WO2015027833A1

WO2015027833A1 - Cyclopentadione oxime ester and application thereof

Info

Publication number: WO2015027833A1
Application number: PCT/CN2014/084541
Authority: WO
Inventors: 赵文超; 麻忠利; 王辰龙; 胡伟静; 姚丽秀; 王永林
Original assignee: 北京英力科技发展有限公司
Priority date: 2013-09-02
Filing date: 2014-08-15
Publication date: 2015-03-05
Also published as: CN105694582A; JP6328642B2; CN103998422B; CN105694582B; KR20160096233A; KR101985054B1; WO2015027702A1; JP2016500710A; CN103998422A; TWI617539B; TW201509888A

Abstract

The present invention relates to compounds represented by general formulas I, IIa, lib and III and preparation method therefor. Ar1 is substituted o-arylene or o-heteroarylene; Ar2 is bis(o-arylene) or bis(o-heteroarylene) connected in various ways; X is O, S or NR19; Y1 is O, S, NR20, BR20, CR15R16, SiR15R16, S=O or C=O; Z1 is a axial bond, C1-C10 alkylene or arylene; R1, R15, R16, R18, R19 or R20 is respectively hydrogen atom, alkyl or alkoxy, alkyl or alkoxy substituted with any group, cycloalkyl, aryl substituted with any group or acyl. The present invention also relates to a photocurable composition containing compounds represented by general formulas I, IIa, lIb and III as photoinitiator. The composition presents very excellent comprehensive performance when used for preparing photoresist elements such as a color filter for display screen.

Description

Cyclopentanone oxime ester and its application

The present invention relates to an oxime ester compound characterized by an esterified derivative of an arylene-cyclopentanedione oxime having an esterified fluorenyl group in the 2-position which has utility as a photoinitiator in a photocurable composition.

Background technique

The oxime ester compound has been discovered as a photoinitiator. The oxime ester compound is disclosed as a photoinitiator in both of the patents 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 of OXE01 and OXE02 are marketed for sale 304.

In addition to this, there are many other patents for oxime ester photoinitiators, such as: WO2006018973, WO2007071497, CN1805955B, CN1922142B, CN1928715A, CN101508744B, CN 102020727, but they are all on the side of the 3, 6, and 9 positions of carbazole. Various modifications are made to the chain, some have an increased molecular weight, and there is no improvement in the photo-curing efficiency of the photo-sensing property, and it is often difficult to manufacture. For example, the substituted carbazole-heterocyclic diketone ester described in the CN102046667B patent is very difficult to manufacture.

In the patent JP201133793 of Fujifilm Co., Ltd., a class of oxime esters is disclosed, and the structural formula is as follows:

After the synthesis and performance evaluation of such compounds, it was found that such compounds have low photocuring efficiency as a photoinitiator and are difficult to be used as an industrial photoresist photoinitiator. Summary of the invention

The purpose of the application is to provide a novel oxime ester photoinitiator product with high photocuring efficiency, good solubility in formulation, and suitable for industrial manufacture, and a preparation and application method thereof to meet the market demand for high-end oxime ester photoinitiation. The urgent need for agents.

Surprisingly, it has been found that the following series of compounds of the formulae I, II a, li b and III have very excellent photocuring efficiency, and the resulting photocurable composition has excellent image clarity.

Li b)

(III)

Series 1 : Compounds of the formula I, II a, li b and III, of which

A _ri is an ortho-arylene or an ortho-heteroaryl group, and an ortho-arylene or an ortho-heteroaryl group is bonded to a carbonyl group by two adjacent atoms to form a ring structure, and the atoms other than the R ₁₈ X substituent The substituents are each independently a hydrogen atom, a halogen atom, a dC ₁₂ alkyl group, a C ₅ -C ₇ cycloalkyl group, a dC ₄ alkyl group substituted by a C ₅ -C ₇ cycloalkyl group, a phenyl group, optionally Or a plurality of dC ₄ alkyl, carboxy, dC ₁₂ alkyl acyl or arylcarbonyl, heteroarylcarbonyl, XR ₁₇ , phenyl, halogen atom, CN substituted phenyl, dC ₄ alkylbenzyloxy, F^qO D substituted dC ₄ alkoxy, d-alkylenedioxy, [^[(0)0, d-Cualkylthio, d-Ci alkylphenylthio,! ^: (0) 0 substituted d-Ci alkylthio, CN, carboxyl, (^-(: ₁₂ alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, XR _18; Or an adjacent substituent of the above substituents of An or between the substituents and 4 (" ₁ is connected by a straight bond, a carbon atom, a carbonyl group to form a cyclic structure;

X is 0, S or NR ₁₉ ;

a straight bond, a d-do straight or branched alkylene group, attached to a terminal group or an inserted C ₂ -C _1Q straight or branched alkylene group by one or more oxygen or sulfur atoms, without a substituent or a subaromatic group having a substituent;

丫 is a straight key, 0, S, NR ₂ . , BR ₂ . , CRisRis, SiRisRis, C=0 or Y ₃ -Z ₂ -Y ₃ ;

Z ₂ is dd. A linear or branched alkylene group, bonded to one or more oxygen atoms, a sulfur atom to a terminal group or an inserted C ₂ -d. a linear or branched alkylene group having no substituent or a substituted subaromatic group;

Y ₃ is 0, S, NR ₂ . , BR ₂ . Or OC(O);

Is a hydrogen atom, Crds alkyl or (^-(; ₁₈ alkoxy, optionally substituted by one or more d-alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, dC ₄ alkoxy, dC ₄ alkylthio, aryloxy, arylthio, dC ₄ alkanoyloxy, aroyloxy substituted dC ₁₈ fluorenyl;

Or ^ is optionally substituted by one or more dC ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, dC ₄ alkanoyloxy, aroyloxy and / or C ₂ -C ₁₈ alkyl group inserted by C ₅ -C ₇ cycloalkylene, phenylene, 0, S, NR ₁₇ ; dC ₄ alkanoyloxy, aroyloxy substituted and/or C _5- C ₇ cycloalkylene, phenylene, 0, S, NR ₁₇ inserted C ₂ -C ₁₈ alkyl;

Or ^ is C ₂ -C ₁₈ alkenyl, optionally substituted by one or more halogen atoms, CrC ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, d- Alkanoyloxy, aroyloxy substituted and/or inserted into C ₂ -C ₁₈ alkenyl by C ₅ -C ₇ cycloalkylene, phenylene, 0, S, NR ₁₇ ; or ^C ₅ -C _{a 7} cycloalkyl group, optionally a C ₅ -C ₇ cycloalkyl group substituted by one or more dC ₄ alkyl groups, a phenyl group, a halogen atom, a CN; or a phenyl group, optionally substituted by one or more dC ₄ alkyl groups , dC ₄ alkoxy, phenyl, halogen atom, CN substituted phenyl; or ^ is naphthyl; or ^ is benzoyl, phenoxycarbonyl, wherein phenyl is optionally substituted by one or two halogen atoms, Substituted with R ₁₇ , C ₅ or C ₆ cycloalkyl, CN, 0H, XR ₁₇ ;

Ru, R ₁₂ are each independently a hydrogen atom, a halogen atom, a d-Cu alkyl group, a C ₅ -C ₇ cycloalkyl group, a C ₅ -C ₇ cycloalkyl-substituted d-alkyl group, (^-(: ₁₂₎ Alkoxy, dC ₄ alkylbenzyloxy, phenyl, optionally substituted by one or more dC ₄ alkyl, carboxy, dC ₁₂ alkyl acyl or arylcarbonyl, heteroarylcarbonyl, XR ₁₇ , phenyl , a halogen atom, CN substituted phenyl, dC ₄ alkylbenzyl group, substituted with one or more dC ₁₂ alkoxy, benzyloxy dc ₄ alkyl, F ^ qc ^ o dc _{4-substituted} alkoxy, F^qc^o, CN, carboxy, dc ₁₂ alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, XR ₁₈ , or phenoxy substituted by one or more dC ₄ alkyl groups, by a dC ₈ Alkyl acyl, C ₅ -C ₆ cycloalkyl acyl, arylcarbonyl, heteroarylcarbonyl substituted phenoxy, C ₅ -C ₆ cycloalkyl substituted dC ₄ alkyl acyl phenoxy, dC ₃ alkylenedioxy group, Dc ₁₂ alkylthio, F^qc o substituted d-alkylthio and d-alkylphenylthio, by a d-Cs alkyl acyl, c ₅ -c _s cycloalkyl acyl, aryl An acyl, heteroaryl formyl substituted phenylthio group, a c ₅ -c ₆ cycloalkyl substituted dC ₄ alkyl acyl phenylthio group, or an epoxy propyl group, wherein the epoxy group is optionally bonded to a dC ₄ alkyl group Aldehyde, ketone condensation;

Or the above Ru and R _{12 are} connected to form a saturated or unsaturated cyclic structure;

R ₁₅ and R ₁₆ are each independently a hydrogen atom, a d-ds alkyl group, a carboxyl group-substituted or a d-alkoxyacyl-substituted d-Cs alkyl group, and a F^qc^O-substituted dC ₄ alkyl group, optionally Or a plurality of halogen atoms, dC ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, CrC ₄ alkanoyloxy, aroyloxy substituted or by C ₅ -C ₇ cycloalkylene, phenylene, 0, S, NR ₁₇ inserted C ₂ -C ₁₈ alkyl; or R ₁₅ , R ₁₆ are each independently C ₅ -C ₇ cycloalkyl or optionally Or a plurality of dC ₄ alkyl, phenyl, halogen atom, CN substituted C ₅ -C ₇ cycloalkyl; or R ₁₅ , R ₁₆ are each independently phenyl, optionally substituted by one or more d-alkyl groups, D-alkoxy, carboxy, d-Cualkyl acyl, C ₅ -C ₆ cycloalkyl formyl, C ₅ -C ₆ cycloalkyl substituted C ₂ -C ₄ alkyl acyl, aryl formyl, XR ₁₇ , a phenyl group, a halogen atom, a CN-substituted phenyl group; or the above R ₁₅ , R ₁₆ together with a carbon atom or a silicon atom to which they are bonded form a cyclic group and a ring-constituting atomic number of 4 to 7, or the above R _15, R ₁₆ constitute together with the adjacent substituents Shape and number of atoms in the ring is 4-7;

R ₁₇ is a d-alkyl group;

R ₁₈ is a hydrogen atom, d-ds alkyl, d-alkoxyacyl substituted CrC ₅ alkyl, ^[(0)0 substituted d-alkyl, optionally substituted by one or more halogen atoms, dC ₄ alkane , C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, dC ₄ alkanoyloxy, aroyloxy substituted or C ₅ -C ₇ cycloalkylene, sub a C ₂ -C ₁₈ alkyl group in which phenyl, 0, S, NR _{17 is} inserted; or R ₁₈ is a C ₅ -C ₇ cycloalkyl group, or optionally substituted by one or more dC ₄ alkyl groups, a phenyl group, a halogen atom, CN substituted C ₅ -C ₇ cycloalkyl; or R ₁₈ is phenyl, optionally substituted by one or more (^-(: ₁₂ alkyl, carboxy, dC ₁₂ alkyl acyl, C ₅ -C ₆ cycloalkyl Formyl, aryl acyl, heteroaryl acyl, XR ₁₇ , phenyl, halogen atom, CN or N0 ₂ substituted phenyl, optionally C ₂ -C ₄ alkane substituted with C ₅ -C ₆ cycloalkyl a acyl substituted phenyl group, optionally substituted by a C ₂ -C ₁₂ alkyl acyl group having a phenylene group, 0, S or NR ₁₇ ;

