WO2015188661A1 - Asymmetrical dioxime ester compound and manufacturing method and use thereof - Google Patents

Asymmetrical dioxime ester compound and manufacturing method and use thereof Download PDF

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WO2015188661A1
WO2015188661A1 PCT/CN2015/077138 CN2015077138W WO2015188661A1 WO 2015188661 A1 WO2015188661 A1 WO 2015188661A1 CN 2015077138 W CN2015077138 W CN 2015077138W WO 2015188661 A1 WO2015188661 A1 WO 2015188661A1
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group
alkyl
substituted
phenyl
cycloalkyl
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PCT/CN2015/077138
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French (fr)
Chinese (zh)
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赵文超
王永林
王辰龙
麻忠利
姚丽秀
胡伟静
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北京英力科技发展有限公司
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Priority to JP2016572407A priority Critical patent/JP6261778B2/en
Priority to KR1020167035925A priority patent/KR101883164B1/en
Publication of WO2015188661A1 publication Critical patent/WO2015188661A1/en

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    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
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    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
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    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
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    • C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/45—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms doubly-bound to the carbon skeleton
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    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/47—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
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    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
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    • C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans 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 carbon atoms of the hetero ring
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    • C08F2/00—Processes of polymerisation
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    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

  • the present invention relates to an asymmetric diterpene ester compound characterized by an esterified derivative of an arylene group and a cyclic ketoxime in a molecule, and an esterified fluorenyl group at the ⁇ -position of the carbonyl group, which has Use as a photoinitiator in photocurable compositions.
  • the oxime ester compound has been discovered as a photoinitiator.
  • the oxime ester compound is disclosed as a photoinitiator in both of US Pat. No. 3,558,309 and US Pat. No. 4,255,513.
  • CN1514845A discloses a series of oxime ester compounds, and two varieties OXE01 and OXE02 are marketed, and similar products are oxime esters 305 and 304 disclosed in CN101565472B and CN101508744B.
  • the substituted oxazolo oxacyclohexanone oxime ester described in Chinese patent CN102046667B has an absorption wavelength of up to 405 nm, which is advantageous for curing with LED lamps and visible light curing, but reduces the initiating activity per unit mass due to the increase of molecular weight;
  • the various diterpene ester derivatives of phenyl carbazole as disclosed in WO2008138732 have two oxime ester groups in one molecule, wherein one oxime ester is in the phenyl position of the N-substituted position, and experiments have proved that Such an oxime ester has a low activity and cannot impart an additional contribution to the photoinitiating activity of the molecule, and has no practicality;
  • oxime ester photoinitiators such as: WO2006018973, WO2007071497, CN1805955B, CN1922142B, CN1928715A, CN101508744B, CN102020727, but they are all side chains at the 3, 6, and 9 positions of carbazole. Various modifications were made, and some molecular weights increased without any improvement in photosensitivity.
  • Ar 1 is a C 6 -C 20 o-arylene or C 3 -C 20 o-heteroaryl group substituted by X 1 , a C 6 -C 20 o-arylene group or a C 3 -C 20 o-heteroarylene group
  • Two adjacent atoms are bonded to Y 1 and a carbonyl group to form a ring structure, and the substituents on the remaining atoms are each a hydrogen atom, a halogen atom, a C 1 -C 12 alkyl group, a C 5 -C 7 cycloalkyl group, C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl, C 1 -C 12 alkoxy, by one or more C 1 -C 12 alkoxy, C 1 -C 4 alkylbenzyloxy, R 2 C(O)O substituted C 1 -C 4 alkoxy, phenyl, optionally substituted by one or more C 1
  • Ar 2 is C 6 -C 20 arylene group, C 3 -C 20 heteroarylene group, and Ar 1 are connected via X 1, or both, the substituent ortho to X 1 X 1 1 is connected to Ar by Ar 2 carbon atoms and Ar 1 and then connected to form a ring structure with a direct bond, a carbon atom, a carbonyl group, O, S, NR 18;
  • n 0 or 1
  • X 1 is O, S, NR 18 , or Y 2 -Z 1 -Y 2 ;
  • Z 1 is C 1 -C 10 straight or branched alkylene, substituted by one or more oxygen, sulfur atom or a group attached to the insertion end of the C 1 -C 10 straight chain or branched alkylene group, an unsubstituted group Or a substituted C 6 -C 20 arylene;
  • Y 2 is O, S, NR 18 , O ⁇ C(O);
  • R 1 is a hydrogen atom, C 1 -C 18 alkyl, optionally substituted by one or more C 3 -C 7 cycloalkyl groups, phenyl, OR 20 , C 21 -C 18 alkyl substituted by SR 21 , NR 22 R 23 , C 2 -C 18 alkyl group inserted by C 3 -C 7 cycloalkylene, phenylene, O, S, NR 22 , C 3 -C 8 cycloalkyl, CN, NO 2 , phenyl, the above phenyl is unsubstituted, or optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl , heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy substituted;
  • R 1 is C 1 -C 12 alkyl acyl, C 1 -C 12 alkoxycarbonyl, wherein the alkyl group is optionally substituted by one or two or more halogen atoms, C 1 -C 4 alkyl, C 5 or C 6 ring Alkenyl, phenyl, CN, OH, X 3 R 20 substituted, or wherein the alkyl group is optionally interrupted by one or more phenylene groups, X 3 ;
  • R 1 is benzoyl, phenoxycarbonyl, wherein phenyl is unsubstituted, or optionally substituted by one or two or more halogen atoms, C 1 -C 4 alkyl, C 5 or C 6 cycloalkyl, phenyl , CN, OH, X 2 R 20 substitution;
  • R 1 is diphenylphosphono, di(C 1 -C 4 alkoxy)phosphono
  • R 2 , R 3 are each independently a hydrogen atom, a C 1 -C 18 alkyl group or a C 1 -C 18 alkoxy group;
  • R 2 , R 3 are each independently C 2 -C 18 alkenyl, optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, benzene Substituents, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy substituted and/or inserted into C 2 by C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 ⁇ C 18 alkenyl;
  • R 2 , R 3 are each independently optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy substituted and/or C 2 -C 18 alkyl inserted by C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 ;
  • R 2 are each independently a C 5 -C 7 cycloalkyl, optionally substituted with one or more C 1 -C 4 alkyl group, a phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl ;
  • R 2 , R 3 are each independently phenyl, phenyl optionally substituted by one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenyl, halogen atom, CN;
  • R 2 , R 3 are each independently naphthyl
  • R 2 , R 3 are each independently benzoyl, phenoxycarbonyl, or wherein phenyl is unsubstituted, or optionally substituted by one or more halogen atoms, R 17 , C 5 or C 6 cycloalkyl, CN, OH, XR 17 substituted;
  • R 15 and R 16 are each independently a hydrogen atom, a C 1 -C 18 alkyl group, a carboxy-substituted or C 1 -C 4 alkoxyacyl substituted C 1 -C 5 alkyl group, and R 2 C(O)O substituted C 1 -C 4 alkyl, optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy, or substituted C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 inserted into the C 2 -C 18 alkyl, or R 15, R 16 is independently substituted with one or more C 1 -C 4 alkyl is C 5 -C 7 cycloalkyl or optionally, a phenyl group, a halogen atom
  • R 15 , R 16 are each independently phenyl, optionally substituted by one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, C 1 -C 12 alkyl acyl, C 5 - C 6 cycloalkyl formyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkyl acyl group, benzoyl group, XR 17 , phenyl group, halogen atom, CN substituted phenyl group;
  • R 17 is C 1 -C 4 alkyl
  • R 18 and R 19 are each independently a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 4 alkoxyacyl substituted C 1 -C 5 alkyl group, and a R 2 C(O)O substituted C 1 -C 4 alkyl, optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy, C 1 -C 18 substituted alkyl, optionally substituted with one or more C 3 -C 7 cycloalkylene, phenylene, O, S, NR 17 C inserted 2 -C 18 alkyl;
  • R 18, R 19 are each independently substituted with one or more C 1 -C 4 alkyl is 5 -C 7 cycloalkyl, or optionally C, a phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl base;
  • R 18 , R 19 are each independently phenyl, optionally substituted by one or more C 1 -C 4 alkyl, carboxy, C 1 -C 12 alkyl acyl, C 5 -C 6 cycloalkyl formyl, C 5- C 6 cycloalkyl substituted C 2 -C 4 alkyl acyl, aryl acyl, XR 17 , phenyl, halogen atom, CN substituted phenyl;
  • R 18 is bonded to an aromatic ring in Ar 1 or Ar 2 through a straight bond, a carbon atom or a carbonyl group to form a new ring;
  • R 19 is bonded to an aromatic ring in Ar 1 through a straight bond, a carbon atom or a carbonyl group to form a new ring;
  • R 20 , R 21 , R 22 and R 23 are each independently a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 18 alkyl group substituted by a halogen, CN, a C 1 -C 4 alkoxy group, One or more oxygen atoms, a C 5 -C 7 cycloalkylene group, a C 2 -C 18 alkyl group in which a phenylene group is inserted, a C 1 -C 3 alkane substituted by a phenyl group, a C 3 -C 7 cycloalkyl group Base, C 3 -C 7 cycloalkyl;
  • R 20 , R 21 , R 22 , R 23 are each independently phenyl, naphthyl, benzoyl, wherein phenyl, naphthyl is unsubstituted, or each is optionally halogen, C 1 -C 4 alkyl , C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy, phenylthio, NR 24 R 25 , C 1 -C 12 alkyl acyl, benzoyl substituted;
  • R 24 and R 25 are each a C 1 -C 4 alkyl group; or NR 24 R 25 is a morpholine, piperidine, piperazine, N-methylpiperazine, pyrrole.
  • R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are each independently a hydrogen atom, a halogen atom, a C 1 -C 12 alkyl group, C 5 -C 7 cycloalkyl, C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl, C 1 -C 12 alkoxy, phenyl, optionally substituted by one or more C 1 -C 4 Alkyl, carboxyl, C 1 -C 12 alkyl acyl, aryl acyl, heteroaryl acyl, X 3 R 17 , phenyl, halogen atom, CN substituted phenyl, C 1 -C 4 alkylbenzyloxy , by one or more C 1 -C 12 alkoxy, C 1 -C 4 alkylbenzyl group, R 2 C (O) O-substit
  • R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are each independently C 1 -C 4 alkylphenoxy, C 1 -C 4 alkylphenylthio, C 1 -C 8 alkyl acyl phenoxy, aryl acyl phenoxy, heteroaryl acyl phenoxy, C 5 -C 6 cycloalkyl acyl phenoxy, C 5 ⁇ C 6 cycloalkyl substituted C 1 -C 4 alkyl acyl phenoxy, C 1 -C 3 alkylenedioxy, C 1 -C 12 alkylthio, R 2 C(O)O Substituted C 1 -C 4 alkylthio and C 1 -C 4 alkylphenylthio, C 1 -C 8 alkyl phenyl phenylthio, aryl acyl phenylthio,
  • R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are each independently an epoxypropyl group, wherein the epoxy group is optionally bonded to C 1 -C 4 alkyl aldehyde, ketone condensation;
  • X 1 is O, S or NR 18 ;
  • X 2 is O, S, NR 19 ,
  • Y 1 is O, S, CR 15 R 16 ;
  • R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each a hydrogen atom
  • X 1 is O or S
  • Y 1 is CH 2 , CHCH 3 or C(CH 3 ) 2 ;
  • n 1;
  • R 1 is C 1 -C 12 alkyl, optionally substituted with one or more C 3 -C 7 cycloalkyl, phenyl, OR 20, SR 21, NR 22 R 23 substituted C 1 -C 12 alkyl;
  • R 2 and R 3 are each independently methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylphenyl or 2,6-dimethyl Oxyphenyl group;
  • X 2 is NR 19 ;
  • Y 1 is O, S, CR 15 R 16 ;
  • R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, a C 1 -C 4 alkylbenzyloxy group, C 1 -C 4 alkylthio, C 1 -C 4 alkylphenoxy, C 1 -C 4 alkylphenylthio;
  • Y 1 is CH 2 or CHCH 3 ;
  • n 0;
  • R 1 is C 1 -C 12 alkyl, a C 3 -C 7 cycloalkyl optionally substituted alkyl, phenyl, OR 20, SR 21, NR 22 R 23 substituted C 1 -C 12 alkyl;
  • R 2 and R 3 are each independently methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylphenyl or 2,6-dimethyl Oxyphenyl group;
  • R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a C 1 -C 4 alkoxy group
  • R 19 is C 1 -C 12 alkyl, C 1 -C 3 alkyl substituted by C 3 -C 7 cycloalkyl, phenyl;
  • R 2 C(O) or R 3 C(O) may also be replaced by (R 2 ) 2 P or R 2 S(O 2 ) to form the corresponding phosphorous (phosphine) acid.
  • Esters or sulfonates also have photoinduced free radical or photoinduced cation initiation.
  • the invention also provides a method for producing the compound of the formula I in the series 1, comprising the steps of:
  • the first step selective deuteration on the ortho-methylene group of the cyclopentanone carbonyl group in the IV compound by the oximation reaction of the IV compound with the alkyl nitrite in an acidic solution to obtain a corresponding intermediate Body V;
  • the V compound undergoes the oximation reaction of the carbonyl group in the side chain R 1 CH 2 CO in the hydroxylamine solution to obtain the corresponding intermediate VII compound; when the thiol group is present in the cis-trans isomer, the obtained VI and VII are their respective isomers.
  • Step 3 The above second step of deuteration of intermediate VI or VII with the following acylating reagent
  • an equivalent acylating reagent is esterified to give the corresponding formula I; when the thiol group of the intermediate VI or VII is present in the cis-trans isomer, the obtained I is a mixture of its respective isomers, or is purified. Each of its isomers is obtained, and all the groups of the structures involved in the above reaction are defined as the corresponding structural groups in the series 1.
  • the present invention also provides an asymmetric diketone compound, as shown in Formula IV,
  • the present invention also provides a ketoxime compound, as shown in Formula V,
  • the present invention also provides a diketone oxime compound, as shown in Formula VI, VII,
  • each of the obtained intermediates and the final product of the formula I is a mixture of isomers thereof, and the purified individual isomers are obtained by separation. .
  • the present invention also relates to a photocurable composition
  • a photocurable composition comprising (a) a photoinitiator and (b) at least one carbon-carbon double bond compound capable of undergoing radical polymerization, the photoinitiator (a) comprising at least one of the above-mentioned a compound of formula I.
  • the photocurable composition further contains other additives (d) such as a developable resin, a pigment, an antifoaming agent and the like.
  • the photoinitiator (a) comprises from 0.05 to 25%, preferably from 2 to 15% by weight of the total of the cured composition; the balance of the remaining components in addition to the above components.
  • Component (b) A carbon-carbon double bond compound which is a radically polymerizable monomer, that is, a photocurable monomer, which includes one carbon-carbon double bond or two or more carbon-carbon double bonds in the molecule.
  • the compound containing a carbon-carbon double bond is preferably an acrylate compound, a methacrylate compound, an acrylate or methacrylate of a monohydric alcohol: methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic ring Hexyl ester, isobornyl acrylate, hydroxyethyl acrylate, methyl methacrylate and acrylonitrile, N-dialkyl acrylamide, N-vinyl pyrrolidone, vinyl benzene, vinyl acetate, vinyl ether.
  • Examples of compounds containing two or more carbon-carbon double bonds are alkyl diols, acrylates or methacrylates of polyols or polyester polyols, polyether polyols, epoxy polyols, and polyurethanes.
  • An acrylate of an alcohol, a vinyl ether, and an unsaturated polyester of an unsaturated dicarboxylic acid polyol such as polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, and more Ethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, polyester oligomer acrylate, urethane oligomer acrylate, aromatic epoxy acrylate, maleic acid Ethylene glycol polyester.
  • 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 polymerizable monomer contains an alkali-soluble group such as a carboxylic acid group
  • an alkali-soluble polymer resin can be obtained, which can be used for formulating a photoresist or for formulating a water-dispersed emulsion.
  • co-initiator component (c) in addition to the above-mentioned compounds of the formula I as photoinitiators, other types of commercially available photoinitiators or co-initiators may be compounded as co-initiator component (c), usually alpha-hydroxy, depending on the needs of the use of the composition.
  • Ketones such as 2-hydroxy-2-methyl-1-pyrene, 1-hydroxycyclohexyl benzophenone; ⁇ -aminoketones such as 2-methyl-2-ylmorpholinyl-(4-methylthiobenzene) ) ⁇ 1 ⁇ acetone, 2 ⁇ dimethylamino-2-phenylmethyl-(4-morpholinophenyl)-1-butanone; 2,2 ⁇ Diethoxy-l,2-diacetophenone; methyl benzoylformate, diethylene glycol dibenzoylformic acid, ester polybutylene glycol bisbenzoylformate; (2,4,6 -trimethylbenzoyl)diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; benzophenone and its substituted derivatives such as benzophenone, 4 -methylbenzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, 2'-chloro-4-pheny
  • Component (d) includes pigments, dyes, pigments are necessary components for printing inks and preparation filters, and can be red, green, blue, black, white, yellow, magenta, cyan, and other specific specials as needed. Color, corresponding pigments such as carbon black, indigo blue, titanium dioxide and other commercially available varieties. The pigment concentration generally ranges from 10 to 30% by weight of all solid components of the composition.
  • Component (d) also includes the necessary additives: phenols and hindered amine polymerization inhibitors such as p-methoxyphenol, nitrosophthalide aluminum complex polymerization inhibitor; light absorbers such as 2 ⁇ (2' ⁇ Hydroxyphenyl)-benzotriazole salicylates, triazines; leveling agents such as vinyltriethoxysilane; wetting agents, dispersing agents. They are used in an amount to achieve the properties of the composition and are not specifically required.
  • phenols and hindered amine polymerization inhibitors such as p-methoxyphenol, nitrosophthalide aluminum complex polymerization inhibitor
  • light absorbers such as 2 ⁇ (2' ⁇ Hydroxyphenyl)-benzotriazole salicylates, triazines
  • leveling agents such as vinyltriethoxysilane
  • wetting agents dispersing agents.
  • Component (d) further includes a developable resin, wherein an alkali-soluble developable resin such as a polyacrylate copolymer containing a carboxylic acid side chain, the comonomer may be selected from acrylic acid or methacrylic acid, alkyl acrylate, methyl group. Alkyl acrylate, styrene, low polystyrene; examples of solvent developable resins are cellulose ester and cellulose ether, polyvinyl acetate, polyvinyl butyral, polystyrene, polycarbonate, polyvinyl chloride Conventional varieties of resins such as polyester and polyimide.
  • the developable resin is an alkali-soluble resin, the composition can be used for photoresists and for the production of color filters in display devices.
  • the composition further comprises a thermally dry resin and a thermosetting resin component (e), such as a cellulose solution, a polyisocyanate, a polyimide, which are suitable for the flow requirements of the photocuring, heat curing segmentation process.
  • a thermosetting resin component such as a cellulose solution, a polyisocyanate, a polyimide, which are suitable for the flow requirements of the photocuring, heat curing segmentation process.
  • thermosetting component (f) a compound having an epoxy group may be a known thermosetting epoxy compound such as an aliphatic epoxy resin or an aromatic epoxy resin, preferably a bisphenol S type epoxy resin such as those produced by the Japanese chemical company. BPS-200, bisphenol A type epoxy resin, novolac epoxy resin, etc. and their partial esterified materials, in the composition relative to 100 parts by weight of component (b), component (f) For 30-70 copies.
  • a compound having an epoxy group may be a known thermosetting epoxy compound such as an aliphatic epoxy resin or an aromatic epoxy resin, preferably a bisphenol S type epoxy resin such as those produced by the Japanese chemical company. BPS-200, bisphenol A type epoxy resin, novolac epoxy resin, etc. and their partial esterified materials, in the composition relative to 100 parts by weight of component (b), component (f) For 30-70 copies.
  • the accelerator (g) is optionally used as a synergistic component to provide a good curing promotion effect, and examples are amine accelerators, imidazole accelerators, and other commonly used epoxy resins.
  • the hardener is used in an amount not exceeding 5% by weight of the component (f).
  • Additives (h) which include: one of additives for improving the adhesion and film forming hardness of the composition, etc., is an inorganic filler such as barium sulfate, powdered silica, talc, calcium carbonate, mica powder, etc. Within 30% of the total weight of the composition;
  • the composition can also be used after being diluted with a solvent according to the needs of the application field.
  • Suitable solvents are: ketones such as methyl ethyl ketone, cyclohexanone; hydrocarbons such as toluene, xylene, octane, petroleum ether, stone Brain oil; alcohols such as n-butanol, propylene glycol, etc.; alcohol ethers and esters thereof, such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxypropionic acid Methyl esters and the like; amides such as N,N-dimethylformamide.
  • composition or its solvent-diluted mixture is prepared in the form of an ink production method and stored in the dark.
