KR101883164B1 - Asymmetric dioxime ester compound and manufacturing method and use therof - Google Patents

Abstract

The present invention relates to asymmetric di oxime ether compound, and a manufacturing method represented by the general formula I, in the formula I Ar ₁ is a substituted C ₆ -C ₂₀ o- by X ₁ O-ylidene, C ₃ - and C ₂₀ heteroaryl Oh o- ylidene, Ar ₂ is C ₆ -C ₂₀ O-ylidene, C ₃ -C ₂₀ heteroaryl O-ylidene, and connects the X ₁ and Ar _1, or for connecting the X ₁ and Ar ₁ At the same time a substituent connected to the ortho position straight chain of Ar ₂ carbon atoms in X _1, the carbon atoms, a carbonyl group, O, S, Ar ₁ in advanced by the NR ₁₈ forms a ring-like structure, wherein n is 0 or 1, X ₁ is (CR ₁₅ R ₁₆ ) _m , S (CR ₁₅ R ₁₆ ) _m , NR ₁₈ , O, S, C═O or S═O, Y ₁ is (CH ₂ ) _m CR ₁₅ R ₁₆ , NR ₁₉ , (CR ₁₅ R ₁₆ ) m C═O, S═O, m is 0 or 1, and R ₁ , R _{2 and} R ₃ are each a hydrogen atom, an alkyl group or an alkoxyl group, Naphthyl groups, aryl groups substituted by arbitrary groups Is an acyl group. The present invention further provides a photocuring composition for a photoinitiator wherein the compound represented by the general formula I is used as a photocuring composition and exhibits a very high curing sensitivity when the composition is used, for example, in the production of a photosensitive resist device such as a display plate for a display.

Description

TECHNICAL FIELD The present invention relates to an asymmetric dioxime ether compound, an asymmetric dioxime ether compound,

The present invention relates to an asymmetric dioxime ether compound, characterized in that the molecule is an esterified derivative in which an arylidene ring-coupled ketooxime and a ring-type ketooxime are present at the same time, and the esterified oxime group is located on? Is used as a photoinitiator in the curing composition.

Oxime ester compounds have been discovered very long ago as photoinitiators, and US Pat. No. 3,558,309 and US Pat. No. 4,255,513 disclose the use of oxime ester as a photoinitiator. Some oxime esters have poor thermal stability or low photosensitivity, The performance requirements of the modern electronic industry could not be satisfied. A series of oxime ester compounds have been disclosed in CN1514845A, of which OXE01 and OXE02 are oxime esters 305 and 304, which are already marketed and marketed similarly to products with further advancements to CN101565472B and CN101508744B.

The oxime ester substituted by the carbazole oxygen heterocyclic ketone described in the Chinese patent CN102046667B has an absorption wavelength of 405 nm, which is advantageous for curing by the LED lamp and curing by visible light. However, due to the increase of molecular weight, . A variety of dioxime ether derivatives having a phenylcarbazole base as disclosed in patent WO2008138732 have two oxime ester groups in one molecule and one oxime ester thereof is located on the phenyl group on the N-substitution position. According to experiments, Has been found to be very low and can not realize any additional contribution to the photoinitiator activity of the molecule and does not have practicality.

In addition, various other oxime ester type photoinitiator patents such as WO2006018973, WO2007071497, CN1805955B, CN1922142B, CN1928715A, CN101508744B, CN102020727, but various formulas are carried out in the side chains at positions 3, 6 and 9 of carbazole And some of them could not improve the photosensitivity due to increased molecular weight.

The inventors have found that a series of asymmetric dioxime ether compounds have very good photoinitiator activity.

Series 1: In the compound represented by the general formula I,

(I)

(I)