Or R ₁₈ is dC ₄ alkyl acyl group, dC ₄ conjugated enoyl group, benzoyl group, phenoxycarbonyl group, wherein phenyl group is optionally substituted by one or two or more halogen atoms, Ri ₇ , C ₅ or C ₆ cycloalkyl group , CN, 0H, XR ₁₇ replaced;

Or R ₁₈ is a new ring formed by a straight bond, a carbon atom, a carbonyl group and 4 (" ₁ or 4 (" ₂ aromatic rings);

Rig, R ₂ . Each independently is a hydrogen atom, a d-ds alkyl group, a d-alkyloxy group-substituted d-Cs alkyl group, a ^((0)0 substituted d-alkyl group, optionally substituted with one or more halogen atoms, d - alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, d-alkanoyloxy, aroyloxy substituted or C ₅ -C ₇ cycloalkylene a C ₂ -C ₁₈ alkyl group in which phenylene, 0, S, and NR _{17 are} inserted;

Or ₉ , R ₂ . Are each independently a C ₅ -C ₇ cycloalkyl, or optionally substituted with one or more dC ₄ alkyl group, a phenyl group, a halogen atom, CN C ₅ -C ₇ cycloalkyl;

Or ₉ , each independently a phenyl group, optionally substituted by one or more dC ₄ alkyl groups, a carboxyl group, a dC ₁₂ alkyl acyl group, a C ₅ -C ₆ cycloalkyl formyl group, a C ₅ -C ₆ cycloalkyl group C ₂ -C ₄ alkyl acyl, aryl acyl, XR ₁₇ , phenyl, halogen atom, CN substituted phenyl;

Or R ₁₉ above is formed by a straight bond, a carbon atom, a carbonyl group and 4 (" ₁ or 4 (" ₂ aromatic rings are connected to form a new ring; And when At^ is a substituted carbazole group, it is not (;, 0, S, NR _{20 )} .

Series 2: Compounds of the general formula I, II a, li b and III, wherein 1" ₁ is

Ru, R ₁₂ and R ₁₃ are each independently a hydrogen atom, a halogen atom, a d-Cu alkyl group, a C ₅ -C ₇ cycloalkyl group, a C ₅ -C ₇ cycloalkyl-substituted d-alkyl group, (^- (: ₁₂ alkoxy, substituted with one or more of (^ - (: ₁₂ alkoxy, benzyloxy dc ₄ alkyl, F ^ qc ^ o dc ₄ alkoxy substituted phenyl, optionally substituted with one or a plurality of dC ₄ alkyl, carboxy, dC ₁₂ alkyl acyl or arylcarbonyl, heteroarylcarbonyl, XR ₁₇ , phenyl, halogen atom or CN substituted phenyl, d-alkylbenzyloxy, (0) 0 [(0) 0-substituted d- alkylthio, CN, carboxy, dd j oxycarbonyl, arylcarbonyl, heteroarylcarbonyl group, XR _18, with one or more alkyl groups dC ₄ Substituted phenoxy, phenoxy substituted by a dC ₈ alkyl acyl group, c ₅ -c ₆ cycloalkyl acyl group, aryl acyl group, heteroaryl acyl group, C ₅ -C ₆ cycloalkyl substituted dC ₄ Alkyl acyl phenoxy, dC ₃ alkylenedioxy, d-Cu alkylthio, ^qc o substituted d-alkylthio and d-alkylphenylthio, by a d-Cs alkane acyl, C ₅ -C ₆ cycloalkyl, acyl, aryl, formyl, aryl, heteroaryl formyl taken Phenylthio, or C ₅ -C ₆ cycloalkyl substituted phenylthio dC ₄ alkyl group;

Or Ru, R12, R ₁₃ are each independently a propylene group, wherein the epoxy group is arbitrarily condensed with a d-alkyl aldehyde or a ketone;

Or the adjacent two of the above R _U -R ₁₃ are connected to form a saturated or unsaturated cyclic structure;

X is 0, S or NR ₁₉ ;

Y ₂ is 0, S, NR ₂₀ or Y ₃ -Z ₂ -Y ₃ ;

Ζ ₂ is dd. A linear or branched alkylene group attached to a terminal group or an inserted C ₂ -d by one or more oxygen or sulfur atoms. a linear or branched alkylene group, an unsubstituted or substituted arylene group;

Y ₃ is 0, S, NR ₂ . Or 0-C(0);

^ is ^-^alkyl, c ₅ -c ₇ cycloalkyl, c ₅ -c ₇ cycloalkyl substituted c ₂ -c ₆ alkyl, c ₂ -c ₄ alkenyl, or ^phenyl or any a phenyl group substituted with one or more dc ₄ alkyl groups, dC ₄ alkoxy group, benzoyl group;

R ₁₅ and R ₁₆ are each independently a hydrogen atom, a d-Cu alkyl group, a carboxyl group-substituted d-Cs alkyl group, ^[(0)0 substituted d-alkyl group, or ₅ , and Ris are each a C ₅ - C ₇ cycloalkyl, or R ₁₅ , R ₁₆ are each independently phenyl or optionally substituted by one or more dC ₄ alkyl, dC ₄ alkoxy, carboxy, dC ₁₂ alkyl acyl, C ₅ -C ₆ ring An alkyl formyl group, a C ₅ -C ₆ cycloalkyl substituted dC ₄ alkyl acyl group or a benzoyl substituted phenyl group; or the above R ₁₅ , R ₁₆ together with the carbon atom or silicon atom to which they are attached And the number of atoms in the ring is 4-7; Or R ₁₅ and R ₁₆ described above together with adjacent substituents form a cyclic ring and the number of atoms formed is 4-7;

R ₁₇ is a d-alkyl group;

R ₁₈ is a Crds alkyl group, a dC ₄ alkoxyacyl substituted dC ₅ alkyl group, ^[(0)0 substituted dC ₄ alkyl group, optionally substituted by one or more halogen atoms, d-alkyl group, C ₅ - C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, d-alkanoyloxy, aroyloxy substituted C ₂ -C ₁₈ alkyl, C ₅ -C ₇ cycloalkylene a C ₂ -C ₁₈ alkyl group in which phenylene, 0, S, and NR _{17 are} inserted;

Or R ₁₈ is C ₅ -C ₇ cycloalkyl, optionally substituted by one or more d-alkyl, phenyl, halogen atom, CN substituted C ₅ -C ₇ cycloalkyl; or R ₁₈ is phenyl, optionally C ₂ -C ₄ alkyl acyl substituted by one or more dC ₁₂ alkyl, carboxy, dC ₁₂ alkyl acyl, C ₅ -C ₆ cycloalkyl formyl, C ₅ -C ₆ cycloalkyl, aryl An acyl group, a heteroaryl acyl group, an XR ₁₇ group, a phenyl group, a halogen atom, a CN or a NO ₂ substituted phenyl group, optionally substituted by a C ₂ -C ₁₂ alkyl group having a phenylene group, 0, S or NR ₁₇ inserted Phenyl group;

Or R ₁₈ is dC ₄ alkyl acyl group, dC ₄ conjugated enoyl group, benzoyl group, phenoxycarbonyl group, wherein phenyl group is optionally substituted by one or two or more halogen atoms, Ri ₇ , C ₅ or C ₆ cycloalkyl group , CN, OH, XR ₁₇ replaced;

Rig, R ₂ . Each independently is a hydrogen atom, a d-ds alkyl group, a d-alkyloxy group-substituted d-Cs alkyl group, a ^((0)0 substituted d-alkyl group, optionally substituted with one or more halogen atoms, d - alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, d-alkanoyloxy, aroyloxy substituted or C ₅ -C ₇ cycloalkylene , phenylene, 0, S, NR ₁₇ inserted C ₂ -C ₁₈ alkyl, or C ₅ -C ₇ cycloalkyl, or any one or more dC ₄ alkyl, phenyl, halogen atom , CN substituted C ₅ -C ₇ cycloalkyl, or phenyl and optionally by one or more dC ₄ alkyl, carboxy, dC ₁₂ alkyl acyl, C ₅ -C ₆ cycloalkyl formyl, C ₅ a -C ₆ cycloalkyl substituted C ₂ -C ₄ alkyl acyl group, an aryl acyl group, XR ₁₇ , a phenyl group, a halogen atom, a CN substituted phenyl group.

Series 3: Compounds of the general formula I, II a, li b and III, wherein 1" ₁ is

Ru, R ₁₂ and R ₁₃ are each independently a hydrogen atom, a dC ₄ alkoxy group substituted by one or more CrC ₁₂ alkoxy groups, d-alkylbenzyloxy group, ^[(0)0, by one or a plurality of dC ₄ alkyl substituted phenoxy groups, a phenoxy group substituted by a dC ₈ alkyl acyl group, an aryl carbonyl group, a heteroaryl formyl group, a C ₅ -C ₆ cycloalkyl group, C ₅ -C ₆ cycloalkyl substituted dC ₄ alkyl acyl phenoxy, dC ₃ alkylenedioxy, Ρϊ (0) 0, dc ₁₂ alkylthio, F^qc o substituted d-alkylthio, D-alkylphenylthio, F^qc o substituted d-alkylphenylthio, by a CrC ₈ alkyl acyl group, arylformyl group, heteroaryl formyl group, C ₅ -C ₆ cycloalkyl group Substituted phenylthio, or C ₅ -C ₆ cycloalkyl substituted d-alkyl acyl phenylthio;

Yi is CH ₂ , CHCH ₃ or C(CH ₃ ) ₂ ;

丄 is a direct bond or 1,3-phenylene;

Is methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylphenyl or 2,6-dimethoxyphenyl; wherein R ₂ o is a CrCs sulfhydryl group. Other groups in the formulae I, IIa, IIb, III and IV define the group definitions of the corresponding compounds in series 2.

Series 4: Compounds of the formula I, II a, lib and III, wherein in the substituent of A _ri , R ₁₈ X is in the para position to the carbonyl group attached to A _ri ; in Ar ₂ , the 0 atom or the N atom is attached to the benzene ring The alignment of the carbonyl group. Each group in the formulae I, IIa, IIb, III and IV defines the group definition of the corresponding compound in series 3.