  • composition is for the manufacture of one of the following products, colored or transparent: paint, adhesive or ink, photoresist and photoresist, which is then used for printing, 3D printing, display Color filter production, image reproduction technology, printed circuit board dielectric layer, electronic device package, optical switch, three-dimensional mold, quartz fiber protective layer, medical products.
  • the present invention provides a method of curing a carbon-carbon double bond compound in the photocurable composition, that is, the composition is applied onto a substrate, and the coating layer is cured by irradiation with light at 190 to 600 nm.
  • Light comes from the sun, mercury lamps, high pressure mercury lamps or LED lights.
  • the composition comprises irradiating the composition with light waves in the range of 190-600 nm or light waves of the output light wavelength through the grating, or by curing the composition with an LED light source of any wavelength range between 360 nm-410 nm, such as a 365 nm LED light source.
  • the LED is defined as a light emitting semiconductor diode.
  • the photocurable composition is prepared by first diluting the photocurable composition with a solvent; then, applying the diluted photocurable composition to a substrate, and drying, exposing, and developing the method. The exposed portion gives a raised pattern.
  • composition containing at least one compound of the formula I, a monomer, an alkali-soluble resin, a pigment and an additive in the present invention can be used as a photoresist, has high photosensitivity, is easily developed by an alkaline aqueous solution, and does not swell and deform. Clear imaging effect, suitable for etching photoresist, solder resist photoresist; for image display and recording materials; inkjet ink cured with LED lamps; used in the production process of LCD, OLED, PDP It can be used in the manufacture of various printing plates and in the production of electronic circuit boards or integrated circuits, and can also be used to form barrier coatings for various electronic components.
  • the composition has excellent anti-oxidation inhibition and heat-resistant processing properties, meets the requirements of the color filter production process, and is particularly suitable for the production of liquid crystal displays and organic semiconductor electroluminescent displays.
  • composition of the present invention is used as a photoresist, and a black, red, green and blue three-color pattern is sequentially formed through coating, exposure, development, and heat treatment to obtain a complete color filter.
  • the substrate of these color filters may be a glass or organic polymer film and a ceramic sheet.
  • the present invention also encompasses color filters made with the above compositions.
  • composition is coated on a flat or curved substrate, and dried to obtain a film layer; the unexposed portion is removed by mask exposure and development to obtain a convex image.
  • a color filter comprising black, red, green, and blue pixels is coated with a composition comprising a compound of the formula I, II, III, and IV of the present invention, a monomer, an alkali-soluble resin, and a corresponding pigment or auxiliary. Fabric, exposure, development, heat treatment process. It also includes the necessary processing such as cleaning.
  • composition of the present invention is uniformly applied to the substrate to be coated by coating techniques commonly used in the art such as spin coating, roll coating, spray coating, transfer, and the like.
  • the amount of coating is determined as desired, and the usual thickness is from 0.1 micron to 1 mm.
  • the solvent is volatilized by a heating method such as drying at 80 ° C, and the non-volatile component forms a gel layer remaining on the substrate.
  • the next step is exposure. If the UV laser is not used for direct exposure, the mask with the image is placed on the glue layer, and the ultraviolet or visible light source emits a range of wavelengths of light to set the energy through the transparent portion of the mask for exposure. Thus, the adhesive layer is cured by the light-receiving portion, and the shielded portion is not cured.
  • the development process is operated with parameters well known to those skilled in the art, such as spraying at 30 ° C, rinsing. It is usually developed with an alkaline aqueous solution, such as an alkali metal hydroxide, an aqueous solution of a carbonate, ammonia water, or a quantitative wetting agent such as a surfactant, an organic solvent such as cyclohexanone or acetone may be added to the aqueous solution as necessary. Ethylene glycol ether and the like.
  • the development method of immersing the exposure film in the developer bath or spraying the developer onto the exposure film is possible, and the specific development temperature and time depend on the development effect.
  • the alkali solution for development is to dissolve an alkaline substance in water or an aqueous solution containing a water-soluble organic solvent, and examples of the alkaline substance are sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and carbonic acid.
  • the final heat treatment process optimizes image fastness and is typically baked in a hot oven at 200-260 ° C for 15 - 45 minutes.
  • the color filter device can be manufactured by using the composition of the present invention, and exhibits excellent processing performance, clear array, high light transmittance, and is used for producing a high quality display. .
  • Example 1 The product of Example 1 was weighed to give 5-phenylthioindan-1-one 24.04 g (0.1 mol) dissolved in 120 ml of 1,2-dichloroethane, cooled to 5-10 ° C, and added with 28 g (0.21 mol) of anhydrous Aluminum trichloride, 17.9g (0.11mol) of octanoyl chloride was added dropwise with stirring. After the addition, the mixture was stirred for 4 hours. The reaction solution was treated with dilute hydrochloric acid. The organic solution was separated, washed once, and concentrated to recover 1,2-dichloroethane.
  • Example 2 The product obtained in Example 2 was obtained as 5-(4-octanoylphenylthio)indan-1,2-dione-2-indole 7.95 g (0.02 mol), dissolved in 40 ml of dimethyl sulfoxide, and added 36% thick.
  • the activated carbon was separated by hot filtration, 15 ml of n-hexane was added to the filtrate, cooled and cooled, crystals were precipitated, suction filtered, and the filter cake was vacuum dried to obtain a yellow crystalline product of 4.47 g, content: 98.0%, yield: 87.8%; melting range and 1 H-NMR ( CDCl 3 ), ⁇ (ppm) value data are shown in Table 1.
  • Example 3 According to the deuteration reaction method of Example 3, the product of Example 6 was used as a raw material, and dimethylation reaction was carried out by using dimethyl sulfoxide instead of ethanol as a solvent, and HPLC analysis revealed that the mono-deuterated product was not isolated.
  • Example 7 In the reaction liquid of Example 7, the same weight of n-butyl nitrite was continuously added dropwise to carry out the second deuteration reaction, and after 10 h, the yellow solid was obtained by the method of Example 4, and the purity was 96.50%, wherein the cis isomer content. 3.30%, the trans isomer content was 93.20%, and the yield was 85.0%; 1 H-NMR data indicated that the obtained product was a double telluride.
  • Example 5 According to the reaction method of Example 5, the product of Example 8 was used as a raw material, and the esterification reaction was carried out to obtain a yellow solid with a purity of 98.65%, wherein the cis isomer content was 1.25%, and the trans isomer content was 97.40. %, yield 60.3%; 1 H-NMR data showed that the obtained product was IIA6; 1 H-NMR (CDCl 3 ), ⁇ (ppm) value data is shown in Table 1.
  • Example 4 According to the reaction method of Example 4, the product of Example 11 was used as a raw material, and the second deuteration reaction was carried out by using isoamyl nitrite instead of n-butyl nitrite to obtain a yellow solid with a purity of 95.50%, wherein cis is isomer content of 5.10%, trans isomer content of 90.40%, yield 88.3%; 1 H-NMR data show that the obtained product was bis oxime compound.
  • Example 5 According to the reaction method of Example 5, the product of Example 12 was used as a raw material, and the esterification reaction was carried out to obtain a yellow solid with a purity of 98.65%, wherein the cis isomer content was 1.50%, and the trans isomer content was 97.15. %, yield 60.3%; 1 H-NMR data indicated that the obtained product was IIA3; 1 H-NMR (CDCl 3 ), ⁇ (ppm) value data is shown in Table 1.
  • the above liquid composition was applied to the surface of the glass by a wire bar method, baked at 80 ° C for 3 minutes, and the solvent PMA was volatilized, and the thickness of the remaining film was measured to be 2 ⁇ m.
  • a 21-step gray gradient ruler was placed on the film, and a 2000 W high-pressure mercury light line was filtered with a 365 nm grating filter, and the distance between the film and the grating was 10 cm, so that the exposure amount reached 800 mJ/cm 2 .
  • composition of the formulas 15A, 15B, 15C, and 15D in Table 2 of the above Example 15 was applied to the surface of the glass by a wire bar method, and baked at 80 ° C for 3 minutes to evaporate the solvent PMA, and the thickness of the remaining film was measured to be 2 Micron.
  • the 2000 W high-pressure mercury light line was filtered with a 365 nm grating filter, and the distance between the film and the grating was 10 cm, so that the exposure amount reached 200,400,600 mJ/cm 2 , respectively.
  • the sample was wrapped with a stainless steel mesh, and the weight W 1 was weighed and soaked in acetone for 72 hours.
  • the residual film weight W 2 was measured by drying, and W 1 /W 2 was gel conversion rate gel%. The results are shown in Table 4.
  • the photocurable compositions 15A, 15B, 15C, and 15D of Example 15 were applied to the surface of the glass by a wire bar method, baked at 80 ° C for 3 minutes, and the solvent PMA was volatilized, and the thickness of the remaining film was measured to be 2 ⁇ m. Then, the curing was carried out in the following manner.
  • Curing device LEDUV curing device, model: UV-101D (Beijing Iwata Boyuan Technology Co., Ltd.)
  • UV-LED point source diameter: 10mm; wavelength: 365nm, maximum illumination: 40mw/cm 2
  • the curing efficiency characterization method is as follows: after irradiating with a point light source for 1 s, the whole glass piece is immersed in acetone solution for 5 s, and after taking out, the cured film pattern diameter is measured.
  • Table 5 For the measurement results. It can be seen from the measurement results in Table 5 that when the photosensitive composition for the solder resist ink or the photoresist is cured by the LED light source, the photosensitive composition provided by the present invention is a photoinitiator with OXE01 and OXE02 as compared with the existing one. The composition has a higher light sensitivity.
  • Photocurable composition 15A 15B 15C 15D Diameter mm 16.2 15.5 12.1 10.0
  • Formula composition ratio 50 parts of epoxy resin acrylate prepolymer (Changxing Chemical 621-100), 10 parts of polyester acrylate prepolymer (Changxing Chemical 6311-10), 30 parts of TPGDA (Changxing Chemical EM223), carbon black (Degussa P25) 4 parts, 6 parts of photoinitiator; mixed and ground to a fineness of 2 um or less to obtain ink samples 18A-18D.
  • the gel conversion rate gel% was measured by the method of Example 16 using a 420 mesh screen printing onto an aluminum plate and solidified by a high pressure mercury lamp. Table 6 shows the measurement results. It can be seen from the measurement results in Table 6 that the gel conversion rate of the compound of the present invention produced by the high pressure mercury lamp was significantly higher than that of the control compound.
  • Formulation ratio 50 parts of epoxy acrylate prepolymer, 10 parts of polyester acrylate prepolymer, 30 parts of TPGDA, 4 parts of yellow 3G (BASF), 6 parts of photoinitiator; mixed grinding to fineness 2um Ink samples 19A-19D were obtained below, applied to a glass plate; cured with a 365 nm LED surface light lamp, with an exposure of 86 mJ/cm 2 .
  • the gel conversion gel% was measured as in Example 16. The measurement results are shown in Table 7. From the measurement results in Table 7, it can be seen that the gel conversion rate of the compound of the present invention was significantly higher than that of the control compound by irradiation with a 365 nm LED light source.
  • the filter film is prepared by photoresist and exposed to light
  • Formulation composition 500 parts of alkali-soluble resin solution (Example 14), 100 parts of dipentaerythritol hexaacrylate (Cytec DPHA), 100 parts of photoinitiator, co-initiator BCIM (2,2'-di-o-chlorophenyl- 4,4',5,5'-tetraphenylbiimidazole) 20 parts, carbon black (Degussa P25) dispersion 500 parts (containing carbon black 20%).
  • BCIM co-initiator
  • BCIM 2,2'-di-o-chlorophenyl- 4,4',5,5'-tetraphenylbiimidazole
  • carbon black Degussa P25
  • the filter film is prepared by photoresist and exposed to light
  • Formulation composition 500 parts of an alkali-soluble resin solution (Example 14), 100 parts of dipentaerythritol hexaacrylate (Cytec), 100 parts of a photoinitiator, and 100 parts of a red pigment L3920 (BASF Corporation). It was uniformly ground according to the ink preparation method to obtain five inks of 21A-21E.
  • the filter film is prepared by photoresist and exposed to light
  • Formulation composition 500 parts of an alkali-soluble resin solution (Example 14), 100 parts of dipentaerythritol hexaacrylate (Cytec), 10 parts of a photoinitiator, and 100 parts of a red pigment L3920 (BASF Corporation). It was uniformly ground according to the ink preparation method to obtain five kinds of inks of 22A-22E.

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Abstract

The present invention relates to an asymmetrical dioxime ester compound represented by general formula I and manufacturing method thereof. In general formula I, Ar1 is C6-C20 o-arylene or C3-C20 O-hetroarylene substituted by X1; Ar2 is C6-C20 arylene or C3-C20 hetroarylene, and is connected to Ar1 by X1; or when connected to Ar1 by X1, an ortho Ar2 carbon atom of the substituent group X1 thereof is connected to Ar1 by an axial bond, a carbon atom, carbonyl, O, S, or NR18 to form a ring structure; n is 0 or 1; X1 is NR18, O, or S, where C=O or S=O; Y1 is (CH2)mCR15R16, NR19, O(CR15R16)m, S(CR15R16)m, (CR15R16)m, where C=O and S=O; m is 0 or 1; R1, R2, and R3 are respectively a hydrogen atom, alkyl or alkoxy, alkyl or alkoxy and cycloalkyl substituted by any group, aryl and acyl substituted by any group. The present invention also relates to a photo-cured composition using the compound of general formula I as a photoinitiator, and the composition shows very high curing sensitivity when used for preparing a photo resistance device such as a display screen color filter.

Description

不对称二肟酯化合物及其制造方法与应用Asymmetric diterpene ester compound and preparation method and application thereof 技术领域Technical field
本发明涉及不对称二肟酯化合物，其特征是分子中亚芳基并环状酮肟和链状酮肟同时存在的酯化衍生物，酯化的肟基处于羰基α-位，其具有在光固化组合物中作为光引发剂的用途。The present invention relates to an asymmetric diterpene ester compound characterized by an esterified derivative of an arylene group and a cyclic ketoxime in a molecule, and an esterified fluorenyl group at the α-position of the carbonyl group, which has Use as a photoinitiator in photocurable compositions.
背景技术Background technique
肟酯化合物作为光引发剂很早就被发现，US3558309、US4255513两份专利中都公开了肟酯化合物作为光引发剂，但是，一些结构的肟酯热稳定性不佳或感光度低，难以在热稳定性、感光度等性能方面满足现代电子工业的使用要求。CN1514845A公开了一系列肟酯化合物，并有两个品种OXE01和OXE02上市销售，性能相近的产品还有CN101565472B和CN101508744B公开的肟酯305和304。The oxime ester compound has been discovered as a photoinitiator. The oxime ester compound is disclosed as a photoinitiator in both of US Pat. No. 3,558,309 and US Pat. No. 4,255,513. However, some structures of oxime esters have poor thermal stability or low sensitivity, and are difficult to Thermal stability, sensitivity and other performance aspects meet the requirements of the modern electronics industry. CN1514845A discloses a series of oxime ester compounds, and two varieties OXE01 and OXE02 are marketed, and similar products are oxime esters 305 and 304 disclosed in CN101565472B and CN101508744B.
Figure PCTCN2015077138-appb-000001
Figure PCTCN2015077138-appb-000001
中国专利CN102046667B描述的取代咔唑并氧杂环酮肟酯具有长达405nm的吸收波长，有利于使用LED灯固化、可见光固化，但因其分子量的加大而减少了单位质量的引发活性；专利WO2008138732中公开的以苯基咔唑为母体的各种二肟酯衍生物在一个分子中有了两个肟酯基团，其中一个肟酯处于N取代位置上的苯基对位，实验证明，这样的肟酯活性很低，不能给该分子的光引发活性带来额外的贡献，不具有实用性；The substituted oxazolo oxacyclohexanone oxime ester described in Chinese patent CN102046667B has an absorption wavelength of up to 405 nm, which is advantageous for curing with LED lamps and visible light curing, but reduces the initiating activity per unit mass due to the increase of molecular weight; The various diterpene ester derivatives of phenyl carbazole as disclosed in WO2008138732 have two oxime ester groups in one molecule, wherein one oxime ester is in the phenyl position of the N-substituted position, and experiments have proved that Such an oxime ester has a low activity and cannot impart an additional contribution to the photoinitiating activity of the molecule, and has no practicality;
除此之外也有不少其他肟酯类光引发剂的专利，如：WO2006018973、WO2007071497、CN1805955B、CN1922142B、CN1928715A、CN101508744B、CN102020727，但他们都是在咔唑的3、6、9位置的侧链上进行各种修饰，有的分子量增大，对感光性能没有任何提高。In addition, there are many other patents for oxime ester photoinitiators, such as: WO2006018973, WO2007071497, CN1805955B, CN1922142B, CN1928715A, CN101508744B, CN102020727, but they are all side chains at the 3, 6, and 9 positions of carbazole. Various modifications were made, and some molecular weights increased without any improvement in photosensitivity.
发明内容Summary of the invention
惊讶地发现一系列不对称二肟酯化合物具有非常优良的光引发活性。Surprisingly, it has been found that a series of asymmetric diterpene ester compounds have very excellent photoinitiating activity.