here,

Ar ₁ is C ₆ -C ₂₀ o-arylidene substituted by X ₁ or C ₃ -C ₂₀ o -heteroarylidene and C ₆ -C ₂₀ o-arylidene is C ₃ -C ₂₀ o - the heteroarylidene is connected to Y ₁ and a carbonyl group to form a condensed ring structure, and the substituents on the other atoms are each a hydrogen atom; A halogen atom; A C ₁ -C ₁₂ alkyl group; A C ₅ -C ₇ naphthyl group; A C ₁ -C ₄ alkyl group substituted by a C ₅ -C ₇ naphthyl group; A C ₁ -C ₁₂ alkoxyl group; One or more C ₁ -C ₁₂ alkoxyl groups, C ₁ -C ₄ alkyl group benzyloxy groups, C ₁ -C ₄ alkoxyl groups substituted by R ₂ C (O) O; A phenyl group; Optionally one or more C ₁ -C ₄ alkyl group, a carboxy group, C ₁ -C ₁₂ alkyl group an acyl group, an aryl group, an acyl group, a heteroaryl group, an acyl group, X ₃ R _17, phenyl group, a phenyl group substituted by a halogen atom, CN ; A C1-C4 alkyl group, a benzyloxy group; A C ₁ -C ₄ alkoxyl group substituted by R ₂ C (O) O; A C ₁ -C ₃ alkylidene diepoxide group; R _{2 is} C (O) O; C ₁ -C ₁₂ alkylsulfinyl; C ₁ -C ₄ alkyl group benzenesulfenyl; CN; A carboxy group; A C ₁ -C ₁₂ alkoxylcarbonyl group; An aryl group carbonyl group; A heteroaryl group carbonyl group; X ₃ R ₁₈ ; A C ₁ -C ₄ alkyl group phenoxy group; C ₁ -C ₈ alkyl group acyl group phenoxy group; A C ₅ -C ₆ naphthyl group, a phenoxy group; A C ₁ -C ₄ alkyl group substituted by a C ₅ -C ₆ naphthyl group, an acyl group phenoxy group; C ₁ -C ₃ alkylidene diepoxide group; aryl group acyl group phenoxy group; A heteroaryl group acyl group phenoxy group; C ₁ -C ₄ alkylsulfinyl substituted by R ₂ C (O) O; C ₁ -C ₄ alkyl group benzenesulfenyl; C ₁ -C ₈ alkyl group acyl group benzenesulfenyl; C ₅ -C ₆ naphthyl group, benzenesulfenyl group or C ₁ -C ₄ alkyl group substituted by C ₅ -C ₆ naphthyl group; Aryl-acyl group benzenesulfenyl; Or a glycidyl group, wherein the epoxy group is optionally condensed with a C ₁ -C ₄ alkyl group aldehyde, a ketone, X ₃ is O, S or NR ₂₂ ,

Ar ₂ is C ₆ -C ₂₀ O-ylidene, C ₃ -C ₂₀ heteroaryl O-ylidene, and through X ₁ is connected to the Ar _1, or through X ₁ at the same time connected to the Ar ₁ the substituent of the ortho-X ₁ Ar ₂ carbon atoms of the seat is through a straight chain, a carbon atom, a carbonyl group, O, S, NR ₁₈ by one step further connected to the Ar ₁ constitute a cyclic structure,

n is 0 or 1,

X ₁ is O, S, NR ₁₈ or Y ₂ -Z ₁ -Y ₂ ,

Y ₁ is (CH ₂ ) _m CR ₁₅ R ₁₆ , NR ₁₉ , O (CR ₁₅ R ₁₆ ) _m , S (CR ₁₅ R ₁₆ ) _m , (CR ₁₅ R ₁₆ ) _m C = O, S = m is 0 or 1,

Z ₁ is C ₁ -C ₁₀ straight chain or branched chain alkylidene, one or more oxygen atoms, connected to the terminal group through a sulfur atom, or the inserted C ₁ -C ₁₀ straight chain or branched chain alkylidene, substituted A C ₆ -C ₂₀ arylidene of a non-substituted or substituted group,

Y ₂ is O, S, NR ₁₈ , OC (O), R ₁ is a hydrogen atom; A C ₁ -C ₁₈ alkyl group; A C ₁ -C ₁₈ alkyl group optionally substituted by one or more C ₃ -C ₇ naphthyl groups, phenyl groups, OR ₂₀ , SR ₂₁ , NR ₂₂ R ₂₃ ; C ₃ -C ₇ cycloalkylene, a phenylene group, a C ₂ -C ₁₈ alkyl group inserted by O, S, NR ₂₂ ; A C ₃ -C ₈ naphthyl group; CN; NO ₂ ; C ₁ -C ₄ alkyl group, C ₅ -C ₇ naphthyl group, heteronaphthyl group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkyl group, or phenyl group in which at least one phenyl group is unsubstituted or optionally substituted with one or more halogen atoms, Substituted by an alkane acyloxy group, an aryl acyloxy group,

