JP2016500710A - Cyclopentanedione oxime ester and its application - Google Patents

Abstract

The present invention relates to compounds of general formulas I, IIa, IIb, III and IV and processes for their preparation, wherein Ar1 is a substituted orthoarylene or orthoheteroarylene and Ar2 is a double orthoarylene or double orthoheteroarylene linked in various ways. Y1 is O, S, NR20, BR20, CR15R16, SiR15R16, S = O, C = O, Z1 is a straight bond, a C1-C10 alkylene group, an arylene group, R1, R15, R16, Each of the R20 groups is a hydrogen atom, an alkyl group or an alkoxy group, an alkyl group or alkoxy group substituted with an arbitrary group, a cycloalkyl group, an aryl group substituted with an arbitrary group, or an acyl group. The present invention further relates to a photocuring composition using the compounds of general formulas I, IIa, IIb, III and IV as photopolymerization initiators. Excellent overall performance is shown. [Selection figure] None

Description

  The present invention is characterized in that an esterified derivative of cyclopentanedione oxime is condensed to an arylene group, and the esterified oxime group is located at the 2-position, and functions as a photopolymerization initiator in a photocuring composition Relates to compounds.

Oxime ester compounds have long been found as photopolymerization initiators, and Patent Documents US3558309 and US4255513 both disclose that oxime ester compounds are used as photopolymerization initiators. Since the stability is not good or the photosensitivity is low, the needs of the modern electronics industry cannot be satisfied in the performance such as thermal stability and photosensitivity. CN1514845A discloses a series of oxime ester compounds, of which OXE01 and OXE02 are marketed. Products with similar performance include oxime esters 305 and 304 disclosed in CN101565472B and CN101508744B.

  Patents relating to other oxime ester photopolymerization initiators include WO2006018973, WO2007071497, CN1805955B, CN1922142B, CN1928715A, CN101508744B, CN102020727, etc. When the modification is performed and the molecular weight is increased, the photosensitivity cannot be improved at all, and it is very difficult to produce such as the substituted carbazoloheterocyclodione oxime ester described in CN102046667B.

It was unexpectedly discovered that the compounds of the following general formulas I, IIa, IIb, III and IV have extremely excellent photopolymerization initiator activity.
Series 1: compounds of general formula I, IIa, IIb, III and IV, where
Ar ₁ is linked to Y1 and a carbonyl group by two adjacent atoms to form a condensed ring structure, and the substituents at the other atoms are a hydrogen atom, a halogen atom, a C ₁ -C ₁₂ alkyl group, C _{5, respectively.} -C ₇ cycloalkyl group, C ₁ -C ₄ alkyl group substituted with C ₅ -C ₇ cycloalkyl group, phenyl group; one or more C1-C4 alkyl group, carboxyl group, C ₁ -C ₁₂ alkyl Amyl group or arylformyl group, heteroarylformyl group, XR ₁₇ , phenyl group, halogen atom, phenyl group optionally substituted with CN; C ₁ -C ₄ alkylbenzyloxy group, substituted with R ₁ C (O) O C ₁ -C ₄ alkoxy group, C ₁ -C ₃ alkylenedioxy group, R ₁ C (O) O, C ₁ -C ₁₂ alkylthio group, C ₁ -C ₄ alkylphenylthio group, R ₁ C ( O) C ₁ -C ₄ alkylthio group substituted by O, CN, carboxyl group, C ₁ -C ₁₂ alkoxyformyl group, aryl Ruhorumiru group, a heteroaryl formyl group, ortho arylene or ortho heteroarylene is XR _18.
Alternatively, two adjacent substituents in the above substituent of Ar ₁ , or between the substituent and Ar ₁ are linked via a straight bond, a carbon atom, or a carbonyl group to form a ring structure.
X is O, S or NR ₁₉ .
Y ₁ is O, S, NR ₂₀ , BR ₂₀ , CR ₁₅ R ₁₆ , SiR ₁₅ R ₁₆ , S═O or C═O.
Ar ₂
It is.
Z ₁ is a straight bond, a C ₁ -C ₁₀ linear or branched alkylene group, one or more oxygen, sulfur atoms linked to a terminal group, or inserted into one or more oxygen, sulfur atoms A C ₂ -C ₁₀ linear or branched alkylene group, an unsubstituted or substituted arylene group.
Y ₂ is straight bond, O, S, NR ₂₀ , BR ₂₀ , CR ₁₅ R ₁₆ , SiR ₁₅ R ₁₆ , C═O or Y ₃ —Z ₂ —Y ₃ .
Z ₂ is C ₂ to be inserted into a straight-chain or branched-chain alkylene group having one or more oxygen, or one or more oxygen sulfur atom is linked to the end groups, the sulfur atom of the C ₁ -C ₁₀ straight or branched chain alkylene group having -C _10, an arylene group which is unsubstituted or substituted group.
Y ₃ is O, S, NR ₂₀ , BR ₂₀ or OC (O).
R ₁ is a hydrogen atom, a C ₁ -C ₁₈ alkyl group or a C ₁ -C ₁₈ alkoxy group; one or more halogen atoms, a C ₁ -C ₄ alkyl group, a C ₅ -C ₇ cycloalkyl group, a heterocycloalkyl group , Phenyl group, heteroaryl group, CN, optionally substituted by C ₁ -C ₄ alkylacyloxy, arylacyloxy, and / or inserted in C ₅ -C ₇ cycloalkylene group, phenylene group, O, S, NR ₁₇ C ₂ -C ₁₈ alkyl group; C ₂ -C ₁₈ alkenyl group, one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group , Heteroaryl group, CN, C ₁ -C ₄ alkanoyloxy, aroyloxy optionally substituted and / or C ₅ -C ₇ cycloalkylene group, phenylene group, C ₂ inserted in O, S, NR ₁₇ -C ₁₈ is an alkenyl group.
Or, R ₁ is a C ₅ -C ₇ cycloalkyl group, one or more C ₁ -C ₄ alkyl groups, a phenyl group, a halogen atom, or a C ₅ -C ₇ cycloalkyl group optionally substituted with CN. Yes; or R ₁ is a phenyl group; one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups, phenyl groups, halogen atoms, phenyl groups optionally substituted with CN; or R ₁ is naphthyl; or R ₁ is benzoyl or phenoxycarbonyl group, provided that the phenyl group is one or more halogen atoms, R ₁₇ , C ₅ or C ₆ cycloalkyl group, CN, OH, XR ₁₇ Is replaced by
Each of R ₁₁ and R ₁₂ is a C ₁ -C ₄ alkyl substituted with a hydrogen atom, a halogen atom, a C ₁ -C ₁₂ alkyl group, a C ₅ -C ₇ cycloalkyl group, or a C ₅ -C ₇ cycloalkyl group. Group, C ₁ -C ₁₂ alkoxy group, C ₁ -C ₄ alkylbenzyloxy, phenyl group; one or more C ₁ -C ₄ alkyl group, carboxyl group, C ₁ -C ₁₂ alkyl acyl group or arylformyl group , Heteroarylformyl group, XR ₁₇ , phenyl group, halogen atom, phenyl group optionally substituted by CN; C ₁ -C ₄ alkylbenzyloxy group; one or more C ₁ -C ₁₂ alkoxy groups, C ₁ -C ₄ alkylbenzyl group, R ₁ C (O) alkoxy group is replaced by _{O; R 1 C (O)} O, CN, carboxyl group, C ₁ -C ₁₂ alkoxycarbonyl group, an arylcarbonyl group, heteroarylene substituted or one or more C ₁ -C ₄ alkyl group; carbonyl group, XR ₁₈ Phenoxy groups; substituted C ₅ -C ₆ cycloalkyl group; a C ₁ -C ₈ alkyl acyl, C ₅ -C ₆ cycloalkyl acyl group, an aryl formyl group, a phenoxy group substituted in the heteroaryl formyl group C ₁ -C ₄ alkyl acylphenoxy group, C ₁ -C ₃ alkylenedioxy group, C ₁ -C ₁₂ alkylthio group, C ₁ -C ₄ alkylthio group substituted by R ₁ C (O) O and C ₁ -C ₄ alkylphenylthio group; phenylthio group substituted by one C ₁ -C ₈ alkyl acyl group, C ₅ -C ₆ cycloalkyl acyl group, aryl forsyl group, heteroaryl forsyl group; or C A C ₁ -C ₄ alkyl acylphenylthio group substituted by a _5- C ₆ cycloalkyl group, or an epoxypropyl group, in which the epoxy group is optionally condensed with an alkyl aldehyde or a ketone.
Alternatively, R ₁₁ and R ₁₂ are connected to form a saturated or unsaturated structure.
R ₁₅ and R ₁₆ are each a hydrogen atom, a C ₁ -C ₁₈ alkyl group, a C ₁ -C ₅ alkyl group substituted by a carboxyl group or a C ₁ -C ₄ alkoxyacyl group, R ₁ C (O) C ₁ -C ₄ alkyl group substituted by O; one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, hetero C ₂ -C ₁₈ optionally substituted with an aryl group, CN, C ₁ -C ₄ alkylacyloxy, arylacyloxy, or inserted into a C ₅ -C ₇ cycloalkylene group, phenylene group, O, S, NR ₁₇ Each of R ₁₅ and R ₁₆ is a C ₅ -C ₇ cycloalkyl group; or C optionally substituted by one or more C ₁ -C ₄ alkyl groups, a phenyl group, a halogen atom, or CN. ₅ -C ₇ cycloalkyl group; or, R _15, each R _16, a phenyl group; one or more C ₁ -C ₄ al Le group, C ₁ -C ₄ alkoxy group, a carboxyl group, C ₁ -C ₁₂ alkyl acyl, C ₅ -C ₆ cycloalkyl formyl group, C ₂ -C ₄ substituted into C ₅ -C ₆ cycloalkyl group An alkylacyl group, a benzoyl group, XR ₁₇ , a phenyl group, a halogen atom, and a phenyl group optionally substituted with CN.
Or it said R _15, R ₁₆ together with the carbon atom or silicon atom linked jointly R _15, R _16, the number of atoms constituting the cyclic structure is a 4-7, or the R _15, R ₁₆ are each , Together with adjacent substituents, constitutes a cyclic structure having 4-7 atoms.
R ₁₇ is a C ₁ -C ₄ alkyl group.
R ₁₈ is a hydrogen atom, C ₁ -C ₁₈ alkyl group, C ₁ -C ₄ alkoxy amyl C ₁ -C ₅ alkyl group substituted in the group, C ₁ -C ₄ substituted in R ₁ C (O) O Alkyl group; one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxy, optionally substituted aryl acyloxyalkyl, or C ₅ -C ₇ cycloalkylene group, a phenylene group, O, is C ₂ -C ₁₈ alkyl group that is inserted S, the NR _17; or R ₁₈ is C ₅ -C ₇ cycloalkyl group; or one or more C ₁ -C ₄ alkyl groups, a phenyl group, a halogen atom, a C ₅ -C ₇ cycloalkyl group optionally substituted with CN; or R ₁₈ is a phenyl group, inserting one or more C ₁ -C ₁₂ alkyl group, a carboxyl group, C ₁ -C ₁₂ alkyl acyl group, or a phenylene, O, S, a NR ₁₇ C ₁ -C ₁₂ alkyl acyl, C ₅ -C ₆ cycloalkyl formyl group, C ₂ -C ₄ alkyl acyl group substituted on the C ₅ -C ₆ cycloalkyl which, aryl formate sill group, a heteroaryl Hol Sill group , XR ₁₇ , a phenyl group, a halogen atom, CN, and a phenyl group optionally substituted with NO ₂ .
Or R ₁₈ is a C ₁ -C ₄ alkyl acyl group, a C ₁ -C ₄ conjugated enoyl group, a benzoyl group, or a phenoxycarbonyl group, provided that the phenyl group is one or more halogen atoms, R ₁₇ , C Substituted by a ₅ or C ₆ cycloalkyl group, CN, OH, XR ₁₇ .
Alternatively, R ₁₈ is connected to the aromatic ring in Ar ₁ or Ar ₂ by a straight bond, a carbon atom, or a carbonyl group to form a new ring.
Each R _19, R _20, a hydrogen atom, C ₁ -C ₁₈ alkyl group, C ₁ -C ₅ alkyl group substituted C ₁ -C ₄ alkoxy-amyl, substituted in R ₁ C (O) O C ₁ -C ₄ alkyl group; one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxyalkyl, optionally substituted aryl acyloxyalkyl, or C ₅ -C ₇ cycloalkylene group, a C ₂ -C ₁₈ alkyl group that is inserted phenylene group, O, S, a NR _17.
Or each of R ₁₉ and R ₂₀ is a C ₅ -C ₇ cycloalkyl group; or C ₅ -C optionally substituted with one or more C ₁ -C ₄ alkyl groups, phenyl groups, halogen atoms, CN _{7 is a} cycloalkyl group.
Or each of R ₁₉ and R ₂₀ is a phenyl group; one or more C ₁ -C ₄ alkyl groups, carboxyl groups, C ₁ -C ₁₂ alkyl acyl groups, C ₅ -C ₆ cycloalkylformyl groups, C ₅ A C ₂ -C ₄ alkyl acyl group substituted with a —C ₆ cycloalkyl group, an arylamyl group, XR ₁₇ , a phenyl group, a halogen atom, and a phenyl group optionally substituted with CN.
Alternatively, R ₁₉ is connected to an aromatic ring in Ar ₁ or Ar ₂ by a straight bond, a carbon atom, or a carbonyl group, thereby forming a new ring.
And when Ar ₁ is a substituted carbazole group, Y ₁ is not C, O, S, NR ₂₀ .

Series 2: Compounds of the general formulas I, IIa, IIb, III and IV, wherein Ar ₁ is an orthoarylene group or an orthoheteroarylene group, but the condensed ring is formed by two or more of the aromatic ring and the heterocycle. The orthoarylene group or orthoheteroarylene group, not the constructed orthoarylene group or orthoheteroarylene group, is linked to Y ₁ and the carbonyl group by two adjacent atoms to form a condensed ring structure, and in the remaining atoms C ₁ -C ₄ alkyl group substituted by hydrogen atom, halogen atom, C ₁ -C ₁₂ alkyl group, C ₅ -C ₇ cycloalkyl group, C ₅ -C ₇ cycloalkyl group, respectively Phenyl optionally substituted with one or more C ₁ -C ₄ alkyl groups, carboxyl groups, C ₁ -C ₁₂ alkyl acyl groups or aryl amyl groups, XR ₁₇ , phenyl groups, halogen atoms, CN Group; C ₁ -C ₄ alkylbenzyloxy group, C ₁ -C ₄ alkoxy group substituted by R ₁ C (O) O, C ₁ -C ₃ alkylenedioxy group, R ₁ C (O) O, C ₁ -C ₁₂ alkylthio group C ₁ -C ₄ alkylphenylthio group, R ₁ C (O) O substituted C ₁ -C ₄ alkylthio group, CN, carboxyl group, C ₁ -C ₁₂ alkoxyformyl group, arylformyl group, heteroarylformyl is a group and XR _18; or, when ortho arylene group or an ortho heteroarylene group is a monocyclic structure, two adjacent substituents can configure a ring structure linked, fused ring aromatic hydrocarbon structure Do not configure. When the orthoarylene group or the orthoheteroarylene group is a non-fused ring structure having two or more rings, two adjacent substituents can be linked to form a cyclic structure.
The definitions of other groups in the structural formulas of general formulas I, IIa, IIb, III, and IV are the same as the related definitions in series 1.