系列1：通式Ⅰ化合物， Series 1: Compounds of formula I,
Figure PCTCN2015077138-appb-000002
Figure PCTCN2015077138-appb-000002
其中among them
Ar1为被X1取代的C6‐C20邻亚芳基或C3‐C20邻亚杂芳基，C6‐C20邻亚芳基或C3‐C20邻亚杂芳基以相邻的两个原子与Y1和羰基相连构成并环结构，其余原子上的取代基各自为氢原子，卤素原子，C1‐C12烷基，C5‐C7环烷基，C5‐C7环烷基取代的C1‐C4烷基，C1‐C12烷氧基，被一个或多个C1‐C12烷氧基、C1‐C4烷基苄氧基、R2C(O)O取代的C1‐C4烷氧基，苯基，任意被一个或多个C1‐C4烷基、羧基、C1‐C12烷基酰基、芳基酰基、杂芳基酰基、X3R17、苯基、卤素原子、CN取代的苯基，C1‐C4烷基苄氧基，R2C(O)O取代的C1‐C4烷氧基，C1‐C3亚烷基二氧基，R2C(O)O，C1‐C12烷基硫基，C1‐C4烷基苯硫基，CN，羧基，C1‐C12烷氧基羰基，芳基羰基，杂芳基羰基，X3R18，C1‐C4烷基苯氧基，C1‐C8烷基酰基苯氧基，C5‐C6环烷基酰基苯氧基，C5‐C6环烷基取代的C1‐C4烷基酰基苯氧基，C1‐C3亚烷基二氧基，芳基酰基苯氧基，杂芳基酰基苯氧基，R2C(O)O取代的C1‐C4烷基硫基以及C1‐C4烷基苯硫基，C1‐C8烷基酰基苯硫基，C5‐C6环烷基酰基苯硫基或C5‐C6环烷基取代的C1‐C4烷基酰基苯硫基，芳基酰基苯硫基，杂芳基酰基苯硫基；或为环氧丙基，其中环氧基任意地与C1‐C4烷基醛、酮缩合，X3为O、S或NR22；Ar 1 is a C 6 -C 20 o-arylene or C 3 -C 20 o-heteroaryl group substituted by X 1 , a C 6 -C 20 o-arylene group or a C 3 -C 20 o-heteroarylene group Two adjacent atoms are bonded to Y 1 and a carbonyl group to form a ring structure, and the substituents on the remaining atoms are each a hydrogen atom, a halogen atom, a C 1 -C 12 alkyl group, a C 5 -C 7 cycloalkyl group, C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl, C 1 -C 12 alkoxy, by one or more C 1 -C 12 alkoxy, C 1 -C 4 alkylbenzyloxy, R 2 C(O)O substituted C 1 -C 4 alkoxy, phenyl, optionally substituted by one or more C 1 -C 4 alkyl, carboxy, C 1 -C 12 alkyl acyl, aryl acyl, Heteroaryl acyl, X 3 R 17 , phenyl, halogen atom, CN substituted phenyl, C 1 -C 4 alkylbenzyloxy, R 2 C(O)O substituted C 1 -C 4 alkoxy , C 1 -C 3 alkylenedioxy, R 2 C(O)O, C 1 -C 12 alkylthio, C 1 -C 4 alkylphenylthio, CN, carboxyl, C 1 -C 12 alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, X 3 R 18 , C 1 -C 4 alkylphenoxy, C 1 -C 8 alkyl acyl phenoxy, C 5 -C 6 naphthenic Acylbenzene Group, C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkyl group a phenoxy group, C 1 -C 3 alkylenedioxy, phenoxy aryl group, a heteroaryl group a phenoxy group , R 2 C(O)O substituted C 1 -C 4 alkylthio and C 1 -C 4 alkylphenylthio, C 1 -C 8 alkyl phenyl phenylthio, C 5 -C 6 naphthenic a C 1 -C 4 alkyl phenyl phenylthio group substituted with a C 5 -C 6 cycloalkyl group, an aryl acyl phenyl thio group, a heteroaryl acyl phenyl thio group; or an epoxy propyl group; Wherein the epoxy group is arbitrarily condensed with a C 1 -C 4 alkyl aldehyde, a ketone, and X 3 is O, S or NR 22 ;
Ar2为C6‐C20亚芳基、C3‐C20亚杂芳基，通过X1与Ar1相连接，或通过X1与Ar1相连接同时，其取代基X1邻位的Ar2碳原子通过直键、碳原子、羰基、O、S、NR18再与Ar1相连接构成环状结构；Ar 2 is C 6 -C 20 arylene group, C 3 -C 20 heteroarylene group, and Ar 1 are connected via X 1, or both, the substituent ortho to X 1 X 1 1 is connected to Ar by Ar 2 carbon atoms and Ar 1 and then connected to form a ring structure with a direct bond, a carbon atom, a carbonyl group, O, S, NR 18;
n为0或1；n is 0 or 1;
X1为O、S、NR18，或Y2-Z1-Y2；X 1 is O, S, NR 18 , or Y 2 -Z 1 -Y 2 ;
Y1为(CH2)mCR15R16、NR19、O(CR15R16)m、S(CR15R16)m、(CR15R16)m C＝O、S＝O；m为0或1；Y 1 is (CH 2) m CR 15 R 16, NR 19, O (CR 15 R 16) m, S (CR 15 R 16) m, (CR 15 R 16) m C = O, S = O; m Is 0 or 1;
Z1为C1‐C10直链或支链亚烷基、被一个或多个氧、硫原子连在端基或***的C1‐C10直链或支链亚烷基、无取代基或有取代基的C6‐C20亚芳基；Z 1 is C 1 -C 10 straight or branched alkylene, substituted by one or more oxygen, sulfur atom or a group attached to the insertion end of the C 1 -C 10 straight chain or branched alkylene group, an unsubstituted group Or a substituted C 6 -C 20 arylene;
Y2为O、S、NR18、O‐C(O)；R1为氢原子，C1‐C18烷基，任意被一个或多个C3‐C7环烷基、苯基、OR20、SR21、NR22R23取代的C1‐C18烷基，被C3‐C7亚环烷基、亚苯基、O、S、NR22***的C2‐C18烷基，C3‐C8环烷基，CN，NO2，苯基，以上苯基未被取代，或任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代；Y 2 is O, S, NR 18 , O‐C(O); R 1 is a hydrogen atom, C 1 -C 18 alkyl, optionally substituted by one or more C 3 -C 7 cycloalkyl groups, phenyl, OR 20 , C 21 -C 18 alkyl substituted by SR 21 , NR 22 R 23 , C 2 -C 18 alkyl group inserted by C 3 -C 7 cycloalkylene, phenylene, O, S, NR 22 , C 3 -C 8 cycloalkyl, CN, NO 2 , phenyl, the above phenyl is unsubstituted, or optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl , heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy substituted;
或R1为C1‐C12烷基酰基，C1‐C12烷氧基羰基，其中烷基任意被一个或两个以上卤素原子、C1‐C4烷基、C5或C6环烷基、苯基、CN、OH、X3R20取代，或其中烷基任意被一个或两个以上亚苯基、X3***； Or R 1 is C 1 -C 12 alkyl acyl, C 1 -C 12 alkoxycarbonyl, wherein the alkyl group is optionally substituted by one or two or more halogen atoms, C 1 -C 4 alkyl, C 5 or C 6 ring Alkenyl, phenyl, CN, OH, X 3 R 20 substituted, or wherein the alkyl group is optionally interrupted by one or more phenylene groups, X 3 ;
或R1为苯甲酰基，苯氧基羰基，其中苯基未被取代，或任意被一个或两个以上卤素原子、C1‐C4烷基、C5或C6环烷基、苯基、CN、OH、X2R20取代；Or R 1 is benzoyl, phenoxycarbonyl, wherein phenyl is unsubstituted, or optionally substituted by one or two or more halogen atoms, C 1 -C 4 alkyl, C 5 or C 6 cycloalkyl, phenyl , CN, OH, X 2 R 20 substitution;
或R1为二苯基膦酰基，二(C1‐C4烷氧基)膦酰基；Or R 1 is diphenylphosphono, di(C 1 -C 4 alkoxy)phosphono;
R2，R3各自独立地为氢原子，C1‐C18烷基或C1‐C18烷氧基；R 2 , R 3 are each independently a hydrogen atom, a C 1 -C 18 alkyl group or a C 1 -C 18 alkoxy group;
或R2，R3各自独立地为C2‐C18烯基，任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代和/或被C5‐C7环亚烷基、亚苯基、O、S、NR17***C2‐C18烯基；Or R 2 , R 3 are each independently C 2 -C 18 alkenyl, optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, benzene Substituents, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy substituted and/or inserted into C 2 by C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 ‐C 18 alkenyl;
或R2，R3各自独立地为任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代和/或被C5‐C7环亚烷基、亚苯基、O、S、NR17***的C2‐C18烷基；Or R 2 , R 3 are each independently optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy substituted and/or C 2 -C 18 alkyl inserted by C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 ;
或R2，R3各自独立地为C5‐C7环烷基，任意被一个或多个C1‐C4烷基、苯基、卤素原子、CN取代的C5‐C7环烷基；Or R 2, R 3 are each independently a C 5 -C 7 cycloalkyl, optionally substituted with one or more C 1 -C 4 alkyl group, a phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl ;
或R2，R3各自独立地为苯基，任意被一个或多个C1‐C4烷基、C1‐C4烷氧基、苯基、卤素原子、CN取代的苯基；Or R 2 , R 3 are each independently phenyl, phenyl optionally substituted by one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenyl, halogen atom, CN;
或R2，R3各自独立地为萘基；Or R 2 , R 3 are each independently naphthyl;
或R2，R3各自独立地为苯甲酰基，苯氧基羰基，或其中苯基未被取代，或任意被一个或两个以上卤素原子、R17、C5或C6环烷基、CN、OH、XR17取代；Or R 2 , R 3 are each independently benzoyl, phenoxycarbonyl, or wherein phenyl is unsubstituted, or optionally substituted by one or more halogen atoms, R 17 , C 5 or C 6 cycloalkyl, CN, OH, XR 17 substituted;
R15，R16各自独立地为氢原子，C1‐C18烷基，羧基取代或C1‐C4烷氧基酰基取代的C1‐C5烷基，R2C(O)O取代的C1‐C4烷基，任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代或被C5‐C7亚环烷基、亚苯基、O、S、NR17***的C2‐C18烷基，或R15，R16各自独立地为C5‐C7环烷基或任意被一个或多个C1‐C4烷基、苯基、卤素原子、CN取代的C5‐C7环烷基；R 15 and R 16 are each independently a hydrogen atom, a C 1 -C 18 alkyl group, a carboxy-substituted or C 1 -C 4 alkoxyacyl substituted C 1 -C 5 alkyl group, and R 2 C(O)O substituted C 1 -C 4 alkyl, optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy, or substituted C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 inserted into the C 2 -C 18 alkyl, or R 15, R 16 is independently substituted with one or more C 1 -C 4 alkyl is C 5 -C 7 cycloalkyl or optionally, a phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl;
或R15，R16各自独立地为苯基，任意被一个或多个C1‐C4烷基、C1‐C4烷氧基、羧基、C1‐C12烷基酰基、C5‐C6环烷基甲酰基、C5‐C6环烷基取代的C2‐C4烷基酰基、苯甲酰基、XR17、苯基、卤素原子、CN取代的苯基；Or R 15 , R 16 are each independently phenyl, optionally substituted by one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, C 1 -C 12 alkyl acyl, C 5 - C 6 cycloalkyl formyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkyl acyl group, benzoyl group, XR 17 , phenyl group, halogen atom, CN substituted phenyl group;
或上述R15，R16与其共同所连的碳原子或硅原子一起构成环状且成环的原子数为4‐7，或上述R15，R16分别与相邻的取代基一起构成环状且成环的原子数为4‐7；Or R 15 , R 16 together with the carbon atom or silicon atom to which they are attached together form a cyclic ring and the number of atoms formed is 4-7, or R 15 and R 16 together form an annular ring together with an adjacent substituent. And the number of atoms in the ring is 4-7;
R17为C1‐C4烷基；R 17 is C 1 -C 4 alkyl;
R18，R19各自独立地为氢原子，C1‐C18烷基，C1‐C4烷氧基酰基取代的C1‐C5烷基，R2C(O)O取代的C1‐C4烷基，任意被一个或多个卤素原子、C1‐C4烷基、C3‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代的C1‐C18烷基，被任意被一个或多个C3‐C7亚环烷基、亚苯基、O、S、NR17***的C2‐C18烷基；R 18 and R 19 are each independently a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 4 alkoxyacyl substituted C 1 -C 5 alkyl group, and a R 2 C(O)O substituted C 1 -C 4 alkyl, optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy, C 1 -C 18 substituted alkyl, optionally substituted with one or more C 3 -C 7 cycloalkylene, phenylene, O, S, NR 17 C inserted 2 -C 18 alkyl;
或R18，R19各自独立地为C5‐C7环烷基，或任意被一个或多个C1‐C4烷基、苯基、卤素原子、CN取代的 C5‐C7环烷基；Or R 18, R 19 are each independently substituted with one or more C 1 -C 4 alkyl is 5 -C 7 cycloalkyl, or optionally C, a phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl base;
或R18，R19各自独立地为苯基，任意被一个或多个C1‐C4烷基、羧基、C1‐C12烷基酰基、C5‐C6环烷基甲酰基、C5‐C6环烷基取代的C2‐C4烷基酰基、芳基酰基、XR17、苯基、卤素原子、CN取代的苯基；Or R 18 , R 19 are each independently phenyl, optionally substituted by one or more C 1 -C 4 alkyl, carboxy, C 1 -C 12 alkyl acyl, C 5 -C 6 cycloalkyl formyl, C 5- C 6 cycloalkyl substituted C 2 -C 4 alkyl acyl, aryl acyl, XR 17 , phenyl, halogen atom, CN substituted phenyl;
或上述R18通过直键、碳原子、羰基与Ar1或Ar2中的芳环相连构成新的环；Or the above R 18 is bonded to an aromatic ring in Ar 1 or Ar 2 through a straight bond, a carbon atom or a carbonyl group to form a new ring;
或上述R19通过直键、碳原子、羰基与Ar1中的芳环相连构成新的环；Or the above R 19 is bonded to an aromatic ring in Ar 1 through a straight bond, a carbon atom or a carbonyl group to form a new ring;
R20，R21，R22，R23各自独立地为氢原子，C1‐C18烷基，被卤素、CN、C1‐C4烷氧基取代的C1‐C18烷基，被一个或多个氧原子、C5‐C7亚环烷基、亚苯基***的C2‐C18烷基，被苯基、C3‐C7环烷基取代的C1‐C3烷基，C3‐C7环烷基；R 20 , R 21 , R 22 and R 23 are each independently a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 18 alkyl group substituted by a halogen, CN, a C 1 -C 4 alkoxy group, One or more oxygen atoms, a C 5 -C 7 cycloalkylene group, a C 2 -C 18 alkyl group in which a phenylene group is inserted, a C 1 -C 3 alkane substituted by a phenyl group, a C 3 -C 7 cycloalkyl group Base, C 3 -C 7 cycloalkyl;
或R20，R21，R22，R23各自独立地为苯基，萘基，苯甲酰基，其中苯基、萘基未被取代，或各自任意地被卤素、C1‐C4烷基、C1‐C4烷氧基、C1‐C4烷基硫基、苯氧基、苯硫基、NR24R25、C1‐C12烷基酰基、苯甲酰基取代；Or R 20 , R 21 , R 22 , R 23 are each independently phenyl, naphthyl, benzoyl, wherein phenyl, naphthyl is unsubstituted, or each is optionally halogen, C 1 -C 4 alkyl , C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy, phenylthio, NR 24 R 25 , C 1 -C 12 alkyl acyl, benzoyl substituted;
R24，R25各自为C1‐C4烷基；或NR24R25为吗啉，哌啶，哌嗪，N‐甲基哌嗪，吡咯。R 24 and R 25 are each a C 1 -C 4 alkyl group; or NR 24 R 25 is a morpholine, piperidine, piperazine, N-methylpiperazine, pyrrole.
系列2：通式Ⅱ、ⅢA及ⅢB所示化合物，Series 2: compounds of the general formula II, IIIA and IIIB,
Figure PCTCN2015077138-appb-000003
Figure PCTCN2015077138-appb-000003
Figure PCTCN2015077138-appb-000004
Figure PCTCN2015077138-appb-000004
其中among them
R4，R5，R6，R7，R8，R9，R10，R11，R12，R13，R14各自独立地为氢原子，卤素原子，C1-C12烷基，C5-C7环烷基，C5-C7环烷基取代的C1-C4烷基，C1-C12烷氧基，苯基，任意被一个或多个C1-C4烷基、羧基、C1-C12烷基酰基、芳基酰基、杂芳基酰基、X3R17、苯基、卤素原子、CN取代的苯基，C1-C4烷基苄氧基，被一个或多个C1-C12烷氧基、C1-C4烷基苄氧基、R2C(O)O取代的C1-C4烷氧基，R2C(O)O，CN，羧基，C1-C12烷氧基羰基，芳基羰基，杂芳基羰基，X3R18；R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are each independently a hydrogen atom, a halogen atom, a C 1 -C 12 alkyl group, C 5 -C 7 cycloalkyl, C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl, C 1 -C 12 alkoxy, phenyl, optionally substituted by one or more C 1 -C 4 Alkyl, carboxyl, C 1 -C 12 alkyl acyl, aryl acyl, heteroaryl acyl, X 3 R 17 , phenyl, halogen atom, CN substituted phenyl, C 1 -C 4 alkylbenzyloxy , by one or more C 1 -C 12 alkoxy, C 1 -C 4 alkylbenzyl group, R 2 C (O) O-substituted C 1 -C 4 alkoxy, R 2 C (O) O, CN, carboxyl, C 1 -C 12 alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, X 3 R 18 ;
或R4，R5，R6，R7，R8，R9，R10，R11，R12，R13，R14各自独立地为C1‐C4烷基苯氧基，C1‐C4烷基苯硫基，C1‐C8烷基酰基苯氧基，芳基酰基苯氧基，杂芳基酰基苯氧基，C5‐C6环烷基酰基苯氧基，C5‐C6环烷基取代的C1‐C4烷基酰基苯氧基，C1‐C3亚烷基二氧基，C1‐C12烷基硫基，R2C(O)O取代的C1‐C4烷基硫基以及C1‐C4烷基苯硫基，C1‐C8烷基酰基苯硫基，芳基酰基苯硫基，杂芳基酰基苯硫基，C5‐C6环烷基酰基苯硫基或C5‐C6环烷基取代的C1‐C4烷基酰基苯硫基；Or R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are each independently C 1 -C 4 alkylphenoxy, C 1 -C 4 alkylphenylthio, C 1 -C 8 alkyl acyl phenoxy, aryl acyl phenoxy, heteroaryl acyl phenoxy, C 5 -C 6 cycloalkyl acyl phenoxy, C 5 ‐C 6 cycloalkyl substituted C 1 -C 4 alkyl acyl phenoxy, C 1 -C 3 alkylenedioxy, C 1 -C 12 alkylthio, R 2 C(O)O Substituted C 1 -C 4 alkylthio and C 1 -C 4 alkylphenylthio, C 1 -C 8 alkyl phenyl phenylthio, aryl acyl phenylthio, heteroaryl acyl phenylthio, a C 5 -C 6 cycloalkyl phenyl phenylthio group or a C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkyl acyl phenylthio group;
或R4，R5，R6，R7，R8，R9，R10，R11，R12，R13，R14各自独立地为环氧丙基，其中环氧基任意地与C1‐C4烷基醛、酮缩合；。Or R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are each independently an epoxypropyl group, wherein the epoxy group is optionally bonded to C 1 -C 4 alkyl aldehyde, ketone condensation;
X1为O，S或NR18；X 1 is O, S or NR 18 ;
X2为O、S、NR19，X 2 is O, S, NR 19 ,
Y1为O，S，CR15R16；Y 1 is O, S, CR 15 R 16 ;
其他取代基定义同系列1。Other substituents are defined in the same series 1.
系列3：通式Ⅱ化合物，其中Series 3: Compounds of the general formula II, wherein
R4，R5，R6，R7，R8，R9，R10均为氢原子；R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each a hydrogen atom;
X1为O或S；X 1 is O or S;
Y1为CH2、CHCH3或C(CH3)2； Y 1 is CH 2 , CHCH 3 or C(CH 3 ) 2 ;
n＝1；n=1;
R1为C1‐C12烷基，任意被一个或多个C3‐C7环烷基、苯基、OR20、SR21、NR22R23取代的C1‐C12烷基；R 1 is C 1 -C 12 alkyl, optionally substituted with one or more C 3 -C 7 cycloalkyl, phenyl, OR 20, SR 21, NR 22 R 23 substituted C 1 -C 12 alkyl;
R2，R3各自独立地为甲基，乙基，苯基，2‐甲基苯基，3‐甲基苯基，2,4,6‐三甲基苯基或2,6‐二甲氧基苯基；R 2 and R 3 are each independently methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylphenyl or 2,6-dimethyl Oxyphenyl group;
其他基团定义同系列2中通式Ⅱ相应基团定义。Other group definitions are as defined for the corresponding groups of formula II in series 2.
系列4：通式ⅢA和ⅢB化合物，其中Series 4: Compounds of the formulae IIIA and IIIB, wherein
X2为NR19；X 2 is NR 19 ;
Y1为O，S，CR15R16；Y 1 is O, S, CR 15 R 16 ;
R11，R12，R13，R14各自独立地为氢原子，卤素原子，C1‐C4烷基，C1‐C4烷氧基，C1‐C4烷基苄氧基，C1‐C4烷基硫基，C1‐C4烷基苯氧基，C1‐C4烷基苯硫基；R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, a C 1 -C 4 alkylbenzyloxy group, C 1 -C 4 alkylthio, C 1 -C 4 alkylphenoxy, C 1 -C 4 alkylphenylthio;
其他取代基定义同系列2中通式ⅢA和ⅢB相应基团定义。Other substituent definitions are as defined for the corresponding groups of formulas IIIA and IIIB in series 2.
系列5：通式ⅢA和ⅢB化合物，其中Series 5: Compounds of the formulae IIIA and IIIB, wherein
Y1为CH2或CHCH3；Y 1 is CH 2 or CHCH 3 ;
n＝0；n=0;
R1为C1‐C12烷基，任意被一个C3‐C7环烷基、苯基、OR20、SR21、NR22R23取代的C1‐C12烷基；R 1 is C 1 -C 12 alkyl, a C 3 -C 7 cycloalkyl optionally substituted alkyl, phenyl, OR 20, SR 21, NR 22 R 23 substituted C 1 -C 12 alkyl;
R2，R3各自独立地为甲基，乙基，苯基，2‐甲基苯基，3‐甲基苯基，2,4,6‐三甲基苯基或2,6‐二甲氧基苯基；R 2 and R 3 are each independently methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylphenyl or 2,6-dimethyl Oxyphenyl group;
R11，R12，R13，R14各自独立地为氢原子，C1‐C4烷氧基；R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a C 1 -C 4 alkoxy group;
R19为C1‐C12烷基，被C3‐C7环烷基、苯基取代的C1‐C3烷基；R 19 is C 1 -C 12 alkyl, C 1 -C 3 alkyl substituted by C 3 -C 7 cycloalkyl, phenyl;
其他基团定义同系列4中通式ⅢA和ⅢB中相应基团定义。Other group definitions are as defined for the corresponding groups in formulas IIIA and IIIB of series 4.
上述通式Ⅰ、ⅡA和ⅡB中，R2C(O)或R3C(O)还可以被(R2)2P或R2S(O2)代替生成对应的亚磷(膦)酸酯或磺酸酯，也具有光致自由基或光致阳离子引发作用。In the above formulae I, IIA and IIB, R 2 C(O) or R 3 C(O) may also be replaced by (R 2 ) 2 P or R 2 S(O 2 ) to form the corresponding phosphorous (phosphine) acid. Esters or sulfonates also have photoinduced free radical or photoinduced cation initiation.