Representative structures in the compounds of formulae I, IIa, lib and III in -4:

( ID1) ( I D2) ( I D3)

(IIIB)

The present invention also provides a process for the preparation of the compounds of the formulae I, II a, li b and III of the series 1-5, comprising the steps of:

(1) First step: Selective deuteration on the carbonyl ortho-methylene group of V or Via, VIb compound (where An, Y!, Ar ₂ has the same definition as previously described). The alkylation of an alkyl nitrate in an acidic alcohol solution gives one of the corresponding intermediate VII or Via, VIb compounds respectively (when the oxime group has a cis-trans stereo chirality, a single chiral VII or Villa is obtained. , VIb compounds or mixtures of the respective isomers);

ο ο

c II _ ο一c II Or the intermediate Villa, VIb compound with the following acylating reagents

O O 0

Rj— C II — O— C II — Rj — C II — CI

Or an equivalent acylating reagent is esterified to obtain a corresponding compound of the general formula II a, li b;

When the intermediate VII or Villa, Vlllb compound has a stereo chirality, a single chiral compound of the formula I, III, IV or II a, li b or a mixture of the respective isomers is obtained, respectively, and the definition of Some descriptions are the same.

The present invention also relates to 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 of the above formulas I, II a, li b and Compound of III.

The photoinitiator further comprises, in addition to any one of the compounds of the formulae I, II a, li b and III, or a combination of any two or more of the compounds, other commercially available photoinitiators as co-initiator components.

The photocurable composition further contains an additive such as a developable resin, a pigment, an antifoaming agent, and the like.

The photoinitiator comprises from 0.05 to 25%, preferably from 2 to 15% by weight of the total of the cured composition, of the above-mentioned photocurable composition; the remaining components account for the remaining percentage other than the above components.

Component (b) A carbon-carbon double bond compound which is capable of undergoing radical polymerization, and 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, 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.

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 is obtained, which can be used for formulating a photoresist or for formulating a water-dispersed emulsion.

In addition to the above-mentioned compounds of the formulae I, II a, li b and III as photoinitiators, other types of commercially available photoinitiators or co-initiators may be compounded as co-initiator components depending on the needs of the composition ( c), usually α-hydroxyketones such as 2-hydroxy-2-methyl-1-propiophenone, 1-hydroxycyclohexylbenzophenone; α-aminoketones such as 2-methyl-2-morpholinyl -(4-methylthiobenzene)-1-propanone, 2-dimethylamino-2-benzyl-(4-morpholinophenyl)-1-butanone; 2,2-diethoxy -1,2-diacetophenone; methyl benzoylformate, diethylene glycol dibenzoylformic acid, ester polybutylene glycol bisbenzoylformate; (2,4,6-trimethyl Benzoyl) diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; Benzene and its substituted derivatives such as benzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, 2'-chloro-4-phenyl Benzophenone, 4-methylthiobenzophenone, 4-(2-hydroxyethylthio)benzophenone, 4-hydroxybenzophenone laurate benzophenone-4-oxyacetic acid Ethylene glycol ester; thioxanthone and its substituted derivatives such as 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 1-chloro-4-propoxy thioxanthone , thioxanthone-2-carboxylic acid polyethylene glycol ester, thioxanthone-2-oxyacetic acid polyethylene glycol ester; halogenated methyl triazine such as 2-(4-methoxyphenyl)-4 , 6-bis(trichloromethyl)-[1,3,5]-triazine; hexaaryldiimidazoles such as hexa-chlorophenyldiimidazole; ferrocene compounds; ferrocene compounds; Soybean; camphor; acridine such as 9-phenyl acridine; amines such as 4,4'-bis(diethylamino)benzophenone, ethyl 4-dimethylaminobenzoate, triethanolamine, a methyl diethanolamine or a reactive amine compound such as diethylamine and an ethoxylated trimethylolpropane triacrylate adduct; a phosphite such as triphenyl phosphite, Trilauryl phosphite; chain transfer agents such as hexanedithiol, octyl mercaptan.

Component (d) includes pigments, dyes, and pigments, which are essential components for printing inks and preparation filters. They can be red, green, blue, black, white, yellow, magenta, cyan, and other specific specialties 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. Their amount is limited to the properties of the composition and is not specifically required.

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 the group consisting of 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 , polyester, polyimide, and other conventional resins. 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.

The photocurable composition may further comprise 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.

At least one compound having an epoxy group may also be added as a thermosetting component (0 and an epoxy group curing accelerator (g) in the photocurable composition. A compound having an epoxy group as a thermosetting component (0) A well-known thermosetting epoxy compound such as an aliphatic epoxy resin or an aromatic epoxy resin may be used, preferably a bisphenol S type epoxy resin such as BPS-200 produced by Nippon Chemical Co., Ltd., bisphenol A type epoxy resin, linear type A phenolic epoxy resin or the like and a part of their esterified product, the component (0 is used in an amount of 30 to 70 parts by weight relative to 100 parts by weight of the component (b).

When the component (0 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. Dosage, do not exceed the composition (5% by weight of 5%.

In addition to the above components (a), (b), (c), (d), (e), (f), (g), other additives commonly used in the art can be used in the composition (h). They include: one of the additives for improving the adhesion and film forming hardness of the composition, such as barium sulfate, powdered silica, talc, calcium carbonate, mica powder, etc., in an amount of the total composition Within 30% of the weight; The photocurable composition may also be used according to the needs of the application field or diluted with a solvent. Suitable solvents are: ketones such as methyl ethyl ketone, cyclohexanone; hydrocarbons such as toluene, xylene, octane Alkanes, petroleum ethers, naphtha; 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 Methyl methoxypropionate or the like; amides such as hydrazine, hydrazine-dimethylformamide.

The photocurable composition or the solvent-diluted mixture thereof is prepared in the form of an ink production method and stored in the dark.

The use of a photocurable composition is for the manufacture of one of the following products, colored or transparent: coatings, adhesives or inks, photoresists and photoresists, which are then used for printing, 3D printing , production of color filters in display devices, image reproduction technology, printed circuit board dielectric layers, electronic device packaging, optical switches, three-dimensional molds, quartz fiber protective layers, 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. Including 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 and 410 nm, such as a 365 nm LED light source. Coating layer. The LED is defined as a light emitting semiconductor diode.

The photocurable composition is formed by applying a photocurable composition containing a solvent onto a substrate, and removing the unexposed portion by drying, exposure, and development to obtain a raised pattern.

The composition containing at least one compound of the formula I, II a, li b. III and IV, a monomer, an alkali-soluble resin, a pigment, an additive and a solvent in the present invention can be used as a photoresist, and has high photosensitivity. Easy to be developed by alkaline aqueous solution, non-swelling deformation, clear imaging effect, suitable for etching photoresist, resisting photoresist; for image display and recording materials; inkjet ink cured with LED lamp; In the production process of LCD, OLED, and PDP, it can also 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 photocurable 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.

The photocurable composition of the present invention is used as a photoresist, and is sequentially subjected to coating, exposure, development, and heat treatment to form a black, red, green, and blue three-color pattern 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 includes a color filter manufactured using the above photocurable composition.

The photocurable 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, blue pixels via a composition comprising a compound of the formula I, II, III and IV of the invention, a monomer, an alkali soluble resin and corresponding pigments, additives and solvents Coating, exposure, development, heat treatment process. It also includes the necessary processing such as cleaning.

The composition of the present invention is uniformly applied to a substrate to be coated by a coating technique commonly used in the art such as spin coating, roll coating, spray coating, transfer, etc., and the coating amount is determined as required, and the usual thickness is 0.1 μm to 1 mm. When the composition contains a solvent component, the solvent is volatilized by a heating method such as 8CTC drying, and the non-volatile component forms a gel layer to remain 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. 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.

Next, development is performed, and the unexposed portion is removed to obtain a raised pattern. The developing process is operated with parameters well known to those skilled in the art, such as 3CTC spraying, rinsing. It is usually developed with an alkaline aqueous solution, such as an alkali metal hydroxide, an aqueous carbonate solution, ammonia water, or a quantitative wetting agent such as a surfactant, an organic solvent such as cyclohexanone or acetone, if necessary, to the aqueous solution. 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, weight concentration range of 0.1-10%; the above aqueous solution may also be added to a surfactant concentration of 0.05-5% by weight.

The final heat treatment process optimizes image fastness and is typically baked in a 200-26 CTC oven for 15-45 minutes.

Based on the production process of the known color filter, the color filter device can be manufactured by using the photocurable composition of the present invention, and exhibits excellent processability, clear array, high light transmittance, and high production efficiency. Quality display.

detailed description

The examples are illustrative of the invention in more detail, all in terms of amounts, unless otherwise indicated.

Example 1

Synthesis of 5-methylthioindan-1,2-dione-2-indole-0-B

La, synthesis 5-methylthioindan-1-1 - etherification method A

Weigh 3.33g (0.02mol) of 5-chloro-1-indanone in a 50ml three-necked flask, add 15ml of hydrazine, hydrazine-dimethylacetamide, 4.2g (0.03mol) of 50% sodium thiomethoxide solution, nitrogen Protection, 20-25 Ό stirred for 5 h, the reaction solution was added to 100 ml of water, extracted twice with 25 ml of 1,2-dichloroethane, combined with 1,2-dichloroethane solution, washed twice with 10 ml of water, concentrated organic The solution was dried to dryness, and the residue was crystallized from ethanol, and dried to yield white crystals (yield: 70.2%, yield: 70.2%; analytical purity 98.02%, melting range 105-106 °C).

Lb, synthesis of 5-methylthioindan-1,2-dione-2-indole

Take 1.8g (O.Olmol) of the etherified product obtained from la, dissolve it in 100ml three-necked flask with 30ml of methanol, add 2g of concentrated hydrochloric acid 2g, water bath The mixture was stirred at 15-20 ° C, and 1.55 g (0.015 mol) of n-butyl nitrite was added dropwise in 15 min. After stirring for 2 h, the reaction solution was concentrated to about 10 g under reduced pressure, and the residue was cooled to 5-10 ° C, and the precipitated yellow was filtered. The solid was 1.90 g after drying, and the analytical purity was 99.15%, the melting range was 210-211 ° C, and the yield was 91.8%.

Lc, synthesis 5-methylthioindan-1,2-dione-2-indole-0-acetate monoesterification A

Take lb product 1.04g (0.005mol) dissolved in 25ml, 2-dichloroethane, add l.lg (O.Ollmol) acetic anhydride, react in water bath at 25-30 °C for 1h; reaction solution with 25ml 5% NaHC03 The solution is washed with water, the aqueous phase is separated, the organic phase is washed once with 25 ml of water, and the aqueous layer is separated; the organic phase is dried over 1.5 g of anhydrous sodium sulfate for 2 h, filtered to remove the desiccant, and the filtrate is evaporated to dryness under reduced pressure; Ethyl ester, heated to full solubility, added 0.05g of activated carbon for 0.5h, hot filtered separation of activated carbon, filtrate cooling, precipitation of crystals, suction filtration, drying the filter cake to obtain a light yellow solid powder product 1.05g, content 97.65%, yield 84.3% The measured melting range is: 166.0~167.0°C; H-Li R (CDC1 ₃ ), δ ( _PP m) value data are shown in Table 1. Example 2

Synthesis of 5-(2-acetoxyethylthio)indan-1, --2-indole-0-acetate

2a, according to the etherification method A of Example 1, replacing 50% sodium methanethiolate solution with 2-mercaptoethanol and sodium hydroxide, and reacting with 5-fluoro-1-indolone to synthesize 5-(2-hydroxyethyl) Thio)indan-1-one, pale yellow crystal, yield 91.1%.