Series 3: Compounds of the general formulas I, IIa, IIb, III and IV, wherein Ar ₁ is the following orthoarylene group or orthoheteroarylene group.
R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each a hydrogen atom, a halogen atom, a C ₁ -C ₁₂ alkyl group, a C ₅ -C ₇ cycloalkyl group, or a C ₅ -C ₇ cycloalkyl group. Substituted C ₁ -C ₄ alkyl group, C ₁ -C ₁₂ alkoxy group; one or more C ₁ -C ₁₂ alkoxy group, C ₁ -C ₄ alkyl benzyloxy group, R ₁ C (O) O Substituted C ₁ -C ₄ alkoxy group; phenyl group; one or more C ₁ -C ₄ alkyl group, carboxyl group, C ₁ -C ₁₂ alkyl acyl group or arylformyl group, heteroarylformyl group, XR ₁₇ , Phenyl group, halogen atom, phenyl group optionally substituted by CN; C ₁ -C ₄ alkylbenzyloxy group, R ₁ C (O) O, C ₁ -C substituted by R ₁ C (O) O ₄ alkylthio group, CN, carboxyl group, C ₁ -C ₁₂ alkoxycarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, XR ₁₈ , one or more C ₁ -C ₄ phenoxy groups are substituted in the alkyl group; a C ₁ -C ₈ alkyl acyl, C ₅ -C ₆ cycloalkyl acyl group, an aryl formate sill group, a phenoxy group substituted in the heteroaryl Hol Sill group; C ₁ -C ₄ alkyl acylphenoxy group substituted by a C ₅ -C ₆ cycloalkyl group; C ₁ -C ₃ alkylenedioxy group, C ₁ -C ₁₂ alkylthio group; R ₁ C (O) O substituted C ₁ -C ₄ alkylthio group and C ₁ -C ₄ alkylphenylthio group; substituted with one C ₁ -C ₈ alkyl acyl group, C ₅ -C ₆ cycloalkyl amyl group, aryl formyl group, heteroaryl formyl group Or a C ₁ -C ₄ alkylamylphenylthio group substituted by a C ₅ -C ₆ cycloalkyl group.
Or each of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ is an epoxypropyl group, provided that the epoxy group is optionally condensed with a C ₁ -C ₄ alkyl aldehyde, a ketone;
Or in R ₁₁ -R ₁₄ , adjacent ones are connected to form a saturated or unsaturated cyclic structure.
X is O, S or NR ₁₉ .
Y ₁ is O, S, NR ₂₀ , CR ₁₅ R ₁₆ or C═O.
Ar ₂
It is.
Y ₂ is O, S, NR ₂₀ or Y ₃ —Z ₂ —Y ₃ ; Z ₂ is a C ₁ -C ₁₀ linear or branched alkylene group, one or more oxygen, sulfur atoms are terminal groups Or a C ₂ -C ₁₀ linear or branched alkylene group which is linked to or inserted into one or more oxygen or sulfur atoms, an unsubstituted or substituted arylene group.
Y ₃ is O, S, NR ₂₀ or OC (O).
R ₁ is a C ₁ -C ₄ alkyl group, a C ₅ -C ₇ cycloalkyl group, a C ₂ -C ₆ alkyl group substituted by a C ₅ -C ₇ cycloalkyl group, a C ₂ -C ₄ alkenyl group, or R ₁ is a phenyl group or a phenyl group optionally substituted with one or more C ₁ -C ₄ alkyl groups or C ₁ -C ₄ alkoxy groups; a benzoyl group.
Each of R ₁₅ and R ₁₆ is a hydrogen atom, a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₅ alkyl group substituted with a carboxyl group, or a C ₁ -C ₄ substituted with R ₁ C (O) O. An alkyl group, or R ₁₅ and R ₁₆ are each a C ₅ -C ₇ cycloalkyl group, or R ₁₅ and R ₁₆ are each a phenyl group or one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy group, carboxyl group, C ₁ -C ₁₂ alkyl acyl group, C ₅ -C ₆ cycloalkylformyl group, C ₁ -C ₄ alkyl acyl group substituted by C ₅ -C ₆ cycloalkyl group, or A phenyl group optionally substituted with a benzoyl group.
Or said R _15, R ₁₆ each, R _15, atoms together with the carbon atom or硅原terminal connected to R ₁₆ constitutes an annular is 4-7. Alternatively, each of R ₁₅ and R ₁₆ together with the adjacent substituent forms a ring having 4-7 atoms.
R ₁₈ is C ₁ -C ₁₈ alkyl group, C ₁ -C ₄ alkoxy amyl group C ₁ -C ₅ alkyl group substituted, C ₁ -C ₄ alkyl group substituted on R ₁ C (O) O, one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, a heterocycloalkyl group, a phenyl group, a heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxyalkyl, aryl acyloxyalkyl An optionally substituted C ₂ -C ₁₈ alkyl group; a C ₅ -C ₇ cycloalkylene group, a phenylene group, a C ₂ -C ₁₈ alkyl group inserted into O, S, NR ₁₇ .
Or R ₁₈ is a C ₅ -C ₇ cycloalkyl group, one or more C ₁ -C ₄ alkyl groups, a phenyl group, a halogen atom, or a C ₅ -C ₇ cycloalkyl group optionally substituted with CN.
Or R ₁₈ is a phenyl group, one or more C ₁ -C ₁₂ alkyl groups, a carboxyl group, a C ₁ -C ₁₂ alkyl acyl group, a phenylene group, or C ₂ -C inserted in O, S or NR _{17 12} alkyl acyl group, C ₅ -C ₆ cycloalkylformyl group, C ₂ -C ₄ alkyl acyl group substituted by C ₅ -C ₆ cycloalkyl group, aryl acyl group, heteroaryl acyl group, XR ₁₇ , phenyl group , A phenyl group optionally substituted with a halogen atom, CN or NO ₂ .
Or R ₁₈ is a C ₁ -C ₄ alkyl acyl group, a C ₁ -C ₄ conjugated enoyl group, a benzoyl group, or a phenoxycarbonyl group, provided that the phenyl group has one or more halogen atoms, R ₁₇ , C It is optionally substituted with a ₅ or C ₆ cycloalkyl group, CN, OH, XR ₁₇ .
Each R _19, R _20, a hydrogen atom, C ₁ -C ₁₈ alkyl group, C ₁ -C ₅ alkyl group which is substituted in the C ₁ -C ₄ alkoxy-amyl, substituted in R ₁ C (O) O C ₁ -C ₄ alkyl group; one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxyalkyl, optionally substituted aryl acyloxyalkyl, or C ₅ -C ₇ cycloalkylene group, a phenylene group, O, S, C ₂ -C ₁₈ alkyl groups are inserted arbitrarily NR _17; or C _{A 5-} C ₇ cycloalkyl group; or a C ₅ -C ₇ cycloalkyl group optionally substituted with one or more C ₁ -C ₄ alkyl groups, a phenyl group, a halogen atom, CN; or a phenyl group and one or more C ₁ -C ₄ alkyl group, carboxyl group, C ₁ -C ₁₂ alkyl acyl, C ₅ -C ₆ cycloalkyl formate Group, a C ₅ -C ₆ cycloalkyl C ₂ -C ₄ alkyl acyl group substituted in groups, aryl acyl group, XR _17, a phenyl group, a halogen atom, a phenyl group optionally substituted in the CN.
The definitions of other groups in the structural formulas of general formulas I, IIa, IIb, III and IV are the same as the definitions of the groups of related compounds in series 2.

Series 4: compounds of general formulas I, IIa, IIb, III and IV,
Ar ₁

And
Each of R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ is a hydrogen atom; substituted with one or more C ₁ -C ₁₂ alkoxy groups, C ₁ -C ₄ alkylbenzyloxy groups, R ₁ C (O) O A C ₁ -C ₄ alkoxy group; a phenoxy group substituted by one or more C ₁ -C ₄ alkyl groups; one C ₁ -C ₈ alkyl acyl group, an arylformyl group, a heteroarylformyl group, C ₅ -C ₆ phenoxy group are substituted cycloalkyl _{amyl; C 5 -C 6 C 1 -C} 4 alkyl acyl phenoxy group is replaced by a cycloalkyl group; C ₁ -C ₃ alkylenedioxy group, R ₁ C (O) O, C ₁ -C ₁₂ alkylthio group; C ₁ -C ₄ alkylthio group substituted by R ₁ C (O) O; C ₁ -C ₄ alkylphenylthio group; R ₁ C (O) O C ₁ -C ₄ alkyl phenylthio group are substituted; one of C ₁ -C ₈ alkyl acyl group, an aryl formyl group, substituted phenyl C ₅ -C ₆ cycloalkyl amyl group A or C ₅ -C ₆ C ₁ -C ₄ alkyl amyl phenyl thio group which is substituted in the cycloalkyl group; O group.
Y ₁ is CH ₂ , CHCH ₃ or C (CH ₃ ) ₂ .
Ar ₂
It is.
Z ₁ is a straight bond or a 1,3-phenylene group.
R ₁ is a methyl group, an ethyl group, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 2,4,6-trimethylphenyl group or a 2,6-dimethoxyphenyl group.
R ₂₀ is a C ₁ -C ₈ alkyl group. The definitions of other groups in the structural formulas of general formulas I, IIa, IIb, III and IV are the same as the definitions of the groups of related compounds in series 3.

Series 5: Compounds of general formula I and IIa and IIb and III and IV, the substituents of Ar _1, at least one substituent is in the para position of the carboxyl group linked with Ar _1; in Ar ₂ , O atom or N atom is in the para position of the carboxyl group linked to the benzene ring.

Series 6: Compounds of the general formulas I, IIa, IIb, III and IV, wherein Ar1 is an orthoarylene group or an orthoheteroarylene group, and the orthoarylene group or the orthoheteroarylene group is bonded to Y ₁ by two adjacent atoms. Connected to a carboxyl group to form a condensed ring structure, and each of the substituents in the remaining atoms is a hydrogen atom, a halogen atom, a C ₁ -C ₁₂ alkyl group, a C ₅ -C ₇ cycloalkyl group, a C ₅ -C ₇ cycloalkyl substituted basis C ₁ -C ₄ alkyl group, a phenyl group, one or more C ₁ -C ₄ alkyl group, carboxyl group, C ₁ -C ₁₂ alkyl acyl or aryl acyl group, XR ₁₇ Phenyl group optionally substituted with phenyl group, halogen atom, CN; C ₁ -C ₄ alkylbenzyloxy group; C ₁ -C ₄ alkoxy group substituted with R ₁ C (O) O; C ₁ -C ₃ alkylene dioxy group, R ₁ C (O) O, C ₁ -C ₁₂ alkylthio Group, C ₁ -C ₄ alkylphenylthio group; C ₁ -C ₄ alkylthio group substituted by R ₁ C (O) O; CN, carboxyl group, C ₁ -C ₁₂ alkoxycarbonyl group, arylcarbonyl group, hetero arylene group, a XR _18.
Alternatively, in the substituent, a ring structure can be formed by connecting two adjacent substituents or between the substituent and Ar ₁ through a straight bond, a carbon atom, or a carbonyl group.
X is O, S or NR ₁₉ .
Y ₁ is CR ₁₅ R ₁₆ . The definitions of other groups in the structural formulas of general formulas I, IIa, IIb, III and IV are the same as the definitions of the groups of related compounds in series 1.

Series 7: compounds of general formula I,
Ar ₁ is ortho arylene group or an ortho heteroarylene group, ortho arylene group or an ortho heteroarylene group is linked to Y ₁ and the carbon atom by two adjacent atoms constitute a fused ring structure, the substituent in the remaining atoms Are a hydrogen atom, a C ₁ -C ₁₂ alkyl group, a C ₅ -C ₇ cycloalkyl group, a C ₁ -C ₄ alkyl group substituted with a C ₅ -C ₇ cycloalkyl group, and XR ₁₈ .
Alternatively, two adjacent substituents in the above substituent or between the substituent and Ar ₁ can be linked via a straight bond, a carbon atom, or a carbonyl group to form a cyclic structure. However, Ar ₁ is not a substituted carbazole group.
X is O, S or NR ₁₉ .
Y ₁ is O, S, CR ₁₅ R ₁₆ , C = O.
R ₁ is a hydrogen atom, a C ₁ -C ₁₈ alkyl group or an alkoxy group; one or more halogen atoms, a C ₁ -C ₄ alkyl group, a C ₅ -C ₇ cycloalkyl group, a heterocycloalkyl group, a phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxyalkyl, optionally substituted aryl acyloxyalkyl, and / or C ₅ -C ₇ cycloalkylene group, C ₂ to be inserted phenylene group, O, S, a NR ₁₇ -C ₁₈ alkyl radical; C ₂ -C ₁₈ alkenyl group; one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, a heterocycloalkyl group, phenyl group, heteroaryl group C ₂ -C ₁₈ optionally substituted with C ₁ , C ₁ -C ₄ alkylacyloxy, arylacyloxy, and / or inserted into a C ₅ -C ₇ cycloalkylene group, phenylene group, O, S, NR ₁₇ An alkenyl group. Or R ₁ is a C ₅ -C ₇ cycloalkyl group or one or more C ₁ -C ₄ alkyl groups, a phenyl group, a halogen atom, or a C ₅ -C ₇ cycloalkyl group optionally substituted with CN. Or R ₁ is a phenyl group; or one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups, phenyl groups, halogen atoms, and phenyl groups optionally substituted with CN. Or, R ₁ is a naphthyl group. Or R ₁ is a benzoyl group or a phenoxycarbonyl group, provided that the phenyl group is optionally substituted with one or more halogen atoms, R ₁₇ , C ₅ or C ₆ cycloalkyl groups, CN, OH, XR ₁₇ Is done.
Each of R ₁₅ and R ₁₆ is a hydrogen atom, a C ₁ -C ₁₈ alkyl group; one or more halogen atoms, a C ₁ -C ₄ alkyl group, a C ₅ -C ₇ cycloalkyl group, a heterocycloalkyl group, Phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxy, aryl acyloxy optionally substituted, or C ₅ -C ₇ cycloalkylene group, phenylene group, O, S, C inserted into NR ₁₇ it is ₂ -C ₁₈ alkyl group; or a C ₅ -C ₇ cycloalkyl group. Or each of R ₁₅ and R ₁₆ is a phenyl group; or a phenyl group optionally substituted with one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups, phenyl groups, halogen atoms, CN It is.
Alternatively, R ₁₅ and R ₁₆ together with the carbon atoms connected together form a ring having 4-7 atoms.
R ₁₇ is a C ₁ -C ₄ alkyl group.
R ₁₈ is a phenyl group; substituted by one or more C ₁ -C ₁₂ alkyl groups, C ₁ -C ₁₂ alkyl acyl groups, C ₅ -C ₆ cycloalkylformyl groups, C ₅ -C ₆ cycloalkyl groups A C ₂ -C ₄ alkyl acyl group, an aryl acyl group, a heteroaryl acyl group, a phenyl group optionally substituted with XR ₁₇ or NO ₂ ; a phenyl group substituted with one C ₂ -C ₁₂ alkyl acyl group The alkyl group therein is optionally inserted into a phenylene group, O, S or NR ₁₇ . An arylacyl group is an unsubstituted benzoyl group, which is a benzoyl group that is substituted with one or more halogens, C ₁ -C ₈ alkyl groups, or C ₁ -C ₈ alkoxy groups.
Alternatively, R ₁₈ is linked to the aromatic ring in Ar ₁ via a straight bond, a carbon atom, or a carbonyl group to form a new ring.
R ₁₉ is a hydrogen atom, C ₁ -C ₁₈ alkyl group, C ₁ -C ₄ alkoxy amyl C ₁ -C ₅ alkyl group substituted in the group, C ₁ -C ₄ substituted in R ₁ C (O) O Alkyl group; one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxy, A C ₂ -C ₁₈ alkyl group optionally substituted with an arylacyloxy or inserted into a C ₅ -C ₇ cycloalkylene group, a phenylene group, O, S, NR ₁₇ ; or a C ₅ -C ₇ cycloalkyl group; Or one or more C ₁ -C ₄ alkyl groups, a phenyl group, a halogen atom, a C ₅ -C ₇ cycloalkyl group optionally substituted with CN; or a phenyl group; and one or more C ₁ -C ₄ alkyl group, carboxyl group, C ₁ -C ₁₂ alkyl acyl, C ₅ -C ₆ cycloalkyl formyl group, C ₅ -C ₆ cycloalk C ₂ -C ₄ alkyl acyl group, an aryl acyl group, XR ₁₇ is replaced by a group, a phenyl group, a halogen atom, a phenyl group optionally substituted in the CN.
Alternatively, R ₁₉ can be connected to the aromatic ring in Ar ₁ via a straight bond, a carbon atom, or a carbonyl group to form a new ring. The definitions of the other groups in the structural formula of general formula I are the same as the definitions of the groups of related compounds in series 1.
In the above general formulas I, IIa, IIb, III and IV, R ₁ C (O) is replaced with (R ₁ ) ₂ P or R ₁ S (O ₂ ) to produce the corresponding phosphite or sulfonate ester And has the function of inducing photoinduced free radicals or photoinduced cations.