系列6：上述系列1-5中的各自的通式Ⅰ、Ⅱ、和ⅢA和ⅢB化合物，其具体结构有Series 6: respective compounds of the formulae I, II, and IIIA and IIIB in the above series 1-5, the specific structure of which has
Figure PCTCN2015077138-appb-000005
Figure PCTCN2015077138-appb-000005
Figure PCTCN2015077138-appb-000006
Figure PCTCN2015077138-appb-000006
本发明还提供所述的系列1中通式Ⅰ化合物的制造方法，包含以下步骤：The invention also provides a method for producing the compound of the formula I in the series 1, comprising the steps of:
(1)第一步：在Ⅳ化合物中环戊酮羰基的邻位亚甲基上进行选择性肟化，方法是Ⅳ化合物与亚硝酸烷基酯在酸性溶液中发生肟化反应，得到对应的中间体Ⅴ；(1) The first step: selective deuteration on the ortho-methylene group of the cyclopentanone carbonyl group in the IV compound by the oximation reaction of the IV compound with the alkyl nitrite in an acidic solution to obtain a corresponding intermediate Body V;
Figure PCTCN2015077138-appb-000007
Figure PCTCN2015077138-appb-000007
(2)第二步：将中间体Ⅴ化合物继续进行第二肟化，方法A是Ⅴ化合物与亚硝酸烷基酯在酸性溶液中发生肟化反应，得到对应的中间体Ⅵ化合物；方法B是Ⅴ化合物在羟胺溶液中发生侧链R1CH2CO中羰基的肟化反应，得到对应的中间体Ⅶ化合物；当肟基存在顺反异构体时，得到的Ⅵ、Ⅶ是其各自异构体的混合物； (2) The second step: the intermediate V compound is further subjected to a second deuteration, and the method A is a deuteration reaction between the V compound and the alkyl nitrite in an acidic solution to obtain a corresponding intermediate VI compound; The V compound undergoes the oximation reaction of the carbonyl group in the side chain R 1 CH 2 CO in the hydroxylamine solution to obtain the corresponding intermediate VII compound; when the thiol group is present in the cis-trans isomer, the obtained VI and VII are their respective isomers. a mixture of bodies;
Figure PCTCN2015077138-appb-000008
Figure PCTCN2015077138-appb-000008
(3)第三步：将上述第二步肟化中间体Ⅵ或Ⅶ与下列酰化试剂(3) Step 3: The above second step of deuteration of intermediate VI or VII with the following acylating reagent
Figure PCTCN2015077138-appb-000009
Figure PCTCN2015077138-appb-000009
或其等价酰化试剂发生酯化反应得到对应的通式Ⅰ；当中间体Ⅵ或Ⅶ的肟基存在顺反异构体时，得到的Ⅰ是其各自异构体的混合物，或经过提纯得到其各个异构体，上述反应过程中所涉及结构的所有基团定义同系列1中相应结构基团定义。Or an equivalent acylating reagent is esterified to give the corresponding formula I; when the thiol group of the intermediate VI or VII is present in the cis-trans isomer, the obtained I is a mixture of its respective isomers, or is purified. Each of its isomers is obtained, and all the groups of the structures involved in the above reaction are defined as the corresponding structural groups in the series 1.
本发明还提供一种不对称二酮化合物，如通式Ⅳ所示，The present invention also provides an asymmetric diketone compound, as shown in Formula IV,
Figure PCTCN2015077138-appb-000010
Figure PCTCN2015077138-appb-000010
其中among them
基团Ar1，Ar2，X1，Y1，R1的定义同系列1中通式Ⅰ化合物相应基团定义。The definitions of the groups Ar 1 , Ar 2 , X 1 , Y 1 , R 1 are as defined for the corresponding groups of the compounds of the formula I in series 1.
本发明还提供一种酮肟化合物，如通式Ⅴ所示，The present invention also provides a ketoxime compound, as shown in Formula V,
Figure PCTCN2015077138-appb-000011
Figure PCTCN2015077138-appb-000011
其中among them
基团Ar1，Ar2，X1，Y1，R1的定义同系列1中通式Ⅰ化合物相应基团定义。The definitions of the groups Ar 1 , Ar 2 , X 1 , Y 1 , R 1 are as defined for the corresponding groups of the compounds of the formula I in series 1.
本发明还提供一种二酮肟化合物，如通式Ⅵ，Ⅶ所示，The present invention also provides a diketone oxime compound, as shown in Formula VI, VII,
Figure PCTCN2015077138-appb-000012
Figure PCTCN2015077138-appb-000012
Figure PCTCN2015077138-appb-000013
Figure PCTCN2015077138-appb-000013
其中among them
基团Ar1，Ar2，X1，Y1，R1的定义同系列1中通式Ⅰ化合物相应基团定义。The definitions of the groups Ar 1 , Ar 2 , X 1 , Y 1 , R 1 are as defined for the corresponding groups of the compounds of the formula I in series 1.
当通式Ⅴ，Ⅵ，Ⅶ中的肟基有顺反异构体时，得到的各中间体及最终产物通式Ⅰ化合物是其异构体的混合物，经分离可以得到纯化的各个异构体。When the thiol group of the formula V, VI, VII has a cis-trans isomer, each of the obtained intermediates and the final product of the formula I is a mixture of isomers thereof, and the purified individual isomers are obtained by separation. .
本发明还涉及一种光固化组合物，含有(a)光引发剂和(b)至少一种可进行自由基聚合的碳碳双键化合物，该光引发剂(a)包含至少一种上述通式Ⅰ化合物。The present invention also relates to a photocurable composition comprising (a) a photoinitiator and (b) at least one carbon-carbon double bond compound capable of undergoing radical polymerization, the photoinitiator (a) comprising at least one of the above-mentioned a compound of formula I.
光引发剂(a)除了含有至少一种上述通式Ⅰ化合物外，还进一步包含其他市售光引发剂作为共引发剂组分(c)。The photoinitiator (a), in addition to the at least one compound of the above formula I, further comprises other commercially available photoinitiators as co-initiator component (c).
该光固化组合物，进一步含有其他添加剂(d)，例如可显影树脂、颜料、消泡剂等必要功能组分。The photocurable composition further contains other additives (d) such as a developable resin, a pigment, an antifoaming agent and the like.
以重量计，光引发剂(a)占全部固化组合物的0.05‐25％，优选2‐15％；其余组分占除上述组分外的剩余百分比。The photoinitiator (a) comprises from 0.05 to 25%, preferably from 2 to 15% by weight of the total of the cured composition; the balance of the remaining components in addition to the above components.
组分(b)可进行自由基聚合的碳碳双键化合物即光固化单体，其分子中包括一个碳碳双键或两个及两个以上碳碳双键。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，例子有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。Component (b) A carbon-carbon double bond compound which is a radically polymerizable monomer, that is, a photocurable monomer, which includes one carbon-carbon double bond or two or more carbon-carbon double bonds in the molecule. The compound containing a carbon-carbon double bond is preferably an acrylate compound, a methacrylate compound, an acrylate or methacrylate of a monohydric alcohol: methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic ring Hexyl ester, isobornyl acrylate, hydroxyethyl acrylate, methyl methacrylate and acrylonitrile, N-dialkyl acrylamide, N-vinyl pyrrolidone, vinyl benzene, vinyl acetate, vinyl ether.
包含两个及两个以上碳碳双键的化合物例子有烷基二元醇、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。Examples of compounds containing two or more carbon-carbon double bonds are alkyl diols, acrylates or methacrylates of polyols or polyester polyols, polyether polyols, epoxy polyols, and polyurethanes. An acrylate of an alcohol, a vinyl ether, and an unsaturated polyester of an unsaturated dicarboxylic acid polyol, such as polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, and more Ethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, polyester oligomer acrylate, urethane oligomer acrylate, aromatic epoxy acrylate, maleic acid Ethylene glycol polyester.
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。当聚合单体中含有碱溶性基团例如羧酸基时，得到具有碱溶性的聚合物树脂，可用于配制光致抗蚀剂或用于配制水分散乳液。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. When the polymerizable monomer contains an alkali-soluble group such as a carboxylic acid group, an alkali-soluble polymer resin can be obtained, which can be used for formulating a photoresist or for formulating a water-dispersed emulsion.
除上述结构通式Ⅰ化合物作为光引发剂外，根据组合物用途的需要，还可以复配其他类型市售光引发剂或助引发剂作为共引发剂组分(c)，通常是α‐羟基酮类如2‐羟基‐2‐甲基‐1‐苯丙酮、1‐羟基环己基苯甲酮；α‐氨基酮类如2‐甲基‐2‐吗啉基‐(4‐甲硫基苯)‐1‐丙酮、2‐二甲基氨基‐2‐苯甲基‐(4‐吗啉代苯基)‐1‐丁酮；2,2‐ 二乙氧基‐1,2‐二苯乙酮；苯甲酰基甲酸甲酯、二乙二醇双苯甲酰基甲酸、酯聚丁二醇双苯甲酰基甲酸酯；(2,4,6‐三甲基苯甲酰基)二苯基氧化膦、二(2,4,6‐三甲基苯甲酰基)苯基氧化膦；二苯甲酮及其取代衍生物如二苯甲酮、4‐甲基二苯甲酮、4‐氯二苯甲酮、4‐苯基二苯甲酮、2’‐氯‐4‐苯基二苯甲酮、4‐甲硫基二苯甲酮、4‐(2‐羟乙基硫代)二苯甲酮、4‐羟基二苯甲酮月桂酸酯二苯甲酮‐4‐氧乙酸聚乙二醇酯；硫杂蒽酮及其取代衍生物如2‐异丙基硫杂蒽酮、2,4‐二乙基硫杂蒽酮、1‐氯‐4‐丙氧基硫杂蒽酮、硫杂蒽酮‐2‐甲酸聚乙二醇酯、硫杂蒽酮‐2‐氧乙酸聚乙二醇酯；卤代甲基三嗪如2‐(4‐甲氧基苯基)‐4,6‐二(三氯甲基)‐[1,3,5]‐三嗪；六芳基二咪唑类例如六邻氯苯基二咪唑；二茂铁类化合物；二茂钛类化合物；香豆素；樟脑醌；吖啶类如9‐苯基吖啶；胺类如4,4’‐二(二乙基氨基)二苯甲酮、4‐二甲氨基苯甲酸乙酯、三乙醇胺、甲基二乙醇胺或活性胺类化合物，如二乙胺与乙氧基化三羟甲基丙烷三丙烯酸酯加成物；亚磷酸酯类如亚磷酸三苯酯、亚磷酸三月桂酯；链转移剂例如己二硫醇、辛硫醇。In addition to the above-mentioned compounds of the formula I as photoinitiators, other types of commercially available photoinitiators or co-initiators may be compounded as co-initiator component (c), usually alpha-hydroxy, depending on the needs of the use of the composition. Ketones such as 2-hydroxy-2-methyl-1-pyrene, 1-hydroxycyclohexyl benzophenone; α-aminoketones such as 2-methyl-2-ylmorpholinyl-(4-methylthiobenzene) )‐1‐acetone, 2‐dimethylamino-2-phenylmethyl-(4-morpholinophenyl)-1-butanone; 2,2‐ Diethoxy-l,2-diacetophenone; methyl benzoylformate, diethylene glycol dibenzoylformic acid, ester polybutylene glycol bisbenzoylformate; (2,4,6 -trimethylbenzoyl)diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; benzophenone and its substituted derivatives such as benzophenone, 4 -methylbenzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, 2'-chloro-4-phenylbenzophenone, 4-methylthiobenzophenone, 4 ‐(2-hydroxyethylthio)benzophenone, 4-hydroxybenzophenone laurate benzophenone-4-methoxyacetate polyethylene glycol ester; thioxanthone and its substituted derivatives 2 - isopropyl thioxanthone, 2,4 - diethyl thiazinone, 1 - chloro-4-yl propoxy thioxanthone, thioxanthone -2-carboxylic acid polyethylene glycol ester, Thiophenone-2-methoxyacetic acid polyethylene glycol ester; halomethyltriazine such as 2-(4-methoxyphenyl)-4-,6-di(trichloromethyl)-[1,3 , 5]-triazine; hexaaryldiimidazoles such as hexa-chlorophenyldiimidazole; ferrocene compounds; ferrocene compounds; coumarin; camphorquinone; Such as 9-phenyl acridine; amines such as 4,4'-di(diethylamino)benzophenone, ethyl 4-dimethylaminobenzoate, triethanolamine, methyldiethanolamine or active amines a compound such as diethylamine and an ethoxylated trimethylolpropane triacrylate adduct; a phosphite such as triphenyl phosphite, trilauryl phosphite; a chain transfer agent such as hexanedithiol or octyl Mercaptan.
组分(d)包括颜料、染料，颜料是印刷油墨和制备滤光器的必要成分，按使用需要可以分别是红色、绿色、蓝色、黑色、白色、黄色、品红、青色及其他特定专用颜色，相应的颜料如炭黑、酞青蓝、二氧化钛等市售品种。颜料浓度一般占组合物所有固体组分重量的10‐30％。Component (d) includes pigments, dyes, pigments are necessary components for printing inks and preparation filters, and can be red, green, blue, black, white, yellow, magenta, cyan, and other specific specials as needed. Color, corresponding pigments such as carbon black, indigo blue, titanium dioxide and other commercially available varieties. The pigment concentration generally ranges from 10 to 30% by weight of all solid components of the composition.
组分(d)还包括必要的添加剂：酚类和受阻胺类阻聚剂例如对甲氧基苯酚、亚硝基苯胲铝络合物阻聚剂；光吸收剂如2‐(2’‐羟基苯基)‐苯并三氮唑类水杨酸酯类、三嗪类；流平剂例如乙烯基三乙氧基硅烷；润湿剂、分散剂。它们的用量以达到组合物性质指标为限，并无特别要求。Component (d) also includes the necessary additives: phenols and hindered amine polymerization inhibitors such as p-methoxyphenol, nitrosophthalide aluminum complex polymerization inhibitor; light absorbers such as 2‐(2'‐ Hydroxyphenyl)-benzotriazole salicylates, triazines; leveling agents such as vinyltriethoxysilane; wetting agents, dispersing agents. They are used in an amount to achieve the properties of the composition and are not specifically required.
组分(d)还包括可显影树脂，其中碱溶性可显影树脂，例如含有羧酸侧链的聚丙烯酸酯共聚物，共聚单体可选自丙烯酸或甲基丙烯酸、丙烯酸烷基酯、甲基丙烯酸烷基酯、苯乙烯、低聚苯乙烯；溶剂可显影树脂例子有纤维素酯和纤维素醚、聚乙酸乙烯酯、聚乙烯醇缩丁醛、聚苯乙烯、聚碳酸酯、聚氯乙烯、聚酯、聚酰亚胺这些常规品种的树脂。当可显影树脂为碱溶性树脂时，该组合物可用于光致抗蚀剂和用于显示器件中彩色滤光片的生产。Component (d) further includes a developable resin, wherein an alkali-soluble developable resin such as a polyacrylate copolymer containing a carboxylic acid side chain, the comonomer may be selected from acrylic acid or methacrylic acid, alkyl acrylate, methyl group. Alkyl acrylate, styrene, low polystyrene; examples of solvent developable resins are cellulose ester and cellulose ether, polyvinyl acetate, polyvinyl butyral, polystyrene, polycarbonate, polyvinyl chloride Conventional varieties of resins such as polyester and polyimide. When the developable resin is an alkali-soluble resin, the composition can be used for photoresists and for the production of color filters in display devices.
组合物进一步含有热干燥树脂和热固性树脂组分(e)，例如纤维素溶液、聚异氰酸酯、聚酰亚胺，他们适合于光固化、热固化分段处理的流程要求。The composition further comprises a thermally dry resin and a thermosetting resin component (e), such as a cellulose solution, a polyisocyanate, a polyimide, which are suitable for the flow requirements of the photocuring, heat curing segmentation process.
组合物中还允许加入至少一种具有环氧基团的化合物作为热固性组分(f)和一种环氧基固化促进剂(g)。具有环氧基团的化合物作为热固性组分(f)可以使用公知的热固性环氧化合物，例如脂肪族环氧树脂或芳香族环氧树脂，优选双酚S型环氧树脂如日本化学公司生产的BPS‐200，双酚A型环氧树脂，线型酚醛环氧树脂等及他们的部分酯化物，在组合物中相对于100份重量比例的组分(b)，组分(f)的用量为30‐70份。It is also permissible to add at least one compound having an epoxy group as a thermosetting component (f) and an epoxy curing accelerator (g). As the thermosetting component (f), a compound having an epoxy group may be a known thermosetting epoxy compound such as an aliphatic epoxy resin or an aromatic epoxy resin, preferably a bisphenol S type epoxy resin such as those produced by the Japanese chemical company. BPS-200, bisphenol A type epoxy resin, novolac epoxy resin, etc. and their partial esterified materials, in the composition relative to 100 parts by weight of component (b), component (f) For 30-70 copies.
当使用组分(f)时，任选地使用促进剂(g)作为协同组分能起到良好的固化促进作用，例子有胺类促进剂、咪唑类促进剂及其他通常使用的环氧树脂硬化剂，用量不超过组分(f)重量的5％。When component (f) is used, the accelerator (g) is optionally used as a synergistic component to provide a good curing promotion effect, and examples are amine accelerators, imidazole accelerators, and other commonly used epoxy resins. The hardener is used in an amount not exceeding 5% by weight of the component (f).
除上述组分(a)、(b)、(c)、(d)、(e)、(f)、(g)外，组合物中还可以使用本领域技术所常用的其他 添加剂(h)，它们包括：用于改善组合物的粘合性和成膜硬度等的添加剂之一是无机填料，例如硫酸钡、粉末二氧化硅、滑石粉、碳酸钙、云母粉等，用量占组合物总重量的30％以内；In addition to the above components (a), (b), (c), (d), (e), (f), (g), other materials commonly used in the art may be used in the composition. Additives (h), which include: one of additives for improving the adhesion and film forming hardness of the composition, etc., is an inorganic filler such as barium sulfate, powdered silica, talc, calcium carbonate, mica powder, etc. Within 30% of the total weight of the composition;
组合物还可以根据应用领域的需要被溶剂稀释后使用，合适的溶剂是：酮类，例如甲基乙基酮，环己酮；烃类，例如甲苯、二甲苯、辛烷、石油醚、石脑油；醇类，例如正丁醇、丙二醇等；醇醚及其酯类，例如丙二醇单甲醚、二乙二醇单甲醚、丙二醇单甲醚乙酸酯、3‐甲氧基丙酸甲酯等；酰胺类例如N,N‐二甲基甲酰胺。The composition can also be used after being diluted with a solvent according to the needs of the application field. Suitable solvents are: ketones such as methyl ethyl ketone, cyclohexanone; hydrocarbons such as toluene, xylene, octane, petroleum ether, stone Brain oil; alcohols such as n-butanol, propylene glycol, etc.; alcohol ethers and esters thereof, such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxypropionic acid Methyl esters and the like; amides such as N,N-dimethylformamide.
上述组合物或其被溶剂稀释的混合物按油墨的生产方法配制完成后，避光保存。The above composition or its solvent-diluted mixture is prepared in the form of an ink production method and stored in the dark.
组合物的用途是用于制造带有颜色的或透明的下列制品之一：涂料、粘合剂或油墨、光致抗蚀剂及光阻剂，再将该制品用于印刷、3D打印、显示器件中彩色滤光片的生产、图像复制技术、印刷电路板介质层、电子器件封装、光学开关、三维模具、石英纤维保护层、医疗制品。The use of the composition is for the manufacture of one of the following products, colored or transparent: paint, adhesive or ink, photoresist and photoresist, which is then used for printing, 3D printing, display Color filter production, image reproduction technology, printed circuit board dielectric layer, electronic device package, optical switch, three-dimensional mold, quartz fiber protective layer, medical products.
本发明提供一种使所述光固化组合物中碳碳双键化合物进行固化的方法，即组合物被涂布于基材上，用190‐600nm光线照射使涂布层固化。光线来自太阳，汞灯，高压汞灯或LED灯。包括用190‐600nm范围内的光波或者是经过光栅控制输出光波长的光波辐射该组合物，也可以用360nm‐410nm之间任一一定波长范围的LED光源例如365nmLED光源照射固化该组合物的涂布层。所述LED的定义为发光半导体二极管。The present invention provides a method of curing a carbon-carbon double bond compound in the photocurable composition, that is, the composition is applied onto a substrate, and the coating layer is cured by irradiation with light at 190 to 600 nm. Light comes from the sun, mercury lamps, high pressure mercury lamps or LED lights. The composition comprises irradiating the composition with light waves in the range of 190-600 nm or light waves of the output light wavelength through the grating, or by curing the composition with an LED light source of any wavelength range between 360 nm-410 nm, such as a 365 nm LED light source. Coating layer. The LED is defined as a light emitting semiconductor diode.
该光固化组合物制作凸起图案的方法是，先将光固化组合物用溶剂稀释；后将稀释后的该光固化组合物涂布于基材上，经烘干、曝光、显影方法除去未曝光部分得到凸起图案。The photocurable composition is prepared by first diluting the photocurable composition with a solvent; then, applying the diluted photocurable composition to a substrate, and drying, exposing, and developing the method. The exposed portion gives a raised pattern.