Or R ₁ is a C ₁ -C ₁₂ alkyl group acyl group or a C ₁ -C ₁₂ alkoxyl group carbonyl group, wherein the alkyl group is optionally substituted with one or two or more halogen atoms, a C ₁ -C ₄ alkyl group, a C ₅ or C ₆ naphthyl group, Phenyl, CN, OH, X ₃ R ₂₀ , or the alkyl group is optionally interrupted by one or two or more phenylene groups, X ₃ ,

Or R ₁ is a benzoyl group or a phenoxycarbonyl group, wherein the phenyl group is unsubstituted or optionally substituted with one or more halogen atoms, a C ₁ -C ₄ alkyl group, a C ₅ or C ₆ naphthyl group, a phenyl group, CN, OH, X ₂ R ₂₀ ,

Or R ₁ is a diphenyl-phosphono or di (C ₁ -C ₄ alkoxyl group) phosphono group,

R ₂ and R ₃ are each independently a hydrogen atom, a C ₁ -C ₁₈ alkyl group or a C ₁ -C ₁₈ alkoxyl group,

Or R ₂ and R ₃ are each independently a C ₂ -C ₁₈ alkenyl group and are optionally substituted with one or more halogen atoms, a C ₁ -C ₄ alkyl group, a C ₅ -C ₇ naphthyl group, a heteronaphthyl group, a phenyl group, a heteroaryl C ₁ -C ₄ alkanyl acyloxy group, an aryl acyloxy group and / or a C ₅ -C ₇ cycloalkylidene group, a phenylene group, an O, S, NR ₁₇ group, C ₂ -C ₁₈ alkenyl group,

Or R _2, R ₃ are each independently optionally one or a number of halogen atoms, C ₁ -C ₄ alkyl, C ₅ -C ₇ tingi naphthyl, heteroaryl tingi naphthyl, a phenyl group, a heteroaryl group, CN, C ₁ -C ₄ An alkenyl acyloxy group, an aryl acyloxy group and / or a C ₅ -C ₇ cycloalkylidene group, a phenylene group, a C ₂ -C ₁₈ alkyl group inserted by O, S, NR ₁₇ ,

Or R ₂ and R ₃ are each independently a C ₅ -C ₇ naphthyl group, optionally one or more C ₁ -C ₄ alkyl groups, phenyl groups, halogen atoms, C ₅ -C ₇ naphthyl groups substituted by CN, Or R ₂ and R ₃ are each independently phenyl and are optionally substituted with one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxyl groups, phenyl groups, halogen atoms and CN,

Or R ₂ and R ₃ are each independently a naphthyl group,

Or R ₂ and R ₃ are each independently a benzoyl group or a phenoxy group carbonyl group, or the phenyl group therein is unsubstituted or optionally substituted with one or two or more halogen atoms, R ₁₇ , C ₅ or C ₆ naphthyl groups, CN, OH , Substituted by XR ₁₇ ,

R ₁₅ and R ₁₆ each independently represent a hydrogen atom; A C ₁ -C ₁₈ alkyl group; A C ₁ -C ₅ alkyl group substituted by a carboxy group or substituted by a C ₁ -C ₄ alkoxyl group acyl group; A C ₁ -C ₄ alkyl group substituted by R ₂ C (O) O; Optionally one or a number of halogen atoms, C ₁ -C ₄ alkyl, C ₅ -C ₇ tingi naphthyl, heteroaryl tingi naphthyl, a phenyl group, a heteroaryl group, CN, C ₁ -C ₄ alkanes one acyloxy group, aryl group acyloxy Or a C ₂ -C ₁₈ alkyl group inserted by a C ₅ -C ₇ cycloalkylene group, a phenylene group, O, S, NR ₁₇ , or R ₁₅ and R ₁₆ are each independently C ₅ -C ₇ naphthyl and tingi or optionally one or a C ₅ -C ₇ tingi naphthyl substituted by a plurality of C ₁ -C ₄ alkyl group, a phenyl group, a halogen atom, CN,

Or R _15, R ₁₆ are each independently a phenyl group, optionally one or more C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxyl group, carboxyl group, C ₁ -C ₁₂ alkyl group an acyl group, C ₅ -C ₆ naphthyridin A C ₂ -C ₄ alkyl group substituted by a C ₅ -C ₆ naphthyl group, a benzoyl group, an XR ₁₇ group, a phenyl group, a halogen atom, a phenyl group substituted by CN,

Or R ₁₅ and R ₁₆ may form a ring with a carbon atom or a silicon atom bonded to each other at the same time, and the number of atoms constituting the ring is 4 to 7, or R ₁₅ and R ₁₆ may be ring- And the number of atoms constituting the ring type is 4 to 7,

