.
The oxime ester compound prepared in all the above examples was used for the preparation of a photocurable resin composition. Wherein the acrylic ester copolymer comprises benzyl methacrylate, methacrylic acid and methyl methacrylate (the mass ratio of the three substances is 50:15:30) copolymer, and Mw=15000.
In the above-mentioned photocurable resin composition, the photoinitiator is an oxime ester photoinitiator of the structures represented by the general formulae (I) to (IV) in the foregoing description of the present application or a photoinitiator of the same type known in the prior art for comparison. The amounts of the components used in examples 1 to 8 and comparative examples 1 and 2 are shown in Table 1, and the amounts of the components used in examples 9 to 15 are shown in Table 2.
TABLE 1
Example 9
The difference from example 1 is that: the weight part of the compound A-1 (oxime ester photoinitiator) is 1 part, and the other components are used in the same amounts as in example 1.
Example 10
The difference from example 1 is that: the weight part of the compound A-1 (oxime ester photoinitiator) is 5 parts, and the other components are used in the same amounts as in example 1.
Example 11
The difference from example 1 is that: the weight part of the compound A-1 (oxime ester photoinitiator) was 0.5 part, and the amounts of the other components were the same as in example 1, respectively.
Example 12
The difference from example 1 is that: the weight part of the acrylate copolymer (alkali-soluble resin) was 10 parts, and the amounts of the other components were the same as in example 1, respectively.
Example 13
The difference from example 1 is that: the weight part of the acrylate copolymer (alkali-soluble resin) was 5 parts, and the amounts of the other components were the same as in example 1, respectively.
Example 14
The difference from example 1 is that: the dipentaerythritol hexaacrylate (polymer monomer) was 10 parts by weight, and the other components were used in the same amounts as in example 1, respectively.
Example 15
The difference from example 1 is that: the dipentaerythritol hexaacrylate (polymerized monomer) was 5 parts by weight, and the other components were used in the same amounts as in example 1, respectively.
TABLE 2
(1) Sensitivity test
The photocurable resin composition was stirred in the dark and coated on a PET film with a 6# wire rod to form a coating film having a wet film thickness of about 5. Mu.m. The film was exposed to light at different wavelengths by using a mercury lamp (RW-LED-YT 200 gl) and an LED lamp (exposure model number: EXECURE 4000), and cured to form a film, which was evaluated by a finger touch method. The sensitivities measured in examples 1 to 8 and comparative examples 1 and 2 of the present application are shown in table 3, and the sensitivities measured in examples 9 to 15 are shown in table 4.
The finger touch evaluation criteria were as follows: 1: oil, not solid; 2: surface oil and bottom layer solidification; 3: the surface is sticky, and the fingerprint is heavier after hand touch; 4: basic surface dryness, slightly astringent after touching with hands, and light fingerprint; 5: completely cured, smooth in surface and free of fingerprints after hand touch.
TABLE 3 Table 3
TABLE 4 Table 4
Light source Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15
Hg lamp 4 5 3 5 5 5 5
385nm-LED 4 5 3 5 5 5 5
(2) Evaluation of film Forming Property
Film Forming Performance test referring to the specific formulations shown in Table 1, photocurable resin compositions were formulated. The above photocurable resin composition was stirred in a yellow room, and then the composition was applied onto a tin plate using a 15# bar to prepare a 10 μm coating film, which was exposed to light using an exposure machine (type of exposure: EXECURE 4000, wavelength 385nm, exposure amount 1500mJ/cm under nitrogen atmosphere and air atmosphere, respectively) 2 ) The coating film is exposed to light and cured to form a film. The film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of KOH at 25℃for 100 seconds after light irradiation, developed and washed with a light-transmitting portion (pattern) having a side length of 10 μm and regular quadrangles at an interval of 100. Mu.m, and then dried in an oven at 220℃for 20 minutes, and the hardness of the film-formed product was measured (GB/T6739-1996). The hardness test results of the coating films prepared in examples 1 to 8 and comparative examples 1 and 2 of the present application are shown in Table 5, examples The hardness test results of the coating films 9 to 15 are shown in Table 6.