本发明中含有至少一种通式Ⅰ化合物、单体、碱溶性树脂、颜料及添加剂的组合物可以用作光刻胶，具有高的光敏感性，易于被碱性水溶液显影，不溶胀变形，成像效果清晰，适合于制成刻蚀光刻胶，阻焊光刻胶；用于图像显示和记录材料；用LED灯固化的喷墨油墨；用于LCD、OLED、PDP的生产过程中，也能用于各种印刷版的制造及电子线路版或集成电路的生产过程中，还能用于形成各种电子组件的隔离涂层。The composition containing at least one compound of the formula I, a monomer, an alkali-soluble resin, a pigment and an additive in the present invention can be used as a photoresist, has high photosensitivity, is easily developed by an alkaline aqueous solution, and does not swell and deform. Clear imaging effect, suitable for etching photoresist, solder resist photoresist; for image display and recording materials; inkjet ink cured with LED lamps; used in the production process of LCD, OLED, PDP It can be used in the manufacture of various printing plates and in the production of electronic circuit boards or integrated circuits, and can also be used to form barrier coatings for various electronic components.
该组合物具有优良的抗氧气阻聚作用和耐热加工性能，满足彩色滤光片生产工艺要求，特别适合于液晶显示器、有机半导体电致发光显示器的生产。The composition has excellent anti-oxidation inhibition and heat-resistant processing properties, meets the requirements of the color filter production process, and is particularly suitable for the production of liquid crystal displays and organic semiconductor electroluminescent displays.
使用本发明的组合物作为光阻剂，依序经过涂布、曝光、显影、热处理过程而形成黑色及红绿蓝三色图案，得到完整的彩色滤光片。这些滤色器的基材可以是玻璃或有机聚合物膜及陶瓷片。The composition of the present invention is used as a photoresist, and a black, red, green and blue three-color pattern is sequentially formed through coating, exposure, development, and heat treatment to obtain a complete color filter. The substrate of these color filters may be a glass or organic polymer film and a ceramic sheet.
本发明的内容还包括用上述组合物制造的彩色滤光片。The present invention also encompasses color filters made with the above compositions.
将组合物涂布于平板或曲面基材上，经烘干得到膜层；经掩膜曝光、显影方法除去未曝光部分得到凸起图像。包含黑色、红色、绿色、蓝色像素的彩色滤光片经由含有本发明的通式Ⅰ、Ⅱ、Ⅲ和Ⅳ的化合物、单体、碱溶性树脂及相应颜料、助剂构成的组合物的涂布、曝光、显影、热处理过程得到。其中也包含清洗等必要的处理过程。The composition is coated on a flat or curved substrate, and dried to obtain a film layer; the unexposed portion is removed by mask exposure and development to obtain a convex image. A color filter comprising black, red, green, and blue pixels is coated with a composition comprising a compound of the formula I, II, III, and IV of the present invention, a monomer, an alkali-soluble resin, and a corresponding pigment or auxiliary. Fabric, exposure, development, heat treatment process. It also includes the necessary processing such as cleaning.
使用本领域通常使用的涂布技术如旋涂、辊涂、喷涂、转印等方法将本发明组合物均匀涂覆于待涂基 材上，涂布量依所需确定，通常的厚度为0.1微米至1毫米。组合物含有溶剂组分时，用加热法例如80℃干燥法使溶剂挥发，而不挥发组分形成胶层留在基材上。The composition of the present invention is uniformly applied to the substrate to be coated by coating techniques commonly used in the art such as spin coating, roll coating, spray coating, transfer, and the like. The amount of coating is determined as desired, and the usual thickness is from 0.1 micron to 1 mm. When the composition contains a solvent component, the solvent is volatilized by a heating method such as drying at 80 ° C, and the non-volatile component forms a gel layer remaining on the substrate.
下一步是曝光，如果不是使用UV激光直接曝光，就将具有图像的掩膜置于胶层上，紫外或可见光光源发射一定范围波长的光线以设定能量穿过掩膜透光部分进行曝光，于是，胶层受光部分产生固化，被遮蔽部分不产生固化。The next step is exposure. If the UV laser is not used for direct exposure, the mask with the image is placed on the glue layer, and the ultraviolet or visible light source emits a range of wavelengths of light to set the energy through the transparent portion of the mask for exposure. Thus, the adhesive layer is cured by the light-receiving portion, and the shielded portion is not cured.
接下来是显影，除去未曝光部分得到凸起图案。显影工艺以本领域熟练技术人员公知的参数操作，例如30℃喷淋，漂洗。通常使用碱性水溶液显影，例如碱金属的氢氧化物、碳酸盐的水溶液，氨水，也可在必要时向水溶液中添加定量润湿剂如表面活性剂、有机溶剂如环己酮、丙酮、乙二醇***等。将曝光膜浸入显影液浴或将显影液喷雾到曝光膜上的显影方式都是可以的，具体的显影温度和时间视显影效果而定。用于显影的碱溶液是将碱性物质溶解于水或含有水溶性有机溶剂的水溶液中，其中碱性物质的例子有氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、三乙醇胺、吗啉、磷酸三钠，重量浓度范围0.1‐10％；上述水溶液还可以加入重量浓度0.05‐5％的表面活性剂。Next is development, removing the unexposed portions to obtain a raised pattern. The development process is operated with parameters well known to those skilled in the art, such as spraying at 30 ° C, rinsing. It is usually developed with an alkaline aqueous solution, such as an alkali metal hydroxide, an aqueous solution of a carbonate, ammonia water, or a quantitative wetting agent such as a surfactant, an organic solvent such as cyclohexanone or acetone may be added to the aqueous solution as necessary. Ethylene glycol ether and the like. The development method of immersing the exposure film in the developer bath or spraying the developer onto the exposure film is possible, and the specific development temperature and time depend on the development effect. The alkali solution for development is to dissolve an alkaline substance in water or an aqueous solution containing a water-soluble organic solvent, and examples of the alkaline substance are sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and carbonic acid. Potassium hydrogen, triethanolamine, morpholine, trisodium phosphate, the concentration range of 0.1-10%; the above aqueous solution can also add 0.05-5% by weight of surfactant.
最后的热处理过程能够优化图像牢度，一般是在200‐260℃热炉中烘烤15‐45分钟。The final heat treatment process optimizes image fastness and is typically baked in a hot oven at 200-260 ° C for 15 - 45 minutes.
基于此按照公知的彩色滤光片的生产工艺，使用本发明组合物可以制造出彩色滤光片器件，并显示出优良的加工性能，阵列清晰、光透过率高，用于生产高质量显示器。Based on the production process of the known color filter, the color filter device can be manufactured by using the composition of the present invention, and exhibits excellent processing performance, clear array, high light transmittance, and is used for producing a high quality display. .
具体实施方式detailed description
实施例能够更详细地说明本发明，涉及用量时都以重量计，特别指出的除外。The examples are illustrative of the invention in more detail, all in terms of amounts, unless otherwise indicated.
实施例1合成5-苯硫基茚满-1-酮Example 1 Synthesis of 5-phenylthioindan-1-one
Figure PCTCN2015077138-appb-000014
Figure PCTCN2015077138-appb-000014
称量33.3g(0.2mol)5-氯-1-茚酮在50ml三口瓶中，加入30mlN,N-二甲基甲酰胺(DMF)，30.0g(0.27mol)苯硫酚，36g无水碳酸钾，氮气保护，40-45℃搅拌6h；减压回收DMF，将剩余物加入到100ml水中，用25ml 1,2-二氯乙烷萃取两次，合并1,2-二氯乙烷溶液，用10ml水洗涤两次，在布氏漏斗中铺滤纸，用它抽滤有机相，滤液浓缩至干，剩余物用甲醇重结晶，干燥后得浅黄色结晶43.4g，收率90.3％，HPLC分析纯度98.2％。熔程46.0-48.0℃。Weigh 33.3g (0.2mol) of 5-chloro-1-indanone in a 50ml three-necked flask, add 30ml of N,N-dimethylformamide (DMF), 30.0g (0.27mol) of thiophenol, 36g of anhydrous carbonic acid Potassium, nitrogen protection, stirring at 40-45 ° C for 6 h; DMF was recovered under reduced pressure, the residue was added to 100 ml of water, extracted twice with 25 ml of 1,2-dichloroethane, and the solution of 1,2-dichloroethane was combined. Wash twice with 10 ml of water, filter the paper in a Buchner funnel, filter the organic phase with the filtrate, concentrate the filtrate to dryness, and recrystallize the residue with methanol to give 43.4 g of pale yellow crystals, yield 90.3%, HPLC analysis The purity is 98.2%. The melting range is 46.0-48.0 °C.
实施例2合成5-(4-辛酰基苯硫基)茚满-1-酮Example 2 Synthesis of 5-(4-octanoylphenylthio)indan-1-one
Figure PCTCN2015077138-appb-000015
Figure PCTCN2015077138-appb-000015
称取实施例1的产物5-苯硫基茚满-1-酮24.04g(0.1mol)溶于120ml1,2-二氯乙烷，降温到5-10℃，加入28g(0.21mol)无水三氯化铝，搅拌滴加17.9g(0.11mol)辛酰氯，加完后搅拌4h,用稀盐酸处理反应液，分离有机溶液，再水洗一次，浓缩回收1,2-二氯乙烷，将剩余物在100ml乙醇中重结晶，得到白色结晶33.1g，收率90.1％，熔程74.3-75.2℃，1H-NMR数据表明所得产物为5-(4-辛酰基苯硫基)茚满-1-酮；1H-NMR(CDCl3)，δ(ppm)值数据:0.8848(t,3H,CH3)，1.2892-1.3412(m,8H,4CH2)，1.7359(m,2H,CH2)，2.7066(t,2H,c-CH2)，2.9526(t,2H,CH2)，3.0961(t,2H,c-CH2)，7.2740/7.3008(d,1H,ArH)，7.3734(s,1H,ArH)，7.4525/7.4797(d,2H,2ArH)，7.6677/7.6945(d,1H,ArH)，7.9221/7.9493(d,2H,2ArH)。The product of Example 1 was weighed to give 5-phenylthioindan-1-one 24.04 g (0.1 mol) dissolved in 120 ml of 1,2-dichloroethane, cooled to 5-10 ° C, and added with 28 g (0.21 mol) of anhydrous Aluminum trichloride, 17.9g (0.11mol) of octanoyl chloride was added dropwise with stirring. After the addition, the mixture was stirred for 4 hours. The reaction solution was treated with dilute hydrochloric acid. The organic solution was separated, washed once, and concentrated to recover 1,2-dichloroethane. The residue was recrystallized from 100 ml of ethanol to give white crystals (33.1 g, yield: 90.1%, melting, 74.3-75.2 ° C, 1 H-NMR data indicated that the product was 5-(4-octanoylphenylthio)indole- 1-ketone; 1 H-NMR (CDCl 3 ), δ (ppm) value data: 0.8848 (t, 3H, CH 3 ), 1.2892-1.3412 (m, 8H, 4CH 2 ), 1.7359 (m, 2H, CH 2 ), 2.7066 (t, 2H, c-CH 2 ), 2.9526 (t, 2H, CH 2 ), 3.0961 (t, 2H, c-CH 2 ), 7.2740/7.3008 (d, 1H, ArH), 7.3734 (s) , 1H, ArH), 7.4525/7.4797 (d, 2H, 2ArH), 7.6677/7.6945 (d, 1H, ArH), 7.9221/7.9493 (d, 2H, 2ArH).
实施例3合成5-(4-辛酰基苯硫基)茚满-1,2-二酮-2-肟Example 3 Synthesis of 5-(4-octanoylphenylthio)indan-1,2-dione-2-indole
Figure PCTCN2015077138-appb-000016
Figure PCTCN2015077138-appb-000016
取实施例2所得产物5-(4-辛酰基苯硫基)茚满-1-酮18.4g(0.05mol)，用150ml乙醇溶解在250ml三口瓶中，再加36％浓盐酸2g，水浴15-20℃保温搅拌，15min内滴加6.2g(0.06mol)亚硝酸正丁酯，25℃搅拌5h后将反应液降温到5-10℃，过滤析出的黄色固体，干燥后18.7g，分析纯度98.90％，熔程162.7-164.0℃，1H-NMR数据表明所得产物为5-(4-辛酰基苯硫基)茚满-1,2-二酮-2-肟，收率94.2％；1H-NMR(CDCl3)，δ(ppm)值数据:0.8866(t,3H,CH3)，1.2965-1.3512(m,8H,4CH2)，1.7493(m,2H,CH2)，2.9737(t,2H,CH2)，3.7977(s,2H,c-CH2)，7.2674/7.2943(d,1H,ArH)，7.3320(s,1H,ArH)，7.5281/7.5558(d,2H,2ArH)，7.7707/7.7977(d,1H,2ArH)，7.9648/7.9925(d,2H,2ArH)，12.4460(s,1H,NOH)。Take the product obtained in Example 2, 5-(4-octanoylphenylthio)indan-1-one, 18.4 g (0.05 mol), dissolved in 250 ml of three-necked flask with 150 ml of ethanol, and added 36% concentrated hydrochloric acid 2 g, water bath 15 The mixture was stirred at -20 ° C, and 6.2 g (0.06 mol) of n-butyl nitrite was added dropwise in 15 min. After stirring at 25 ° C for 5 h, the reaction solution was cooled to 5-10 ° C, and the precipitated yellow solid was filtered, and 18.7 g after drying, the purity was analyzed. 98.90%, melting range 162.7-164.0 ℃, 1 H-NMR data show that the product obtained is 5- (4-octanoyl-phenylthio) -1,2-indan-2-oxime, 94.2% yield; 1 H-NMR (CDCl 3 ), δ (ppm) value data: 0.8866 (t, 3H, CH 3 ), 1.2965-1.3512 (m, 8H, 4CH 2 ), 1.7493 (m, 2H, CH 2 ), 2.9737 (t , 2H, CH 2), 3.7977 (s, 2H, c-CH 2), 7.2674 / 7.2943 (d, 1H, ArH), 7.3320 (s, 1H, ArH), 7.5281 / 7.5558 (d, 2H, 2ArH), 7.7707/7.7977 (d, 1H, 2ArH), 7.9648/7.9925 (d, 2H, 2ArH), 12.4460 (s, 1H, NOH).
实施例4合成二肟化物Example 4 Synthesis of Ditelluride
Figure PCTCN2015077138-appb-000017
Figure PCTCN2015077138-appb-000017
取实施例2所得产物5-(4-辛酰基苯硫基)茚满-1,2-二酮-2-肟7.95g(0.02mol)，用二甲基亚砜40ml溶解，加入36％浓盐酸0.5g，水浴20-25℃保温搅拌，15min内滴加3.1g(0.03mol)亚硝酸正丁酯，搅拌10h后将反应液降温到5-10℃，过滤析出的黄色固体，干燥后7.72g，分析纯度96.80％，收率90.5％；熔程171.0-173.0℃，1H-NMR数据表明所得产物为双肟化物。1H-NMR(DMSO-d6)，δ(ppm)值数据:0.850(t,3H,CH3)，1.272-1.492(m,8H,4CH2)，2.616(t,2H,CH2)，3.738(s,2H,c-CH2)，7.299/7.319(d,1H,ArH)，7.435(s,1H,ArH)，7.557/7.578(d,2H,2ArH)，7.719/7.739(d,1H,2ArH)，7.847/7.867(d,2H,2ArH)，12.446(s,1H,NOH)，12.651(s,1H,NOH)。The product obtained in Example 2 was obtained as 5-(4-octanoylphenylthio)indan-1,2-dione-2-indole 7.95 g (0.02 mol), dissolved in 40 ml of dimethyl sulfoxide, and added 36% thick. 0.5g hydrochloric acid, water bath 20-25 ° C heat stirring, adding 3.1g (0.03mol) n-butyl nitrite in 15min, stirring for 10h, the reaction liquid is cooled to 5-10 ° C, the precipitated yellow solid is filtered, after drying 7.72 g, analyzed for purity 96.80%, yield 90.5%; melting range 171.0-173.0 ℃, 1 H-NMR data show that the obtained product was bis oxime compound. 1 H-NMR (DMSO-d 6 ), δ (ppm) value data: 0.850 (t, 3H, CH 3 ), 1.272-1.492 (m, 8H, 4CH 2 ), 2.616 (t, 2H, CH 2 ), 3.738(s, 2H, c-CH 2 ), 7.299/7.319 (d, 1H, ArH), 7.435 (s, 1H, ArH), 7.557/7.578 (d, 2H, 2ArH), 7.719/7.739 (d, 1H) , 2ArH), 7.847/7.867 (d, 2H, 2ArH), 12.446 (s, 1H, NOH), 12.651 (s, 1H, NOH).
实施例5合成二肟酯ⅡA1 Example 5 Synthesis of Diterpene Ester IIA1
Figure PCTCN2015077138-appb-000018
Figure PCTCN2015077138-appb-000018
取实施例4产物4.27g(0.01mol)溶于25ml1,2-二氯乙烷，滴加3.1g(0.03mol)醋酐，20-25℃水浴中反应6h；反应液用25ml水洗涤两次，分出水相，有机相用1.5g无水硫酸钠干燥2h，过滤去除干燥剂，减压蒸干滤液；剩余物中加入15ml乙酸乙酯，加热至全溶，加入0.05g活性炭回流0.5h，热过滤分离活性炭，向滤液中加入15ml正己烷，冷却降温，析出结晶，抽滤，真空干燥滤饼得到黄色结晶产物4.47g，含量98.0％，收率87.8％；熔程和1H-NMR(CDCl3)，δ(ppm)值数据见表1。4.27 g (0.01 mol) of the product of Example 4 was dissolved in 25 ml of 1,2-dichloroethane, 3.1 g (0.03 mol) of acetic anhydride was added dropwise, and the reaction was carried out for 6 h in a water bath at 20-25 ° C; the reaction solution was washed twice with 25 ml of water. The aqueous phase was separated, and the organic phase was dried over 1.5 g of anhydrous sodium sulfate for 2h. The desiccant was removed by filtration, and the filtrate was evaporated to dryness under reduced pressure. 15 ml of ethyl acetate was added to the residue and heated to dissolve. The activated carbon was separated by hot filtration, 15 ml of n-hexane was added to the filtrate, cooled and cooled, crystals were precipitated, suction filtered, and the filter cake was vacuum dried to obtain a yellow crystalline product of 4.47 g, content: 98.0%, yield: 87.8%; melting range and 1 H-NMR ( CDCl 3 ), δ (ppm) value data are shown in Table 1.
实施例6合成5-(4-戊酰基苯硫基)茚满-1-酮Example 6 Synthesis of 5-(4-pentanoylphenylthio)indan-1-one
Figure PCTCN2015077138-appb-000019
Figure PCTCN2015077138-appb-000019
按实施例2的方法，用戊酰氯代替辛酰氯，得到5-(4-戊酰基苯硫基)茚满-1-酮，收率93.0％，熔程74.1-75.8℃，1H-NMR数据表明所得产物为5-[4-(3-环戊基丙酰基)苯硫基]茚满-1-酮；1H-NMR(CDCl3)，δ(ppm)值数据:0.9590(t,3H,CH3)，1.3533-1.4768(sextet,2H,CH2)，1.7274(quintet,2H,CH2)，2.7047(t,2H,c-CH2Ar)，2.9585(t,2H,CH2)，3.0961(t,2H,c-CH2CO)，7.2745/7.3030(d,1H,ArH)，7.3760(s,1H,ArH)，7.4513/7.4791(d,2H,2ArH)，7.6683/7.6952(d,1H,ArH)，7.9213/7.9490(d,2H,2ArH)。In the same manner as in Example 2, pentanoyl chloride was used instead of octanoyl chloride to obtain 5-(4-pentanoylphenylthio)indan-1-one, yield 93.0%, melting range 74.1-75.8 ° C, 1 H-NMR data. The product was found to be 5-[4-(3-cyclopentylpropanoyl)phenylthio]indan-1-one; 1 H-NMR (CDCl 3 ), δ (ppm) value data: 0.9590 (t, 3H) , CH 3), 1.3533-1.4768 (sextet , 2H, CH 2), 1.7274 (quintet, 2H, CH 2), 2.7047 (t, 2H, c-CH 2 Ar), 2.9585 (t, 2H, CH 2), 3.0961(t, 2H, c-CH 2 CO), 7.2745/7.3030 (d, 1H, ArH), 7.3760 (s, 1H, ArH), 7.4513/7.4791 (d, 2H, 2ArH), 7.6683/7.6952 (d, 1H, ArH), 7.9213/7.9490 (d, 2H, 2ArH).
实施例7合成5-(4-戊酰基苯硫基)茚满-1,2-二酮-2-肟Example 7 Synthesis of 5-(4-pentanoylphenylthio)indan-1,2-dione-2-indole
Figure PCTCN2015077138-appb-000020
Figure PCTCN2015077138-appb-000020
按照实施例3的肟化反应方法，以实施例6的产物为原料，用二甲基亚砜代替乙醇作为溶剂进行肟化反应，HPLC分析产生单肟化产物，不分离出单肟化产物。According to the deuteration reaction method of Example 3, the product of Example 6 was used as a raw material, and dimethylation reaction was carried out by using dimethyl sulfoxide instead of ethanol as a solvent, and HPLC analysis revealed that the mono-deuterated product was not isolated.