Series 8: Typical structures in the compounds of the general formulas I, IIa, IIb, III and IV described in the above series 1 to 7 are
It is.

The present invention further provides a process for preparing compounds of general formulas I, IIa, IIb, III and IV in series 1-8. Specifically, the following steps are included.
(1) Step 1: Acidify with alkyl nitrite in the cycloalkylene group at the ortho position of the carboxyl group of the compound of V or VIa and VIb (Ar ₁ , Y ₁ and Ar ₂ are as defined above) Oxidation is selectively performed by a method in which an oximation reaction is generated in an alcohol solution, and each of the corresponding intermediates VII, VIIIa, and VIIIb is obtained (when the oxime group has cis-antisteric chirality) A single chiral VII or VIIIa, VIIIb compound or a mixture of isomers thereof.)
(2) Step 2: Intermediate VII compound is converted into the following acylating reagent
Alternatively, an esterification reaction with an equivalent acylating reagent is generated to obtain the corresponding general formula I, III and IV compounds.
Or intermediate VIIIa or VIIIb compound
Alternatively, an esterification reaction with an equivalent acylating reagent is generated to obtain the corresponding compound of the general formula IIa or IIb.
When the intermediate VIIIa and VIIIb compounds have stereochiral chirality, single chiral general formulas I, III, IV or IIa, IIb compounds or mixtures of the respective isomers are obtained, and the definitions of R ₁ and Z ₁ are as described above. It is the same as the description.

The present invention further provides compounds of the general formula V, in which:
Ar ₁ is linked to Y ₁ and a carbonyl group by two adjacent atoms to form a condensed ring structure, and each of the substituents in the remaining atoms is a hydrogen atom, a C ₁ -C ₁₂ alkyl group, a C _5- A C ₇ cycloalkyl group, a C ₁ -C ₄ alkyl group substituted with a C ₅ -C ₇ cycloalkyl group, an orthoarylene group or an orthoheteroarylene group which is XR ₁₈ , or a substituent of the Ar ₁ A ring structure is formed by connecting a straight bond, a carbon atom, or a carbonyl group between two adjacent substituents or between the substituent and Ar ₁ . X is O, S, NR ₁₉ where Ar ₁ is not a substituted carbazole group.
Y ₁ is O, S, CR ₁₅ R ₁₆ , C = O.
Each of R ₁₅ and R ₁₆ is a hydrogen atom, a C ₁ -C ₁₈ alkyl group; one or more halogen atoms, a C ₁ -C ₄ alkyl group, a C ₅ -C ₇ cycloalkyl group, a heterocycloalkyl group, Phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxy, aryl acyloxy optionally substituted, or C ₅ -C ₇ cycloalkylene group, phenylene group, O, S, C inserted into NR _{17 2} -C ₁₈ alkyl radical; C ₅ -C ₇ cycloalkyl group, a phenyl group; one or several C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxy group, a phenyl group, a halogen atom, optionally in the CN It is a substituted phenyl group.
Alternatively, R ₁₅ and R ₁₆ together with a carbon atom jointly connected to both form a ring having 4-7 atoms.
R ₁₇ is a C ₁ -C ₄ alkyl group.
R ₁₈ is a phenyl group; one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₁₂ alkyl acyl groups, phenylene groups, or C ₂ -C ₁₂ alkyl acyl groups inserted into O, S or NR ₁₇ , C ₅ -C ₆ cycloalkylformyl group, C ₂ -C ₄ alkyl acyl group substituted by C ₅ -C ₆ cycloalkyl group, arylformyl group, heteroarylformyl group, XR ₁₇ or NO ₂ optionally substituted The arylacyl group is an unsubstituted benzoyl group, one or more halogens, a C ₁ -C ₈ alkyl group, a benzoyl group substituted by a C ₁ -C ₈ alkoxy group.
R ₁₉ is a hydrogen atom, C ₁ -C ₁₈ alkyl group, C ₁ -C ₄ alkoxy amyl C ₁ -C ₅ alkyl group substituted in the group, C ₁ -C ₄ substituted in R ₁ C (O) O Alkyl group; one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxy, A C ₂ -C ₁₈ alkyl group optionally substituted with an arylacyloxy or inserted into a C ₅ -C ₇ cycloalkylene group, a phenylene group, O, S, NR ₁₇ ; or a C ₅ -C ₇ cycloalkyl group; Or one or more C ₁ -C ₄ alkyl groups, a phenyl group, a halogen atom, a C ₅ -C ₇ cycloalkyl group optionally substituted with CN; or a phenyl group; and one or more C ₁ -C ₄ alkyl group, carboxyl group, C ₁ -C ₁₂ alkyl acyl, C ₅ -C ₆ cycloalkyl formyl group, C ₅ -C ₆ cycloalk C ₂ -C ₄ alkyl acyl group, an aryl acyl group, XR ₁₇ is replaced by a group, a phenyl group, a halogen atom, a phenyl group optionally substituted in the CN.

  The present invention further includes a photocurable composition comprising a photopolymerization initiator comprising at least one compound of the general formulas I, IIa, IIb, III and IV, and at least one carbon-carbon double bond compound capable of radical polymerization. Related to things.

  The photopolymerization initiator includes any one of the compounds of the general formulas I, IIa, IIb, III and IV, or a combination of any two or more compounds. A polymerization initiator is included as a co-initiator component.

  The photocurable composition further contains additives such as essential functional components such as developable resins, pigments, and antifoaming agents.

  The photopolymerization initiator accounts for 0.05 to 25% by weight, preferably 2 to 15% by weight in the entire composition, and the other components occupy the remaining proportion excluding the above components.

  Component (b) is a radically polymerizable carbon-carbon double bond compound, and the molecule contains one carbon-carbon double bond or two or more carbon-carbon double bonds. Compounds containing one carbon-carbon double bond are, for example, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, isobornyl acrylate, hydroxyethyl acrylate, acrylates or methacrylates of monohydric alcohols with methyl methacrylate. Preferred are acrylate compounds, methacrylate compounds and acrylonitrile, N-dialkylacryloamide, N-vinylpyrrolidone, vinylbenzene, vinyl acetate and vinyl ether.

  Compounds containing two or more carbon-carbon double bonds include, for example, alkyl diols, polyol acrylates or methacrylates or polyester polyols, polyether polyols, epoxy resin polyols, polyurethane polyol acrylates, vinyl ethers and unsaturated dicarboxylic acid polyols. There is unsaturated polyester. Examples include polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, multiethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, polyester oligomer acrylate, urethane oligomer acrylate, aromatic Group epoxy resin acrylate and maleic glycol polyester.

  These carbon-carbon double bonds may be used alone or in combination of two or more, or are copolymerized in advance between the mixtures to constitute an oligomer used for producing the composition. When the polymerizable monomer contains an alkali-soluble group such as a carboxylic acid group, a polymer resin having alkali solubility for producing a photoresist or a water-dispersible emulsion can be obtained.

  In addition to the compounds of the above general formulas I, IIa, IIb, III and IV as photoinitiators, other types of commercially available photoinitiators or auxiliary initiators are jointly used depending on the use of the composition. It can also arrange | position simultaneously as an initiator component (c). Usually, α-hydroxy ketones such as 2-hydroxy-2-methyl-1-propiophenone and 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-2-morpholino- (4-methylthiophenyl) -1- Α-amino ketones such as acetone, 2-dimethylamino-2-benzyl- (4-morpholinophenyl) -1-butanone, 2,2-diethoxy-1,2-acetophenone, methylphenylglyoxylate and diethylene glycol bisbenzoyl Formic acid and ester polybutylene glycol bisbenzoyl formate, (2,4,6-trimethylbenzoyl) diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and substituted derivatives such as benzophenone and benzophenone 4-methylbenzophenone, 4-chlorobenzophenone and 4-phenylbenzophenone 2'-chloro-4-phenylbenzophenone and 4-methylthiobenzophenone, 4- (2-hydroxyethylthio) benzophenone and 4-hydroxybenzophenone laurate and benzophenone-4-oxyacetic acid polyethylene glycol ester, 2-isopropylthioxanthone and 2 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthone-2-formic acid polyethylene glycol ester and thioxanthone such as thioxanthone-2-oxo acid polyethylene glycol ester and substituted derivatives thereof, 2 (4-methoxyphenyl-4 Halomethyltriazines such as 1,6-bis (trichloromethyl)-[1,3,5] -triazine, hexaarylbisimidazoles such as 6-hexaorthochlorophenylbiimidazole, ferrocene compounds, titanocene compounds, Acridines such as phosphorus, camphorquinone, 9-phenylacridine, amines such as 4,4-bis (diethylamino) benzophenone and 4-dimethylaminobenzoic acid ethyl ester, triethanolamine and methyldiethanolamine, or diethylamide and ethoxyl Active amine compounds such as trimethylolpropane triacrylate adduct, phosphites such as triphenyl phosphite and trilauryl phosphite, chain transfer agents such as hexanedithiol, octyl mercaptan.

  Component (d) contains pigments and dyes, which are essential ingredients for manufacturing printing inks and filters, depending on your needs, red, green, blue, black, white, yellow, magenta, cyan and other Specific colors that have been identified, and the corresponding pigments are commercially available such as carbon black, phthalocyanine blue, and titanium dioxide. The pigment concentration represents 10% to 30% of the weight of all solid components of the composition.

  Component (d) includes phenols and hindered amine polymerization inhibitors such as p-methoxyphenol and nitrosophenylhydroxylamine aluminum complex polymerization inhibitors, 2- (2'-hydroxyphenyl group) benzotriazole salicylic acid esters, triazines It further includes essential additives such as light absorbers such as leveling agents, leveling agents such as vinyltriethoxysilane, wetting agents, dispersing agents and the like. The amount of these used is not particularly limited as long as the property index of the composition can be reached.

  Component (d) further includes a developable resin. The alkali-soluble developable resin includes, for example, a polyacrylate copolymer having a carboxylic acid side chain, and the comonomer is acrylic or methacrylic acid, alkyl acrylate. Methacrylic acid alkyl ester, styrene, styrene oligomer. Examples of the solvent developable resin include conventional resins such as cellulose ester, cellulose ether, polyvinyl acetate, polyvinyl butyral, polystyrene, polycarbonate, PVC, polyester, and polyimide. When the developable resin is an alkali-soluble resin, the composition is used for manufacturing a photoresist and a color filter in a display device.

  The composition can further comprise a heat-drying resin and a thermosetting resin component (e) such as cellulose liquid, polyisocyanate, polyimide, etc., which meet the flow requirements of photocuring and thermosetting stage treatments. To do.

  In the composition, a compound having at least one epoxy group may be added as the thermosetting component (f), and one epoxy curing accelerator (g) may be added. As the compound having an epoxy group, a known thermosetting epoxy compound can be used as the thermosetting component (f). For example, an aliphatic epoxy resin or an aromatic epoxy resin, such as BPS-200 manufactured by Nippon Chemical Company, bisphenol S type epoxy resin, bisphenol A type epoxy resin, linear novolac type epoxy resin, and partial esters thereof The amount of the component (f) used is 30 to 70% with respect to 100% by weight of the component (b) in the composition.

  When the component (f) is used, if the accelerator (g) is used as a synergistic component, an excellent curing acceleration effect can be achieved. Examples include amine accelerators, imidazole accelerators, and other commonly used epoxy resin curing agents, and the amount used is less than 5% of the weight of component (f).

  In addition to the components (a), (b), (c), (d), (e), (f), and (g), the composition has the adhesion of the composition and the hardness of the film. As one of the additives to be improved, other additives (h) often used in this field including inorganic fillers such as barium sulfate, silica powder, talc, calcium carbonate, mica may be used. .

  The composition may be used after being diluted in a solvent according to the needs of the application field. Suitable solvents include ketones such as methyl ethyl ketone and cyclohexanone, toluene, xylene, octane, petroleum ether, and naphtha. Hydrocarbons such as, alcohols such as n-butanol and propanediol, alcohol ethers such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and esters thereof And amides such as N, N-dimethylformamide.

  The composition or the mixture diluted in a solvent is prepared by an ink manufacturing method and then stored in the dark.

  The composition can be used for the production of colored or transparent paints, binders or inks, and photoresists, and further printing of these products, 3D printing, production of color filters in display devices, image copy technology, printing It is used for circuit board media layers, electronic device packages, optical switches, three-dimensional molds, quartz fiber protective layers, medical products.

  The present invention provides a method for curing a carbon-carbon double bond compound in the photocuring composition. That is, the composition is applied to a substrate and irradiated with light of 190 to 600 nm to cure the coating layer. The light is emitted by the sun, mercury, high pressure mercury, or LED lamp. The composition is radiated by a light wave in a range of 190 to 600 nm or a light wave whose light wavelength is output by lattice control. The coating layer of the composition may be irradiated and cured by an LED light source having a predetermined wavelength range between 360 nm and 410 nm, for example, a 365 nm LED light source. The LED is a light emitting semiconductor diode.

  The method of creating a projection pattern from the cured composition is as follows. First, the cured composition is diluted with a solvent, the diluted photocured composition is applied to a substrate, and the portion not exposed by drying, exposure, and development. As a result, the protrusion pattern is obtained.

  In the present invention, a composition comprising at least one compound of general formulas I, IIa, IIb, III, and IV, a monomer, an alkali-soluble resin, a pigment, and an additive is used as a photoresist, and has high photosensitivity. It is easy to develop in an alkaline solvent, does not swell and deform, has a good imaging effect, and is applied to etching resist and resistance welding resist, image display and recording material, inkjet ink cured by LED lamp, LCD, OLED, It may be used in the manufacture of PDPs, in the manufacture of various printed versions and in the manufacture of electronic circuit boards or integrated circuits, and may be used in isolating coating layers for various electrical components.

  The composition has excellent oxidation resistance, polymerization resistance, and heat-resistant processing performance, satisfies the requirements of the production process of color filters, and is applied particularly to the production of liquid crystal displays and organic semiconductor electroluminescent displays.

  Using the composition of the present invention as a photoresist, through the processes of coating, exposure, development, and heat treatment, black, red, green, and blue are constituted in order, and a complete color filter is obtained. The base materials for these filters are glass or organic polymer films and ceramic pieces.

The present invention further includes producing a color filter with the above composition.
The composition is applied to a tablet and a curved substrate, and dried to obtain a film layer. By a mask exposure and development method, an unexposed portion is removed to obtain a projection pattern. A color filter including black, red, green and blue pixels is a composition comprising a compound comprising the general formulas I, IIa, IIb, III and IV of the present invention, a monomer, an alkali-soluble resin, and a corresponding pigment and additive. Obtained through coating, exposure, development, and heat treatment. It includes processing procedures such as cleaning.

  The composition of the present invention is evenly applied to the substrate to be applied by spin coating, roll coating, spray coating, transfer, and other coating techniques that are normally used in this field, and the coating amount depends on the needs. As usual, the typical thickness is 0.1 micron to 1 mm. When a solvent component is contained in the composition, the solvent is volatilized by a heating method such as an 80 ° C. drying method, and the non-volatile component becomes a Gale layer and remains on the base material.

  The next step is exposure, but when direct exposure with UV leather is not used, a mask with a pattern is placed on the galley layer, and light with a wavelength in a predetermined range is emitted by an ultraviolet light source or visible light source, and the energy is transferred to the transparent part of the mask. By passing through and exposing, the light receiving portion of the galle layer is cured, and the shielded portion is not cured.

  Subsequently, the unexposed part is removed by development to obtain a projection pattern. The development process is operated by parameters well known to those skilled in the art such as, for example, 30 ° C. spraying, rinsing and the like. Usually, development is carried out with an alkaline solvent such as an alkali metal hydroxide, carbonate solution or ammonia, and if necessary, a predetermined amount of a wetting agent such as a surfactant, cyclohexanone, acetone, ethylene glycol ethyl is added to the solution. An organic solvent such as ether may be added. The exposure film may be immersed in the developer or the developer may be sprayed onto the exposure film, but the specific development temperature and time are determined by development and curing. An alkaline solution for development is obtained by melting an alkaline substance into water or a solution containing a water-soluble organic solvent. As the alkaline substance, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, carbonate There are potassium hydrogen, triethanolamine, morpholino, and trisodium phosphate. The concentration range is 0.1 to 10% by weight, and a surfactant having a concentration of 0.05 to 5% by weight can be added to the above solution.