R ₁₇ is a C ₁ -C ₄ alkyl group,

R ₁₈ and R ₁₉ each independently represent a hydrogen atom; A C ₁ -C ₁₈ alkyl group; A C ₁ -C ₅ alkyl group substituted by a C ₁ -C ₄ alkoxyl group acyl group; A C ₁ -C ₄ alkyl group substituted by R ₂ C (O) O; Optionally one or a number of halogen atoms, C ₁ -C ₄ alkyl, C ₃ -C ₇ tingi naphthyl, heteroaryl tingi naphthyl, a phenyl group, a heteroaryl group, CN, C ₁ -C ₄ alkanes one acyloxy group, aryl group acyloxy A substituted C ₁ -C ₁₈ alkyl group; Optionally substituted with one or more C ₃ -C ₇ cycloalkylene groups, phenylene groups, C ₂ -C ₁₈ alkyl groups inserted by O, S, NR ₁₇ ,

Or R _18, R ₁₉ are each independently C ₅ -C ₇ tingi naphthyl, and or optionally one or more C ₁ -C ₄ alkyl group, a phenyl group, a halogen atom, a CN substituted by C ₅ -C ₇ tingi naphthyl and ,

Or R _18, R ₁₉ are each independently a phenyl group, and optionally one or more C ₁ -C ₄ alkyl group, a carboxy group, C ₁ -C ₁₂ alkyl group an acyl group, C ₅ -C ₆ tingi naphthyl formyl group, C ₅ -C _6, the C ₂ -C ₄ alkyl substituted by naphthyl groups tin acyl group, an aryl group, an acyl group, XR _17, a phenyl group, a phenyl group substituted by a halogen atom, CN,

Or wherein R ₁₈ is a straight chain through a carbon atom, Ar ₁ or Ar ₂ kareubonilgieul Constituting a new ring connected to the aromatic ring in the ring,

Or R < ₁₉ > is connected to the aromatic ring in Ar < 1 > via a straight chain, a carbon atom or a carbonyl group to form a new ring,

R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom; A C ₁ -C ₁₈ alkyl group; Halogen, CN, a C ₁ -C ₁₈ alkyl group substituted by a C ₁ -C ₄ alkoxyl group; One or more oxygen atoms, a C ₅ -C ₇ cycloalkylene group, a C ₂ -C ₁₈ alkyl group inserted by a phenylene group; A phenyl group, a C ₁ -C ₃ alkyl group substituted by a C ₃ -C ₇ naphthyl group; C ₃ -C ₇ naphthyl group,

Or _{R 20, R 21, R 22} , R 23 are each independently a phenyl group, a naphthyl group, a benzoyl group, wherein the phenyl and naphthyl groups substituted or not, or respectively optionally halogen, C ₁ -C ₄ alkyl, C ₁ A C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkylsulfinyl group, a phenoxy group, a benzenesulfinyl group, a NR ₂₄ R ₂₅ , a C ₁ -C ₁₂ alkyl group acyl group, a benzoyl group,

R ₂₄ and R ₂₅ are each a C ₁ -C ₄ alkyl group, or NR ₂₄ R ₂₅ is morpholine, piperidine, piperazine, N-methylpiperazine, pyrrole.

Series 2: compounds represented by the general formulas II, IIIA and IIIB,

(II)

(II)

(IIIA)

(IIIA)

(IIIB)

(IIIB)

here,

R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom; A halogen atom; A C ₁ -C ₁₂ alkyl group; A C ₅ -C ₇ naphthyl group; A C ₁ -C ₄ alkyl group substituted by a C ₅ -C ₇ naphthyl group; A C ₁ -C ₁₂ alkoxyl group; A phenyl group; Optionally one or more C ₁ -C ₄ alkyl group, a carboxy group, C ₁ -C ₁₂ alkyl group an acyl group, an aryl group, an acyl group, a heteroaryl group, an acyl group, X ₃ R _17, phenyl group, a phenyl group substituted by a halogen atom, CN ; A C ₁ -C ₄ alkyl group, a benzyloxy group; One or more C ₁ -C ₁₂ alkoxyl groups, C ₁ -C ₄ alkyl group benzyloxy groups, C ₁ -C ₄ alkoxyl groups substituted by R ₂ C (O) O; R _{2 is} C (O) O; CN; A carboxy group; A C ₁ -C ₁₂ alkoxylcarbonyl group; An aryl group carbonyl group; A heteroaryl group carbonyl group; X ₃ R ₁₈ ,