实施例8合成二肟化物Example 8 Synthesis of Ditelluride
Figure PCTCN2015077138-appb-000021
Figure PCTCN2015077138-appb-000021
在实施例7的反应液中继续滴加同样重量的亚硝酸正丁酯进行第二肟化反应，10h后按实施例4的方法处理得黄色固体，纯度96.50％，其中顺式异构体含量3.30％，反式异构体含量93.20％，收率85.0％；1H-NMR数据表明所得产物为双肟化物。1H-NMR(DMSO-d6)，δ(ppm)值数据:0.9073(t,3H,CH3)， 1.4514-1.5741(sextet,2H,CH2)，2.5879(t,2H,CH2)，3.7380(s,2H,c-CH2)，7.2916/7.3192(d,1H,ArH)，7.5172(s,1H,ArH)，7.5562/7.5836(d,2H,2ArH)，7.7166/7.7437(d,1H,ArH)，7.8505/7.8779(d,2H,2ArH)，12.4769(s,1H,NOH)，12.6651(s,1H,NOH)。In the reaction liquid of Example 7, the same weight of n-butyl nitrite was continuously added dropwise to carry out the second deuteration reaction, and after 10 h, the yellow solid was obtained by the method of Example 4, and the purity was 96.50%, wherein the cis isomer content. 3.30%, the trans isomer content was 93.20%, and the yield was 85.0%; 1 H-NMR data indicated that the obtained product was a double telluride. 1 H-NMR (DMSO-d 6 ), δ (ppm) value data: 0.9073 (t, 3H, CH 3 ), 1.4514-1.5741 (sextet, 2H, CH 2 ), 2.5879 (t, 2H, CH 2 ), 3.7380(s,2H,c-CH 2 ),7.2916/7.3192(d,1H,ArH),7.5172(s,1H,ArH),7.5562/7.5836(d,2H,2ArH),7.7166/7.7437(d,1H , ArH), 7.8505/7.8779 (d, 2H, 2ArH), 12.4769 (s, 1H, NOH), 12.6661 (s, 1H, NOH).
实施例9合成二肟酯ⅡA6Example 9 Synthesis of Diterpene Ester IIA6
Figure PCTCN2015077138-appb-000022
Figure PCTCN2015077138-appb-000022
按照实施例5的反应方法，以实施例8的产物为原料，进行酯化反应，经纯化处理得黄色固体，纯度98.65％，其中顺式异构体含量1.25％，反式异构体含量97.40％，收率60.3％；1H-NMR数据表明所得产物为ⅡA6；1H-NMR(CDCl3)，δ(ppm)值数据见表1According to the reaction method of Example 5, the product of Example 8 was used as a raw material, and the esterification reaction was carried out to obtain a yellow solid with a purity of 98.65%, wherein the cis isomer content was 1.25%, and the trans isomer content was 97.40. %, yield 60.3%; 1 H-NMR data showed that the obtained product was IIA6; 1 H-NMR (CDCl 3 ), δ (ppm) value data is shown in Table 1.
实施例10合成5-[4-(3-环戊丙酰基)苯硫基]茚满-1-酮Example 10 Synthesis of 5-[4-(3-cyclopentanoyl)phenylthio]indan-1-one
Figure PCTCN2015077138-appb-000023
Figure PCTCN2015077138-appb-000023
按实施例2的方法，用3-环戊基丙酰氯代替辛酰氯，得到5-[4-(3-环戊丙酰基)苯硫基]茚满-1-酮，收率92.0％，熔程88.5-90.0℃，1H-NMR数据表明所得产物为5-[4-(3-环戊基丙酰基)苯硫基]茚满-1-酮；1H-NMR(CDCl3)，δ(ppm)值数据:1.1072(m,2H,CH2)，1.5328-1.8691(m,9H,4CH2+1CH)，2.7067(t,2H,c-CH2)，2.9689(t,2H,CH2)，3.0974(t,2H,c-CH2)，7.278/7.3048(d,1H,ArH)，7.3766(s,1H,ArH)，7.4531/7.4803(d,2H,2ArH)，7.6695/7.7963(d,1H,2ArH)，7.9245/7.9517(d,2H,2ArH)。In the same manner as in Example 2, 3-cyclopentylpropionyl chloride was used instead of octanoyl chloride to obtain 5-[4-(3-cyclopentanoyl)phenylthio]indan-1-one in a yield of 92.0%. The procedure of 88.5-90.0 ° C, 1 H-NMR data indicated that the product obtained was 5-[4-(3-cyclopentylpropionyl)phenylthio]indan-1-one; 1 H-NMR (CDCl 3 ), δ (ppm) value data: 1.1072 (m, 2H, CH 2 ), 1.5328-1.8691 (m, 9H, 4CH 2 +1CH), 2.7067 (t, 2H, c-CH 2 ), 2.9689 (t, 2H, CH 2 ), 3.0974 (t, 2H, c-CH 2 ), 7.278 / 7.3048 (d, 1H, ArH), 7.3766 (s, 1H, ArH), 7.4531 / 7.4803 (d, 2H, 2ArH), 7.6695/7.7963 (d , 1H, 2ArH), 7.9245/7.9517 (d, 2H, 2ArH).
实施例11合成5-[4-(3-环戊基丙酰基)苯硫基]茚满-1,2-二酮-2-肟Example 11 Synthesis of 5-[4-(3-cyclopentylpropionyl)phenylthio]indan-1,2-dione-2-indole
Figure PCTCN2015077138-appb-000024
Figure PCTCN2015077138-appb-000024
按照实施例3的肟化反应方法，以实施例10的产物为原料，用亚硝酸异戊酯代替亚硝酸正丁酯进行肟化反应，析出黄色固体产物，烘干溶剂，纯度96％，1H-NMR数据表明所得产物为5-[4-(3-环戊基丙酰基)苯硫基]茚满-1,2-二酮-2-肟，收率95.5％；1H-NMR(DMSO-d6)，δ(ppm)值数据:1.1081(m,2H,CH2)，1.4795-1.7602(m,9H,4CH2)，3.0258(t,2H,CH2)，3.7342(s,2H,c-CH2)，7.3186/7.3451(d,1H,ArH)，7.5243(s,1H,ArH)，7.5667/7.5923(d,2H,2ArH)，7.7103/7.7370(d,1H,2ArH)，7.9987/8.0238(d,2H,2ArH)， 12.6685(s,1H,NOH)。Oximation according to the method of Example 3, to the product of Example 10 as starting material in place of isoamyl nitrite with n-butyl nitrite oximation reaction, the precipitated yellow solid, drying the solvent, a purity of 96%, 1 H-NMR data indicated that the obtained product was 5-[4-(3-cyclopentylpropanoyl)phenylthio]indane-1,2-dione-2-indole, yield 95.5%; 1 H-NMR ( DMSO-d 6 ), δ (ppm) value data: 1.1081 (m, 2H, CH 2 ), 1.4795-1.7602 (m, 9H, 4CH 2 ), 3.0258 (t, 2H, CH 2 ), 3.7342 (s, 2H , c-CH 2 ), 7.3186/7.3451 (d, 1H, ArH), 7.5243 (s, 1H, ArH), 7.5667/7.5923 (d, 2H, 2ArH), 7.7103/7.7370 (d, 1H, 2ArH), 7.9987 /8.0238 (d, 2H, 2ArH), 12.6685 (s, 1H, NOH).
实施例12合成二肟化物Example 12 Synthesis of Ditelluride
Figure PCTCN2015077138-appb-000025
Figure PCTCN2015077138-appb-000025
按照实施例4的反应方法，以实施例11的产物为原料，用亚硝酸异戊酯代替亚硝酸正丁酯进行第二肟化反应，经纯化处理得黄色固体，纯度95.50％，其中顺式异构体含量5.10％，反式异构体含量90.40％，收率88.3％；1H-NMR数据表明所得产物为双肟化物。1H-NMR(DMSO-d6)，δ(ppm)值数据:1.1766-1.6286(m,8H,4CH2)，2.1325(heptet,1H,CH)，2.6489/2.6739(d,2H,CH2)，3.7410(s,2H,c-CH2)，7.2981/7.3249(d,1H,ArH)，7.5258/7.5529(d,2H,2ArH)，7.5879(s,1H,ArH)，7.7188/7.7459(d,1H,2ArH)，7.8404/7.8680(d,2H,2ArH)，12.4514(s,1H,NOH)，12.6649(s,1H,NOH)。According to the reaction method of Example 4, the product of Example 11 was used as a raw material, and the second deuteration reaction was carried out by using isoamyl nitrite instead of n-butyl nitrite to obtain a yellow solid with a purity of 95.50%, wherein cis is isomer content of 5.10%, trans isomer content of 90.40%, yield 88.3%; 1 H-NMR data show that the obtained product was bis oxime compound. 1 H-NMR (DMSO-d 6 ), δ (ppm) value data: 1.1766-1.6286 (m, 8H, 4CH 2 ), 2.1325 (heptet, 1H, CH), 2.6489/2.6739 (d, 2H, CH 2 ) , 3.7410 (s, 2H, c-CH 2 ), 7.2981 / 7.3249 (d, 1H, ArH), 7.5258 / 7.5529 (d, 2H, 2ArH), 7.5879 (s, 1H, ArH), 7.7188 / 7.7459 (d, 1H, 2ArH), 7.8404/7.8680 (d, 2H, 2ArH), 12.4514 (s, 1H, NOH), 12.6649 (s, 1H, NOH).
实施例13合成二肟酯ⅡA3Example 13 Synthesis of Diterpene Ester IIA3
Figure PCTCN2015077138-appb-000026
Figure PCTCN2015077138-appb-000026
按照实施例5的反应方法，以实施例12的产物为原料，进行酯化反应，经纯化处理得黄色固体，纯度98.65％，其中顺式异构体含量1.50％，反式异构体含量97.15％，收率60.3％；1H-NMR数据表明所得产物为ⅡA3；1H-NMR(CDCl3)，δ(ppm)值数据见表1。According to the reaction method of Example 5, the product of Example 12 was used as a raw material, and the esterification reaction was carried out to obtain a yellow solid with a purity of 98.65%, wherein the cis isomer content was 1.50%, and the trans isomer content was 97.15. %, yield 60.3%; 1 H-NMR data indicated that the obtained product was IIA3; 1 H-NMR (CDCl 3 ), δ (ppm) value data is shown in Table 1.
表1实施例5,9,13所得化合物结构和数据Table 1 Structures and data of the compounds obtained in Examples 5, 9, and 13.
Figure PCTCN2015077138-appb-000027
Figure PCTCN2015077138-appb-000027
Figure PCTCN2015077138-appb-000028
Figure PCTCN2015077138-appb-000028
实施例14碱溶性树脂制备Example 14 Preparation of alkali soluble resin
将甲基丙烯酸苄酯180g、甲基丙烯酸60g、甲基丙烯酸羟乙酯60g、偶氮二异丁腈15g、十二硫醇6g与甲苯1000ml混匀并放入恒压滴液漏斗中；将1000ml甲苯放入三口烧瓶，安装搅拌、恒压滴液漏斗和温度计，开启搅拌，用氮气置换烧瓶中气体；加热烧瓶使溶剂温度达到80-85℃，保温，开始滴加单体混合溶液，约1h滴完；继续反应6h；自然冷却降温，停止搅拌，等树脂沉降后，吸取上部澄清溶液，过滤下部含溶剂的树脂，并用500ml甲苯淋洗树脂滤饼；减压烘干滤饼，得到白色粉末状固体树脂250g；将其用PMA(丙二醇甲醚醋酸酯)1000g溶解为20％溶液备用。180 g of benzyl methacrylate, 60 g of methacrylic acid, 60 g of hydroxyethyl methacrylate, 15 g of azobisisobutyronitrile, 6 g of dodecyl mercaptan and 1000 ml of toluene were mixed and placed in a constant pressure dropping funnel; 1000 ml of toluene was placed in a three-necked flask, and a stirring, constant-pressure dropping funnel and a thermometer were installed, stirring was started, and the gas in the flask was replaced with nitrogen; the flask was heated to a temperature of 80-85 ° C, and the mixture was kept warm, and the monomer mixed solution was started to be dropped. 1h drop; continue to react for 6h; cool down naturally, stop stirring, wait for the resin to settle, then absorb the upper clear solution, filter the lower solvent-containing resin, and rinse the resin cake with 500ml of toluene; dry the filter cake under vacuum to obtain white 250 g of a powdery solid resin; it was dissolved in a 20% solution with 1000 g of PMA (propylene glycol methyl ether acetate) for use.
实施例15光刻胶的制备及显影Example 15 Preparation and Development of Photoresist
按表2中配方15A、15B、15C(光引发剂为OXE01作为对照品)、15D(光引发剂为OXE02作为对照品)的重量配比将所有组分按油墨的制备方法制成光固化组合物，呈流动性液态。According to the weight ratio of formula 15A, 15B, 15C (photoinitiator is OXE01 as control) and 15D (photoinitiator is OXE02 as control) in Table 2, all components are made into photocurable combination according to the preparation method of ink. The substance is in a liquid liquid state.
应用线棒法将上述液态组合物涂布于玻璃表面，经80℃烘烤3分钟，将溶剂PMA挥发掉，测量剩余物胶膜厚度为2微米。 The above liquid composition was applied to the surface of the glass by a wire bar method, baked at 80 ° C for 3 minutes, and the solvent PMA was volatilized, and the thickness of the remaining film was measured to be 2 μm.
在膜上放置21阶灰梯度尺，用365nm光栅过滤器过滤2000W高压汞灯光线，膜与光栅距离10cm，使曝光量达到800mJ/cm2。A 21-step gray gradient ruler was placed on the film, and a 2000 W high-pressure mercury light line was filtered with a 365 nm grating filter, and the distance between the film and the grating was 10 cm, so that the exposure amount reached 800 mJ/cm 2 .
在30℃的1％碳酸钠溶液浴中浸泡1min，记录能够显示的最大留膜阶数，数字越大，所测量的组合物光感度越强，光刻胶的光固化率和成膜性能越高，结果列于表3。Soak for 1 min in a 1% sodium carbonate solution bath at 30 ° C, and record the maximum film retention order that can be displayed. The higher the number, the stronger the photo-sensitivity of the measured composition, and the more the photocuring rate and film-forming property of the photoresist High, the results are listed in Table 3.
表2组合物原料配比表Table 2 composition raw material ratio table
  15A15A 15B15B 15C15C 15D15D 来源source
实施例9光引发剂Example 9 Photoinitiator 1010       实施例9Example 9
实施例13光引发剂Example 13 Photoinitiator   1010     实施例13Example 13
OXE01OXE01     1010   市售品Commercial item
OXE02OXE02       1010 市售品Commercial item
碱溶性树脂溶液Alkali soluble resin solution 500500 500500 500500   实施例14Example 14
二季戊四醇六丙烯酸酯Dipentaerythritol hexaacrylate 100100 100100 100100   Cytec公司Cytec
表3显影结果Table 3 development results
  15A15A 15B15B 15C15C 15D15D
最大留膜阶数Maximum film retention order 1010 1111 66 66
表3中的显影结果显示，使用实施例9和实施例13的光引发剂配制的光固化组合物，其光感度显著优于使用OXE01和OXE02配制的光固化组合物，提高了光刻胶的光固化率和成膜性能。The development results in Table 3 show that the photocurable composition formulated using the photoinitiators of Example 9 and Example 13 has a light sensitivity significantly superior to that of the photocurable composition formulated using OXE01 and OXE02, improving the photoresist. Light curing rate and film forming properties.
实施例16光固化组合物凝胶转化率测试实验Example 16 Photocuring composition gel conversion rate test experiment
应用线棒法将上述实施例15表2中配方15A、15B、15C、15D的组合物涂布于玻璃表面，经80℃烘烤3min，将溶剂PMA挥发掉，测量剩余物胶膜厚度为2微米。The composition of the formulas 15A, 15B, 15C, and 15D in Table 2 of the above Example 15 was applied to the surface of the glass by a wire bar method, and baked at 80 ° C for 3 minutes to evaporate the solvent PMA, and the thickness of the remaining film was measured to be 2 Micron.
用365nm光栅过滤器过滤2000W高压汞灯光线，膜与光栅距离10cm，使曝光量分别达到200，400，600mJ/cm2。固化后用不锈钢网包裹样板，称量重量W1，丙酮浸泡72小时，烘干测量残余膜重量W2，W1/W2为凝胶转化率gel％，结果见表4。The 2000 W high-pressure mercury light line was filtered with a 365 nm grating filter, and the distance between the film and the grating was 10 cm, so that the exposure amount reached 200,400,600 mJ/cm 2 , respectively. After curing, the sample was wrapped with a stainless steel mesh, and the weight W 1 was weighed and soaked in acetone for 72 hours. The residual film weight W 2 was measured by drying, and W 1 /W 2 was gel conversion rate gel%. The results are shown in Table 4.
表4凝胶转化率测试结果Table 4 gel conversion rate test results
gel％Gel% 15A15A 15B15B 15C15C 15D15D
200mJ/cm2200mJ/cm2 92.892.8 93.993.9 78.278.2 75.775.7
400mJ/cm2400mJ/cm2 95.395.3 96.196.1 83.783.7 81.181.1
600mJ/cm2600mJ/cm2 96.596.5 97.297.2 85.985.9 84.084.0
由表4可以得出结论：在光刻胶配方中，实施例9和实施例13的光引发剂使双键聚合度更高，具有显著更高的活性。 From Table 4 it can be concluded that the photoinitiators of Examples 9 and 13 gave a higher degree of double bond polymerization and significantly higher activity in the photoresist formulation.
实施例17 LED光源固化光敏性组合物及固化效率测试实验Example 17 LED light source curing photosensitive composition and curing efficiency test experiment
将实施例15中光固化组合物15A、15B、15C、15D，用线棒法涂布于玻璃表面，经80℃烘烤3min，将溶剂PMA挥发掉，测量剩余物胶膜厚度为2微米，然后按照下面方法进行固化。The photocurable compositions 15A, 15B, 15C, and 15D of Example 15 were applied to the surface of the glass by a wire bar method, baked at 80 ° C for 3 minutes, and the solvent PMA was volatilized, and the thickness of the remaining film was measured to be 2 μm. Then, the curing was carried out in the following manner.
固化装置：LEDUV固化装置，型号：UV-101D(北京岩田博远科技股份有限公司)Curing device: LEDUV curing device, model: UV-101D (Beijing Iwata Boyuan Technology Co., Ltd.)
光源：UV-LED点光源，直径：10mm；波长：365nm，最大照度：40mw/cm2 Light source: UV-LED point source, diameter: 10mm; wavelength: 365nm, maximum illumination: 40mw/cm 2
固化条件：工作距离：21mm；照射时间：1sCuring conditions: working distance: 21mm; irradiation time: 1s
固化效率表征方法为：用点光源照射1s后，将整个玻璃片置于丙酮溶液中浸泡5s，取出后，测量固化膜图形直径，数值越大说明其感光度高，固化效率越高，表5为测量结果。从表5中的测量结果可以看出，以LED光源固化阻焊油墨或光刻胶用光敏性组合物时，本发明所提供的光敏组合物相对于现有的以OXE01、OXE02为光引发剂的组合物具有更高的光敏感度。The curing efficiency characterization method is as follows: after irradiating with a point light source for 1 s, the whole glass piece is immersed in acetone solution for 5 s, and after taking out, the cured film pattern diameter is measured. The larger the value, the higher the sensitivity and the higher the curing efficiency, Table 5 For the measurement results. It can be seen from the measurement results in Table 5 that when the photosensitive composition for the solder resist ink or the photoresist is cured by the LED light source, the photosensitive composition provided by the present invention is a photoinitiator with OXE01 and OXE02 as compared with the existing one. The composition has a higher light sensitivity.
表5显影结果Table 5 development results
光固化组合物Photocurable composition 15A15A 15B15B 15C15C 15D15D
直径mmDiameter mm 16.216.2 15.515.5 12.112.1 10.010.0
实施例18Example 18
印刷油墨配制和高压汞灯固化Printing ink formulation and high pressure mercury lamp curing
配方组成比例：环氧树脂丙烯酸酯预聚物(长兴化学621-100)50份，聚酯丙烯酸酯预聚物(长兴化学6311-10)10份，TPGDA(长兴化学EM223)30份，炭黑(Degussa公司P25)4份，光引发剂6份；混合研磨到细度2um以下，得到油墨样品18A-18D。用420目丝网印刷到铝板上，通过高压汞灯下固化，按实施例16方法测凝胶转化率gel％，表6为测量结果。从表6中的测量结果可以看出，经高压汞灯照射，本发明化合物产生的凝胶转化率显著高于对照化合物。Formula composition ratio: 50 parts of epoxy resin acrylate prepolymer (Changxing Chemical 621-100), 10 parts of polyester acrylate prepolymer (Changxing Chemical 6311-10), 30 parts of TPGDA (Changxing Chemical EM223), carbon black (Degussa P25) 4 parts, 6 parts of photoinitiator; mixed and ground to a fineness of 2 um or less to obtain ink samples 18A-18D. The gel conversion rate gel% was measured by the method of Example 16 using a 420 mesh screen printing onto an aluminum plate and solidified by a high pressure mercury lamp. Table 6 shows the measurement results. It can be seen from the measurement results in Table 6 that the gel conversion rate of the compound of the present invention produced by the high pressure mercury lamp was significantly higher than that of the control compound.