  The final heat treatment optimizes image fastness and is usually baked in a 200-260 ° C. heat oven for 15-45 minutes.

  Based on the known color filter production process, using the composition of the present invention, a color filter device can be manufactured, and excellent processing performance is shown, the array is clear, the light transmittance is high, and the quality is high. It can be applied to display production.

  The examples can explain the invention in more detail. All usage is calculated by weight unless otherwise indicated.

Example 1
Synthesis of 5-methylthioindane-1,2-dione-2-oxime-O-acetate

1a, Synthesis of 5-methylthioindane-1-ketone (etherification method A)

Put 3.33 g (0.02 mol) 5-chloro-1-indanone in a 50 ml three-necked flask, add 15 ml of N, N-dimethylacetamide, 4.2 g (0.03 mol) of 50% sodium thiomethoxide, protect with nitrogen, 20 Stir at -25 ° C for 5 h, add the reaction solution to 100 ml of water, extract twice with 25 ml of 1,2-dichloroethane, combine the 1,2-dichloroethane solution, wash twice with 10 ml of water, organic solution The residue is recrystallized with ethanol to give 2.5 g of off-white crystals after drying, yield 70.2%, analytical purity 98.02%, melting range 105-106 ° C.

1b, Synthesis of 5-methylthioindane-1,2-dione-2-oxime (oximation method A)

Melt 1.8 g (0.01 mol) of the etherified product obtained in 1a in a 100 ml three-necked flask with 30 ml of methanol, add 2 g of 36% concentrated hydrochloric acid, soak it in water and stir at 15 to 20 ° C. while keeping it warm. , Drop 1.55 g (0.015 mol) of butyl nitrite within 15 min, stir for 2 h, concentrate the reaction solution under reduced pressure to about 10 g, lower the temperature to 5-10 ° C., and filter to precipitate Yellow solid is 1.90 g after drying, analytical purity 99.15%, melting range 210-211 ° C., yield 91.8%.

1c, Synthesis of 5-methylthioindane-1,2-dione-2-oxime-O-acetate (esterification method A)
Melt 1.04 g (0.005 mol) of the product of 1b in 25 ml of 1,2-dichloroethane, drop 1.1 g (0.011 mol) of acetic anhydride into it, immerse in water at 25-30 ° C. and react for 1 h. The reaction is washed with 25 ml of 5% NaHCO3 solution until an aqueous phase is formed, and the organic phase is washed again with 25 ml of water until an aqueous layer is formed. The organic phase is dried with 1.5 g of anhydrous sodium sulfate for 2 h, filtered to remove the desiccant and the filtrate is dried under reduced pressure. Add 25 ml of ethyl acetate to the rest, heat until completely melted, add 0.05 g of activated charcoal and run for 0.5 h. Activated carbon is separated by hot filtration, the filtrate is cooled, crystals are precipitated, extraction filtration and dry filtration are performed to obtain 1.05 g of a light yellow solid powder product, content 97.65%, yield 84.3%. . The measured melting range is: 166.0 to 167.0 ° C. See Table 1 for data on ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Example 2
Synthesis of 5- (2-acetoxyethylthio) indan-1,2-dione-2-oxime-O-acetate
2a, according to etherification method A of example 1a, replacing 50% sodium thiomethoxide with 2-mercaptoethanol and sodium hydroxide and reacting with 5-fluoro-1-indanone to give 5- (2- Hydroxyethylthio group) indan-1-ketone was synthesized with pale yellow crystals in 91.1% yield.
2b, according to the oximation method of 1b of Example 1, using the product obtained in 2a as a raw material, an oximation reaction was performed, and after passing through methanol crystals, a light yellow solid product 5- (2-hydroxyethylthio group) indane- 1,2-Dione-2-oxime is obtained with a yield of 83.2%.
2c, according to the esterification method of 1c of Example 1, the reaction temperature was raised to 45-50 ° C. and purified to a pale yellow powdered diacetate product 5- (2-acetoxyethylthio group) indane-1,2 -Dione-2-oxime-O-acetate was obtained, purity 99.23%, yield 85.2%, see Table 1 for data on melting range and ¹ H-NMR (CDCl ₃ ) and δ (ppm) values .

Example 3
Synthesis of 5- (4-isopropylphenylthio) indan-1,2-dione-2-oxime-O-acetate

3a, Synthesis of 5- (4-Isopropylphenylthio group) indan-1-ketone (etherification method B)

3.33 g (0.02 mol) 5-Chloro-1-indanone is placed in a 50 ml three-necked flask, 30 ml of N, N-dimethylformamide (DMF), 4.2 g (0.027 mol) of 4-isopropylthiophenol, and 3.0 ml of anhydrous sodium carbonate are added. Add g, protect with nitrogen and stir at 40-45 ° C. for 6 h. DMF is depressurized and recovered, the rest is added to 100 ml of water, extracted twice with 25 ml of 1,2-dichloroethane, combined with 1,2-dichloroethane solution and selected twice with 10 ml of water . Place 3 cm of silicone in a Buchner funnel, extract and filter the organic phase, and concentrate the filtrate to dryness. The remaining one was recrystallized with methanol to obtain 5.11 g of pale yellow crystals after drying, yield 90.6%. It has an analytical purity of 98.2% and a melting range of 60.0-62.0 ° C.

3b, Synthesis of 5- (4-Isopropylphenylthio group) indan-1,2-dione-2 oxime (oximation method A)

2.83 g (0.01 mol) of the etherified product obtained in 3a is melted in 30 ml methanol into a 100 ml three-necked flask, and 2 g of 36% concentrated hydrochloric acid is added, and the mixture is kept warm at 15 to 20 ° C. while being immersed in water. After dropping 1.55 g (0.015 mol) of butyl nitrite within 15 min and stirring for 5 h, the reaction solution was cooled to 5-10 ° C., filtered, and the deposited yellow solid was 2.50 g after drying. The purity is 98.90%, the melting range is 194-195 ° C., and the yield is 80.3%.

3c, Synthesis of 5- (4-Isopropylphenylthio group) indane-1,2-dione-2-oxime-O-acetate (esterification method A)
Melt 1.56g (0.005mol) of 3c-1, 3b product in 25ml 1,2-dichloroethane, drop 1.1g (0.011mol) acetic anhydride, soak in water at 25-30 ℃ and react for 1h. The reaction is washed with 25 ml of 5% NaHCO3 solution until an aqueous phase is formed, and the organic phase is washed again with 25 ml of water until an aqueous layer is formed. The organic phase is dried with 1.5 g of anhydrous sodium sulfate for 2 h, the desiccant is removed by filtration, and the filtrate is dried under reduced pressure to give a yellow solid residue. Add 15 ml of ethyl acetate to the rest, heat until completely melted, add 0.05 g activated charcoal and run for 0.5 h. The activated carbon is subjected to hot filtration separation, cooling of the filtrate, precipitated crystals, and extraction filtration, and the filter cake is dried to obtain 1.58 g of a pale yellow sheet-like crystal product with a content of 98.15% and a yield of 89.5%. See Table 1 for data on melting range and ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Melt 1.56 g (0.005 mol) of 3c-2 and 3b in 25 ml of toluene, drop 1.1 g (0.011 mol) of acetic anhydride, and immerse in water at 25-30 ° C. for 1 h. The reaction is selected with 25 ml of 5% NaHCO 3 solution until an aqueous phase is formed and washed again with 25 ml of organic phase until an aqueous layer is formed. The organic phase is dried over 1.5 g of anhydrous sodium sulfate for 2 h, the desiccant is removed by filtration, and 20 ml toluene is evaporated under reduced pressure. Add 5 ml of petroleum ether (boiling range 60-90) to the rest, completely melt, filter through hot filtration, cool the filtrate, precipitate crystals, extract and filter, dry the filter cake and yellow granular crystals 1.61 g of product is obtained with a content of 99.3% and a yield of 91.2%. Refer to Table 1 for the melting range. ¹ H-NMR (CDCl ₃ ) and δ (ppm) values are the same as for the 3c-1 product.

Example 4
Synthesis of 5- (4-isopropylphenylthio) indan-1,2-dione-2-oxime-O- (2-methylbenzoic acid) ether

4c, acetic anhydride was replaced with O-methylbenzoyl chloride according to esterification method A of 3c of Example 3, and the pale yellow powdery product 5- (4-isopropylphenylthio group) indan-1,2-dione-2- Oxime-O- (2-methylbenzoic acid) ether is obtained. The purity is 98.53%. Refer to Table 1 for data on melting range, ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Example 5
Synthesis of 5-phenylthioindane-1,2-dione-2-oxime-O-acetate

5a, according to etherification method B of Example 3 3a, 4-isopropylthiophenol was replaced with thiophenol, anhydrous sodium carbonate was replaced with anhydrous potassium carbonate, and 5-phenylthioindan-1-ketone was synthesized. Yellow crystals, yield 90.3%, purity 97.2%.

5b, according to the oximation method A of 3b of Example 3, using the product obtained in 5a as a raw material, an oximation reaction was performed, and a yellow solid 5-phenylthioindane-1,2-dione-2 was obtained as a product from the reaction solution. -Oxime is precipitated, yield 98.2%, purity 95%.

5c, according to esterification method A of 3c of Example 3, the reaction product was obtained by crystallization purification of acetone to obtain a light yellow crystalline product 5-phenylthioindane-1,2-dione-2-oxime-O-acetate, The yield is 88.5% and the purity is 98.1%. Refer to Table 1 for data on melting range, ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Example 6
Synthesis of 5-n-butoxyindane-1,2-dione-2-oxime-O-acetate

6a, Synthesis of 5-n-butoxyindane-1-ketone (etherification method C)

2.97 g (0.02 mol) of 5-hydroxy-1-indanone is placed in a 50 ml three-necked flask, 30 ml of acetonitrile, 5.2 g (0.037 mol) of bromobutane and 5.0 g of anhydrous potassium carbonate are added, protected with nitrogen, 55-60 ° C. Stir for 3 h. Acetonitrile was collected under reduced pressure, and the rest was added to 100 ml of water and stirred. When a solid was precipitated, it was extracted and filtered, the filter cake was leached twice with 10 ml of water, and the filter cake was washed with ethanol. Crystallization again and drying yields 3.67 g of white crystals, yield 89.8%, analytical purity 98.5%, melting range 53.0-54.0 ° C.
6b, Synthesis of 5-n-butoxyindane-1,2-dione-2-oxime (oximation method B)

Melt 2.05 g (0.01 mol) of the etherified product obtained in 6a in a 100 ml three-necked flask with 30 ml of methanol, add 2 g of 36% concentrated hydrochloric acid, soak in brine and stir at 5-10 ° C., within 15 min. 1.55 g (0.015 mol) of butyl nitrite was dropped on the solution, stirred for 5 hours, the temperature of the reaction solution was lowered to 5-10 ° C., and the white solid precipitated by filtration was 1.98 g after drying, with an analytical purity of 98.20% The melting range is 134.0 to 136.0 ° C., and the yield is 85%.
6c, Synthesis of 5-n-butoxyindane-1,2-dione-2-oxime-O-acetate (esterification B)
1.17 g (0.005 mol) of the product of 6b is melted in 25 ml of 1,2-dichloroethane, 1.1 g (0.011 mol) of acetic anhydride is dropped, and the mixture is immersed in water at 20 to 25 ° C. for 6 hours. The reaction is selected with 25 ml water until an aqueous phase is formed, the organic phase is dried over 1.5 g anhydrous sodium sulfate for 2 h, the desiccant is filtered off and the filtrate is dried under vacuum. Add 15 ml of ethyl acetate to the rest, heat until completely melted, add 0.05 g of activated charcoal and let it flow for 0.5 h. Activated charcoal is separated by hot filtration, and 15 ml of n-hexane is added to the filtrate, cooled and cooled down, crystals are precipitated, filtered by filtration, and the filter cake is dried to obtain 1.18 g of white needle-like crystal product. The content is 97.8% and the yield is 85.8%. See Table 1 for data on melting range and ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Example 7
Synthesis of 5- (2-methylphenylmethoxy) indan-1,2-dione-2-oxime-O-acetate

7a, Synthesis of 5- (2-methylphenylmethoxy) indan-1-ketone

According to etherification method B of Example 6a, replacing bromobutane with 1-bromoisopentane to synthesize 5- (3-methylbutoxy) indan-1-ketone, a pale yellow liquid, yield 96.8%, purity 98.0 %.
7b, according to oximation method B of 6b of Example 6, using the product obtained in 7a as a raw material, performing an oximation reaction, and after purification, light yellow powdery 5- (3-methylbutoxy) indan-1,2- Dione-2-oxime is obtained with a yield of 92.1%, a melting range of 153.0-154.0 ° C. and a purity of 99.51%.

According to esterification B of 7c and 6c of Example 6, the product of 7b reacts with acetic anhydride, and the reaction product is recrystallized and purified by a mixed solvent of ethyl acetate and hexane to obtain a white crystalline product. The rate is 89.3% and the purity is 99.65%. See Table 1 for data on melting range and ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Example 8
Synthesis of 5- (2-methylphenylmethoxy) indan-1,2-dione-2-oxime-O-acetate

8a, Synthesis of 5- (2-methylphenylmethoxy) indan-1-ketone

According to etherification method C of Example 6a, bromobutane was replaced with O-methylbenzyl chloride to synthesize 5- (2-methylphenylmethoxy) indan-1-ketone, white crystals were obtained, yield 95.5% , Purity 99.0%, melting range 100.0-101.0 ° C.
8b, according to oximation method B of 6b of Example 6, using the product obtained in 8a as a raw material, an oximation reaction was performed, and after purification, white solid 5- (2-methylphenylmethoxy) indane-1,2- Dione-2-oxime is obtained, yield 90.2%, melting range 193.0-194.0 ° C., purity 96.31%.

According to esterification B of 8c, 6c of Example 6, the reaction product of the previous step and acetic anhydride react, and the product is recrystallized and purified by a mixed solvent of ethyl acetate and 1,2-dichloroethane to obtain a white solid A powder product is obtained with a yield of 91.3% and a purity of 97.8%. Refer to Table 1 for data on melting range and ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Example 9
Synthesis of 5-methoxyindane-1,2-dione-2-oxime-O-acetate

9b, according to oximation method B of 6b of Example 6, using 5-methoxyindane-1-ketone as a raw material, an oximation reaction was performed, and after purification, white solid 5-methoxyindane-1,2-dione-2- An oxime is obtained, yield 90.2%, melting range 224.0-225.0 ° C., purity 96.31%.

9c, according to the esterification B of 6c of Example 6, using the product obtained in 9b as a raw material, an esterification reaction was performed, and the product was recrystallized and purified through ethyl acetate to obtain a white solid powder product 5-methoxyindane- 1,2-Dione-2-oxime-O-acetate was obtained, yield 90.6%, purity 98.4%, melting range and ¹ H-NMR (CDCl ₃ ), δ (ppm) data are shown in Table 1. Please refer.

Example 10
Synthesis of 5-chloroindene-1,2-dione-2-oxime-O-acetate

10b, Synthesis of 5-chloroindane-1,2-dione-2-oxime (nitrite oxime conversion method)

Weigh 3.33 g (0.02 mol) of 5-chloro-1-indanone in a 100 ml reaction bottle, put it in 40 ml of methanol, and keep it warm at 35-45 ° C. Drop 3.1 g (0.3 mol) of isobutyl nitrite into the reaction bottle and react at 45 ° C for 3 h. After the stirring was stopped and the temperature returned to room temperature, crystals were precipitated from the reaction solution, extracted and filtered, and the filter cake was leached with 10 ml of methanol and dried to a light yellow solid with a content of 97.44% and a yield of 90%. 3.52 g of product is obtained.