TABLE 5
TABLE 6
Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15
Nitrogen atmosphere 5H 5H 5H 5H 4H 5H 4H
Air atmosphere 5H 5H 5H 5H 4H 5H 4H
(3) Small molecule fragment (outgas)
The sample films prepared in the same way are respectively taken 5g and cut into proper sizes by adopting a GC-MS test method and put into a headspace bottle for standby. With headspace injection, it was observed whether small molecule fragments (outgas) were produced (excluding carbon dioxide and self-carried solvent peaks). The test results of examples 1 to 8 and comparative examples 1 and 2 of the present application are shown in Table 7, and the test results of examples 9 to 15 are shown in Table 8.
The equipment and test conditions used were as follows:
agilent 7890B gas chromatograph, column: agilent HP-5ms chromatographic column; vaporization temperature: 280 ℃; programming temperature: maintaining at 60deg.C for 3min, heating at 20deg.C/min, and maintaining at 280 deg.C for 10min;
agilent 7697A headspace injector, headspace conditions: heating box: 110 ℃; quantitative ring: 120 ℃; a transmission line: 140 ℃; equilibration time: 30min;
agilent 7010B mass spectrometer, mass spectrometry conditions: ion source temperature: 280 ℃; electron energy: 70eV; scan range (m/z): 30-400.
TABLE 7
TABLE 8
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
(1) As can be seen from Table 1, each example differs from the comparative example only in the type of photoinitiator employed. As can be seen from the combination of the sensitivity test results in table 3, the curing efficiency of the photocurable composition in comparative example 2 under irradiation of 385nm-LED was inferior to that of examples 1 to 8, respectively, and only a basic surface dry was achieved; meanwhile, the curing efficiency is very low under the irradiation of 385nm-LED, so that the curing cannot be realized, and the finger touch surface is sticky. Whereas the photocurable resin compositions of examples 1 to 8 were capable of achieving a complete curing effect under irradiation of both Hg lamp and 385 nm-LED. Therefore, the oxime ester photoinitiator with the specific structure can improve the curing efficiency of the photo-curing resin composition under the irradiation of an Hg lamp and a 385nm-LED, which indicates that the oxime ester photoinitiator has better anti-oxidation polymerization resistance.
Comparing examples 1, 9 to 11, the amount of compound A-1 in example 11 is significantly smaller than the preferred range of the present application, while the amounts of compound A-1 in examples 9 and 10 are each values within the preferred range of the present application, and the photo-curable resin film prepared in example 11 is sticky on the surface and has a relatively heavy fingerprint after hand touch, as can be seen from the combination of the sensitivity test results shown in Table 4; whereas the films prepared in examples 1 and 10 were fully cured, example 9 was substantially dry. It is thus understood that limiting the amount of the photoinitiator to the range of the present application is advantageous in improving the curing speed and curing effect (especially in improving the photocuring effect under the light condition of 385 nm) of the photocurable resin composition.
(2) As can be seen from table 5, the photocurable resin film prepared from the compound a in comparative example 1 had a poor hardness (4H) and the photocurable resin film prepared from the compound B in comparative example 2 had a poor hardness (4H) in an air atmosphere as compared with examples 1 to 8 (5H). This shows that the oxime ester photoinitiator provided by the application has better anti-oxidation and polymerization inhibition performance in an air atmosphere under the irradiation of 385nm-LED, so that the prepared photo-curing resin film has higher hardness.
Comparing examples 1, 12 and 13, and examples 1, 14 and 15, respectively, it is understood that the amount of the acrylate copolymer in example 13 is significantly smaller than the preferred range of the present application, that the amount of dipentaerythritol hexaacrylate in example 15 is also significantly smaller than the preferred range of the present application, and that the hardness (4H) of the photocurable resin film produced in example 13 is significantly smaller than examples 1 (5H) and 12 (5H) and that the hardness (4H) of the photocurable resin film produced in example 15 is significantly smaller than examples 1 (5H) and 14 (5H) in combination with the coating film hardness test results in Table 6. It is clear that limiting the amount of the alkali-soluble resin and the amount of the polymerizable monomer to the preferred ranges of the present application is advantageous in improving the film forming properties such as the hardness of the coating film.