表6印刷油墨配方和高压汞灯固化结果Table 6 Printing ink formulation and high pressure mercury lamp curing results
油墨编号Ink number 18A18A 18B18B 18C18C 18D18D
光引发剂样品Photoinitiator sample 实施例5Example 5 实施例9Example 9 OXE01OXE01 OXE02OXE02
gel％Gel% 92.392.3 93.193.1 62.062.0 63.063.0
实施例19Example 19
印刷油墨配制和LED面光源固化Printing ink preparation and LED surface light source curing
配方组成比例：环氧树脂丙烯酸酯预聚物50份，聚酯丙烯酸酯预聚物10份，TPGDA 30份，黄3G(BASF公司)4份，光引发剂6份；混合研磨到细度2um以下得到油墨样品19A-19D，涂布到玻璃板上；用365nmLED面光源灯固化，曝光量86mJ/cm2。按实施例16方法测凝胶转化率gel％。测量结果见表7,从表7中的测量结果可以看出，经365nmLED光源照射，本发明化合物产生的凝胶转化率显著高于对照化合物。 Formulation ratio: 50 parts of epoxy acrylate prepolymer, 10 parts of polyester acrylate prepolymer, 30 parts of TPGDA, 4 parts of yellow 3G (BASF), 6 parts of photoinitiator; mixed grinding to fineness 2um Ink samples 19A-19D were obtained below, applied to a glass plate; cured with a 365 nm LED surface light lamp, with an exposure of 86 mJ/cm 2 . The gel conversion gel% was measured as in Example 16. The measurement results are shown in Table 7. From the measurement results in Table 7, it can be seen that the gel conversion rate of the compound of the present invention was significantly higher than that of the control compound by irradiation with a 365 nm LED light source.
表7印刷油墨配方和LED光源固化结果Table 7 Printing ink formulation and LED light source curing results
油墨编号Ink number 19A19A 19B19B 19C19C 19D19D
光引发剂样品Photoinitiator sample 实施例9Example 9 实施例13Example 13 OXE01OXE01 OXE02OXE02
gel％Gel% 91.591.5 92.192.1 80.080.0 81.581.5
实施例20Example 20
滤光膜用光阻油墨配制和曝光显影The filter film is prepared by photoresist and exposed to light
配方组成：碱溶性树脂溶液500份(实施例14)，二季戊四醇六丙烯酸酯(Cytec公司DPHA)100份，光引发剂100份，助引发剂BCIM(2,2’-二邻氯苯基-4,,4’,5,5’-四苯基联咪唑)20份，炭黑(Degussa公司P25)分散液500份(含炭黑20％)。按油墨制备方法研磨均匀，按其所用光引发剂不同，共有20A-20E五种油墨。Formulation composition: 500 parts of alkali-soluble resin solution (Example 14), 100 parts of dipentaerythritol hexaacrylate (Cytec DPHA), 100 parts of photoinitiator, co-initiator BCIM (2,2'-di-o-chlorophenyl- 4,4',5,5'-tetraphenylbiimidazole) 20 parts, carbon black (Degussa P25) dispersion 500 parts (containing carbon black 20%). According to the ink preparation method, the polishing is uniform, and according to the photoinitiator used, there are five kinds of inks of 20A-20E.
分别涂布，减压烘干，厚1um，覆以图案掩膜，用365nmLED面光源曝光，曝光量100mJ/cm2，用含1％氢氧化钠和2％丙酮的水溶液显影30S，用体视电子显微镜检测图案形态和牢度。形态和牢度观察评价：1曝光部分完整无脱落；2曝光部分无脱落有翘边；3曝光部分边缘不齐；4曝光部分不完整；5曝光部分已脱落。Coated separately, dried under reduced pressure, thick 1um, covered with a pattern mask, exposed with 365nm LED surface light source, exposure amount 100mJ/cm 2 , developed with 30% aqueous solution of 1% sodium hydroxide and 2% acetone, with stereoscopic The morphology and fastness of the pattern were examined by an electron microscope. Morphology and fastness observation and evaluation: 1 the exposed part is intact without falling off; 2 the exposed part has no peeling and curling; 3 the exposed part is not edged; 4 the exposed part is incomplete; 5 the exposed part has fallen off.
实验结果评价见表8，从表8的结果可以看出，含有本发明化合物的油墨曝光显影后图案边缘清晰整齐，牢固无脱落，本发明化合物性能表现显著优于对照化合物。The evaluation of the experimental results is shown in Table 8. From the results of Table 8, it can be seen that the ink containing the compound of the present invention has a clear and tidy pattern edge after exposure and development, and is firm and non-shedding, and the performance of the compound of the present invention is significantly better than that of the control compound.
表8黑色光阻油墨曝光评价Table 8 black photoresist ink exposure evaluation
油墨编号Ink number 20A20A 20B20B 20C20C 20D20D 20E20E
光引发剂样品Photoinitiator sample 实施例5Example 5 实施例9Example 9 实施例13Example 13 OXE01OXE01 OXE02OXE02
评价Evaluation 11 11 11 44 33
实施例21Example 21
滤光膜用光阻油墨配制和曝光显影The filter film is prepared by photoresist and exposed to light
配方组成：碱溶性树脂溶液500份(实施例14)，二季戊四醇六丙烯酸酯(Cytec公司)100份，光引发剂100份，红颜料L3920(BASF公司)100份。按油墨制备方法研磨均匀，得到21A-21E五种油墨。Formulation composition: 500 parts of an alkali-soluble resin solution (Example 14), 100 parts of dipentaerythritol hexaacrylate (Cytec), 100 parts of a photoinitiator, and 100 parts of a red pigment L3920 (BASF Corporation). It was uniformly ground according to the ink preparation method to obtain five inks of 21A-21E.
涂布，减压烘干，厚2um，覆以图案掩膜，用365nmLED面光源曝光，曝光量86mJ/cm2，用含1％氢氧化钠和2％丙酮的水溶液显影30S，用体视电子显微镜检测图案牢度和形态，评价方法同实施例20。实验结果评价见表9，从表9的结果可以看出，含有本发明化合物的油墨曝光显影后图案边缘清晰整齐，牢固无脱落，本发明化合物性能表现显著优于对照化合物。Coating, drying under reduced pressure, 2 μm thick, covered with a pattern mask, exposed with a 365 nm LED surface light source, exposure amount 86 mJ/cm 2 , developed with an aqueous solution containing 1% sodium hydroxide and 2% acetone for 30S, using stereoscopic electrons The pattern was examined for the film fastness and morphology, and the evaluation method was the same as in Example 20. The evaluation of the experimental results is shown in Table 9. From the results of Table 9, it can be seen that the ink containing the compound of the present invention has a clear and tidy edge after exposure and development, and is firm and non-shedding, and the performance of the compound of the present invention is significantly superior to that of the control compound.
表9红色光阻油墨曝光评价Table 9 red photoresist ink exposure evaluation
油墨编号Ink number 21A21A 21B21B 21C21C 21D21D 21E21E
光引发剂样品Photoinitiator sample 实施例5Example 5 实施例9Example 9 实施例13Example 13 OXE01OXE01 OXE02OXE02
评价Evaluation 11 11 11 33 33
实施例22Example 22
滤光膜用光阻油墨配制和曝光显影The filter film is prepared by photoresist and exposed to light
配方组成：碱溶性树脂溶液500份(实施例14)，二季戊四醇六丙烯酸酯(Cytec公司)100份，光引发剂10份，红颜料L3920(BASF公司)100份。按油墨制备方法研磨均匀，得到22A-22E五种油墨。Formulation composition: 500 parts of an alkali-soluble resin solution (Example 14), 100 parts of dipentaerythritol hexaacrylate (Cytec), 10 parts of a photoinitiator, and 100 parts of a red pigment L3920 (BASF Corporation). It was uniformly ground according to the ink preparation method to obtain five kinds of inks of 22A-22E.
涂布，减压烘干，厚2um，覆以图案掩膜，用365nmLED面光源曝光，曝光量86mJ/cm2，用含1％氢氧化钠和2％丙酮的水溶液显影30S，用体视电子显微镜检测图案牢度和形态，评价方法同实施例20。实验结果评价见表10，从表10的结果可以看出，含有本发明化合物的油墨曝光显影后图案边缘清晰整齐，牢固无脱落，本发明化合物性能表现显著优于对照化合物。Coating, drying under reduced pressure, 2 μm thick, covered with a pattern mask, exposed with a 365 nm LED surface light source, exposure amount 86 mJ/cm 2 , developed with an aqueous solution containing 1% sodium hydroxide and 2% acetone for 30S, using stereoscopic electrons The pattern was examined for the film fastness and morphology, and the evaluation method was the same as in Example 20. The evaluation of the experimental results is shown in Table 10. From the results of Table 10, it can be seen that the ink containing the compound of the present invention has a clear and tidy pattern edge after exposure and development, and is firm and non-shedding, and the performance of the compound of the present invention is remarkably superior to that of the control compound.
表10红色光阻油墨曝光评价Table 10 red photoresist ink exposure evaluation
油墨编号Ink number 22A22A 22B22B 22C22C 22D22D 22E22E
光引发剂样品Photoinitiator sample 实施例5Example 5 实施例9Example 9 实施例13Example 13 OXE01OXE01 OXE02OXE02
评价Evaluation 11 11 11 55 44

Claims (21)

  1. 通式Ⅰ化合物，a compound of formula I,
    Figure PCTCN2015077138-appb-100001
    Figure PCTCN2015077138-appb-100001
    其中among them
    Ar1为被X1取代的C6‐C20邻亚芳基或C3‐C20邻亚杂芳基，C6‐C20邻亚芳基或C3‐C20邻亚杂芳基以相邻的两个原子与Y1和羰基相连构成并环结构，其余原子上的取代基各自为氢原子，卤素原子，C1‐C12烷基，C5‐C7环烷基，C5‐C7环烷基取代的C1‐C4烷基，C1‐C12烷氧基，被一个或多个C1‐C12烷氧基、C1‐C4烷基苄氧基、R2C(O)O取代的C1‐C4烷氧基，苯基，任意被一个或多个C1‐C4烷基、羧基、C1‐C12烷基酰基、芳基酰基、杂芳基酰基、X3R17、苯基、卤素原子、CN取代的苯基，C1‐C4烷基苄氧基，C1‐C3亚烷基二氧基，R2C(O)O，C1‐C12烷基硫基，C1‐C4烷基苯硫基，CN，羧基，C1‐C12烷氧基羰基，芳基羰基，杂芳基羰基，X3R18，C1‐C4烷基苯氧基，C1‐C8烷基酰基苯氧基，C5‐C6环烷基酰基苯氧基，C5‐C6环烷基取代的C1‐C4烷基酰基苯氧基，芳基酰基苯氧基，杂芳基酰基苯氧基R2C(O)O取代的C1‐C4烷基硫基以及C1‐C4烷基苯硫基，C1‐C8烷基酰基苯硫基，C5‐C6环烷基酰基苯硫基或C5‐C6环烷基取代的C1‐C4烷基酰基苯硫基，芳基酰基苯硫基，杂芳基酰基苯硫基；或为环氧丙基，其中环氧基任意地与C1‐C4烷基醛、酮缩合，X3为O、S或NR22；Ar 1 is a C 6 -C 20 o-arylene or C 3 -C 20 o-heteroaryl group substituted by X 1 , a C 6 -C 20 o-arylene group or a C 3 -C 20 o-heteroarylene group Two adjacent atoms are bonded to Y 1 and a carbonyl group to form a ring structure, and the substituents on the remaining atoms are each a hydrogen atom, a halogen atom, a C 1 -C 12 alkyl group, a C 5 -C 7 cycloalkyl group, C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl, C 1 -C 12 alkoxy, by one or more C 1 -C 12 alkoxy, C 1 -C 4 alkylbenzyloxy, R 2 C(O)O substituted C 1 -C 4 alkoxy, phenyl, optionally substituted by one or more C 1 -C 4 alkyl, carboxy, C 1 -C 12 alkyl acyl, aryl acyl, Heteroaryl acyl, X 3 R 17 , phenyl, halogen atom, CN substituted phenyl, C 1 -C 4 alkylbenzyloxy, C 1 -C 3 alkylenedioxy, R 2 C(O O, C 1 -C 12 alkylthio, C 1 -C 4 alkylphenylthio, CN, carboxyl, C 1 -C 12 alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, X 3 R 18, C 1 -C 4 alkyl group, C 1 -C 8 alkyl phenoxy group, C 5 -C 6 cycloalkyl group a phenoxy group, C 5 -C 6 cycloalkyl substituted C 1 C 4 alkyl group a phenoxy group, an aryl group a phenoxy group, a phenoxy group heteroaryl group R 2 C (O) O-substituted C 1 -C 4 alkylthio and C 1 -C 4 alkyl a thio group, a C 1 -C 8 alkyl acyl phenylthio group, a C 5 -C 6 cycloalkyl phenyl phenylthio group or a C 5 -C 6 cycloalkyl group substituted C 1 -C 4 alkyl phenyl phenylthio group, An aryl acyl phenylthio group, a heteroaryl acyl phenyl thio group; or a glycidyl group in which an epoxy group is arbitrarily condensed with a C 1 -C 4 alkyl aldehyde, a ketone, and X 3 is O, S or NR 22 ;
    Ar2为C6‐C20亚芳基、C3‐C20亚杂芳基，通过X1与Ar1相连接，或通过X1与Ar1相连接同时，其取代基X1邻位的Ar2碳原子通过直键、碳原子、羰基、O、S、NR18再与Ar1相连接构成环状结构；Ar 2 is C 6 -C 20 arylene group, C 3 -C 20 heteroarylene group, and Ar 1 are connected via X 1, or both, the substituent ortho to X 1 X 1 1 is connected to Ar by Ar 2 carbon atoms and Ar 1 and then connected to form a ring structure with a direct bond, a carbon atom, a carbonyl group, O, S, NR 18;
    n为0或1；n is 0 or 1;
    X1为O、S、NR18，或Y2-Z1-Y2；X 1 is O, S, NR 18 , or Y 2 -Z 1 -Y 2 ;
    Y1为(CH2)mCR15R16、NR19、O(CR15R16)m、S(CR15R16)m、(CR15R16)mC＝O、S＝O；m为0或1；Y 1 is (CH 2 ) m CR 15 R 16 , NR 19 , O(CR 15 R 16 ) m , S(CR 15 R 16 ) m , (CR 15 R 16 ) m C=O, S=O; m Is 0 or 1;
    Z1为C1‐C10直链或支链亚烷基、被一个或多个氧、硫原子连在端基或***的C1‐C10直链或支链亚烷基、无取代基或有取代基的C6‐C20亚芳基；Z 1 is C 1 -C 10 straight or branched alkylene, substituted by one or more oxygen, sulfur atom or a group attached to the insertion end of the C 1 -C 10 straight chain or branched alkylene group, an unsubstituted group Or a substituted C 6 -C 20 arylene;
    Y2为O、S、NR18、O‐C(O)；R1为氢原子，C1‐C18烷基，任意被一个或多个C3‐C7环烷基、苯基、OR20、SR21、NR22R23取代的C1‐C18烷基，被C3‐C7亚环烷基、亚苯基、O、S、NR22***的C2‐C18烷基，C3‐C8环烷基，CN，NO2，苯基，以上苯基未被取代及任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代；Y 2 is O, S, NR 18 , O‐C(O); R 1 is a hydrogen atom, C 1 -C 18 alkyl, optionally substituted by one or more C 3 -C 7 cycloalkyl groups, phenyl, OR 20 , C 21 -C 18 alkyl substituted by SR 21 , NR 22 R 23 , C 2 -C 18 alkyl group inserted by C 3 -C 7 cycloalkylene, phenylene, O, S, NR 22 , C 3 -C 8 cycloalkyl, CN, NO 2 , phenyl, unsubstituted phenyl and optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, Heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy substituted;
    或R1为C1‐C12烷基酰基，C1‐C12烷氧基羰基，其中烷基任意被一个或两个以上卤素原子、C1‐C4烷基、C5或C6环烷基、苯基、CN、OH、X3R20取代，或其中烷基任意被一个或两个以上亚苯基、X3***；Or R 1 is C 1 -C 12 alkyl acyl, C 1 -C 12 alkoxycarbonyl, wherein the alkyl group is optionally substituted by one or two or more halogen atoms, C 1 -C 4 alkyl, C 5 or C 6 ring Alkenyl, phenyl, CN, OH, X 3 R 20 substituted, or wherein the alkyl group is optionally interrupted by one or more phenylene groups, X 3 ;
    或R1为苯甲酰基，苯氧基羰基，其中苯基未被取代，或任意被一个或两个以上卤素原子、C1‐C4烷基、 C5或C6环烷基、苯基、CN、OH、X2R20取代；Or R 1 is benzoyl, phenoxycarbonyl, wherein phenyl is unsubstituted, or optionally substituted by one or two or more halogen atoms, C 1 -C 4 alkyl, C 5 or C 6 cycloalkyl, phenyl , CN, OH, X 2 R 20 substitution;
    或R1为二苯基膦酰基，二(C1‐C4烷氧基)膦酰基；Or R 1 is diphenylphosphono, di(C 1 -C 4 alkoxy)phosphono;
    R2，R3各自独立地为氢原子，C1‐C18烷基或C1‐C18烷氧基；R 2 , R 3 are each independently a hydrogen atom, a C 1 -C 18 alkyl group or a C 1 -C 18 alkoxy group;
    或R2，R3各自独立地为C2‐C18烯基，任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代和/或被C5‐C7环亚烷基、亚苯基、O、S、NR17***C2‐C18烯基；Or R 2 , R 3 are each independently C 2 -C 18 alkenyl, optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, benzene Substituents, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy substituted and/or inserted into C 2 by C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 ‐C 18 alkenyl;
    或R2，R3各自独立地为任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代和/或被C5‐C7环亚烷基、亚苯基、O、S、NR17***的C2‐C18烷基；Or R 2 , R 3 are each independently optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy substituted and/or C 2 -C 18 alkyl inserted by C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 ;
    或R2，R3各自独立地为C5‐C7环烷基，任意被一个或多个C1‐C4烷基、苯基、卤素原子、CN取代的C5‐C7环烷基；Or R 2, R 3 are each independently a C 5 -C 7 cycloalkyl, optionally substituted with one or more C 1 -C 4 alkyl group, a phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl ;
    或R2，R3各自独立地为苯基，任意被一个或多个C1‐C4烷基、C1‐C4烷氧基、苯基、卤素原子、CN取代的苯基；Or R 2 , R 3 are each independently phenyl, phenyl optionally substituted by one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenyl, halogen atom, CN;
    或R2，R3各自独立地为萘基；Or R 2, R 3 are each independently a naphthyl group;
    或R2，R3各自独立地为苯甲酰基，苯氧基羰基，或其中苯基未被取代，或任意被一个或两个以上卤素原子、R17、C5或C6环烷基、CN、OH、XR17取代；Or R 2 , R 3 are each independently benzoyl, phenoxycarbonyl, or wherein phenyl is unsubstituted, or optionally substituted by one or more halogen atoms, R 17 , C 5 or C 6 cycloalkyl, CN, OH, XR 17 substituted;
    R15，R16各自独立地为氢原子，C1‐C18烷基，羧基取代或C1‐C4烷氧基酰基取代的C1‐C5烷基，R2C(O)O取代的C1‐C4烷基，任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代或被C5‐C7亚环烷基、亚苯基、O、S、NR17***的C2‐C18烷基，或R15，R16各自独立地为C5‐C7环烷基或任意被一个或多个C1‐C4烷基、苯基、卤素原子、CN取代的C5‐C7环烷基；R 15 and R 16 are each independently a hydrogen atom, a C 1 -C 18 alkyl group, a carboxy-substituted or C 1 -C 4 alkoxyacyl substituted C 1 -C 5 alkyl group, and R 2 C(O)O substituted C 1 -C 4 alkyl, optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 5 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy, or substituted C 5 -C 7 cycloalkylene, phenylene, O, S, NR 17 inserted into the C 2 -C 18 alkyl, or R 15, R 16 is independently substituted with one or more C 1 -C 4 alkyl is C 5 -C 7 cycloalkyl or optionally, a phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl;
    或R15，R16各自独立地为苯基，任意被一个或多个C1‐C4烷基、C1‐C4烷氧基、羧基、C1‐C12烷基酰基、C5‐C6环烷基甲酰基、C5‐C6环烷基取代的C2‐C4烷基酰基、苯甲酰基、XR17、苯基、卤素原子、CN取代的苯基；Or R 15 , R 16 are each independently phenyl, optionally substituted by one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, C 1 -C 12 alkyl acyl, C 5 - C 6 cycloalkyl formyl, C 5 -C 6 cycloalkyl substituted C 2 -C 4 alkyl acyl group, benzoyl group, XR 17 , phenyl group, halogen atom, CN substituted phenyl group;
    或上述R15，R16与其共同所连的碳原子或硅原子一起构成环状且成环的原子数为4‐7，或上述R15，R16分别与相邻的取代基一起构成环状且成环的原子数为4‐7；Atoms or said R 15, R 16 together with its attached carbon atom or a silicon atom and together form a cyclic ring of 4-7, or said R 15, R 16, respectively adjacent substituents together constitute a cyclic And the number of atoms in the ring is 4-7;
    R17为C1‐C4烷基；R 17 is C 1 -C 4 alkyl;
    R18，R19各自独立地为氢原子，C1‐C18烷基，C1‐C4烷氧基酰基取代的C1‐C5烷基，R2C(O)O取代的C1‐C4烷基，任意被一个或多个卤素原子、C1‐C4烷基、C3‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代的C1‐C18烷基，被任意被一个或多个C3‐C7亚环烷基、亚苯基、O、S、NR17***的C2‐C18烷基；R 18 and R 19 are each independently a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 4 alkoxyacyl substituted C 1 -C 5 alkyl group, and a R 2 C(O)O substituted C 1 -C 4 alkyl, optionally substituted by one or more halogen atoms, C 1 -C 4 alkyl, C 3 -C 7 cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, C 1 -C 4 alkanoyloxy, aroyloxy, C 1 -C 18 substituted alkyl, is optionally substituted with one or more C 3 -C 7 cycloalkylene, phenylene, O, S, NR 17 C inserted 2 -C 18 alkyl;
    或R18，R19各自独立地为C5‐C7环烷基，或任意被一个或多个C1‐C4烷基、苯基、卤素原子、CN取代的C5‐C7环烷基； Or R 18, R 19 are each independently substituted with one or more C 1 -C 4 alkyl is 5 -C 7 cycloalkyl, or optionally C, a phenyl group, a halogen atom, CN substituted C 5 -C 7 cycloalkyl base;
    或R18，R19各自独立地为苯基，任意被一个或多个C1‐C4烷基、羧基、C1‐C12烷基酰基、C5‐C6环烷基甲酰基、C5‐C6环烷基取代的C2‐C4烷基酰基、芳基酰基、XR17、苯基、卤素原子、CN取代的苯基；Or R 18 , R 19 are each independently phenyl, optionally substituted by one or more C 1 -C 4 alkyl, carboxy, C 1 -C 12 alkyl acyl, C 5 -C 6 cycloalkyl formyl, C 5- C 6 cycloalkyl substituted C 2 -C 4 alkyl acyl, aryl acyl, XR 17 , phenyl, halogen atom, CN substituted phenyl;
    或上述R18通过直键、碳原子、羰基与Ar1或Ar2中的芳环相连构成新的环；Or the above R 18 is bonded to an aromatic ring in Ar 1 or Ar 2 through a straight bond, a carbon atom or a carbonyl group to form a new ring;
    或上述R19通过直键、碳原子、羰基与Ar1中的芳环相连构成新的环；Or the above R 19 is bonded to an aromatic ring in Ar 1 through a straight bond, a carbon atom or a carbonyl group to form a new ring;
    R20，R21，R22，R23各自独立地为氢原子，C1‐C18烷基，被卤素、CN、C1‐C4烷氧基取代的C1‐C18烷基，被一个或多个氧原子、C5‐C7亚环烷基、亚苯基***的C2‐C18烷基，被苯基、C3‐C7环烷基取代的C1‐C3烷基，C3‐C7环烷基；R 20 , R 21 , R 22 and R 23 are each independently a hydrogen atom, a C 1 -C 18 alkyl group, a C 1 -C 18 alkyl group substituted by a halogen, CN, a C 1 -C 4 alkoxy group, One or more oxygen atoms, a C 5 -C 7 cycloalkylene group, a C 2 -C 18 alkyl group in which a phenylene group is inserted, a C 1 -C 3 alkane substituted by a phenyl group, a C 3 -C 7 cycloalkyl group Base, C 3 -C 7 cycloalkyl;
    或R20，R21，R22，R23各自独立地为苯基，萘基，苯甲酰基，其中苯基、萘基未被取代，或各自任意地被卤素、C1‐C4烷基、C1‐C4烷氧基、C1‐C4烷基硫基、苯氧基、苯硫基、NR24R25、C1‐C12烷基酰基、苯甲酰基取代；Or R 20 , R 21 , R 22 , R 23 are each independently phenyl, naphthyl, benzoyl, wherein phenyl, naphthyl is unsubstituted, or each is optionally halogen, C 1 -C 4 alkyl , C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, phenoxy, phenylthio, NR 24 R 25 , C 1 -C 12 alkyl acyl, benzoyl substituted;
    R24，R25各自为C1‐C4烷基；或NR24R25一起为吗啉，哌啶，哌嗪，N‐甲基哌嗪，吡咯。R 24 and R 25 are each a C 1 -C 4 alkyl group; or NR 24 R 25 together are morpholine, piperidine, piperazine, N-methylpiperazine, pyrrole.