10c, Synthesis of 5-chloroindene-1,2-dione-2-oxime-O-acetate (anhydrous esterification)
1 g (0.0051 mol) of the product from the previous step is dissolved in 50 ml of dichloroethane, 1.1 g (0.011 mol) of acetic anhydride is dropped, and the mixture is immersed in water at 25 to 30 ° C. for 1 hour. The reaction is selected with 50 ml 5% NaHCO3 solution until an aqueous phase is formed and the organic phase is washed again with 50 ml water until an aqueous layer is formed. The organic phase is dried over 3 g of anhydrous sodium sulfate for 2 h, the desiccant is filtered off and the filtrate is dried under reduced pressure. Add 15 ml of ethanol to the rest, heat until completely melted, add 0.05 g of activated charcoal and let it flow for 0.5 h. Activated carbon is separated by hot filtration, the filtrate is cooled and cooled, crystals are precipitated, it is filtered by extraction, and the filter cake is dried to obtain a white solid powder product 1.03 with a content of 98.88% and a yield of 85.0%. g is obtained. The measured melting range is: 163.0-165.0 ° C. See Table 1 for data on ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Example 11
Synthesis of 5,6-dimethoxyindane-1,2-dione-2-oxime-O-acetate

11b, according to oximation method B of 6b of Example 6, using 5,6-dimethoxyindane-1-ketone as a raw material, subjected to oximation reaction, and after purification, yield 90.5%, purity 96.10%, melting range: A pale yellow solid 5,6-dimethoxyindane-1,2-dione-2-oxime that decomposes at 240 ° C. is obtained.

According to the esterification B of 11c and 6c of Example 6, an esterification reaction was performed using the product obtained in 11b as a raw material, and the product was a 90% yield and 98.5% purity after recrystallization and purification of ethyl acetate. A yellow solid powder product 5,6-dimethoxyindane-1,2-dione-2-oxime-O-acetate is obtained. See Table 1 for data on melting range and ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Example 12
Synthesis of 5,6-dibutoxyindane-1,2-dione-2-oxime-O-acetate

Production of 5,6-dihydroxyindane-1-ketone

Add 2 g (0.0104 mol) of 5,6-dimethoxyindane-1-ketone to a 100 ml three-necked flask and melt with 20 ml of glacial acetic acid. Add 20 g of 40% aqueous hydrogen bromide, then stir and heat to a temperature of 100 ° C. Stop the reaction after 9 hours. By distillation under reduced pressure, 0.8 g (0.0049 mol) of a pale gray solid having a content of 97.36% is extracted from the remaining reaction mixture. ¹ H-NMR proved to be 46.9% of 5,6-dihydroxyindan-1-ketone.
12a, according to etherification method C of 6a of Example 6, using the product 5,6-dihydroxyindan-1-ketone of the previous step as a raw material, an etherification reaction was performed, and after the treatment, yield 95.5%, purity 95.2 % Light yellow solid 5,6-dibutoxyindane-1-ketone is obtained.
12b, according to oximation method B of 6b of Example 6, using 5,6-dibutoxindan-1-ketone as a raw material, an oximation reaction was performed, and after purification, yield 91.2%, purity 99.2%, melting range: 180 A yellow solid 5,6-dibutoxyindane-1,2-dione-2-oxime which is ˜182 ° C. is obtained.

In accordance with esterification B of 12c, 6c of Example 6, the product obtained in 12b was used as a raw material, an esterification reaction was performed, and the product was a light yellow of 89% yield and 98% purity by recrystallization and purification of ethyl acetate. The solid powder product 5,6-dibutoxyindane-1,2-dione-2-oxime-O-acetate is obtained. See Table 1 for data on melting range and ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Example 13
Synthesis of 6-ethyl-9- (2-methylbenzoyl) -1H, 6H-cyclopenta [3,4-c] carbazole-2,3-dione-2- (O-acetyloxime)

Synthesis of 9-ethyl-3- (2-methylbenzoyl) carbazole

Add 20.0 g (0.1 mol) of ethylcarbazole to a 250 ml 4-neck flask and melt with 100 ml of 1,2-dichloroethane. Add 15.0g of anhydrous aluminum chloride, lower the temperature to -5 ° C and add 2-methylbenzoyl chloride to 17g. The reaction is carried out at -5 ° C to 0 ° C for 3 hours. The reaction solution is hydrolyzed with 30 ml of concentrated hydrochloric acid and 100 ml of water. Recrystallization from petroleum ether gives a white product weighing 28 g after drying, yield 89.3%, melting range 96.5-98.3 ° C. 1H-NMR has proven to be 9-ethyl-3- (2-methylbenzoyl) -carbazole.

Synthesis of 9-ethyl-6- (2-methylbenzoyl) -3- (3-chloropropionyl) carbazole

Add 15.7 g (0.05 mol) of 9-ethyl-3- (2-methylbenzoyl) carbazole to a 250 ml 4-necked flask and melt with 80 ml of 1,2-dichloroethane. Add 15.0 g of anhydrous aluminum chloride and add 7 g (0.055 mol) of 3-chloropropionyl chloride when the temperature is lowered to -5 ° C. The reaction is carried out at -5 ° C to 0 ° C for 3 hours. The reaction solution is hydrolyzed with 30 ml of concentrated hydrochloric acid and 100 ml of water. Is a pale yellow solid with a weight of 19.8 g and a yield of 98%. 1H-NMR has proven to be 9-ethyl-6- (2-methylbenzoyl) -3- (3-chloropropionyl) -carbazole.

13a, Synthesis of 6-ethyl-9- (2-methylbenzoyl) -1H, 2H, 6H-cyclopenta [2,3-c] carbazole-3-ketone

Concentrated sulfuric acid 55 g was placed in a 100 ml 4-necked flask, stirred and heated to 70 ° C. to 80 ° C., 9-ethyl-6- (2-methylbenzoyl) -3- ( Add 4.1 g (0.01 mol) of 3-chloropropionyl) -carbazole. After 3 hours of reaction, the reaction solution is poured into 120 ml of water to produce a gray solid. After filtration, the solid was melted with 100 ml of 1,2-dichloroethane, washed until the pH became neutral, the solution was concentrated, and methanol was added, and the weight after drying was 2.8 g, yield 76 %, Melting range: 175 to 179 ° C. yellow powdered solid is precipitated. 1H-NMR has proven to be 6-ethyl-9- (2-methylbenzoyl) -1H, 2H, 6H-cyclopenta [2,3-c] carbazole-3-ketone.

Synthesis of 13b, 6-ethyl-9- (2-methylbenzoyl) -1H, 6H-cyclopenta [3,4-c] carbazole-2,3-dione-2-oxime
Place 1.5g (0.0041mol) of 13a product, 20g of methanol, 0.5g of concentrated hydrochloric acid and 1.5g of butyl nitrite into a 50ml 1-neck flask. Stir by magnetic force and react at room temperature for 4 h, confirming yellow insolubles. The solution is cooled to −5 ° C. and filtered to give a yellow solid product with a dry weight of 1.5 g and a yield of 92.3%.

Synthesis of 13c, 6-ethyl-9- (2-methylbenzoyl) -1H, 6H-cyclopenta [3,4-c] carbazole-2,3-dione, 2- (O-acetyloxime)
In a 50 ml 1-necked flask, 1.0 g (0.0025 mol) of the reaction product of 13b in the previous step and 15 g of acetic anhydride were added, stirred at room temperature for 72 h, and separated to obtain 0.95 g of a yellow solid. Recrystallization from an ethyl mixed solvent gives 0.8 g of yellow crystals having a content of 96.64% and a yield of 73%. See Table 1 for data on melting range, 1H-NMR (DMSO-d6) and δ (ppm) values.

Example 14
6-Chlorobenzofuran-2,3-dione-2-oxime-O-acetate

14b, Synthesis of 6-chlorobenzofuran-2,3-dione-2-oxime

According to the oximation method of 10b of Example 10, 6-chlorobenzofuran-3-ketone was used as a raw material, an oximation reaction was performed, and after purification, a yield of 88.5%, purity 98.60%, melting range: 210 ° C. A yellow solid 6-chlorobenzofuran-2,3-dione-2-oxime is obtained.

Synthesis of 14c, 6-chlorobenzofuran-2,3-dione-2-oxime-O-acetate According to the esterification method of Example 10 10c, the product 6-chlorobenzofuran-2,3-dione obtained in 14b -2-Oxime is used as the raw material, and esterification is performed. The product is recrystallized from ethyl acetate and purified to yield a light yellow solid powder product 6-chlorobenzofuran-2,3-dione with a yield of 91.0% and a purity of 99.4%. -2-oxime-O-acetate is obtained. See Table 1 for data on ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Example 15
Synthesis of 4,6-dimethoxybenzofuran-2,3-dione-2-oxime-O-acetate

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

Dissolve 8.4 g (0.05 mol) of 1,3,5-trimethoxybenzene in 30 ml of 1,2-dichloroethane, cool to 5 ° C., add 7.4 g of anhydrous aluminum chloride, stir until melted, and chloroacetyl Drop 6.2 g (0.055 mol) of chloride, continue stirring for 2 h, hydrolyze, and separate crystals to obtain 9.9 g of white needle crystals, mp139-140 ° C., ¹ H-NMR yield 85.8% Proven to be the product of

15a, 4,6-dimethoxybenzofuran-3-ketone

The product α-chloro-2-hydroxy-4,6-dimethoxyacetophenone 2.3g (0.01 mol) from the previous step was dissolved in 20 ml of ethanol, 1.5 g of anhydrous Na ₂ CO ₃ was dropped and stirred at room temperature for 5 h. The solid was filtered and rotary evaporated under reduced pressure to remove the solvent, yielding 1.85 g of solidified white surplus, ¹ H-NMR proved to be product with mp116-117 ° C, yield 95.2% Yes.

15b, Synthesis of 4,6-dimethoxybenzofuran-2,3-dione-2-oxime

According to the oximation method of 6b of Example 6, using 4,6-dimethoxybenzofuran-3-ketone as a raw material, an oximation reaction was performed, and after purification, yield 81.5%, purity 96.3%, melting range: 230 ° C. A white solid 4,6-dimethoxybenzofuran-2,3-dione-2-oxime is obtained which decomposes with

15c, Synthesis of 4,6-dimethoxybenzofuran-2,3-dione-2-oxime-O-acetate The product 4,6-dimethoxybenzofuran-2 obtained in 15b according to the esterification method of 6c of Example 6 , 3-Dione-2-oxime is used as a raw material, esterification reaction is performed, the product is recrystallized and purified by 1,2-dichloroethane, yields 90.5%, 98.0% purity solid powder of similar color to white The product 4,6-dimethoxybenzofuran-2,3-dione-2-oxime-O-acetate is obtained. See Table 1 for data on ¹ H-NMR (DMSO-d6) and δ (ppm) values.

Example 16
Synthesis of 6H-6-ethyl-1H, 11H-dicyclopenta [3,4,3,4'-c, g] carbazole-2,3,9,10-tetron, 2,10-di (O-acetyloxime)

9H-9-ethyl-3,6-di (3-chloropropionyl) carbazole

Add 10.0 g (0.051 mol) of ethylcarbazole to a 250 ml 4-neck flask and melt with 60 ml of 1,2-dichloroethane. Add 15.0 g of anhydrous aluminum chloride and drop 13.2 g (0.104 mol) 3-chloropropionyl chloride when the temperature drops to -5 ° C. The reaction is allowed to proceed overnight at -5 ° C to 0 ° C, the reaction solution is hydrolyzed with 50 ml of concentrated hydrochloric acid and 100 ml of water, a large amount can be fixed, the insoluble matter is filtered, the filter cake is thoroughly washed with water, and 100 ml of 1,2 -Charged into dichloroethane, heated until completely melted, then cooled down and crystallized to filter a white solid with a dry weight of 12g, yield 62.5%, melting point: 188 ° C-189 ° C. ¹ H-NMR has proven to be 9H-9-ethyl-3,6-di (3-chloropropionyl) carbazole.

Synthesis of 16a, 6H-6-ethyl-1H, 2H, 10H, 11H-dicyclopenta [2,3,2,3'-c, g] carbazole-3,9-dione

30 g of 98% concentrated sulfuric acid is placed in a 100 ml 4-neck flask, stirred and heated to 60-65 ° C, and 2.0 g (0.0032 mol) intermediate 9-ethyl-3,6-di (3-chloropropionyl) ) Carbazole is added ten times and then heated to 85-90 ° C. to react. After reacting for 3 h, the reaction solution is cooled, poured into 100 ml of water, extracted by adding 50 ml of 1,2-dichloroethane, a light yellow solution is obtained, and concentrated until crystals are precipitated. The solution is allowed to cool naturally, filtered and dried to precipitate pale yellow crystals with a dry weight of 1.1 g and a yield of 68.4%. ¹ H-NMR has been proven to be 6H-6-ethyl-1H, 2H, 10H, 11H-dicyclopenta [2,3,2,3′-c, g] carbazole-3,9-dione. ¹ H-NMR (DMSO-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 / 7.5137 (d, 2H, 2ArH); 7.9345 / 7.9628 (d, 2H, 2ArH).

Synthesis of 16b, 6H-6-ethyl-1H, 11H-dicyclopenta [3,4,3,4'-c, g] carbazole-2,3,9,10-tetron, 2,10-dioxime

Into a 50 ml one-necked flask is placed 1.0 g (0.0032 mol) of intermediate 16a, 10 ml of methanol, 0.5 g of concentrated hydrochloric acid, and 1.5 g of butyl nitrite. Stir by magnetic force at 25-30 ° C. for 24 hours. Extraction filtration and washing with methanol yield a yellow solid filter cake with a dry weight of 0.98 g and a yield of 85%.

16c, 6H-6-ethyl-1H, 11H-dicyclopenta [3,4,3,4'-c, g] carbazole-2,3,9,10-tetron-2,10-di (O-acetyloxime) Synthesis of
Take 0.5 g (0.0014 mol) of Intermediate 16b and 10 g of acetic anhydride, put in a 25 ml round bottom flask, soak in 50-55 ° C. water and stir for 10 h. Filtration gives a yellow filter cake, which is washed with 5 ml of ether, drained, and dried to give 0.45 g of a yellow powdery product with a content of 96.32% and a yield of 71.4%. See Table 1 for data on ¹ H-NMR (DMSO-d6) and δ (ppm) values.

Example 17
Synthesis of di [5- (4-isopropylphenylthio) indan-1,2-dione-2-oxime-O] -oxalate "

1.53 g (0.005 mol) of the intermediate 3b of Example 3 is taken and dissolved in 25 ml of 1,2-dichloroethane, 0.32 g (0.0025 mol) of oxalyl chloride is dropped, and the mixture is immersed in water at 20 to 25 ° C. and reacted for 10 hours. A yellow solid is precipitated from the reaction solution. A filter cake is obtained by filtration, melted in 20 ml 1,2-dichloroethane, heated until completely melted and then filtered, the filtrate was cooled, crystals were precipitated, filtered and dried, and the filter cake was dried. As a result, 1.35 g of a yellow powdery product having a content of 98.32% and a yield of 80% is obtained. See Table 1 for data on melting range and ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Example 18
2- [5- (4-Isopropylphenylthio) indan-1,2-dione-2-oxime-O] -isophthalate

Take 1.56 g (0.005 mol) of intermediate 3b of Example 3 and melt it in 25 ml of 1,2-dichloroethane. . A yellow solid is precipitated from the reaction solution. A filter cake is obtained by filtration, a mixture of dissolved 5 ml 1,2-dichloroethane and 5 ml ethyl acetate is melted, heated until completely melted and then filtered hot, and the liquid cooling is filtered to precipitate crystals, Extraction filtration is performed, and the filter cake is dried to obtain 1.1 g of a yellow needle-like product having a content of 97.48% and a yield of 59%. See Table 1 for data on melting range and ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Example 19
Synthesis of 5- (4-octanoylphenylthio) indane-1,2-dione-2-oxime-O-acetate

19a, 24.04 g (0.1 mol) of the intermediate 5a of Example 5 was taken and melted in 100 ml of 1,2-dichloroethane, the temperature was kept at 10 ° C., 28 g (0.21 mol) of anhydrous aluminum chloride was added, and the mixture was stirred. Drop 17.9 g (0.11 mol) of noyl chloride, and after 4 h, treat the reaction solution with dilute hydrochloric acid, separate the organic solution, wash again, condense and recover 1,2-dichloroethane, Recrystallization with 100 ml of ethanol gives 33 g of white crystals with a yield of 90.1% and a melting range of 74.3-75.2 ° C. ¹ H-NMR data proves that the resulting intermediate 19a is 5- (4-octanoylphenylthio) indan-1-ketone. ¹ H-NMR (DMSO-d ₆ ), δ (ppm) 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 7.4525 / 7.4797 (d, 2H, 2ArH); 7.6677 / 7.6945 (d, 1H, 2ArH); 7.9221 / 7.9493 (d, 2H, 2ArH).