Or R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a C ₁ -C ₄ alkyl group phenoxy group; C ₁ -C ₄ alkyl group benzenesulfenyl; C ₁ -C ₈ alkyl group acyl group phenoxy group; An aryl-acyl group phenoxy group; A heteroaryl group acyl group phenoxy group; A C ₅ -C ₆ naphthyl group, a phenoxy group; A C ₁ -C ₄ alkyl group substituted by a C ₅ -C ₆ naphthyl group, an acyl group phenoxy group; A C ₁ -C ₃ alkylidene diepoxide group; C ₁ -C ₁₂ alkylsulfinyl; C ₁ -C ₄ alkylsulfenyl substituted by R ₂ C (O) O and benzenesulfenyl C ₁ -C ₄ alkyl group; C ₁ -C ₈ alkyl group acyl group benzenesulfenyl; Aryl-acyl group benzenesulfenyl; Heteroaryl group acyl group benzenesulfenyl; C ₅ -C ₆ naphthyl group, benzenesulfenyl group or C ₁ -C ₄ alkyl group substituted by a C ₅ -C ₆ naphthyl group,

Or _{R 4, R 5, R 6} , R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14 is a group-glycidyl each alone, wherein the epoxy group is an optionally C ₁ - C ₄ alkyl group aldehyde, condensed with ketone,

X < ₁ > is O, S or NR < ₁₈ &

X ₂ is O, S, NR ₁₉ ,

Y ₁ is O, S, CR ₁₅ R ₁₆ ,

The definition of other substituents is the same as in series 1.

Series 3: For compounds represented by the general formula II,

R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are all hydrogen atoms,

X < ₁ > is O or S,

Y ₁ is CH ₂ , CHCH ₃ or C (CH ₃ ) ₂ ,

n = 1,

R ₁ is a C ₁ -C ₁₂ alkyl group, optionally one or more C ₃ -C ₇ naphthyl groups, phenyl group, a C ₁ -C ₁₂ alkyl group substituted by OR ₂₀ , SR ₂₁ , NR ₂₂ R ₂₃ ,

R ₂ and R ₃ are each independently methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylphenyl or 2,6-

The definitions of other groups are the same as those of corresponding groups in general formula II of series 2.

Series 4: For the compounds represented by the general formulas IIIA and IIIB,

X ₂ is NR ₁₉ ,

Y ₁ is O, S, CR ₁₅ R ₁₆ ,

R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom; A halogen atom; A C ₁ -C ₄ alkyl group; A C ₁ -C ₄ alkoxyl group; A C ₁ -C ₄ alkyl group, a benzyloxy group; C ₁ -C ₄ alkylsulfenyl; A C ₁ -C ₄ alkyl group phenoxy group; C ₁ -C ₄ alkyl group, benzenesulfenyl,

The definitions of other substituents are the same as those of the corresponding groups in the general formulas IIIA and IIIB of series 2.

Series 5: For the compounds represented by the general formulas IIIA and IIIB,

Y ₁ is CH ₂ or CHCH ₃ ,

n = 0,

R ₁ is a C ₁ -C ₁₂ alkyl group, optionally a C ₃ -C ₇ naphthyl group, a phenyl group, a C ₁ -C ₁₂ alkyl group substituted by OR ₂₀ , SR ₂₁ , NR ₂₂ R ₂₃ ,

R ₂ and R ₃ are each independently methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylphenyl or 2,6-dimethoxybenzene,

R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydrogen atom or a C ₁ -C ₄ alkoxyl group,

R ₁₉ is a C ₁ -C ₁₂ alkyl group, a C ₃ -C ₇ naphthyl group, a C ₁ -C ₃ alkyl group substituted by a phenyl group,

The definitions of the other groups are the same as those of the corresponding groups in the general formulas IIIA and IIIB of series 4.

Wherein R ₂ C (O) or R ₃ C (O) is replaced by (R ₂ ) ₂ P or R ₂ S (O ₂ ) in the above general formulas I, IIA and IIB to form the corresponding phosphoric acid ester or sulfonic acid ester And has a free radical or photo cationic initiating action.

Series 6: In the compounds represented by the general formulas I, II, IIIA, and IIIB of each of the series 1 to 5,

(IIA1)

(IIA1)

(IIA2)

(IIA2)

(IIA3)

(IIA3)

(IIA4)

(IIA4)

(IIA5)

(IIA5)

(IIA6)

(IIA6)

(IIB1)

(IIB1)

(IIC1)

(IIC1)

(IIIA1)

(IIIA1)

(IIIA2)

(IIIA2)

(IIIA3)

(IIIA3)

(IIIB1)

(IIIB1)

to be.