  2. 根据权利要求1的通式Ⅰ化合物，其更具体的结构式如通式Ⅱ、ⅢA或ⅢB所示，A compound of formula I according to claim 1 having a more specific structural formula as shown in formula II, IIIA or IIIB,
    Figure PCTCN2015077138-appb-100002
    Figure PCTCN2015077138-appb-100002
    Figure PCTCN2015077138-appb-100003
    Figure PCTCN2015077138-appb-100003
    其中among them
    R4，R5，R6，R7，R8，R9，R10，R11，R12，R13，R14各自独立地为氢原子，卤素原子，C1-C12烷基，C5-C7环烷基，C5-C7环烷基取代的C1-C4烷基，C1-C12烷氧基，苯基，任意被一个或多个C1-C4烷基、羧基、C1-C12烷基酰基、芳基酰基、杂芳基酰基、X3R17、苯基、卤素原子、CN取代的苯基，C1-C4烷基苄氧基，被一个或多个C1-C12烷氧基、C1-C4烷基苄氧基、R2C(O)O取代的C1-C4烷氧基，R2C(O)O，CN，羧基，C1-C12烷氧基羰基，芳基羰基，杂芳基羰基，X3R18；R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are each independently a hydrogen atom, a halogen atom, a C 1 -C 12 alkyl group, C 5 -C 7 cycloalkyl, C 5 -C 7 cycloalkyl substituted C 1 -C 4 alkyl, C 1 -C 12 alkoxy, phenyl, optionally substituted by one or more C 1 -C 4 Alkyl, carboxyl, C 1 -C 12 alkyl acyl, aryl acyl, heteroaryl acyl, X 3 R 17 , phenyl, halogen atom, CN substituted phenyl, C 1 -C 4 alkylbenzyloxy , by one or more C 1 -C 12 alkoxy, C 1 -C 4 alkylbenzyl group, R 2 C (O) O-substituted C 1 -C 4 alkoxy, R 2 C (O) O, CN, carboxyl, C 1 -C 12 alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, X 3 R 18 ;
    或R4，R5，R6，R7，R8，R9，R10，R11，R12，R13，R14各自独立地为C1-C4烷基苯氧基，C1-C4烷基苯硫基，C1-C8烷基酰基苯氧基，芳基酰基苯氧基，杂芳基酰基苯氧基，C5-C6环烷基酰基苯氧基，C5-C6环烷基取代的C1-C4烷基酰基苯氧基，C1-C3亚烷基二氧基，C1-C12烷基硫基，R2C(O)O取代的C1-C4烷基硫基以及C1-C4烷基苯硫基，C1-C8烷基酰基苯硫基，芳基酰基苯硫基，杂芳基酰基苯硫基，C5-C6环烷基酰基苯硫基或C5-C6环烷基取代的C1-C4烷基酰基苯硫基；Or R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are each independently C 1 -C 4 alkylphenoxy, C 1 -C 4 alkylphenylthio, C 1 -C 8 alkyl acyl phenoxy, aryl acyl phenoxy, heteroaryl acyl phenoxy, C 5 -C 6 cycloalkyl acyl phenoxy, C 5- C 6 cycloalkyl substituted C 1 -C 4 alkyl acyl phenoxy, C 1 -C 3 alkylenedioxy, C 1 -C 12 alkylthio, R 2 C(O)O Substituted C 1 -C 4 alkylthio and C 1 -C 4 alkylthio, C 1 -C 8 alkyl phenyl phenylthio, aryl acyl phenylthio, heteroaryl acyl phenylthio, a C 5 -C 6 cycloalkyl phenyl phenylthio group or a C 5 -C 6 cycloalkyl substituted C 1 -C 4 alkyl acyl phenylthio group;
    或R4，R5，R6，R7，R8，R9，R10，R11，R12，R13，R14各自独立地为环氧丙基，其中环氧基任意地与C1‐C4烷基醛、酮缩合；Or R 4, R 5, R 6 , R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14 are each independently a glycidyl group, wherein the epoxy groups and optionally C 1 -C 4 alkyl aldehyde, ketone condensation;
    X1为O，S或NR18；X 1 is O, S or NR 18 ;
    X2为O、S、NR19，X 2 is O, S, NR 19 ,
    Y1为O，S，CR15R16；Y 1 is O, S, CR 15 R 16 ;
    其他取代基定义同权利要求1。Other substituents are defined as in claim 1.
  3. 根据权利要求2的通式Ⅰ化合物，其中通式Ⅱ化合物中，A compound of formula I according to claim 2, wherein in the compound of formula II,
    R4，R5，R6，R7，R8，R9，R10均为氢原子；R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each a hydrogen atom;
    X1为O或S；X 1 is O or S;
    Y1为CH2、CHCH3或C(CH3)2； Y 1 is CH 2 , CHCH 3 or C(CH 3 ) 2 ;
    n＝1；n=1;
    R1为C1‐C12烷基，任意被一个或多个C3‐C7环烷基、苯基、OR20、SR21、NR22R23取代的C1‐C12烷基；R 1 is C 1 -C 12 alkyl, optionally substituted with one or more C 3 -C 7 cycloalkyl, phenyl, OR 20, SR 21, NR 22 R 23 substituted C 1 -C 12 alkyl;
    R2，R3各自独立地为甲基，乙基，苯基，2‐甲基苯基，3‐甲基苯基，2,4,6‐三甲基苯基或2,6‐二甲氧基苯基；R 2 and R 3 are each independently methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylphenyl or 2,6-dimethyl Oxyphenyl group;
    其他基团定义同权利要求2中所述。Other group definitions are as described in claim 2.
  4. 根据权利要求2的通式Ⅰ化合物，其中通式ⅢA和ⅢB化合物中，A compound of the formula I according to claim 2, wherein among the compounds of the formulae IIIA and IIIB,
    X2为NR19；X 2 is NR 19 ;
    Y1为O，S，CR15R16；Y 1 is O, S, CR 15 R 16 ;
    R11，R12，R13，R14各自独立地为氢原子，卤素原子，C1‐C4烷基，C1‐C4烷氧基，C1‐C4烷基苄氧基，C1‐C4烷基硫基，C1‐C4烷基苯氧基，C1‐C4烷基苯硫基；R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, a C 1 -C 4 alkylbenzyloxy group, C 1 -C 4 alkylthio, C 1 -C 4 alkylphenoxy, C 1 -C 4 alkylphenylthio;
    其他取代基定义同权利要求2。Other substituents are defined in accordance with claim 2.
  5. 根据权利要求4的通式Ⅰ化合物，其中，A compound of the formula I according to claim 4, wherein
    Y1为CH2或CHCH3；Y 1 is CH 2 or CHCH 3 ;
    n＝0；n=0;
    R1为C1‐C12烷基，任意被一个C3‐C7环烷基、苯基、OR20、SR21、NR22R23取代的C1‐C12烷基；R 1 is C 1 -C 12 alkyl, a C 3 -C 7 cycloalkyl optionally substituted alkyl, phenyl, OR 20, SR 21, NR 22 R 23 substituted C 1 -C 12 alkyl;
    R2，R3各自独立地为甲基，乙基，苯基，2‐甲基苯基，3‐甲基苯基，2,4,6‐三甲基苯基或2,6‐二甲氧基苯基；R 2 and R 3 are each independently methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylphenyl or 2,6-dimethyl Oxyphenyl group;
    R11，R12，R13，R14各自独立地为氢原子，C1‐C4烷氧基；R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a C 1 -C 4 alkoxy group;
    R19为C1‐C12烷基，被C3‐C7环烷基、苯基取代的C1‐C3烷基；R 19 is C 1 -C 12 alkyl, C 1 -C 3 alkyl substituted by C 3 -C 7 cycloalkyl, phenyl;
    其他基团定义同权利要求4中所述。Other group definitions are as described in claim 4.
  6. 根据权利要求1的通式Ⅰ化合物，其具体结构为A compound of the formula I according to claim 1 which has a specific structure
    Figure PCTCN2015077138-appb-100004
    Figure PCTCN2015077138-appb-100004
    Figure PCTCN2015077138-appb-100005
    Figure PCTCN2015077138-appb-100005
  7. 一种权利要求1所述通式Ⅰ化合物的制造方法，包含以下步骤：A method of making a compound of formula I according to claim 1 comprising the steps of:
    (1)第一步：在Ⅳ化合物中环戊酮羰基的邻位亚甲基上进行选择性肟化，方法是Ⅳ化合物与亚硝酸烷基酯在酸性溶液中发生肟化反应，得到对应的中间体Ⅴ；(1) The first step: selective deuteration on the ortho-methylene group of the cyclopentanone carbonyl group in the IV compound by the oximation reaction of the IV compound with the alkyl nitrite in an acidic solution to obtain a corresponding intermediate Body V;
    Figure PCTCN2015077138-appb-100006
    Figure PCTCN2015077138-appb-100006
    (2)第二步：将中间体Ⅴ化合物继续进行第二步肟化，方法A是Ⅴ化合物与亚硝酸烷基酯在酸性溶液中 发生肟化反应，得到对应的中间体Ⅵ化合物；方法B是Ⅴ化合物在羟胺溶液中发生侧链R1CH2CO中羰基的肟化反应，得到对应的中间体Ⅶ化合物；(2) The second step: the intermediate V compound is further subjected to the second step of deuteration, and the method A is a deuteration reaction of the V compound with the alkyl nitrite in an acidic solution to obtain a corresponding intermediate VI compound; Is a quinone formation reaction of a carbonyl group in a side chain R 1 CH 2 CO in a hydroxylamine solution to obtain a corresponding intermediate VII compound;
    Figure PCTCN2015077138-appb-100007
    Figure PCTCN2015077138-appb-100007
    (3)第三步：将上述第二步肟化中间体Ⅵ或Ⅶ与下列酰化试剂(3) Step 3: The above second step of deuteration of intermediate VI or VII with the following acylating reagent
    Figure PCTCN2015077138-appb-100008
    Figure PCTCN2015077138-appb-100008
    或其等价酰化试剂发生酯化反应得到对应的通式Ⅰ化合物，上述所有结构式中基团定义同权利要求1中相应基团定义。Or an esterification reaction of an equivalent acylating reagent thereof to give a corresponding compound of the formula I, wherein the group definitions in all of the above formulae are as defined in the corresponding group in claim 1.
  8. 一种不对称二酮化合物，如通式Ⅳ所示，An asymmetric diketone compound, as shown in Formula IV,
    Figure PCTCN2015077138-appb-100009
    Figure PCTCN2015077138-appb-100009
    其中among them
    基团Ar1，Ar2，X1，Y1，R1的定义如权利要求1中相应基团定义。The definition of the groups Ar 1 , Ar 2 , X 1 , Y 1 , R 1 is as defined in the corresponding group in claim 1.
  9. 一种酮肟化合物，如通式Ⅴ所示，a ketoxime compound, as shown in Formula V,
    Figure PCTCN2015077138-appb-100010
    Figure PCTCN2015077138-appb-100010
    其中among them
    基团Ar1，Ar2，X1，Y1，R1的定义如权利要求8中相应基团定义。The definition of the groups Ar 1 , Ar 2 , X 1 , Y 1 , R 1 is as defined in the corresponding group in claim 8.
  10. 一种二酮肟化合物，如通式Ⅵ或Ⅶ所示，a diketone oxime compound, as shown in Formula VI or VII,
    Figure PCTCN2015077138-appb-100011
    Figure PCTCN2015077138-appb-100011
    Figure PCTCN2015077138-appb-100012
    Figure PCTCN2015077138-appb-100012
    其中among them
    基团Ar1，Ar2，X1，Y1，R1的定义如权利要求9中相应基团定义。The definition of the groups Ar 1 , Ar 2 , X 1 , Y 1 , R 1 is as defined in the corresponding group in claim 9.
  11. 一种光固化组合物，含有光引发剂和至少一种可进行自由基聚合的碳碳双键化合物，该光引发剂包含至少一种权利要求1中通式Ⅰ的化合物。A photocurable composition comprising a photoinitiator and at least one carbon-carbon double bond compound capable of undergoing free radical polymerization, the photoinitiator comprising at least one compound of the formula I according to claim 1.
  12. 根据权利要求11的光固化组合物，进一步含有添加剂。The photocurable composition according to claim 11, further comprising an additive.
  13. 根据权利要求12的光固化组合物，以重量计，该光引发剂占全部组合物的0.05-25％，该碳碳双键化合物及该添加剂占除上述组分外的剩余百分比。The photocurable composition according to claim 12, wherein the photoinitiator accounts for 0.05 to 25% by weight of the total composition, and the carbon-carbon double bond compound and the additive account for the remaining percentage other than the above components.
  14. 根据权利要求11或12的光固化组合物，其中该碳碳双键化合物选自于丙烯酸酯化合物及甲基丙烯酸酯化合物。The photocurable composition according to claim 11 or 12, wherein the carbon-carbon double bond compound is selected from the group consisting of an acrylate compound and a methacrylate compound.
  15. 根据权利要求12的光固化组合物，其中该添加剂包括可显影树脂，颜料或染料。The photocurable composition according to claim 12, wherein the additive comprises a developable resin, a pigment or a dye.
  16. 一种光固化组合物的应用，即先将权利要求11或12所述的任一光固化组合物用于制造带有颜色的或透明的下列制品之一：涂料、油墨、粘合剂、光致抗蚀剂及光阻剂；再将该制品用于印刷、3D打印、显示器件中彩色滤光片的生产、电子器件封装、印刷电路板介质层。The use of a photocurable composition for the first use of any of the photocurable compositions of claim 11 or 12 for the manufacture of one of the following colored or transparent articles: coatings, inks, adhesives, photo-resistance Etchant and photoresist; the article is then used in printing, 3D printing, color filter production in display devices, electronic device packaging, printed circuit board dielectric layers.
  17. 一种光固化组合物的固化方法，是将权利要求11或12所述的光固化组合物涂布于基材上，用波长为190-600nm的光线照射使涂布层固化。A method of curing a photocurable composition by applying the photocurable composition according to claim 11 or 12 to a substrate, and curing the coating layer by irradiation with light having a wavelength of from 190 to 600 nm.
  18. 根据权利要求17所述的光固化组合物的固化方法，该光线来自太阳，汞灯，高压汞灯或LED灯。A method of curing a photocurable composition according to claim 17, which is derived from a sun, a mercury lamp, a high pressure mercury lamp or an LED lamp.
  19. 一种以光固化组合物制作凸起图案的方法，先将权利要求11或12所述的任一光固化组合物用溶剂稀释；后将稀释后的该光固化组合物涂布于基材上，经烘干、曝光、显影方法除去未曝光部分得到凸起图案。A method for preparing a convex pattern by using a photocurable composition, which first dilutes any photocurable composition according to claim 11 or 12 with a solvent; and then applies the diluted photocurable composition to a substrate. The drying, exposure, and development methods remove the unexposed portions to obtain a raised pattern.
  20. 一种彩色滤光片，包含黑色、红色、绿色、蓝色像素，由包含至少一种权利要求1或6中通式Ⅰ化合物、光固化单体、碱溶性树脂及颜料及添加剂构成的组合物依序经过涂布、曝光、显影、热处理过程而得到。A color filter comprising black, red, green, blue pixels, a composition comprising at least one compound of the formula I according to claim 1 or 6, a photocurable monomer, an alkali soluble resin, and a pigment and an additive It is obtained by coating, exposure, development and heat treatment in sequence.
  21. 一种彩色滤光片的制造方法，该彩色滤光片包含黑色、红色、绿色、蓝色像素，该制造方法是将含有至少一种权利要求1或6中通式Ⅰ化合物、光固化单体、碱溶性树脂及颜料及添加剂构成的组合物依序进行涂布、曝光、显影、热处理，最后得到该彩色滤光片的过程。 A method of manufacturing a color filter comprising black, red, green, and blue pixels, the method of manufacture comprising containing at least one compound of the formula I in claim 1 or 6 and a photocurable monomer The composition of the alkali-soluble resin, the pigment, and the additive is sequentially coated, exposed, developed, and heat-treated, and finally the color filter is obtained.
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