In accordance with the oximation method A of 19b and 3b of Example 3, an oximation reaction is performed using 19a as a raw material, a yellow solid is precipitated, the solvent is dried, and the purity is 95% and the melting range. ¹ H-NMR data show that the resulting intermediate 19b is 96.2% yield of 5- (4-octanoylphenylthio) indan-1,2-dione-2-oxime. ¹ H-NMR (DMSO-d ₆ ), δ (ppm) 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, 7.7707 / 7.7977 (d, 1H, 2ArH); 7.9648 / 7.9925 (d, 2H, 2ArH); 12.4460 (s, 1H, NOH).

19c, according to esterification A of Example 3c 3c, the intermediate 19b was subjected to esterification reaction, the product was subjected to crystal purification of toluene and hexane (1: 2), yield 85.8%, purity 97.1% The yellow crystalline product 5- (4-octanoylphenylthio) indane-1,2-dione-2-oxime-O-acetate is obtained. See Table 1 for data on melting range and ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Example 20
Synthesis of 5- [4- (3-cyclopentylpropionyl) phenylthio] indane-1,2-dione-2-oxime-O-acetate

20a, 24.04 g (0.1 mol) of the intermediate 5a of Example 5 was taken and melted in 100 ml of 1,2-dichloroethane, the temperature was kept at 10 ° C., and 28 g (0.21 mol) of anhydrous aluminum chloride was added and stirred. -Drop 17.76 g (0.11 mol) of cyclopentylpropionyl chloride, treat the reaction solution with dilute hydrochloric acid after 4 h, separate the organic solution, wash it again, and concentrate and recover 1,2-dichloroethane. The surplus is recrystallized with a mixture of ethyl acetate and hexane (weight ratio 1: 2) to obtain 33.52 g of white crystals with a yield of 92.0% and a melting range of 88.5-90.0 ° C. ¹ H-NMR data indicates that the resulting intermediate 20a is 5- [4- (3-cyclopentylpropionyl) phenylthio] indan-1-ketone. 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).

According to 20b, 19b of Example 19, an oximation reaction is carried out using 20a as a raw material to precipitate a yellow solid product, the solvent is dried, and the purity is 95% and the melting range is 193.5 to 195.5 ° C. ¹ H-NMR data indicate that the resulting intermediate 20b is 95.5% yield of 5- [4- (3-cyclopentylpropionyl) phenylthio] indane-1,2-dione-2-oxime. 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).

20c, according to 19c of Example 19, an esterification reaction was performed on intermediate 20b, and the product was subjected to crystal purification with toluene and hexane (1: 2) to yield a yellow powder product with a yield of 83.4% and a purity of 97.0%. 5- [4- (3-Cyclopentylpropionyl) phenylthio] indane-1,2-dione-2-oxime-O-acetate is obtained. See Table 1 for data on melting range and ¹ H-NMR (CDCl ₃ ) and δ (ppm) values.

Example 21 Preparation of Soluble Resin in Alkaline Solution 180 g of benzyl methacrylate, 60 g of methacrylic acid, 60 g of hydroxyethyl methacrylate, 15 g of azobisisobutyronitrile, 6 g of dodecanethiol, and 1000 ml of toluene are mixed uniformly. Place in dropping funnel. 1000 ml of toluene is put into a three-necked flask, and stirring, a constant pressure dropping funnel and a thermometer are attached, stirring is started, and the gas in the flask is replaced with nitrogen. The flask is heated and kept warm so that the temperature of the solvent is 80 to 85 ° C., and the dropping of the monomer mixed solution is started, and it takes about 1 h until the dropping is finished. Continue to react for 6 h. Cool down at room temperature, lower the temperature, stop stirring, and after the resin sinks, absorb the clear solution in the upper part, filter the resin containing the lower solvent, and leach out the resin filter cake with 500 ml toluene . The filter cake is dried under reduced pressure to obtain 250 g of a white powdery solid resin. Thaw it into a 20% solution with 1000 g of PMA (propylene glycol methyl ether acetate) and set it as standby.

Example 22 Preparation and development of photoresist 22A, 22B, 22C (photopolymerization initiator is OXE01), 22D (photopolymerization initiator is OXE02), 22E (photopolymerization initiator is IHT-PI 910) shown in Table 2 Its chemical name is 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morphophenyl) -1-butanone), and it is a liquid that can flow according to the ink preparation method. The photocuring composition is adjusted.
The liquid composition was applied to the glass surface by a wire rod method, and baked at 80 ° C. for 3 minutes to volatilize the solvent PMA, and the surplus film thickness was measured to be 2 microns.
Leave 21 gray gradient scale to the film, was filtered 2000W high pressure mercury light at 365nm grating filter, the distance between the film and the lattice is 10 cm, made to be the exposure to 800 mJ / cm ^2.
Immerse in a 1% sodium carbonate solution at 30 ° C. for 1 min, record the maximum number of film classes that can be displayed, and the higher the number, the stronger the photosensitivity of the measured composition, and the better the photocuring rate and film forming performance. The results are shown in Table 3.

  As shown in the development results in Table 3, the photocuring compositions prepared with the photopolymerization initiators of Examples 4 and 6 are clearly superior to the photocuring compositions prepared with OXE01 and OXE02. ing. The photocuring rate and film forming performance of the photoresist are improved.

Example 23 Photocuring Composition Gel Conversion Measurement Experiment The composition of 22A, 22B, 22C, 22D, and 22E in Table 2 of Example 22 was applied to the glass surface by the wire rod method, and baked at 80 ° C. for 3 minutes. Thus, the solvent PMA was volatilized and the surplus film thickness was measured to be 2 microns.
The 2000W high-pressure Mercury beam is filtered with a 365nm grating filter, the distance between the film and the grating is 10cm, and the exposure is 200, 400, 600mJ / cm ² respectively. After curing, wrapped sample in stainless steel mesh, measure the mass W _1, soaked for 72 hours in acetone and dried to measure the weight W ₂ of the remaining film, W ₁ / W ₂ is a gel conversion gel%, the result Are shown in Table 4.

  From Table 4, it can be confirmed that, among the components of the photoresist, the photopolymerization initiators of Examples 4 and 6 have higher activity by increasing the degree of polymerization of double bonds.

Example 24 Measurement experiment of LED photocurable photosensitive composition and curing efficiency The photocurable compositions 22A, 22B, 22C, and 22D in Example 22 were applied to the glass surface by the wire rod method and baked at 80 ° C. for 3 minutes. Thus, the solvent PMA is volatilized, the film thickness of the surplus is measured to be 2 microns, and curing is performed by the following method.

Curing device: LEDUV curing device, standard: UV-101D (Beijing Iwata Hiroto Technology Co., Ltd.)
Light source: UV-LED point light source, diameter: 10 mm; wavelength: 365 nm, maximum illuminance: 40 mw / cm ²
Curing conditions: Working distance: 21mm; Irradiation time: 1s
As a method of expressing the curing efficiency, after irradiating with a point light source for 1 s, immerse the whole glass with acetone solution for 5 s and take out, then measure the diameter of the pattern of the cured film. Efficiency will be good. Table 5 shows the measurement results. From the measurement results in Table 5, when the photosensitive composition for welding ink or photoresist is cured with an LED light source, the photosensitive composition according to the present invention uses OXE01 and OXE02 in the existing technology. It can be confirmed that the composition has a higher photosensitivity than the composition used as the polymerization initiator.

Example 25
Preparation of printing ink and high-pressure mercury curing Component ratio: 50 parts of epoxy acrylate prepolymer (Changxing Chemical 621-100), 10 parts of polyester acrylate prepolymer (Changxing Chemical 6311-10), 30 parts of TPGDA (Changxing Chemical EM223), carbon 4 parts of black (Degussa company P25) and 6 parts of photopolymerization initiator are ground to a fineness of 2 um or less to obtain ink sample 25A-25E. It is printed on aluminum with a 420th screen, cured with a high-pressure mercury lamp, and the gel conversion rate gel% is measured by the method of Example 23. Table 6 shows the measurement results. From the measurement results in Table 6, it can be confirmed that the gel conversion rate of the compound of the present invention irradiated to the high-pressure mercury lamp is significantly higher than that of the comparative compound.

Example 26
Adjustment of printing ink and curing of LED surface light source Component ratio: 50 parts of epoxy acrylate prepolymer, 10 parts of polyester acrylate prepolymer, 30 parts of TPGDA, 4 parts of yellow 3G (BASF company), 6 parts of photopolymerization initiator Is ground to 2um or less, and ink samples 26A-26E are obtained and applied to the glass surface. Cured by 365 nm LE surface light source lamp, the exposure amount is 86 mJ / cm ^2. The gel conversion rate gel% was measured by the method of Example 23, and the measurement results are shown in Table 7. From the measurement results in Table 7, it can be confirmed that the gel conversion rate of the compound of the present invention irradiated to the 365 nm LED light source is significantly higher than that of the comparative compound.

Example 27
Adjustment of optical film resist ink and exposure and development Component ratio: 500 parts of resin soluble in alkaline solution (Example 21), 100 parts of dipentaerythritol hexaacrylate (Cytec company DPHA), 100 parts of photopolymerization initiator, co-initiator BCIM (2,2′-diorthochlorophenyl-4,4 ′, 5,5′-tetraphenylbiimidazole) 20 parts, carbon black (Degussa company P25) dispersion 500 parts (containing 20% black). There are six types of inks, 27A-27F, depending on the photopolymerization initiator that is uniformly ground and used by the ink preparation method.
Each coated, dried under reduced pressure, covered with a pattern mask with a thickness of 1 um, exposed with a 365 nm LED surface light source, developed with 30% 1% sodium carbonate solution at an exposure amount of 100 mJ / cm ² , and patterned with a stereo electron microscope Detect form and fastness. Observation and evaluation of morphology and fastness: 1) Exposed part is complete without omission; 2) Exposed part does not fall out but the edge is warped; 3) Exposed part is not aligned; 4) Exposed part is incomplete Yes; 5 Exposed part dropped out.
The experimental results are shown in Table 8. From the results in Table 8, since the ink containing the compound of the present invention has a clear and well-patterned edge after exposure and is robust and does not drop off, the performance of the compound of the present invention is clear compared with the comparative compound. Can be confirmed.

Example 28
Preparation of optical film resist ink and exposure development Component ratio: 500 parts resin soluble in alkaline solution (Example 21), 100 parts dipentaerythritol hexaacrylate (Cytec company), 100 parts photopolymerization initiator, red pigment L3920 (BASF Company) 100 copies. 5 types of ink 28A-28E can be obtained by grinding uniformly by the ink preparation method.
Coating and dried under reduced pressure to a thickness of 2um, covering the pattern mask, and exposed by 365nm of LED surface light source with an exposure dose of 86 mJ / cm ^2, and 30S developed with 1% sodium carbonate solution, the form of a pattern in stereo electron microscope And detect fastness. The evaluation method is the same as in Example 27. The experimental results are shown in Table 9. From the results in Table 9, since the ink containing the compound of the present invention has a clear pattern edge after exposure and is robust and does not drop off, the performance of the compound of the present invention is clear compared with the comparative compound. Can be confirmed.

Example 29
Preparation of optical film resist ink and exposure development Component ratio: 500 parts resin soluble in alkaline solution (Example 21), 100 parts dipentaerythritol hexaacrylate (Cytec company), 10 parts photopolymerization initiator, red pigment L3920 (BASF) Company) 100 copies. Grinding uniformly by the ink preparation method gives five types of ink, 29A-29E.
Coating and dried under reduced pressure to a thickness of 2um, covering the pattern mask, and exposed by 365nm of LED surface light source with an exposure dose of 86 mJ / cm ^2, and 30S developed with 1% sodium carbonate solution, the form of a pattern in stereo electron microscope And detect fastness. The evaluation method is the same as in Example 27. The experimental results are shown in Table 10. The results of Table 10 show that the performance of the compound of the present invention is superior to that of the comparative compound because the ink containing the compound of the present invention has a clear and well-patterned edge after exposure, and is robust and free from dropping. Can be confirmed.

Claims (21)