The present invention further provides a process for preparing a compound represented by the general formula I in series 1 as described above, comprising the steps of:

(1) Step 1: Oxidation is selectively carried out at the methylene group of the ortho-position of the cyclopentanone carbonyl group in the IV compound, and the method is a process wherein an ox compound is reacted with an IV compound and an alkyl- V,

(IV)

(IV)

(V)

(V)

(2) Step 2: The intermediate V compound is subjected to secondary oximation, which is a method of obtaining the corresponding intermediate VI compound by oximating the V compound and the alkyl nitrite ester in an acidic solution, Method B is a method for obtaining the corresponding intermediate VII compound by oximating a carbonyl group in the side chain R < ₁ > CH ₂ CO in a hydroxylamine solution in the presence of a cis-trans isomer, Is a mixture of isomers,

(VI)

(VI)

(VII)

(VII)

(3) Third step: Oxidizing intermediate VI or VII of the second step is reacted with the following acylating agent

,

,

,

,

,

,

Or an acylating agent of the same valence to obtain the corresponding general formula I, and when the cis-trans isomer is present in the oxime group of the intermediate VI or VII, the obtained I is a mixture of the respective isomers, or the isomers are obtained through purification , The definitions of all the groups in the structure during the reaction are the same as those in the corresponding structure in the series 1.

The present invention further provides an asymmetric diketone compound represented by the general formula IV,

(IV)

(IV)

here,

The definitions of Ar ₁ , Ar ₂ , X ₁ , Y ₁ and R ₁ are the same as those of the corresponding groups in the compound represented by formula I of series 1.

The present invention further provides a ketooxime compound represented by the general formula V,

(V)

(V)

here,

The definitions of Ar ₁ , Ar ₂ , X ₁ , Y ₁ and R ₁ groups are the same as those of the corresponding groups in the compound represented by formula I of series 1.

The present invention further provides diketo oxime compounds represented by the general formulas VI and VII,

(VI)

(VI)

(VII)

(VII)

here,

The definitions of Ar ₁ , Ar ₂ , X ₁ , Y ₁ and R ₁ are the same as those of the corresponding groups in the compound represented by formula I of series 1.

When a cis-trans isomer is present in the oxime group in the general formulas V, VI, and VII, each intermediate obtained and the final product, a compound represented by the general formula I, are a mixture of isomers and each purified isomer can be obtained by separation.

(A) a photoinitiator, and (b) a carbon double bond compound capable of carrying out at least one free radical polymerization, wherein the photoinitiator (a) comprises at least one compound represented by the above general formula I A photo-curing composition is provided.

The photoinitiator (a) contains other commercially available photoinitiators as the co-initiator composition (c), in addition to at least one compound represented by Formula I above.

The above-mentioned photo-curable composition further contains other additives (d) such as a necessary functional composition such as a developable resin, a pigment and a defoaming agent.

The photoinitiator (a) accounts for 0.05 to 25% and preferably 2 to 15% of the total curing composition in terms of parts by weight, and the other composition occupies the rest of the composition.

The composition (b) is a carbon double bond compound capable of free-radical polymerization, i.e., a photo-curable monomer, and the molecule contains one carbon double bond or two or more carbon double bonds. The compound containing one carbon double bond is preferably an acrylic acid ester compound or methacrylic acid ester compound, and examples thereof include acrylic acid methyl ester, acrylic acid butyl ester, 2-ethylhexyl acetic acid ester, acrylic acid cyclohexyl ester, isobornyl Acrylic esters of monohydric alcohols such as acrylonitrile, N-dialkylacrylamide, N-vinylpyrrolidinone, vinylbenzene, vinyl acetate, vinyl ether, or the like; Methacrylic acid esters.

As the compound containing two or more carbon double bonds, for example, an alkyl group dihydric alcohol, an acrylate or methacrylate ester of a polyhydric alcohol or a polyester polyhydric alcohol, a polyether polyhydric alcohol, an epoxy resin polyhydric alcohol, Unsaturated polyesters of acrylic acid esters of alcohols, vinyl ethers and unsaturated dicarboxylic acid polyhydric alcohols such as polyethylene glycol diacylate, Neopentyl glycol diacrylate, TMPTA (Trimethylolpropane Triacrylate), ETPTA, pentaerythritol tetraacrylate, Polyester oligomer acrylic acid ester, polyurethane oligomer acrylic acid ester, aromatic epoxy resin acrylic acid ester, and maleic acid ethylene glycol polyester.