2b, according to the lb oximation method of Example 1, using the product obtained from 2a as a raw material, carrying out a oximation reaction, and crystallizing from methanol to obtain a pale yellow solid product 5-(2-hydroxyethylthio)indan-1,2- Diketone-2-indole, yield 83.2%.

2c, according to the lc esterification method of Example 1, raising the reaction temperature to 45-50 ° C, and purifying to obtain a pale yellow powdery diacetate product 5-(2-acetoxyethylthio)indan-1 , 2-dione-2-indole-0-acetate, purity 99.23%, yield 85.2%, melting range and ¹ H-NMR (CDC1 ₃ ), δ ( _PP m) value data are shown in Table 1. Example 3

Synthesis of 5-(4-isopropylphenylthio)indan-1,2-dione-2-indole-0-acetate

3a, synthesis of 5-(4-isopropylphenylthio)indan-1-one-etherification method B

Weigh 3.33g (0.02mol) of 5-chloro-1-indanone in a 50ml three-necked flask, add 30ml of N,N-dimethylformamide (DMF), 4.2g (0.027mol) of 4-isopropylthiophenol , 3.0 g of anhydrous sodium carbonate, 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, and extracted twice with 25 ml of 1,2-dichloroethane to combine 1,2 - Dichloroethane solution, washed twice with 10 ml of water, 3 cm thick silica gel was placed in a Buchner funnel, the organic phase was filtered with suction, the filtrate was concentrated to dryness, and the residue was recrystallized from methanol to give pale yellow crystals. g, yield 90.6%; analytical purity 98.2%, melting range 60.0-62.0 °C.

3b, synthesis of 5-(4-isopropylphenylthio)indan-1,2-dione-2-indenylation method A

Take 2.37g (O.Omol) of the etherified product obtained from 3a, dissolve it in 100ml three-necked flask with 30ml of methanol, add 2g of concentrated hydrochloric acid 2g, stir in water bath at 15-20 °C, add 1.55g (0.015mol) within 15min. n-Butyl nitrite, after stirring for 5 h, the reaction solution was cooled to 5-10 ° C, and the precipitated yellow solid was filtered, 2.50 g after drying, analysis purity 98.90%, melting range 194-195 ° C, yield 80.3%.

3c, synthesis 5-(4-isopropylphenylthio)indan-1,2-dione-2-indole-0-acetate monoesterification A

3c-l Take 3b product 1.56g (0.005mol) dissolved in 25ml, 2-dichloroethane, add l. lg (O.Ollmol) acetic anhydride, react in water bath at 25-30 °C for 1h; reaction solution with 25ml The 5% NaHC03 solution was washed with water, the aqueous phase was separated, and the organic phase was washed once more with 25 ml of water, and the aqueous layer was separated. The organic phase was dried over 1.5 g of anhydrous sodium sulfate for 2 h, filtered and evaporated to dryness. Residue; 15 ml of ethyl acetate was added to the residue, heated to full dissolution, 0.05 g of activated carbon was added to reflux for 0.5 h, activated carbon was separated by hot filtration, the filtrate was cooled, crystals were precipitated, suction filtration, and the filter cake was dried to obtain a pale yellow flaky crystal product 1.58. g, content 98.15%, yield 89.5%; melting range and H-Gu R (CDC1 ₃ ), δ ( _ppm ) value data are shown in Table 1.

3c-2 Take 3b product 1.56g (0.005mol) dissolved in 25ml toluene, add l. lg (O.Ollmol) acetic anhydride, react in water bath at 25-30 °C for 1h; wash the reaction solution with 25ml 5% NaHC03 solution water The aqueous phase was separated, and the organic phase was washed once more with 25 ml of water, and the aqueous layer was separated. The organic phase was dried over 1.5 g of anhydrous sodium sulfate for 2 h, filtered to remove desiccant, 20 ml of toluene was distilled off under reduced pressure, and 5 ml of petroleum ether was added to the residue. boiling range 60-90), holding all dissolved, hot filtered, the filtrate was cooled, the precipitated crystals were filtered off with suction, the filter cake was dried to give 1.61 g of yellow granular crystalline product, content 99.3%, yield 91.2%; melting range in Table ^1;! H - NMR (CDC1 ₃ ), δ (ppm) value data is the same as the 3c-1 product.

Example 4 Synthesis of 5-(4-isopropylphenylthio)indan-1,2-dione-2-indole-0-(2-methylbenzoic acid) ester

4c, according to the 3c esterification method A of Example 3, replacing the acetic anhydride with o-methylbenzoyl chloride to obtain the product 5<4-isopropylphenylthio)indan-1,2-dione as a pale yellow powder. 2-肟- 0-(2-methylbenzoic acid) ester, purity 98.53%, melting range and ¹ H-Li R (CDC1 ₃ ), δ (ppm) value data are shown in Table 1. Example 5

Synthesis of 5-phenylthioindan-1,2-dione-2-indole-0-acetate

5a, according to the 3a etherification method B of Example 3, replacing 4-isopropylthiophenol with thiophenol, and synthesizing 5-phenylthioindan-1-one with anhydrous potassium carbonate instead of anhydrous sodium carbonate. Light yellow crystal, yield 90.3%, purity 97.2%.

5b, according to the 3b deuteration method A of Example 3, using the product obtained as 5a as a raw material, the deuteration reaction is carried out, and a yellow solid is precipitated from the reaction liquid to be a product 5-phenylthioindan-1,2-dione-2 - 肟, yield 98.2%, purity 95%.

5c, according to the 3c esterification method A of Example 3, the reaction product was purified by acetone to obtain the pale yellow crystalline product 5-phenylthioindan-1,2-dione-2-indole-0-acetate. The rate was 88.5%, the purity was 98.1%, the melting range and ¹ H-NMR (CDC1 ₃ ), and the δ (ppm) value data are shown in Table 1. Example

Synthesis of 5-n-butoxyindan-1,2-dione-2-indole-0-acetate

6a, synthesis of 5-n-butoxyindan-1-one-etherification method C

Weigh 2.97 g (0.02 mol) of 5-hydroxy-1-indanone in a 50 ml three-necked flask, add 30 ml of acetonitrile, 5.2 g (0.037 mol) of bromo n-butane, 5.0 g of anhydrous potassium carbonate, and protect with nitrogen, 55- Stirring at 60 ° C for 3 h; recover acetonitrile under reduced pressure, add the residue to 100 ml of water, stir, solid precipitate, suction filtration, filter cake washed with 10 ml of water twice, recrystallize the filter cake with ethanol, white after drying Crystallization 3.67 g, yield 89.8%; analytical purity 98.5%, melting range 53.0-54.0 °C.

6b, synthesis of 5 n-butoxyindan-1,2-dione-2-indenylation method B

Take 6a of the etherified product obtained in 6a (O.Olmol), dissolve it in 100ml three-necked flask with 30ml of methanol, add 2g of concentrated hydrochloric acid 2g, stir in ice water bath 5-10 °C, add 1.55g (0.015) within 15min Mol) n-butyl nitrite, after stirring for 5 h, the reaction solution was cooled to 5-10 ° C, and the precipitated white solid was filtered, 1.98 g after drying, analysis purity 98.20%, melting range 134.0-136.0 ° C, yield 85% .

6c, synthesis 5-n-butoxyindan-1,2-dione-2-indole-0-acetate monoesterification B

Take 6b product 1.17g (0.005mol) dissolved in 25ml, 2-dichloroethane, add l.lg (O.Ollmol) acetic anhydride, react in a water bath at 20-25 ° C for 6h; the reaction solution is washed with 25ml water Then, the aqueous phase was separated, and the organic phase was dried over 1.5 g of anhydrous sodium sulfate for 2 hr. 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, heated to full solvent, and 0.05 g of activated carbon was refluxed for 0.5 h. The activated carbon was separated by hot filtration, 15 ml of n-hexane was added to the filtrate, cooled and cooled, and the crystals were precipitated, suction filtered, and the filter cake was dried to obtain white needle-like crystal product 1.18 g, content 97.8%, yield 85.8%; melting range and ¹ H- Li R (CDC1 ₃ ), δ (ppm) value data are shown in Table 1. Example 7

Synthesis of 5-(2-methylphenylmethoxy)indole-1

7a, synthesis of 5-(2-methylphenylmethoxy) hydrazine

According to the 6a etherification method B of Example 6, substituting 1-bromoisopentane for bromo-n-butane to synthesize 5-(3-methylbutoxy)indan-1-one, light yellow liquid, The rate is 96.8% and the purity is 98.0%.

7b, according to the 6b deuteration method B of Example 6, using the product obtained from 7a as a raw material, carrying out a deuteration reaction, and purifying to obtain a pale yellow powdery form of 5<3-methylbutoxy)indole-1,2-di Keto-2-indole, yield 92.1%, melting range 153.0-154.0 ° C, purity 99.51%.

7c, according to the 6c esterification method B of Example 6, the product of 7b is reacted with acetic anhydride, and the reaction product is recrystallized from a mixed solvent of ethyl acetate and n-hexane to obtain a white crystalline product, yield: 89.3%, purity: 99.65%, melting range And ¹ H_NMR (CDC1 ₃ ), δ (ppm) value data are shown in Table 1. Example 8

Synthesis of 5-(2-methylphenylmethoxy)indan-1,2- -2-indole-0-acetate

8a, synthesis 5-(2-methylphenylmethoxy)indan-1-

Synthesis of 5-(2-methylphenylmethoxy)indan-1-one, white crystals, according to the 6a etherification method C of Example 6, substituting o-methylbenzyl chloride for bromo-n-butane The rate is 95.5%, the purity is 99.0%, and the melting range is 100.0-101.0 °C.

8b, according to the 6b deuteration method B of Example 6, using the product obtained from 8a as a raw material, carrying out a deuteration reaction, and purifying to obtain a white solid 5<2-methylphenylmethoxy)indan-1,2-di Keto-2-indole, yield 90.2%, melting range 193.0-194.0 ° C, purity 96.31%.

8c, according to the 6c esterification method B of Example 6, the reaction product of the previous step is reacted with acetic anhydride, and the product is purified by recrystallization from ethyl acetate and 1,2-dichloroethane to obtain a white solid powder product, yield 91.3. %, purity 97.8%, melting range and ¹ H-NMR (CDC1 ₃ ), δ (ppm) values are shown in Table 1. Example 9

Synthesis of 5-methoxyindan-1,2-dione, 2-indole-0-acetate

9b, according to the 6b deuteration method B of Example 6, using 5-methoxyindan-1-one as a raw material, carrying out a deuteration reaction, and purifying to obtain a white solid 5-methoxyindan-1,2- Diketone-2-indole, yield 90.2%, melting range 224.0-225.0 ° C, purity 96.31%.

9c, according to the 6c esterification method B of Example 6, the product obtained from 9b is used as a raw material, and the esterification reaction is carried out, and the product is purified by recrystallization from ethyl acetate to obtain a white solid powder product 5-methoxyindan-1,2- Diketone-2-indole-0-acetate, yield 90.6%, purity 98.4%, melting range and ¹ H_NMR (CDCb), δ (ppm) values are shown in Table 1.