(3) From the test results in tables 7 and 8, it is understood that small molecule fragments were generated in comparative example 1, whereas none of examples 1 to 15 yielded small molecule fragments. This indicates that the oxime ester photoinitiators provided herein are less prone to small molecule fragments than other types of photoinitiators.
In conclusion, the oxime ester photoinitiator with the specific structure can be applied to a conventional ultraviolet light curing system, can be cured better under a mercury lamp, and is not easy to generate small molecular fragments compared with other types of photoinitiators, and has the characteristics of low outgas and excellent anti-oxidation polymerization inhibition performance.
It should be noted that the terms "first," "second," and the like in the description and in the claims of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described herein.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. An oxime ester compound, characterized in that the oxime ester compound has a structure represented by any one of formulas (I) to (IV):
each R is 1 Are independently selected from C 1 ～C 30 Alkyl, C of (2) 6 ～C 24 Aryl substituted C 1 ～C 20 Alkyl, C 6 ～C 24 Aryloxy substituted C 1 ～C 20 Alkyl, C 1 ～C 20 Haloalkyl, C 6 ～C 24 Aryl, C of (2) 1 ～C 12 Alkyl substituted C 6 ～C 24 Aryl, C 4 ～C 24 Heterocyclic groups of (2), or C interrupted by more than 1 ether or thioether bond 2 ～C 30 Alkyl of (a);
in each structure, R 3 And R is 4 Are each independently selected from hydrogen, nitro, cyano, hydroxy, halogen, C 1 ～C 30 Alkyl, C of (2) 6 ～C 24 Aryl substituted C 1 ～C 20 Alkyl, C 6 ～C 24 Aryloxy substituted C 1 ～C 20 Alkyl, C 1 ～C 20 Haloalkyl, C 2 ～C 8 Acyl group, C 6 ～C 12 Aryl, C of (2) 1 ～C 8 C interrupted by more than 1 ether or thioether bond(s) 2 ～C 30 Is, -C (=o) -O-C (=n) -C (=o) R 2 The group(s) is (are) a radical, R 5 selected from methyl, phenyl or thienyl;
R 2 selected from C 1 ～C 30 Alkyl, C of (2) 6 ～C 24 Aryl substituted C 1 ～C 20 Alkyl, C 6 ～C 24 Aryloxy substituted C 1 ～C 20 Alkyl, C 6 ～C 24 Aryl, C of (2) 1 ～C 12 Alkyl substituted C 6 ～C 24 Aryl, or C interrupted by more than 1 ether or thioether bond 2 ～C 30 Alkyl of (a);
x is a connecting bond, C 1 ～C 10 A linear or branched alkylene group, a substituent formed by substitution of the above-mentioned group with one or more oxygen atoms, sulfur atoms or arylene groups;
Each P is independently selected from 0 or 1;
each A is independently selected from C 1 ～C 3 Alkyl of (a);
in each structure, C m And C n Identical or different, the said C m And said C n Are independently selected from C 1 ～C 3 An alkylene group of (a);
each Y is independently selected from N, O, S or carbonyl.
2. The oxime ester compound according to claim 1, wherein R 1 Said R is 2 Said R is 3 And said R 4 Are independently selected from C 1 ～C 22 Alkyl, C of (2) 6 ～C 20 Aryl substituted C 1 ～C 12 Alkyl, C of (2) 6 ～C 20 Aryloxy substituted C 1 ～C 20 Alkyl, C 1 ～C 10 Haloalkyl, C 6 ～C 20 Aryl, C of (2) 1 ～C 8 Alkyl substituted C 6 ～C 20 Aryl, C 4 ～C 18 Heterocyclic groups of (2), or C interrupted by more than 1 ether or thioether bond 2 ～C 20 Is a hydrocarbon group.