These carbon double bond compounds may be used singly or in combination of two or more thereof, or may be used in the preparation of a composition by forming an oligomer by performing pre-copolymerization between the mixtures. When the polymerizable monomer contains an alkali-soluble group such as a carboxylic acid group, for example, a polymer resin having alkali solubility can be obtained and used for the production of a photosensitive resist or preparation of an aqueous dispersion emulsion.

In addition to using the compound represented by the general formula (I) as a photoinitiator, other types of commercial photoinitiators or auxiliary initiators can be synthesized in accordance with the use demand of the composition to form a co-initiator composition (c) Hydroxy-2-methyl-1-propiophenone, 1-hydroxycyclohexyl phenyl ketone, and other? -Hydroxy group ketones; Methyl-2-morpholine group- (4- (methyldiophenyl) -1-acetone, 2-dimethylamino group-2-benzenemethyl- (4-morpholinophenyl group) -1- Amino group ketones; 2,2-diethoxy-1,2-diphenylethanone; Methyl benzoyl peroxide, diethylene glycol bisbenzoyl acid, and ester polybutylene glycol bisbenzoyl acid ester; (2,4,6-trimethylbenzoyl) diphenyl group oxidized phosphine, di (2,4,6-trimethylbenzoyl) phenyl group oxidized phosphine; Benzophenone, 4-methyldiobenzophenone, 4- (2-chloro-4-phenylbenzophenone, 4-methylbenzophenone, Benzoquephenone, 4-hydroxybenzophenone lauric acid ester benzophenone-4-fluoroacetic acid polyethylene glycol ester, and the like; Thioxanthones such as 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthone-2-acid polyethyleneglycol ester , Thioxanthone-2-fluoroacetic acid polyethylene glycol ester, and the like; Halogenated methyltriazine such as 2- (4-methoxylphenyl group) -4,6-di (trichloromethyl) - [1,3,5] -triamine; Hexaarylbisimidazoles (HABI) such as hexa-o-chlorophenylbiimidazole; A ferrocene type compound; Dichlorotitanate compounds; Coumarin; Camphorquinone; Acridines such as 9-phenylglycidyne; For example, adducts of 4,4'-di (diethylamino group) benzophenone, ethyl 4-dimethylaminobenzoate, triethanolamine, methyldiethanolamine or adducts of diethylamine and ethoxylated TMPTA (trimethylolpropane triacrylate) Amines such as compounds; Phosphorous acid esters such as phosphorous acid tribenzene ester and trilauryl phosphite; For example, chain transfer agents such as ethanethiol and n-octyl mercaptan.

The composition (d) comprises a pigment and a dye, and the pigment is a component necessary for the production of a printing ink and a light field, and the red, green, blue, black, white, yellow, magenta, , And corresponding pigments are commercially available types such as carbon black, phthalocyanine, and titanium dioxide. The concentration of the pigment generally accounts for 10 to 30% of the total weight of the solid composition of the composition.

Composition (d) further includes, for example, phenols and disoriented amine polymerization inhibitors such as p-methoxylphenol and nitrosophenylhydroxylamine aluminum complex polymerization inhibitor; For example, 2- (2 'hydroxy group phenyl group) -benzotriazoles; light absorbers such as salicylic acid esters and triamine; A leveling agent such as triethoxyvinylsilane; Wetting agents, dispersants, and the like. The amount of these used is based on that it reaches the physical property index of the composition and is not particularly limited here.

The composition (d) further contains a developable resin, among which an alkali-soluble developable resin, for example, a polyacrylic acid ester copolymer containing a carboxylic acid side chain, and the comonomer is acrylic acid or methacrylic acid, Acrylic acid esters of methacrylic acid, styrene, and oligomerized styrene, and examples of the solvent developable resin include cellulose ester, cellulose ether, polyvinyl acetate, polyvinyl butyral, polystyrene, polycarbonate, polyvinyl chloride, polyester, There are widely used resin such as midium. When the developable resin is an alkali-soluble resin, the composition can be used in the production of a photosensitive plate and a light guide plate used in a display.

The composition may further comprise a thermally dried resin and a thermosetting resin composition (e) and may contain, for example, a cellulose solution, a polyisocyanate, a polyimide, and such a photocuring, .