Example 10

Synthesis of 5,6-dimethoxyindan-1,2-dione-2-

10b, according to the 6b deuteration method B of Example 6, using 5,6-dimethoxyindan-1-one as a raw material, carrying out a deuteration reaction, and purifying to obtain a pale yellow solid 5,6-dimethoxy Indan-1,2-dione-2-indole, melting range: decomposition at 240 °C.

10c, according to the 6c esterification method B of Example 6, the product obtained from 10b is used as a raw material, and the esterification reaction is carried out, and the product is purified by recrystallization from ethyl acetate to obtain a pale yellow solid powder product 5,6-dimethoxyindan- 1,2-dione-2-indole-0-acetate, yield 90%, purity 98.5%, melting range and -R (CDC1 ₃ ), δ (ppm) values are shown in Table 1. Example 11

Synthesis of 5,6-dibutoxyindan-1,2-dione-2-indole-0-acetate

Preparation of 6-dihydroxyindan-1-one

Add 5,6-dimethoxyindan-1-one 2g (0.0104mol) to a 100ml three-necked flask, dissolve it with 20ml of glacial acetic acid; add 40% hydrogen bromide After the solution is stirred, the mixture is heated to a temperature of 1 OCTC; and the reaction is stopped after 9 hours; and the mixture is distilled off under reduced pressure to obtain a light gray solid, 0.8 g (0. 0049 mol), content: 97. 36%; It was proved to be 5,6-dihydroxyindan-1-one, and the yield was 46.9%.

11a, according to the 6a etherification method C of Example 6, the product of the above step, 5,6-dihydroxyindan-1-one, was used as a raw material, and subjected to an etherification reaction to obtain a pale yellow solid 5,6-dibutyl Oxyindan-1-, yield 95.5%, purity 95.2%.

Lib, according to the 6b deuteration method B of Example 6, using 5,6-dibutoxyindan-1-one as a raw material, carrying out a deuteration reaction, and purifying to obtain a yellow solid 5,6-dibutoxyfluorene Full-1,2-dione-2-indole, : 180-182 °C.

11c, according to the 6c esterification method B of Example 6, the product obtained from lib was used as a raw material, and the esterification reaction was carried out, and the product was purified by recrystallization from ethyl acetate to obtain a pale yellow solid powder product 5,6-dibutoxyindan- 1,2-Dione-2-indole-0-acetate, yield 89%, purity 98%, melting range and -R (CDC1 ₃ ), δ (ppm) values are shown in Table 1. Example 12

Synthesis 6-Ethyl-9-(2-methylbenzoyl)-1 Η,6Η-cyclopenta A carbazole-2,3-dione, 2-(0-acetyl oxime)

Synthesis of 9-ethyl-3-(2-methylbenzamide

20.0g (0.1mol) of ethyl carbazole was added to a 250ml four-necked flask, dissolved in 100ml, 2-dichloroethane; 15.0g of anhydrous aluminum trichloride was added, and when cooled to -5 °C, 17g2 was added dropwise. -Methyl benzoyl chloride; -5 ° C to 0 ° C for 3 h, the reaction solution is hydrolyzed with 30 ml of concentrated hydrochloric acid and 100 ml of water, the organic layer is washed well with water, and 1,2-dichloroethane is distilled off under reduced pressure. The product was recrystallized from petroleum ether to give a white product which, after drying, weighed 28 g; yield: 89.3 %; melting range: 96.5-98.3 °C. 1H-NMR proved to be 9-ethyl-3-(2-methylbenzoyl)-carbazole. Synthesis of 9-ethyl-6-(2-methylbenzyl-3-(3-chloropropionyl)carbazole

Add 15.7 g (0.05 mol) of 9-ethyl-3-(2-methylbenzoyl)-oxazole to a 250 ml four-necked flask, dissolve with 80 ml, 2-dichloroethane; add anhydrous trichlorin 15.0g of aluminum, when cooling to -5 °C, 7 g (0.055 mol) of 3-chloropropionyl chloride was added dropwise; -5 ° C ~ 0 ° C for 3 h, the reaction solution was hydrolyzed with 30 ml of concentrated hydrochloric acid and 100 ml of water, fully water The organic layer was washed, and after the distillation of 1,2-dichloroethane under reduced pressure, the residue was pale yellow solid, weighed 19.8 g; yield 98%; 1H-NMR proved to be 9-ethyl-6-(2-A Benzoyl)-3-(3-chloropropionyl)-carbazole.

12a, synthesis 6-ethyl-9-(2-methyl-1Η, 2Η, 6Η-cyclopenta[2,3-c]carbazole-3-one

Add 55 g of concentrated sulfuric acid to a 100 ml four-necked flask, stir to a temperature of 70 ° C to 80 ° C, and add 4.1 g (0. Olmol) of the product of the previous reaction, 9-ethyl-6-2-methylbenzoyl) -3-(3-chloropropionyl)-carbazole; reacted for 3 h, the reaction solution was poured into 120 ml of water, and a gray solid was produced; after filtration, the solid was dissolved in 100 ml of 2-dichloroethane, and washed with water until the pH was neutral. After concentrating the solution, methanol was added to precipitate a yellow powdery solid, which was 2.8 g after drying, yield 76%, melting range: 175-179 ° C; 1H-NMR proved to be 6-ethyl-9-(2-methyl Benzoyl) -1 Η, 2 Η, 6 Η-cyclopenta[2,3-c]oxazol-3-one.

12b, synthesis 6-ethyl-9-(2-methyl azole-2,3-dione, 2-oxime

Add 12g product 1.5g (0.0041mol), methanol 20g, concentrated hydrochloric acid 0.5g, n-butyl nitrite 1.5g in a 50ml single-mouth bottle; magnetic stirring, 4h at room temperature, visible yellow insolubles; C, filtration gave a yellow solid product, dry weight 1.5 g, yield 92.3%.

12c, Synthesis of 6-ethyl-9-(2-methylbenzoyl)-1Η, 6Η-cyclopenta[3,4-c]carbazole-2,3-dione, 2-(0-acetyl肟)

In a 50 ml single-necked flask, 1.0 g of the reaction product of the previous step 12b, and 15 g of acetic anhydride were added, and the mixture was stirred at room temperature for 72 h to obtain 0.95 g of a yellow solid, which was crystallized from acetonitrile / ethyl acetate. , content: 96.64%; yield 73%. The melting range and 1H-NMR (DMSO-d6), δ (ppm) values are shown in Table 1.

Example 13 Synthesis of 4,6-dimethoxybenzofuran-2,3- 1-2-indole-0-acetate

Synthesis of α-chloro-2-hydroxy-4,6-dimethoxybenzene

1,3,5-trimethoxybenzene 8.4g (0.05mol) was dissolved in 30ml, 2-dichloroethane to 5 ° C, add 7.4g of anhydrous aluminum trichloride, stir to dissolve, add chlorine 6.2 g (0.055 mol) of acetyl chloride was added, stirring was continued for 2 hours, and hydrolysis treatment was carried out to obtain 9.9 g of white needle crystals, mpl 39-140 ° C, and the product was found to be a yield of 85.8%.

13a, synthesis of 4,6-dimethoxybenzofuran-3-one

The above-mentioned product α-chloro-2-hydroxy-4,6-dimethoxyacetophenone 2.3 g (O.Olmol) was dissolved in 20 ml of ethanol, 1.5 g of anhydrous Na ₂ C0 _{3 was} added dropwise, and stirred at room temperature for 5 h. The solid was filtered, and the solvent was evaporated to dryness crystalljjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj

13b, synthesis of 4,6-dimethoxybenzofuran-2,3-dione-2-indole

Purification reaction was carried out according to the 6b deuteration method of Example 6 using 4„6-dimethoxybenzofuran-3-one as a starting material, and purified to give 4,6-dimethoxybenzofuran as a white solid. -2,3-dione-2-indole, yield 81.5%, purity 96.3%, melting range: 23 CTC decomposition.

13c, synthesis 4,6-dimethoxybenzofuran-2,3-dione-2-yt-0-acetate

According to the 6c esterification method of Example 6, the product 4,6-dimethoxybenzofuran-2,3-dione-2-indole obtained from 13b was used as a starting material for esterification reaction, and the product was subjected to 1,2- Recrystallization from dichloroethane gave the white solid powder product 4,6-dimethoxybenzofuran-2,3-dione-2-indole-0-acetate, yield 90.5%, purity 98.0% , ^! H-NMR (DMS0-d6), δ (ppm) value data are shown in Table 1. Example 14

Synthesis of 6H-6-ethyl-oxime, ΙΙΗ-dicyclopenta 3,4 U '-c, g/carbazole-2,3,9,10-tetraketone, 2,10-di(0-acetyl oxime )

Synthesis of 9H-9-ethyl-3,6-bis(3-chloropropionyl)carbazole

Add lO.Og (0.051mo) ethyl oxazole to a 250ml four-necked flask, dissolve with 60ml, 2-dichloroethane; add anhydrous aluminum trichloride

15. 0g, when cooling to -5 ° C, add 13.2g (0.104mol) of 3-chloropropionyl chloride dropwise; -5 ° C ~ 0 ° C reaction overnight, the reaction solution was hydrolyzed with 50ml concentrated hydrochloric acid and 100ml water, there are a large number The solids appeared, the insoluble matter was filtered, and the filter cake was washed with water, and the mixture was poured into 100 ml of 2-dichloroethane. The mixture was heated to complete dissolution and then cooled to crystallize. The white solid was filtered. ; Melting point: 188 ° C ~ 189 ° C. - NMR proved to be 9H-9-ethyl-3,6-bis(3-chloropropionyl)carbazole.

14a, synthesis 611-6-ethyl-1 2 10 1111-di ',3 '-(;, £/carbazole-3,9-dione

Add 30g of 98% concentrated sulfuric acid to a 100ml four-necked flask, stir and heat up and stabilize at 60_65 ° C, add 2. 0g (0.0032mol) of intermediate 9-ethyl-3,6-di (3-chloro Propionyl)carbazole, after the addition is completed, the temperature is raised to 85-90 ° C; after 3 h, the reaction solution is cooled, then poured into 100 ml of water, and added with 50 ml of 2 - dichloroethane to obtain a pale yellow solution, which is concentrated to When crystals are precipitated, the solution is allowed to cool naturally, and the pale yellow crystals are precipitated, and dried by filtration to obtain 1. lg, yield 68.4%; ^! H-NMR proved to be 6H-6-ethyl-1H, 2H, 10H, 11H- Cyclopenta 2,3,2; 3'-c, g-carbazole-3,9-dione. - NMR ( DMS0-d ₆ ) δ ( ppm ) Value data: 1.4949 (t, 3H, CH ₃ ); 2.8656 (t, 2H, CH ₂ ); 3.7988 (t, 2H, CH ₂ ); 4.4586-4.5294 (quartet , 2H, NCH ₂ ); 7.4853⁄47.5137 (d, 2H, 2ArH); 7.9343⁄47.9628 (d, 2H, 2ArH).