Compounds of general formulas I, IIa, IIb, III and IV,
However,
Ar ₁ is linked to Y ₁ and a carbonyl group by two adjacent atoms to form a condensed ring structure, and each of the substituents at other atoms is a hydrogen atom, a halogen atom, a C ₁ -C ₁₂ alkyl group, C _5- C ₇ cycloalkyl group, C ₁ -C ₄ alkyl group substituted with C ₅ -C ₇ cycloalkyl, phenyl group; one or more C ₁ -C ₄ alkyl group, carboxyl group, C ₁ -C ₁₂ alkylacyl group or arylformyl group, heteroarylformyl group, XR ₁₇ , phenyl group, halogen atom, phenyl group optionally substituted with CN; C ₁ -C ₄ alkylbenzyloxy group, R ₁ C (O) C ₁ -C ₄ alkoxy group substituted by O, C ₁ -C ₃ alkylenedioxy group, R ₁ C (O) O, C ₁ -C ₁₂ alkylthio group, C ₁ -C ₄ alkylphenylthio group, R ₁ C (O) O substituted C ₁ -C ₄ alkylthio group, CN, carboxyl, C ₁ -C ₁₂ alkoxy formyl group, a Ruhorumiru group, a heteroaryl formyl group, ortho arylene group or an ortho heteroarylene group is XR _18,
Or, or between substituents and Ar ₁ of the two substituents adjacent in the substituents of Ar ₁ is straight bonds, carbon atoms, are linked by a carbonyl group constitutes the ring structure,
X is O, S or NR ₁₉ ,
Y ₁ is O, S, NR ₂₀ , BR ₂₀ , CR ₁₅ R ₁₆ , SiR ₁₅ R ₁₆ , S = O or C = O,
Ar ₂ is
And
Z ₁ is a straight bond, a C ₁ -C ₁₀ linear or branched alkylene group, one or more oxygen, sulfur atoms linked to a terminal group, or one or more oxygen, sulfur atoms An inserted C ₂ -C ₁₀ linear or branched alkylene group, an unsubstituted or substituted arylene group,
Y ₂ is straight bond, O, S, NR ₂₀ , BR ₂₀ , CR ₁₅ R ₁₆ , SiR ₁₅ R ₁₆ , C = O or Y ₃ -Z ₂ -Y ₃ ,
Z ₂ is a C ₁ -C ₁₀ linear or branched alkylene group, one or more oxygen, sulfur atoms connected to a terminal group or inserted into one or more oxygen, sulfur atoms _{A 2-} C ₁₀ linear or branched alkylene group, an unsubstituted or substituted arylene group,
Y ₃ is O, S, NR ₂₀ , BR ₂₀ or OC (O),
R ₁ is a hydrogen atom, a C ₁ -C ₁₈ alkyl group or a C ₁ -C ₁₈ alkoxy,
Or R ₁ is a C ₂ -C ₁₈ alkenyl group; or one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxyalkyl, optionally substituted aryl acyloxyalkyl, and / or C ₅ -C ₇ cycloalkylene group, a phenylene group, O, C2-C18 alkenyl group that is inserted into S, NR17 And
Or, R1 optionally represents one or more halogen atoms, C1-C4 alkyl group, C5-C7 cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C1-C4 alkanoyloxy, aroyloxy. A C2-C18 alkyl group that is substituted and / or inserted into a C5-C7 cycloalkylene group, a phenylene group, O, S, NR17,
Or, R1 is a C5-C7 cycloalkyl group; or one or more C1-C4 alkyl groups, a phenyl group, a halogen atom, a C5-C7 cycloalkyl group optionally substituted with CN,
Or R ₁ is a phenyl group; or one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups, phenyl groups, halogen atoms, phenyl optionally substituted with CN; or R ₁ is naphthyl,
Or R ₁ is a benzoyl group or a phenoxycarbonyl group, provided that the phenyl group is substituted with one or more halogen atoms, R ₁₇ , C ₅ or C ₆ cycloalkyl group, CN, OH, or XR ₁₇ And
Each of R ₁₁ and R ₁₂ is a C ₁ -C ₄ alkyl substituted with a hydrogen atom, a halogen atom, a C ₁ -C ₁₂ alkyl group, a C ₅ -C ₇ cycloalkyl group, or a C ₅ -C ₇ cycloalkyl group. Group, C ₁ -C ₁₂ alkoxy group, C ₁ -C ₄ alkylbenzyloxy, phenyl group; one or more C ₁ -C ₄ alkyl group, carboxyl group, C ₁ -C ₁₂ alkyl acyl group or arylformyl group , Heteroarylformyl group, XR ₁₇ , phenyl group, halogen atom, phenyl group optionally substituted by CN; C ₁ -C ₄ alkylbenzyloxy group; one or more C ₁ -C ₁₂ alkoxy groups, C ₁ -C ₄ alkylbenzyl group, C ₁ -C ₄ alkoxy groups optionally substituted on the _{R 1 C (O) O;} R 1 C (O) O, CN, carboxyl group, C ₁ -C ₁₂ alkoxycarbonyl group , Arylcarbonyl group, heteroarylcarbonyl group, XR ₁₈ ; or one or more C ₁ -C ₄ alkyl A phenoxy group substituted by a group; a phenoxy group substituted by one C ₁ -C ₈ alkylacyl group, a C ₅ -C ₆ cycloalkylacyl group, an arylformyl group, a heteroarylformyl group; a C ₅ -C ₆ cyclo C ₁ -C ₄ alkyl acylphenoxy group substituted by an alkyl group; C ₁ -C ₃ alkylene dioxy group, C ₁ -C ₁₂ alkylthio group, C ₁ -C ₄ substituted by R ₁ C (O) O alkylthio groups and C ₁ -C ₄ alkyl phenylthio group; a C ₁ -C ₈ alkyl acyl, C ₅ -C ₆ cycloalkyl amyl group, an aryl acyl group, a phenylthio group substituted with a heteroaryl acyl group; or A C ₁ -C ₄ alkyl acylphenylthio group substituted by a C ₅ -C ₆ cycloalkyl group, or an epoxy propyl group, provided that the epoxy group is optionally condensed with an alkyl aldehyde, a ketone,
Or R ₁₁ and R ₁₂ are connected to form a saturated or unsaturated ring structure;
R ₁₅ and R ₁₆ are each a hydrogen atom, a C ₁ -C ₁₈ alkyl group, a C ₁ -C ₅ alkyl group substituted by a carboxyl group or a C ₁ -C ₄ alkoxyamyl group, R ₁ C (O) C ₁ -C ₄ alkyl group substituted by O; one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, hetero C ₂ -C ₁₈ optionally substituted with an aryl group, CN, C ₁ -C ₄ alkylacyloxy, arylacyloxy, or inserted into a C ₅ -C ₇ cycloalkylene group, phenylene group, O, S, NR ₁₇ Each of R ₁₅ and R ₁₆ is a C ₅ -C ₇ cycloalkyl group; or C optionally substituted by one or more C ₁ -C ₄ alkyl groups, a phenyl group, a halogen atom, or CN. a ₅ -C ₇ cycloalkyl group,
Or each of R _{15 and} R ₁₆ is a phenyl group; one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups, carboxyl groups, C ₁ -C ₁₂ alkyl acyl groups, C _5- C ₆ cycloalkylformyl group, C ₂ -C ₄ alkyl acyl group substituted by C ₅ -C ₆ cycloalkyl group, benzoyl group, XR ₁₇ , phenyl group, halogen atom, phenyl group optionally substituted by CN Yes,
Alternatively, the R _15, R _16, together with the carbon atom or silicon atom connecting jointly with R _15, R _16, constitute a ring structure number of atoms is 4-7, or the R _15, R ₁₆ Each form a ring structure of 4-7 atoms with adjacent substituents,
R ₁₇ is a C ₁ -C ₄ alkyl group,
R ₁₈ is a hydrogen atom, C ₁ -C ₁₈ alkyl groups, C ₁ -C ₅ alkyl group substituted C ₁ -C ₄ alkoxy amyl groups, C ₁ -C substituted in R ₁ C (O) O ₄ alkyl group; one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxy A C ₂ -C ₁₈ alkyl group optionally substituted by arylacyloxy or inserted into a C ₅ -C ₇ cycloalkylene group, a phenylene group, O, S, NR ₁₇ ;
Or R ₁₈ represents a C ₅ -C ₇ cycloalkyl group; or a C ₅ -C ₇ cycloalkyl group optionally substituted with one or more C ₁ -C ₄ alkyl groups, a phenyl group, a halogen atom, or CN. And
Or R ₁₈ is a phenyl group; one or more C ₁ -C ₁₂ alkyl groups, carboxyl groups, C ₁ -C ₁₂ alkyl acyl groups, C ₅ -C ₆ cycloalkylformyl groups, arylacyl groups, heteroaryl An acyl group, XR ₁₇ , a phenyl group, a halogen atom, a phenyl group optionally substituted by CN, NO ₂ ; an optional C ₂ -C ₄ alkyl acyl group substituted by a C ₅ -C ₆ cycloalkyl group A substituted phenyl group; a phenyl group substituted by a phenylene group, one C ₂ -C ₁₂ alkyl acyl group inserted in O, S, NR ₁₇ ;
Or, R ₁₈ is a C ₁ -C ₄ alkyl acyl group, a C ₁ -C ₄ conjugated enoyl group,
Or R ₁₈ is a benzoyl group or a phenoxycarbonyl group, provided that the phenyl group is one or more halogen atoms, R ₁₇ , C ₅ or C ₆ cycloalkyl group, CN, OH, XR ₁₇ Is replaced with
Or, R ₁₈ is connected to an aromatic ring in Ar ₁ or Ar ₂ by a straight bond, a carbon atom, or a carbonyl group to form a new ring,
Each R _19, R _20, a hydrogen atom, C ₁ -C ₁₈ alkyl group, C ₁ -C ₅ alkyl group substituted C ₁ -C ₄ alkoxy-amyl, substituted in R ₁ C (O) O C ₁ -C ₄ alkyl group; one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxyalkyl, optionally substituted aryl acyloxyalkyl, or C ₅ -C ₇ cycloalkylene group, a phenylene group, O, a C ₂ -C ₁₈ alkyl group that is inserted S, the NR _17,
Or, R _19, each R _20, C ₅ -C ₇ cycloalkyl group; or one or more C ₁ -C ₄ alkyl group, a phenyl group, a halogen atom, C ₅ optionally substituted in the CN - a C ₇ cycloalkyl group,
Or each of R ₁₉ and R ₂₀ is a phenyl group; one or more C ₁ -C ₄ alkyl groups, carboxyl groups, C ₁ -C ₁₂ alkyl acyl groups, C ₅ -C ₆ cycloalkylformyl groups, C A C ₂ -C ₄ alkyl acyl group substituted with a _5- C ₆ cycloalkyl group, an arylformyl group, XR ₁₇ , a phenyl group, a halogen atom, a phenyl group optionally substituted with CN,
Or each of the R ₁₉ is connected to an aromatic ring in Ar ₁ or Ar ₂ by a straight bond, a carbon atom, or a carbonyl group to form a new ring,
When Ar1 is a substituted carbazole group, Y1 is not C, O, S, or NR20. A compound of general formula I, IIa, IIb, III and IV according to claim 1,
Ar ₁ is an orthoarylene group or an orthoheteroarylene group, but is not an orthoarylene group or an orthoheteroarylene group in which a condensed ring is constituted by two or more of an aromatic ring and a heterocycle, but the orthoarylene group or An orthoheteroarylene group is linked to Y ₁ and a carbonyl group by two adjacent atoms to form a condensed ring structure, and each of the substituents in the remaining atoms is a hydrogen atom, a halogen atom, a C _1- A C ₁₂ alkyl group, a C ₅ -C ₇ cycloalkyl group, a C ₁ -C ₄ alkyl group substituted with a C ₅ -C ₇ cycloalkyl group, a phenyl group; one or more C ₁ -C ₄ alkyl groups, Carboxyl group, C ₁ -C ₁₂ alkyl acyl group or aryl formyl group, XR ₁₇ , phenyl group, halogen atom, phenyl group optionally substituted by CN; C ₁ -C ₄ alkyl benzyloxy group, R ₁ C (O ) Replaced by O C ₁ -C ₄ alkoxy group, C ₁ -C ₃ alkylenedioxy group, R ₁ C (O) O, C ₁ -C ₁₂ alkylthio group, C ₁ -C ₄ alkylphenylthio group, R ₁ C (O C ₁ -C ₄ alkylthio group substituted by O, CN, carboxyl group, C ₁ -C ₁₂ alkoxycarbonyl group, arylformyl group, heteroarylformyl group and XR ₁₈ ; or orthoarylene group or orthohetero When the arylene group has a monocyclic structure, two adjacent substituents can be linked to form a ring structure, but do not form a condensed ring aromatic hydrocarbon structure; an orthoarylene group or an orthoheteroarylene group is 2 In the case of a non-fused ring structure that is one or more rings, two adjacent substituents can be linked to form a ring structure;
The definition of other groups in the structural formula is the same as the related definition in claim 1. A compound of I, IIa, IIb, III and IV according to claim 2,
Ar ₁ is the following orthoarylene group or orthoheteroarylene group,
R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each a hydrogen atom, a halogen atom, a C ₁ -C ₁₂ alkyl group, a C ₅ -C ₇ cycloalkyl group, or a C ₅ -C ₇ cycloalkyl group. Substituted C ₁ -C ₄ alkyl group, C ₁ -C ₁₂ alkoxy group; one or more C ₁ -C ₁₂ alkoxy group, C ₁ -C ₄ alkyl benzyloxy group, R ₁ C (O) O Substituted C ₁ -C ₄ alkoxy group; phenyl group; one or more C ₁ -C ₄ alkyl group, carboxyl group, C ₁ -C ₁₂ alkyl acyl group or arylformyl group, heteroarylformyl group, XR ₁₇ , Phenyl group, halogen atom, or phenyl group optionally substituted by CN; C ₁ -C ₄ alkylbenzyloxy group, R ₁ C (O) O, C ₁ -substituted by R ₁ C (O) O C ₄ alkylthio groups, CN, carboxyl group, C ₁ -C ₁₂ alkoxycarbonyl group, an arylcarbonyl group, heteroarylcarbonyl group, XR _18; one or more C ₁ -C ₄ phenoxy groups are substituted in the alkyl group; a C ₁ -C ₈ alkyl acyl, C ₅ -C ₆ cycloalkyl acyl group, an aryl formyl group, a phenoxy group substituted in the heteroaryl formyl group; C ₁ -C ₄ alkyl acylphenoxy group substituted by a C ₅ -C ₆ cycloalkyl group; C ₁ -C ₃ alkylenedioxy group, C ₁ -C ₁₂ alkylthio group; R ₁ C (O) O substituted C ₁ -C ₄ alkylthio group and C ₁ -C ₄ alkylphenylthio group; substituted with one C ₁ -C ₈ alkyl acyl group, C ₅ -C ₆ cycloalkyl amyl group, aryl formyl group, heteroaryl formyl group A phenylthio group, or a C ₁ -C ₄ alkylamylphenylthio group substituted by a C ₅ -C ₆ cycloalkyl group,
Or each of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ is an epoxypropyl group, provided that the epoxy group is optionally condensed with a C ₁ -C ₄ alkyl aldehyde, a ketone,
Or in R ₁₁ -R ₁₄ , adjacent ones are linked to form a saturated or unsaturated ring structure,
X is O, S or NR ₁₉ ,
Y ₁ is O, S, NR ₂₀ , CR ₁₅ R ₁₆ or C = O,
Ar ₂
And
Y ₂ is O, S, NR ₂₀ or Y ₃ -Z ₂ -Y ₃ ,
Z ₂ is a C ₁ -C ₁₀ linear or branched alkylene group, one or more oxygen, sulfur atoms connected to a terminal group or inserted into one or more oxygen, sulfur atoms _{A 2-} C ₁₀ linear or branched alkylene group, an unsubstituted or substituted arylene group,
Y ₃ is O, S, NR ₂₀ or OC (O);
R ₁ is a C ₁ -C ₄ alkyl group, a C ₅ -C ₇ cycloalkyl group, a C ₂ -C ₆ alkyl group substituted by a C ₅ -C ₇ cycloalkyl group, a C ₂ -C ₄ alkenyl group, or , R ₁ is a phenyl group or one or more C ₁ -C ₄ alkyl groups, a phenyl group optionally substituted with a C ₁ -C ₄ alkoxy group, a benzoyl group,
Each of R ₁₅ and R ₁₆ is a hydrogen atom, a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₅ alkyl group substituted with a carboxyl group, or a C ₁ -C ₄ substituted with R ₁ C (O) O. Each of an alkyl group or R ₁₅ and R ₁₆ is a C ₅ -C ₇ cycloalkyl group, or each of R ₁₅ and R ₁₆ is a phenyl group or one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy group, a carboxyl group, C ₁ -C ₁₂ alkyl acyl, C ₅ -C ₆ cycloalkyl formyl group, C ₁ -C ₄ alkyl acyl group substituted on the C ₅ -C ₆ cycloalkyl group Or a phenyl group optionally substituted with a benzoyl group;
Or each of R ₁₅ and R ₁₆ constitutes a ring having 4 to 7 atoms together with the carbon atom or the heel atom to be linked;
Or each of R ₁₅ and R ₁₆ together with the adjacent substituent constitutes a ring having 4 to 7 atoms,
R ₁₈ is, C ₁ -C ₁₈ alkyl group, C ₁ -C ₄ alkoxy C ₁ -C ₅ alkyl group substituted in amyl group, C ₁ -C ₄ alkyl group substituted on R ₁ C (O) O One or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxy, aryl acyloxy A C ₂ -C ₁₈ alkyl group optionally substituted on a C ₅ -C ₇ cycloalkylene group, a phenylene group, a C ₂ -C ₁₈ alkyl group inserted into O, S, NR ₁₇ ;
Or R ₁₈ is a C ₅ -C ₇ cycloalkyl group; one or more C ₁ -C ₄ alkyl groups, a phenyl group, a halogen atom, a C ₅ -C ₇ cycloalkyl group optionally substituted with CN Yes,
Or R ₁₈ is a phenyl group; one or more C ₁ -C ₁₂ alkyl group, carboxyl group, C ₁ -C ₁₂ alkyl acyl group, C ₅ -C ₆ cycloalkylformyl group, C ₅ -C ₆ cycloalkyl C ₂ -C ₄ alkyl acyl group substituted in groups, aryl acyl, heteroaryl acyl group, XR _17, a phenyl group, a halogen atom, a phenyl group optionally substituted in the CN or NO _2; phenylene group, O, A phenyl group optionally substituted with one C ₂ -C ₁₂ alkyl acyl group inserted into S or NR ₁₇ ;
R ₁₈ is a C ₁ -C ₄ alkyl acyl group, a C ₁ -C ₄ conjugated enoyl group, a benzoyl group, or a phenoxycarbonyl group, provided that the phenyl group has one or more halogen atoms, R ₁₇ , C ₅ or C ₆ cycloalkyl group, optionally substituted with CN, OH, XR ₁₇ ;
Each R _19, R _20, a hydrogen atom, C ₁ -C ₁₈ alkyl group, C ₁ -C ₅ alkyl group substituted C ₁ -C ₄ alkoxy amyl, substituted in R ₁ C (O) O C ₁ -C ₄ alkyl group; one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C _1- A C ₂ -C ₁₈ alkyl group optionally substituted by C ₄ alkylacyloxy, arylacyloxy, or inserted into a C ₅ -C ₇ cycloalkylene group, phenylene group, O, S, NR ₁₇ ; or C ₅ -C ₇ cycloalkyl group; or C ₅ -C ₇ cycloalkyl group optionally substituted with one or more C ₁ -C ₄ alkyl group, phenyl group, halogen atom, CN; or phenyl group and one or more C ₁ -C ₄ alkyl group, carboxyl group, C ₁ -C ₁₂ alkyl acyl group, C ₅ -C ₆ cycloalkylformyl group, C _5- A C ₂ -C ₄ alkyl acyl group substituted with a C ₆ cycloalkyl group, an aryl acyl group, XR ₁₇ , a phenyl group, a halogen atom, and a phenyl group optionally substituted with CN. A compound of I, IIa, IIb, III and IV according to claim 3,
Ar ₁