3. The oxime ester compound according to claim 1 or 2, wherein R 1 Said R is 2 Said R is 3 And said R 4 Respectively are provided withIndependently selected from C 1 ～C 17 Alkyl of (C) is preferred 1 ～C 10 Straight-chain, branched, single-cyclic or condensed polycyclic alkyl groups; or (b)
The R is 1 Said R is 2 Said R is 3 And said R 4 Are independently selected from C 6 ～C 18 Aryl substituted C 1 ～C 10 Alkyl of (C) is preferred 6 ～C 10 Aryl substituted C 1 ～C 6 Alkyl of (a); or (b)
The R is 1 Said R is 2 Said R is 3 And said R 4 Are independently selected from C 6 ～C 18 Aryloxy substituted C 1 ～C 8 Alkyl, preferably C 6 ～C 10 Aryloxy substituted C 1 ～C 4 An alkyl group; or (b)
The R is 1 Said R is 2 Said R is 3 And said R 4 Are independently selected from C 2 ～C 8 Haloalkyl of (C) is preferred 2 ～C 5 A linear or branched haloalkyl group; or (b)
The R is 1 Said R is 2 Said R is 3 And said R 4 Are independently selected from C 6 ～C 18 Aryl of (C) is preferred 6 ～C 10 Aryl of (a); or (b)
The R is 1 Said R is 2 Said R is 3 And said R 4 Are independently selected from C 1 ～C 6 Alkyl substituted C 6 ～C 18 Aryl, preferably C 1 ～C 4 Alkyl substituted C 6 ～C 10 An aryl group; or (b)
The R is 1 Said R is 2 Said R is 3 And said R 4 Are independently selected from C 4 ～C 14 Heterocyclic groups of (C) are preferred 4 ～C 10 An aromatic or alicyclic heterocyclic group; or (b)
The R is 1 Said R is 2 Said R is 3 And said R 4 Independently selected from the group consisting of ether linkages or thioether linkages having 1 or moreC of key interrupt 2 ～C 15 Preferably C interrupted by more than 1 ether or thioether bond(s) 2 ～C 10 Is a hydrocarbon group.
4. An oxime ester compound according to any one of claims 1 to 3 wherein R 1 Selected from methyl, cyclopentyl, ethyl, phenyl, thienyl, o-tolyl, cyclopentyl substituted methylene, or phenyl; the R is 2 Selected from ethyl; the R is 3 And said R 4 Independently selected from hydrogen,
The C is m And said C n Identical, and the C m And said C n Are all-CH 2 -CH 2 -; the A is selected from ethylene; the Y is selected from sulfur atom or oxygen atom; x is methylene, straight-chain butylene, 1-ethylene or phenylene, and P is 0 or 1.
5. The oxime ester compound according to claim 4, wherein the oxime ester compound is selected from one or more of the compounds having the structures shown below:
6. an oxime ester photoinitiator, characterized in that the oxime ester photoinitiator comprises an oxime ester compound as claimed in any one of claims 1 to 5.
7. A photocurable resin composition comprising a photoinitiator, an alkali-soluble resin, and a polymeric monomer, wherein the photoinitiator comprises the oxime ester photoinitiator of claim 6.
8. The photocurable resin composition according to claim 7, wherein said photocurable resin composition comprises, in parts by weight, 1 to 5 parts of said oxime ester photoinitiator, 10 to 100 parts of said alkali-soluble resin and 10 to 50 parts of said polymerized monomer;
preferably, the photocurable resin composition further comprises 0 to 500 parts by weight of a solvent.