14b, Synthesis of 611-6-ethyl-1 1111-dicyclopenta 3,4,3 ',4 '-(;,£/carbazole-2,3,9,10-tetraketone, 2,10- Second

1.0 g (0.0032 mol) of intermediate 14a, 10 ml of methanol, 0.5 g of concentrated hydrochloric acid, 1.5 g of n-butyl nitrite in a 50 ml single-mouth bottle; magnetic stirring reaction at 25-30 ° C for 24 h; suction filtration and washing with methanol, drying yellow solid The filter cake was obtained by 0.98 g, and the yield was 85%;

14c, Synthesis of 6H-6-ethyl-oxime, ΙΙΗ-dicyclopenta 3,4, Uc,g/carbazole-2,3,9,10-tetraketone-2,10-di(0-acetyl oxime Take 0.5g (0.0014mol) of intermediate 14b and 10g of acetic anhydride in a 25ml round bottom flask, stir the reaction in a water bath at 50-55 °C for 10h; filter to obtain a yellow filter cake, wash with 5ml of ether, drain, dry filter The cake obtained 0.45 g of a yellow powdery product, the content was 96.32%, and the yield was 71.4%; ^! H-NMR (DMS0-d6), δ ( _PP m) value data are shown in Table 1. Example 15

Synthesis of bis[5-(4-isopropylphenylthio)indan-1,2-dione-2-indole-0]-oxalate

1.56 g (0.005 mol) of the intermediate 3b of Example 3 was weighed and dissolved in 25 ml, 2-dichloroethane, 0.32 g (0.0025 mol) of oxalyl chloride was added dropwise, and reacted in a 20-25'C water bath for 10 h; Precipitating from the reaction solution; filtering the filter cake, dissolving in 20ml, 2-dichloroethane, heating to full dissolution, hot filtration, cooling the filtrate, crystallizing, suction filtration, drying the filter cake to obtain 1.35g of yellow powdery product. The content is 98.32%, the yield is 80%; the melting range and ¹ H-Li R (CDC1 ₃ ), δ (ppm) value data are shown in Table 1. Example 16

Synthesis of bis[-(4-isopropylphenylthio)indan-1,2-dione-2-oxime-0]-isophthalate

Weigh 1.56g (0.005mol) of the intermediate 3b of Example 3 dissolved in 25ml, 2-dichloroethane, add 0.51g (0.0025mol) of isophthalic acid chloride, and react in a 20-25'C water bath for 24h; A yellow solid is precipitated from the reaction solution; the filter cake is filtered, dissolved in a mixture of 5 ml, 2-dichloroethane and 5 ml of ethyl acetate, heated to full dissolution, hot filtered, the filtrate is cooled, crystals are precipitated, suction filtered, dried The filter cake obtained yellow needle-like product l.lg, content 97.48%, yield 59%; melting range and ¹ H-NMR (CDC1 ₃ ), δ (ppm) value data are shown in Table 1. Example 17

Synthesis of 5-(4-octanoylphenylthio)indan-1,2- 1-2-indole-0-acetate

17a, weighed the intermediate 5a of Example 5 24.04g (0.1mol) dissolved in 100ml, 2-dichloroethane, kept at 10 ° C, added 28g (0.21mol) of anhydrous aluminum trichloride, stirred and added 17.9 g (O.llmol) octanoyl chloride, after 4 hours of addition, the reaction solution was treated with dilute hydrochloric acid, the organic solution was separated, washed once, concentrated to recover 1,2-dichloroethane, and the residue was recrystallized from 100 ml of ethanol to obtain White crystal 33g, yield 90.1%, melting range 74.3-75.2°〇, -Li 1? The resulting data show that Intermediate 17a 5- (4-octanoyl phenyl group) ^{_{indan-1-one; 1 H-NMR (DMS0_d 6}} ), δ (PP m) 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,lH,ArH), 7.3734(s,lH,ArH), 7.4525/7.4797(d,2H,2ArH), 7.6677/7.6945(d, 1 H,2ArH) , 7.9221/7.9493 (d, 2H, 2ArH);

17b, according to the 3b deuteration method A of Example 3, using 17a as a raw material, carrying out a deuteration reaction, precipitating a yellow solid, drying the solvent, purity 95%, melting range, -NMR data showed that the obtained intermediate 17b was 5- ( 4-octanoylphenylthio)indan-1,2-dione-2-indole, yield 96.2%; ^! H-NMR

(DMSO-de), 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, lH, ArH), 7.3320 (s, lH, ArH), 7.5281/7.5558 (d, 2H, 2ArH), 7.7707/ 7.7977 d, lH, 2ArH), 7.9648/7.9925 (d, 2H, 2ArH), 12.4460 (s, lH, NOH) _;

17c, the intermediate 17b was subjected to esterification according to the 3c esterification method A of Example 3, and the product was purified by crystallization from toluene and n-hexane (1:2) to give a yellow crystal product 5-(4-octanoylphenylthio)indole. Full-1,2-dione-2-indole-0-acetate, yield 85.8%, purity 97.1%, melting range and ¹ H_NMR (CDCb), δ (ppm) values are shown in Table 1. Example 18

Synthesis of 5-[4-(3-cyclopentylpropanoyl)phenylthio]indan-1,2-dione-2-indole-0-acetate

18a, weighed the intermediate 5a of Example 5, 24.04g (0.1mol) dissolved in 100ml, 2-dichloroethane, kept at 10 ° C, added 28g (0.21mol) of anhydrous aluminum trichloride, stirred and added 17.76 g (O. llmol) 3-cyclopentylpropionyl chloride, after 4 hours of addition, the reaction solution is treated with dilute hydrochloric acid, the organic solution is separated, washed once, concentrated, and 1,2-dichloroethane is recovered, and the residue is in acetic acid The mixture of ester and n-hexane (weight ratio 1:2) was recrystallized to obtain 33.52 g of white crystals, yield 92.0%, melting range 88.5-90.0 ° C, and _R data indicated that the obtained intermediate 18a was 5-[4- (3-cyclopentylpropanoyl)phenylthio]indan-1-one; - NMR (CDC), δ (ppm) Value data: 1.1072 (m, 2H, CH ₂ ), 1.5328-1.8691 (m, 9H , 4CH ₂ + lCH) , 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, lH, ArH ), 7.3766 (s, lH, ArH), 7.453 l/7.4803 (d, 2H, 2ArH), 7.6695/7.7963 (d, 1 H, 2ArH), 7.9245/7.9517 (d, 2H, 2ArH) _;

18b, according to 17b of Example 17, using 18a as a raw material, carrying out a deuteration reaction, precipitating a yellow solid product, drying the solvent, purity 95%, melting range 193.5-195.5 °C, ^! H-NMR data indicating the obtained intermediate 18b Is 5-[4-(3-cyclopentylpropanoyl)phenylthio]indan-1,2-dione-2-indole, yield 95.5%; ^! H-NMR ( DMSO- d ₆ ), δ (ppm) Value data: 1.108 l(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 ) , 7.3186/7.345 l(d,lH, ArH) , 7.5243(s,lH,ArH) , 7.5667/7.5923(d,2H,2ArH) , 7.7103/7.7370 d,lH,2ArH), 7.9987/8.0238(d,2H , 2ArH), 12.6685 (s, lH, NOH) _;

18c, the intermediate 18b was subjected to esterification according to 17c of Example 17, and the product was purified by crystallised from toluene and n-hexane (1:2) to give a yellow powder product 5-[4-(3-cyclopentylpropanoyl)benzene. Thio]indan-1,2-dione-2-indole-0-acetate, yield 83.4%, purity 97.0%, melting range and -R (CDC1 ₃ ), δ (ppm) value data see Table 1.

Comparative Example 1

Synthesis of indane-1,2-dione, 2-anthracene-0-acetate

2.00g of fluorenone was placed in a 50ml single-mouth bottle, dissolved in 8g of ethanol, and stirred evenly by magnetic force; 0.08g of 35% hydrochloric acid was added dropwise; 2.13g of isoamyl nitrite was added dropwise, and 3CTC reaction was carried out at room temperature; the remaining amount of sampled material was 0.891% after 6h reaction. Filtration and leaching with 10 g of ethanol gave a solid 2.00 g. The content of 99.429%; vacuum drying at 60 ° C for 3 h, yielding 1.70 g of pale yellow needle crystal, melting point 183.2~185.0 ° C, -NMR analysis for intermediate 茚

1.5g of the above intermediate was added to a 50ml single-mouth bottle, 6g of toluene was added, 1.2g of acetic anhydride was added dropwise, magnetically stirred, reacted at 30 ° C for 15h, rotary toluene and residual acetic anhydride were added, and 50ml of dichloroethane was added. twice with 20ml of water, washed three times with water to pH = 7, a part of dichloroethane was evaporated to dryness, petroleum ether was added while hot, and cooled to give a white solid 1.6g, content of 99.917%, m.p. 152.5 ~ 153.7 ° ^C;! H -NMR (CDC1 ₃ ) δ (ppm) value data are shown in Table 1.

Comparative Example 2

Synthesis of 5-chloroindole-1,2-dione-2-indole-0-acetate

b, synthesis of 5-chloroindan-1,2-nitrite esterification

3.33 g (0.02 mol) of 5-chloro-1-indanone was weighed in a 100 ml reaction flask, added to 40 ml of methanol, and kept at 35-45 ° C; 3.1 g (0.3 mol) of nitrite was added dropwise to the reaction flask. The ester was reacted at 45 ° C for 3 h; stirring was stopped. After room temperature, crystals were precipitated in the reaction mixture, filtered, and the filter cake was rinsed with 10 ml of methanol, and dried to give a pale yellow solid product (yield: 97.44%). Yield: 90%.

c Synthesis of 5-chloroindole-1,2-dione-2-indole-0-acetate monoacetic acid esterification

Take the previous product lg (0.0051mol) dissolved in 50ml dichloroethane, drop B l. lg (O.Ollmol) acetic anhydride, 25h reaction in water bath for 15h; reaction solution with 50ml 5% NaHCO3 solution water After washing, the aqueous phase is separated, and the organic phase is washed once with 50 ml of water, and the aqueous layer is separated; the organic phase is dried over 3 g of anhydrous sodium sulfate for 2 h, and the desiccant is removed by filtration, and the filtrate is evaporated to dryness under reduced pressure; Fully dissolved, adding 0.05g of activated carbon to reflux for 0.5h, separating the activated carbon by hot filtration, cooling the filtrate, crystallization, suction filtration, drying the filter cake to obtain 1.03g of white solid powder product, the content is 98.88%, the yield is 85.0%; : 163.0~165. 0. C; H-Li R (CDC1 ₃ ), δ (ppm) value data are shown in Table 1.

8Z

L^Sr80M0ZN3/X3d CC8.Z0/S10J OAV

/3/:5}ZMl>d/ O,s!noiAV

It

I 丽0ZND/工:) d CC8.10/ST0Z OAV Table 1 continued

Example 19 Preparation of alkali soluble resin

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 thermometer were installed, and 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 monomer mixture solution was started to be added dropwise. After about 1 hour, continue to react for 6 hours; 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 500 ml of toluene; 250 g of a white powdery solid resin _; it was dissolved in a 20% solution with PMA (propylene glycol methyl ether acetate) 1000 g. Example 20 Preparation and Development of Photoresist

According to Table 2, formula 20A, 20B, 20C (photoinitiator is OXE01), 20D (photoinitiator is OXE02), 20E (photoinitiator is IHT-PI 910, its chemical name is 2-dimethylamino-2- (4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone), 20F (Comparative Example 1), 20G (Comparative Example 2), by weight ratio, all components The photocurable composition is prepared according to the preparation method of the ink, and is in a fluid liquid state.