And
Each of R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ is a hydrogen atom; substituted with one or more C ₁ -C ₁₂ alkoxy groups, C ₁ -C ₄ alkylbenzyloxy groups, R ₁ C (O) O A C ₁ -C ₄ alkoxy group; a phenoxy group substituted by one or more C ₁ -C ₄ alkyl groups; one C ₁ -C ₈ alkyl acyl group, an arylformyl group, a heteroarylformyl group, C ₅ -C ₆ phenoxy group are substituted cycloalkyl _{amyl; C 5 -C 6 C 1 -C} 4 alkyl acyl phenoxy group is replaced by a cycloalkyl group; C ₁ -C ₃ alkylenedioxy group, R ₁ C (O) O, C ₁ -C ₁₂ alkylthio group; C ₁ -C ₄ alkylthio group substituted by R ₁ C (O) O; C ₁ -C ₄ alkylphenylthio group; R ₁ C (O) O C ₁ -C ₄ alkyl phenylthio group are substituted; one of C ₁ -C ₈ alkyl acyl group, an aryl formyl group, a heteroaryl formyl group, C ₅ -C ₆ cycloalkyl a C ₁ -C ₄ alkyl amyl phenyl thio group which is substituted or C ₅ -C ₆ cycloalkyl group; a phenylthio group substituted in Le group
Y ₁ is CH ₂ , CHCH ₃ or C (CH ₃ ) ₂ ;
Ar ₂
Z ₁ is a straight bond or a 1,3-phenylene group,
R ₁ is a methyl group, an ethyl group, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 2,4,6-trimethylphenyl group, or a 2,6-dimethoxyphenyl group;
R ₂₀ is a C ₁ -C ₈ alkyl group. A compound of I, IIa, IIb, III and IV according to claim 4,
The Ar ₁ substituent has at least one substituent in the para position of the carboxyl group linked to Ar ₁ ; in Ar ₂ , the O or N atom is in the para position of the carboxyl group linked to the benzene ring. A compound of I, IIa, IIb, III and IV according to claim 1,
Ar ₁ is ortho arylene group or an ortho heteroarylene group, ortho arylene group or an ortho heteroarylene group constitutes a fused ring structure linked to Y ₁ and a carboxyl group by two adjacent atoms, in the remaining atoms each substituent is a hydrogen atom, a halogen atom, C ₁ -C ₁₂ alkyl group, C ₅ -C ₇ cycloalkyl group, C ₅ -C ₇ substituted cycloalkyl group specifically C ₁ -C ₄ alkyl group, phenyl A group; one or more C ₁ -C ₄ alkyl groups, carboxyl groups, C ₁ -C ₁₂ alkyl acyl groups or arylformyl groups, XR ₁₇ , phenyl groups, halogen atoms, phenyl groups optionally substituted with CN; C ₁ -C ₄ alkylbenzyloxy group; C ₁ -C ₄ alkoxy group substituted by R ₁ C (O) O; C ₁ -C ₃ alkylenedioxy group, R ₁ C (O) O, C _1- C ₁₂ alkylthio group, C ₁ -C ₄ alkylphenylthio group, R ₁ C (O) O C ₁ -C ₄ alkylthio group substituted, CN, carboxyl group, C ₁ -C ₁₂ alkoxycarbonyl group, an aryl formyl group, a heteroaryl formyl group, a XR _18,
Alternatively, in the above-mentioned substitution, a ring structure can be formed by connecting two adjacent substituents or between the substituent and Ar ₁ via a straight bond, a carbon atom, or a carbonyl group,
X is O, S or NR ₁₉ ,
Y ₁ is CR ₁₅ R ₁₆
The definition of other groups is as described in claim 1. A compound of I, IIa, IIb, III and IV according to claim 1,
Wherein Ar ₁ is ortho arylene group or an ortho heteroarylene group, ortho arylene group or an ortho heteroarylene group constitutes a fused ring structure linked to Y ₁ and carboxy groups by adjacent two atoms, substituted in the remaining atoms each group is a hydrogen atom, C ₁ -C ₁₂ alkyl group, a C ₅ -C ₇ cycloalkyl group, C ₁ -C ₄ alkyl group substituted on the C ₅ -C ₇ cycloalkyl group, a XR _18,
Or, between two adjacent substituents in the substituent, or between the substituent and Ar ₁ can be linked via a straight bond, a carbon atom or a carbonyl group to form a ring structure,
However, Ar ₁ is not a substituted carbazole group,
X is O, S or NR ₁₉ ,
Y ₁ is O, S, CR ₁₅ R ₁₆ , C = O,
R ₁ is a hydrogen atom, a C ₁ -C ₁₈ alkyl group or an alkoxy group,
Or R ₁ is a C ₂ -C ₁₈ alkenyl group; one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group C ₂ -C ₁₈ optionally substituted with C ₁ , C ₁ -C ₄ alkylacyloxy, arylacyloxy, and / or inserted into a C ₅ -C ₇ cycloalkylene group, phenylene group, O, S, NR ₁₇ An alkenyl group,
Or, R ₁ represents one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkylacyloxy, optionally substituted aryl acyloxyalkyl, and / or C ₅ -C ₇ cycloalkylene group, a phenylene group, O, a C ₂ -C ₁₈ alkyl group that is inserted S, the NR _17,
Or, R ₁ is a C ₅ -C ₇ cycloalkyl group or one or more C ₁ -C ₄ alkyl groups, a phenyl group, a halogen atom, or a C ₅ -C ₇ cycloalkyl group optionally substituted with CN. Yes,
Or R ₁ is a phenyl group; one or more C ₁ -C ₄ alkyl groups, a C ₁ -C ₄ alkoxy group, a phenyl group, a halogen atom, a phenyl group optionally substituted with CN; or R 1 Is a naphthyl group,
Or R ₁ is a benzoyl group or a phenoxycarbonyl group, provided that the phenyl group is one or more halogen atoms, R ₁₇ , C ₅ or C ₆ cycloalkyl group, CN, OH, XR ₁₇ Optionally substituted,
Each of R ₁₅ and R ₁₆ is a hydrogen atom, a C ₁ -C ₁₈ alkyl group; one or more halogen atoms, a C ₁ -C ₄ alkyl group, a C ₅ -C ₇ cycloalkyl group, a heterocycloalkyl group, Phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxy, aryl acyloxy optionally substituted, or C ₅ -C ₇ cycloalkylene group, phenylene group, O, S, C inserted into NR ₁₇ be ₂ -C ₁₈ an alkyl group; or a C ₅ -C ₇ cycloalkyl group,
Or each of R ₁₅ and R ₁₆ is a phenyl group; or a phenyl group optionally substituted with one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups, phenyl groups, halogen atoms, CN And
Or R ₁₅ and R ₁₆ together with a carbon atom jointly connected to R ₁₅ and R ₁₆ form a ring having 4 to 7 atoms,
R ₁₇ is a C ₁ -C ₄ alkyl group,
R ₁₈ is a phenyl group; substituted with one or more C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkyl acyl group, C ₅ -C ₆ cycloalkylformyl group, C ₅ -C ₆ cycloalkyl group in one C ₂ -C ₁₂ phenyl group substituted in the alkyl acyl group; that C ₂ -C ₄ alkyl acyl group, an aryl acyl group, a heteroaryl acyl group, a phenyl group optionally substituted in the XR ₁₇ or NO ₂ In which an alkyl group is optionally inserted into a phenylene group, O, S or NR ₁₇ ;
Or, the R ₁₈ is connected to the aromatic ring in Ar ₁ via a straight bond, a carbon atom, or a carbonyl group to form a new ring,
R ₁₉ is a hydrogen atom, C ₁ -C ₁₈ alkyl groups, C ₁ -C ₅ alkyl group substituted C ₁ -C ₄ alkoxy amyl groups, C ₁ -C substituted in R ₁ C (O) O ₄ alkyl group; one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxy , optionally substituted aryl acyloxyalkyl, or C ₅ -C ₇ cycloalkylene group, a phenylene _{group, O, S, C 2 -C} 18 alkyl groups are inserted into NR _17; or C ₅ -C ₇ cycloalkyl group One or more C ₁ -C ₄ alkyl groups, a phenyl group, a halogen atom, a C ₅ -C ₇ cycloalkyl group optionally substituted with CN; or a phenyl group and one or more C ₁ -C ₄ alkyl group, carboxyl group, C ₁ -C ₁₂ alkyl acyl, C ₅ -C ₆ cycloalkyl formyl group, C ₅ -C ₆ cycloalk C ₂ -C ₄ alkyl acyl group substituted in group, an aryl acyl group, XR _17, a phenyl group, a halogen atom, a phenyl group optionally substituted in the CN,
Alternatively, R ₁₉ is linked to the aromatic ring in Ar ₁ via a straight bond, a carbon atom, and a carbonyl group, thereby forming a new ring. A compound of general formula I, IIa, IIb, III and IV according to claim 1 or 6,
The structure of the general formula I is
It is. A process for the preparation of compounds of general formulas I, IIa, IIb, III and IV according to claim 1,
(1) Oxidation is selectively carried out by a method in which an oximation reaction is generated in an acidic alcohol solution with an alkyl nitrite ester at the methylene group which is the ortho position of the carbonyl group of the compound of V or VIa and VIb. Step 1 to obtain any of the corresponding intermediate compounds VII or VIIIa, VIIIb;
(2) The intermediate VII compound is converted into the following acylating reagent:
Or an esterification reaction with an equivalent acylating reagent to give the corresponding compounds of general formulas I, III and IV,
Or any of its intermediates VIIIa or VIIIb
Or an esterification reaction with an equivalent acylating reagent to obtain the corresponding compound of general formula IIa or IIb,
The manufacturing method defined for R ₁ and Z ₁ are the same as defined in Claim 1. A compound of general formula V comprising:

(V)
Ar ₁ is linked to Y ₁ and a carbonyl group by two adjacent atoms to form a condensed ring structure, and each of the substituents in the remaining atoms is a hydrogen atom, a C ₁ -C ₁₂ alkyl group, C ₅ -C ₇ cycloalkyl _{group, C 5 -C 7 C 1 -C} 4 alkyl group substituted on the cycloalkyl group, the ortho arylene group or an ortho heteroarylene group is XR _18,
Or, between two adjacent substituents in the substituent, or between the substituent and Ar ₁ is linked via a straight bond, a carbon atom, a carbonyl group to form a ring structure,
X is O, S, NR ₁₉ ,
However, Ar ₁ is not a substituted carbazole group,
Y ₁ is O, S, CR ₁₅ R ₁₆ , C = O,
Each of R ₁₅ and R ₁₆ is a hydrogen atom, a C ₁ -C ₁₈ alkyl group; one or more halogen atoms, a C ₁ -C ₄ alkyl group, a C ₅ -C ₇ cycloalkyl group, a heterocycloalkyl group, Phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxy, aryl acyloxy optionally substituted, or C ₅ -C ₇ cycloalkylene group, phenylene group, O, S, C inserted into NR _{17 2} -C ₁₈ alkyl group; C ₅ -C ₇ cycloalkyl group; phenyl group; one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups, phenyl groups, halogen atoms, optionally on CN A substituted phenyl group,
Or, R ₁₅ and R ₁₆ together with a carbon atom that is jointly connected to each other constitutes a ring having 4-7 atoms,
R ₁₇ is a C ₁ -C ₄ alkyl group,
R ₁₈ is substituted with a phenyl group; one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₁₂ alkyl acyl groups, C ₅ -C ₆ cycloalkylformyl groups, C ₅ -C ₆ cycloalkyl groups A C ₂ -C ₄ alkyl acyl group, an arylformyl group, a heteroarylformyl group, a phenyl group optionally substituted with XR ₁₇ or NO ₂ ; a C ₂ inserted into a phenylene group, O, S or NR ₁₇ It is -C ₁₂ phenyl optionally substituted alkyl acyl group; the aryl acyl group, unsubstituted benzoyl group; one or more halogen, C ₁ -C ₈ alkyl group, C ₁ -C ₈ alkoxy A benzoyl group substituted by a group,
R ₁₉ is a hydrogen atom, C ₁ -C ₁₈ alkyl groups, C ₁ -C ₅ alkyl group substituted C ₁ -C ₄ alkoxy amyl groups, C ₁ -C substituted in R ₁ C (O) O ₄ alkyl group; one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₅ -C ₇ cycloalkyl group, heterocycloalkyl group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl acyloxy , optionally substituted aryl acyloxyalkyl, or C ₅ -C ₇ cycloalkylene group, a phenylene _{group, O, S, C 2 -C} 18 alkyl groups are inserted into NR _17; or C ₅ -C ₇ cycloalkyl group One or more C ₁ -C ₄ alkyl groups, a phenyl group, a halogen atom, a C ₅ -C ₇ cycloalkyl group optionally substituted with CN; or a phenyl group and one or more C ₁ -C ₄ alkyl group, carboxyl group, C ₁ -C ₁₂ alkyl acyl, C ₅ -C ₆ cycloalkyl formyl group, C ₅ -C ₆ cycloalk C ₂ -C ₄ alkyl acyl group, an aryl acyl group, XR ₁₇ is replaced by a group, a phenyl group, a halogen atom, a phenyl group optionally substituted in the CN.   A photopolymerization initiator comprising at least one compound of general formulas I, IIa, IIb, III and IV in claim 1 or 6, or a compound of general formula I in claim 7 and at least one radical polymerizable carbon. -A photocurable composition containing a carbon double bond compound.   The photocurable composition according to claim 11, further comprising an additive.   13. The photocurable composition according to claim 12, wherein the photopolymerization initiator occupies 0.05 to 25% by weight in the entire composition, and the carbon-carbon double bond compound and the additive occupy the remaining ratio excluding the components. object.   13. The photocurable composition according to claim 11 or 12, wherein the carbon-carbon double bond compound is selected from an acrylate compound and a methacrylate compound.   13. The photocurable composition according to claim 12, wherein the additive contains a developable resin, pigment or dye.   Applying the photocurable composition of any one of claims 11 or 12 to one of the products being a colored or transparent paint, ink, binder, photoresist and photoresist, and further printing the product; Application of photo-curable compositions applied to 3D printing, production of color filters in display devices, electronics packaging, printed circuit board media layers.   13. A method for curing a photocurable composition, wherein the photocurable composition according to claim 11 or 12 is applied to a substrate and irradiated with light having a wavelength of 190 to 600 nm to cure the coating layer.   18. The method for curing a photocurable composition according to claim 17, wherein the light beam uses the sun, a mercury lamp, a high pressure mercury lamp, or an LED lamp.   First, the photocurable composition according to any one of claims 11 and 12 is diluted with a solvent, the diluted photocurable composition is applied to a substrate, dried, exposed, and developed to be exposed. A method for producing a projection pattern by using a photocurable composition that removes a portion that is not present to obtain a projection pattern.   Compound of general formulas I, IIa, IIb, III and IV in claim 1 or 6, or any of the compounds of general formula I in claim 7, monomers, alkali-soluble resins, and corresponding pigments and additions A color filter including black, red, green, and blue pixels obtained by sequentially performing coating, exposure, development, and heat treatment on a composition comprising an agent.   Compound of general formulas I, IIa, IIb, III and IV in claim 1 or 6, or any of the compounds of general formula I in claim 7, monomers, alkali-soluble resins, and corresponding pigments and additions A method for producing a color filter, in which a composition comprising an agent is coated, exposed, developed, and heat-treated in order to obtain a color filter including black, red, green, and blue pixels.