9. The photocurable resin composition according to claim 8, wherein said alkali-soluble resin is selected from carboxyl-containing copolymer molecules; the polymeric monomer is selected from monofunctional, difunctional or multifunctional acrylate monomers;
Preferably, the alkali-soluble resin is selected from the group consisting of (meth) acrylic acid/(meth) acrylic acid methyl ester copolymer, (meth) acrylic acid/(meth) acrylic acid benzyl ester copolymer, (meth) acrylic acid 2-hydroxyethyl/(meth) acrylic acid benzyl ester copolymer, (meth) acrylic acid/(meth) acrylic acid methyl ester/polystyrene macromer copolymer, (meth) acrylic acid/(meth) acrylic acid methyl ester/polymethyl methacrylate macromer copolymer, (meth) acrylic acid benzyl/(meth) acrylic acid benzyl ester/polystyrene macromer copolymer, (meth) acrylic acid benzyl/(meth) acrylic acid benzyl ester/polymethyl methacrylate macromer copolymer, (meth) acrylic acid 2-hydroxyethyl/(meth) acrylic acid benzyl ester/polystyrene macromer copolymer, (meth) acrylic acid 2-hydroxyethyl/(meth) acrylic acid benzyl ester/polymethyl methacrylate macromer copolymer, methacrylic acid/styrene/(meth) acrylic acid benzyl ester/N-phenylmaleimide copolymer, one or more of the group consisting of (meth) acrylic acid/succinic acid mono [2- (meth) acryloyloxyethyl ]/styrene/(meth) acrylic acid benzyl ester/N-phenylmaleimide copolymer, (meth) acrylic acid/succinic acid mono [2- (meth) acryloyloxyethyl ]/styrene/(meth) acrylic acid allyl ester/N-phenylmaleimide copolymer, (meth) acrylic acid/styrene/(meth) acrylic acid benzyl ester/glycerol mono (meth) acrylate/N-phenylmaleimide copolymer, and (meth) acrylic acid/ω -carboxypolycaprolactone mono (meth) acrylate/styrene/(meth) acrylic acid benzyl ester/glycerol mono (meth) acrylate/N-phenylmaleimide copolymer;
Preferably, the polymeric monomer is selected from one or more of the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, isobornyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-trifluoroethyl acrylate, beta-carboxyethyl acrylate, and omega-carboxypolycaprolactone monoacrylate; or (b)
The polymeric monomer is selected from one or more of the group consisting of dicyclopentenyl acrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol a diacrylate, EO modified bisphenol a diacrylate, PO modified bisphenol a diacrylate, hydrogenated bisphenol a diacrylate, EO modified hydrogenated bisphenol a diacrylate, PO modified hydrogenated bisphenol a diacrylate, bisphenol F diacrylate, EO modified bisphenol F diacrylate, PO modified bisphenol F diacrylate, EO modified tetrabromobisphenol a diacrylate, and tricyclodecane dimethylol diacrylate; or (b)
The polymerization monomer is one or more selected from the group consisting of glycerin PO modified triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate and tetramethylolmethane tetraacrylate; or, an ethoxylation product or a propoxylation product of the acrylate monomer;
preferably, the ethoxylation or propoxylation product of the acrylate monomer is selected from one or more of the group consisting of dicyclopentadienyloxyethyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 1, 3-butanediol methyl ether acrylate, butoxyethyl acrylate, monoacryloxyethyl succinate, trimethylsiloxyethyl acrylate, and diphenyl-2-acryloyloxyethyl phosphate.
10. Use of the oxime ester photoinitiator according to claim 6, or the photocurable resin composition according to any one of claims 7 to 9 in the field of photocuring.
CN202210017800.9A 2022-01-07 2022-01-07 Oxime ester compound, photoinitiator containing oxime ester compound, photo-curing resin composition containing oxime ester compound and application of photo-curing resin composition Pending CN116444460A (en)

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CN108170002A (en) * 2016-12-07 2018-06-15 奇美实业股份有限公司 Photosensitive resin composition and application thereof
CN112851547A (en) * 2019-11-12 2021-05-28 常州强力先端电子材料有限公司 Fluorenoxime ester compound, preparation method thereof and photosensitive resin composition

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