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.

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. The distance between the film and the grating was 10 cm, and the exposure amount was 800 mJ/cm ² .

Soak 1mm in a 1% sodium carbonate solution bath at 30 °C, record the maximum film retention order that can be displayed. The higher the number, the stronger the light sensitivity of the measured composition, the photocuring efficiency and film forming properties of the photoresist. The higher the results are listed in Table 3.

Table 2 Composition raw material ratio table

Table 3 Development results

The development results in Table 3 show that the photocurable compositions formulated using the photoinitiators of Examples 4 and 6 exhibited significantly better photosensitivity than the photocurings prepared using the products of Comparative Example 1, Comparative Example 2, OXE01 and OXE02. The composition improves the photocuring efficiency and film forming properties of the photoresist. Example 21 Photocuring composition gel conversion rate test experiment

The composition of the formulations 20A, 20B, 20C, 20D, 20E, 20F, 20G in Table 2 of the above Example 21 was applied to the glass by a wire bar method. The surface of the glass was baked at 80 ° C for 3 mm, and the solvent PMA was volatilized, and the thickness of the remaining film was measured to be 2 μm.

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, weighed, and soaked in acetone for 72 hours. The residual film weight W _{2 was} measured by drying, and W1AV2 was gel% gel yield. The results are shown in Table 4.

Table 4 Gel conversion rate test results

From Table 4, it can be concluded that the photoinitiators of Examples 4 and 6 have a higher degree of double bond polymerization and a significantly higher photocuring efficiency in the photoresist formulation. Example 22 LED light source curing photosensitive composition and curing efficiency test experiment

The photocurable composition 20A, 20B, 20C, 20D, 20F, 20G in Example 20 was applied to the surface of the glass by a wire bar method, baked at 80 ° C for 3 mm, and the solvent PMA was volatilized to measure the thickness of the remaining film. It was 2 μm and then cured as follows.

Curing device: LEDUV curing device, Model: UV-101D (Beijing Iwata Boyuan Technology Co., Ltd.)

Light source: UV-LED point source, diameter: 10mm; Wavelength: 365nm, maximum illumination: 40mw/cm ²

Curing conditions: Working distance: 21mm; Irradiation time: Is

The photocuring efficiency characterization method is as follows: After irradiating Is with a point light source, the whole glass piece is immersed in an acetone solution for 5 s, and after taking out, the cured film pattern diameter is measured. The larger the value, the higher the sensitivity, the higher the curing efficiency, the table 5 is the measurement result. It can be seen from the measurement results in Table 5 that when the photosensitive composition for resisting ink or photoresist is cured by an LED light source, the photosensitive composition provided by the present invention is a photoinitiator with OXE01 and OXE02 as compared with the prior art. The composition had higher light sensitivity, while the composition film of the two control example products was almost completely dissolved by acetone, without clear film remaining.

Table 5 development results

Example 23

Printing ink formulation and high pressure mercury lamp curing

Formula composition ratio: epoxy resin acrylate prepolymer (Changxing Chemical 621-100) 50 parts, polyester acrylate prepolymer (Changxing Chemical 6311-10) 10 parts, TPGDA (Changxing Chemical EM223) 30 parts, carbon black (Degussa P25) 4 parts, 7 parts of photoinitiator; mixed and ground to a fineness of 2 um or less to obtain ink samples 23A-23G. The gel conversion rate gel% was measured by the method of Example 21 using a 420 mesh screen printing onto an aluminum plate and solidified by a high pressure mercury lamp. Table 6 shows the measurement results. As can be seen from the measurement results in Table 6, 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. Table 6 Printing ink formulation and high pressure mercury lamp curing results

Example 24

Printing ink preparation and LED surface light curing

Formulation ratio: 50 parts of epoxy resin 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 The ink samples 26A-26G were obtained and applied to a glass plate; and cured with a 365 nm LED surface light lamp, and the exposure amount was 86 mJ/cm ² . The gel conversion gel% was measured as in Example 21. 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.

Table 7 Printing ink formulation and LED light source curing results

Example 25

The filter film is prepared by photoresist and exposed to light

Formulation composition: 500 parts of alkali-soluble resin solution (Example 19), dipentaerythritol hexaacrylate (Cytec DPHA) 100 parts, photoinitiator 100 parts, co-initiator BCIM (2,2'-di-o-chlorophenyl- 4„4',5,5'-tetraphenylbiimidazole) 20 parts, carbon black (Deg Li P25) Dispersion 500 parts (containing carbon black 20%). According to the ink preparation method, grinding evenly, according to the light used Different initiators, there are a total of 25A-25H eight inks.

Separately coated, dried under reduced pressure, thick lum, covered with a pattern mask, exposed with a 365 nm LED surface light source, exposed at 100 mJ/cm ² , developed with a 1% sodium carbonate solution for 30 seconds, and examined for pattern morphology and fastness by stereo scanning electron microscopy. . Morphological and fastness observation and evaluation: 1 The exposed part is intact without falling off; 2 The exposed part has no peeling and curled edge; 3 The exposed part is not edged; 4 The exposed part is incomplete; 5 The exposed part has fallen off.

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. The performance of the compound of the present invention is significantly better than that of the control compound, and the formed ink has good properties. Imaging clarity.

Table 8 Black photoresist ink exposure evaluation

Example 26

The filter film is prepared by photoresist and exposed to light Formulation composition: 500 parts of an alkali-soluble resin solution (Example 19), 100 parts of dipentaerythritol hexaacrylate (Cytec), 100 parts of a photoinitiator, and 100 parts of a red pigment L3920 (BASF Corporation). It is uniformly ground according to the ink preparation method to obtain six inks of 26A-26F.

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 , 1% sodium carbonate solution developed for 30 seconds, and pattern fastness and morphology were examined by stereo electron microscope. The evaluation method was the same as in Example 25. 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 pattern edge after exposure and development, and is firm and non-shedding. The performance of the compound of the present invention is significantly better than that of the control compound, and the formed ink has good properties. Imaging clarity.

Table 9 Red photoresist ink exposure evaluation

Example 27

The filter film is prepared by photoresist and exposed to light

Formulation composition: Alkali-soluble resin solution 500 parts (Example 19), dipentaerythritol hexaacrylate (Cytec) 100 parts, photoinitiator 10 parts, red pigment L3920 (BASF) 100 parts. It was uniformly ground according to the ink preparation method to obtain 27A-27F six inks.

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 , 1% sodium carbonate solution developed for 30 seconds, and pattern fastness and morphology were examined by stereo electron microscope. The evaluation method was the same as in Example 25. 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. The performance of the compound of the present invention is significantly better than that of the control compound, and the formed ink has good properties. Imaging clarity.

Table 10 red photoresist ink exposure evaluation

Ink number 27A 27B 27C 27D 27E 27F

Photoinitiator sample Example 3 Example 7 Example 18 OXE01 OXE02 Comparative implementation

Example 1 Evaluation 1 1 1 5 4 5

Claims

a compound of formula I, II a, lib and III,

( lib)

(III)

among them,

A _ri is a substituted ortho-arylene or ortho-heteroaryl group, and the ortho-arylene or ortho-heteroaryl group is bonded to Yi and a carbonyl group by two adjacent atoms to form a ring structure, except for the R ₁₈ X substituent. The substituents on the remaining atoms are each independently:

Hydrogen atom, halogen atom, d-Cu alkyl group, C ₅ -C ₇ cycloalkyl group, d-alkyl group substituted by C ₅ -C ₇ cycloalkyl group, phenyl group, optionally substituted by one or more dC ₄ alkyl groups , carboxy, dC ₁₂ alkyl acyl, arylcarbonyl, heteroarylcarbonyl, phenyl, halogen atom, CN substituted phenyl, d-alkylbenzyloxy, F qc^o substituted d-alkoxy , d-alkylenedioxy, ο)ο, d-Cualkylthio, d-alkylphenylthio, F^qc o substituted dC ₄ alkylthio, CN, carboxyl, (^ -(: ₁₂ alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, XRi8;

Or a substituent of the above two substituents of A _ri or a substituent and a substituent of 4 (" ₁ through a direct bond, a carbon atom, a carbonyl group to form a cyclic structure; X is 0, S or NR ₁₉ ;

丫2 is a straight key, 0, S, NR ₂ . , BR ₂ . , CRisRis, SiRi ₅ Ri ₆ or Y ₃ -Z ₂ -Y ₃ ;

Y ₃ is 0, S, NR ₂ . , BR ₂ . Or OC(O);

Ri is a hydrogen atom, CrC ₁₈ alkyl or (^-(; ₁₈ alkoxy;

Or any one or more of d-alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, d-alkoxy, dC ₄ alkylthio, aryloxy a arylthio group, a dC ₄ alkanoyloxy group, an aroyloxy group-substituted dC ₁₈ alkyl group;

Or ^ is optionally substituted by one or more dC ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, dC ₄ alkanoyloxy, aroyloxy and / or C ₂ -C ₁₈ alkyl group inserted by C ₅ -C ₇ cycloalkylene, phenylene, 0, S, NR ₁₇ ;

Or ^ is C ₂ -C ₁₈ alkenyl, optionally substituted by one or more halogen atoms, CrC ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, d- Alkanoyloxy, aroyloxy substituted and/or inserted into C ₂ -C ₁₈ alkenyl by C ₅ -C ₇ cycloalkylene, phenylene, 0, S, NR ₁₇ ; or (; ₅ -( ; ₇ cycloalkyl, optionally substituted with one or more d- alkyl group, a phenyl group, a halogen atom, CN substituted C ₅ -C ₇ cycloalkyl; or ^ is phenyl, optionally substituted with one or more alkoxy dC ₄ a group, a dC ₄ alkoxy group, a phenyl group, a halogen atom, a CN substituted phenyl group; or a naphthyl group;

Or a benzoyl group, a phenoxycarbonyl group, wherein the phenyl group is optionally substituted by one or two or more dC ₄ alkyl groups, C ₅ or C ₆ cycloalkyl groups, CN, XR ₁₇ ;

Ru, R ₁₂ are each independently a hydrogen atom, a halogen atom, a d-Cu alkyl group, a C ₅ -C ₇ cycloalkyl group, a C ₅ -C ₇ cycloalkyl-substituted d-alkyl group, (^-(: ₁₂₎ Alkoxy, dC ₄ alkylbenzyloxy, phenyl, optionally substituted by one or more dC ₄ alkyl, carboxy, dC ₁₂ alkyl acyl or arylcarbonyl, heteroarylcarbonyl, XR ₁₇ , phenyl , a halogen atom, CN substituted phenyl, dC ₄ alkylbenzyl group, substituted with one or more dC ₁₂ alkoxy, benzyloxy dc ₄ alkyl, F ^ qc ^ o dc _{4-substituted} alkoxy, F^qc^o, CN, carboxy, dc ₁₂ alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, XR ₁₈ , or phenoxy substituted by one or more dC ₄ alkyl groups, by a dC ₈ Alkyl acyl group, C ₅ -C ₆ cycloalkyl acyl group, arylcarbonyl group, heteroaryl formyl substituted phenoxy group, C ₅ -C ₆ cycloalkyl substituted dC ₄ alkyl acyl phenoxy group, dC ₃ alkylenedioxy, d-Cualkylthio, F^qc o substituted d-alkylthio and d-alkylphenylthio, by a d-Cs alkyl acyl, c ₅ -c _s cycloalkyl acyl, arylcarbonyl, heteroaryl acyl substituted phenylthio, Or a c ₅ -c ₆ cycloalkyl substituted dC ₄ alkyl acyl phenylthio group, or a propylene group in which an epoxy group is arbitrarily condensed with a dC ₄ alkyl aldehyde or a ketone;

R ₁₅ and R ₁₆ are each independently a hydrogen atom, a d-ds alkyl group, a carboxyl group-substituted or a d-alkoxyacyl-substituted d-Cs alkyl group, and a F^qc^O-substituted dC ₄ alkyl group, optionally Or a plurality of halogen atoms, dC ₄ alkyl, C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, CrC ₄ alkanoyloxy, aroyloxy substituted or by C ₅ -C ₇ cycloalkylene, phenylene, 0, S, NR ₁₇ inserted C ₂ -C ₁₈ alkyl, or R ₁₅ , R ₁₆ are each independently C ₅ -C ₇ cycloalkyl or optionally Or a plurality of dC ₄ alkyl, phenyl, halogen atom, CN substituted C ₅ -C ₇ cycloalkyl; or ₅ , R ₁₆ are each independently phenyl, optionally substituted by one or more dC ₄ alkyl groups, dC ₄ alkoxy, carboxy, dC ₁₂ alkyl group, C ₅ -C ₆ cycloalkyl, formyl, C ₅ -C ₆ cycloalkyl substituted C ₂ -C ₄ alkyl group, a benzoyl group, XR _17, a phenyl group, a halogen atom, a CN substituted phenyl group;

Or the above R ₁₅ , R ₁₆ together with the carbon atom or silicon atom to which they are attached form a cyclic ring and the number of atoms to form a ring 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;

R ₁₇ is a d-alkyl group;

R ₁₈ is a hydrogen atom, d-ds alkyl, d-alkoxyacyl substituted CrC ₅ alkyl, ^[(0)0 substituted d-alkyl, optionally substituted by one or more halogen atoms, dC ₄ alkane , C ₅ -C ₇ cycloalkyl, heterocycloalkyl, phenyl, heteroaryl, CN, dC ₄ alkanoyloxy, aroyloxy substituted or C ₅ -C ₇ cycloalkylene, sub phenyl, 0, S, NR ₁₇ inserted into the C ₂ -C ₁₈ alkyl;

Or R ₁₈ is C ₅ -C ₇ cycloalkyl, or optionally substituted with one or more d- alkyl group, a phenyl group, a halogen atom, CN substituted C ₅ -C ₇ cycloalkyl; or R ₁₈ is phenyl, Any one or more of dC ₁₂ alkyl, carboxy, dC ₁₂ alkyl acyl, C ₅ -C ₆ cycloalkyl formyl, aryl acyl, heteroaryl acyl, XR ₁₇ , phenyl, halogen atom, CN or N0 ₂ substituted phenyl, optionally substituted by a C ₅ -C ₆ cycloalkyl substituted C ₂ -C ₄ alkyl substituted phenyl group, an optionally substituted phenylene, 0, S or NR ₁₇ inserted a C ₂ -C ₁₂ alkyl acyl substituted phenyl group;

Or R ₁₈ is a d-alkyl acyl group, a d-conjugated enoyl group;

Or R ₁₈ is benzoyl or phenoxycarbonyl, wherein phenyl is optionally substituted by one or two or more halogen atoms, R ₁₇ , C ₅ or C ₆ cycloalkyl, CN, 0H, XRi ₇ ;

Or ₉ , R ₂ . Are each independently a C ₅ -C ₇ cycloalkyl, or optionally substituted with one or more dC ₄ alkyl group, a phenyl group, a halogen atom, CN C ₅ -C ₇ cycloalkyl,

Or ₉ , each independently a phenyl group, optionally substituted by one or more dC ₄ alkyl groups, a carboxyl group, a dC ₁₂ alkyl acyl group, a C ₅ -C ₆ cycloalkyl formyl group, a C ₅ -C ₆ cycloalkyl group C ₂ -C ₄ alkyl acyl, aryl formyl, XR ₁₇ , phenyl, halogen atom, CN substituted phenyl;

A compound of the formula I, II a, li b and III according to claim 1, wherein

Ru, R ₁₂ and R ₁₃ are each independently a hydrogen atom, a halogen atom, a d-Cu alkyl group, a C ₅ -C ₇ cycloalkyl group, a C ₅ -C ₇ cycloalkyl-substituted d-alkyl group, (^- (: ₁₂ alkoxy, substituted with one or more of (^ - (: ₁₂ alkoxy, benzyloxy dc ₄ alkyl, F ^ qc ^ o dc ₄ alkoxy substituted phenyl, optionally substituted with one or a plurality of dC ₄ alkyl, carboxyl, dC ₁₂ alkyl or aryl, heteroaryl, XR ₁₇ , phenyl, halogen or CN substituted phenyl, d-alkylbenzyloxy, F ^qc^o, ^qc o substituted d-alkylthio, CN, carboxy, (^-alkoxycarbonyl, arylcarbonyl, heteroarylcarbonyl, XR ₁₈ , by one or more dC ₄ alkyl Substituted phenoxy, phenoxy substituted by a dC ₈ alkyl acyl group, c ₅ -c ₆ cycloalkyl acyl group, aryl acyl group, heteroaryl acyl group, C ₅ -C ₆ cycloalkyl substituted dC ₄ Alkyl acyl phenoxy, dC ₃ alkylenedioxy, d-Cu alkylthio, ^qc o substituted d-alkylthio and d-alkylphenylthio, by a d-Cs alkane acyl, C ₅ -C ₆ cycloalkyl, acyl, aryl, formyl, aryl, heteroaryl formyl taken Phenylthio, or C ₅ -C ₆ cycloalkyl substituted phenylthio dC ₄ alkyl group;

X is 0, S or NR ₁₉ ;

Yi 0, S, NR ₂₀ , or CRisRis;

Y ₂ is 0, S, NR ₂ . Or Υ ₃ -Ζ ₂ -Υ ₃ ;

Y ₃ is 0, S, NR ₂ . Or 0-C(0);

R ₁₅ and R ₁₆ are each independently a hydrogen atom, a d-Cu alkyl group, a carboxyl group-substituted d-Cs alkyl group, a Ρϊ(0)0 substituted d-alkyl group, or ₅ , and Ris are each a C ₅ -C ₇ cycloalkyl, or R ₁₅ , R ₁₆ are each independently phenyl or optionally substituted by one or more dC ₄ alkyl, dC ₄ alkoxy, carboxy, dC ₁₂ alkyl acyl, C ₅ -C ₆ naphthenic a carbamoyl group, a C ₅ -C ₆ cycloalkyl substituted dC ₄ alkyl acyl group or a benzoyl substituted phenyl group; Or R ₁₅ and R ₁₆ respectively form a cyclic ring together with the carbon atom or silicon atom to which they are attached, and the number of atoms in the ring is 4-7;

Or R ₁₅ and R ₁₆ described above together with adjacent substituents form a cyclic ring and the number of atoms formed is 4-7;

R ₁₇ is a d-alkyl group;

3. The compound of formula I, II a, li b and III of claim 2, wherein

丄 is a direct bond or 1,3-phenylene;

^ is methyl, ethyl, phenyl, 2-methylphenyl 3-methylphenyl, 2,4,6-trimethylphenyl or 2,6-dimethoxyphenyl; Where R _{2 is} . Is a CC ₈ alkyl group.

4. The compound of the formula I, II a, lib and III according to claim 3, wherein in the substituent of A _ri , R ₁₈ X is in the para position to the carbonyl group attached to A _ri ; in Ar ₂ , the 0 atom or the N atom is in the benzene group The para position of the ring-linked carbonyl group.

5. The compound of formula I, II a, lib and III of claim 1

( IF) ( IG)

(IIIA)

(IIIB)

6. A method of producing a compound of formula I, II a, li b and III according to claim 1 comprising the steps of:

(1) First step: Selective deuteration on the ortho-methylene group of the carbonyl group of V or VIa, VIb compound by the sulfonation reaction of alkyl nitrite in acidic alcohol solution, respectively One of intermediate VII or Villa, VIb compounds;

(VII) (Via) (VIb)

(2) Step 2: The intermediate VII compound with the following acylating reagent

O O 0 o o

II II II II II

Rj——C——O——C——Rj—C—CI CI——C—— Z “C—CI or its equivalent acylating reagent is esterified to obtain the corresponding compound of formula I, III;

Or one of the intermediate Villa or Vlllb compounds with the following acylating reagents

O O 0

Rj-C II—O—C II—Rj—C II—CI or its equivalent acylating reagent is esterified to give the corresponding compound of formula II a or II b;

Wherein ^ and are as defined in claim 1.

A photocurable composition comprising a photoinitiator and at least one carbon-carbon double bond compound capable of undergoing radical polymerization, the photoinitiator comprising at least one of the formulae I, II a, II b of claim 1. , and compounds of III.

8. The photocurable composition of claim 7 further comprising an additive.

9. The photocurable composition of claim 8 which comprises from 0.05 to 25% by weight of the total composition of the carbon-carbon double bond compound and the additive in excess of the above components.

The photocurable composition according to claim 7 or 8, wherein the carbon-carbon double bond compound is selected from the group consisting of an acrylate compound and a methacrylate compound. Things.

11. The photocurable composition of claim 8, wherein the additive comprises a developable resin, a pigment or a dye.

12. Use of a photocurable composition, i.e., any of the photocurable compositions of claim 7 or 8 for the manufacture of one of the following colored or transparent articles: paint, ink, adhesive, light Resist 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.

A method of curing a photocurable composition, which comprises applying the photocurable composition according to claim 7 or 8 to a substrate, and curing the coating layer by irradiation with light having a wavelength of from 190 to 600 nm.

14. The method of curing a photocurable composition according to claim 13, which is from a sun, a mercury lamp, a high pressure mercury lamp or an LED lamp.

15. The photocurable composition of claim 11 further comprising a solvent.

A method for producing a raised pattern by using a photocurable composition, the photocurable composition according to claim 15 is applied to a substrate, and the unexposed portion is removed by drying, exposure, and development to obtain a bump. pattern.

17. A color filter comprising black, red, green, blue pixels, any compound, monomer, alkali soluble resin comprising a compound of the formula I, II a, li b and III of claim 1. The composition of the corresponding pigment, additive and solvent is sequentially obtained by coating, exposure, development, and heat treatment.

18. A method of fabricating a color filter comprising black, red, green, and blue pixels, the method of manufacture comprising containing the formulas I, II a, li b, and III of claim 1. A composition comprising any of the compounds, a monomer, an alkali-soluble resin, and a corresponding pigment, an additive, and a solvent is sequentially coated, exposed, developed, and heat-treated to finally obtain the color filter.