A compound having at least one epoxy group as a thermosetting composition (f) and an epoxy group curing accelerator (g) may be added to the composition. Known thermosetting epoxy compounds such as aliphatic epoxy resins and aromatic epoxy resins can be used as the compound having an epoxy group as the thermosetting composition (f). Here, for example, BPS-200 Bisphenol A type epoxy resin, novolak epoxy resin, and some ester compounds thereof. The amount of the composition (b) and the amount of the composition (f) is preferably 30 to 100 parts by weight, 70 parts by weight.

When the composition (f) is used, an optional promoter (g) can be used as a cooperative composition to realize a good curing accelerating action. For example, an amine accelerator, an imidazole accelerator and other commonly used epoxy resin curing agents can be used , And the amount thereof used is 5% or less of the weight of the composition (f).

Other additives (h) widely used in the art for the compositions besides the above compositions (a), (b), (c), (d) An inorganic filler such as barium sulfate, silicon oxide powder, talcum powder, calcium carbonate, and mica powder, which is an additive for improving adhesion and hardness of a molded film, and the amount of the filler is within 30% of the total composition.

The composition may be further diluted with a solvent according to the demand of the application field, and suitable solvents include, for example, ketones such as methyl ethyl ketone, cyclohexanone; Hydrocarbons such as toluene, di-toluene, octane, petroleum ether, and naphtha; Alcohols such as normal butanol and propylene glycol; For example, alcohol ethers and esters thereof such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2-acetoxy-1-methoxypropane, methyl 3-methoxylpropanoate and the like; For example, amides such as N, N-dimethylformamide.

A mixture diluted with the above composition or solvent is prepared according to the ink production method, and is then shielded from light.

The composition is used in the production of colored or transparent paints, adhesives or inks, photosensitive resists and photoresists, and furthermore the products are used in the production of printing plates, 3D printing, Electronic device packetization, optical switches, three-dimensional molds, quartz fiber protection layers, and medical products.

The present invention provides a method for curing a carbon double bond compound in the above-mentioned photo-curing composition, which comprises applying a composition to a base and irradiating light with a wavelength of 190 to 600 nm to cure the coating layer. Light rays are provided from the sun, mercury lamps, high-pressure mercury lamps or LED lamps. Includes passing a light wave or a grating in the range of 190 to 600 nm and copying the light wave whose output light wavelength is controlled to the composition, and irradiating the LED light source with an LED light source of any constant wavelength range between 360 nm and 410 nm, for example, an LED light source of 365 nm The coating layer of the composition may be irradiated and cured. The definition of the LED is a light emitting diode semiconductor.

The method of manufacturing a protruding pattern using a photo-curable composition comprises firstly diluting the photo-curing composition in a solvent, then applying the diluted photo-curable composition to a base, removing the unexposed portion through roasting, exposure, .

A composition containing at least one compound represented by the general formula (I) of the present invention, a monomer, an alkali-soluble resin, a pigment, and an additive can be used as a photosensitive resist and can be easily developed by an alkaline aqueous solution It is suitable for the production of etch photosensitive resist, solder mask photosensitive resist, image display and recording material, spray ink which is cured by LED lamp, LCD, OLED and PDP. And can be used for the production of various printed boards and for the production of electronic circuit boards or integrated circuits, or they can be used for barrier coating layers of various electronic products.

The composition has good antioxidant inhibition action and heat-resistant processing capability and can meet the requirements of the production process of a spark plug, and is particularly suitable for the production of a liquid crystal display or an organic semiconductor light emitting display.

The composition of the present invention is applied as a photoresist, followed by coating, exposure, development, and heat treatment to form a black and an orange-red three-color pattern to obtain a perfect whitening plate. The base of such a light guide plate may be a glass or organic polymer film and a ceramic sheet.

The present invention further provides a light guide plate made of the above composition.

The composition is applied to a flat or curved base and roasted to obtain a film layer, followed by mask exposure and development to remove unexposed portions to obtain protrusion images. A light guide plate comprising black, red, green and blue pixels is formed by mixing a compound represented by the general formulas I, II, III and IV of the present invention, a monomer, an alkali-soluble resin and a corresponding pigment and an auxiliary Exposure, development, and heat treatment to the composition. Here, it also includes necessary treatment processes such as cleaning.

For example, the composition of the present invention can be uniformly applied to a base to be coated by a coating technique which is widely used in the fields of spin coating, roller coding, spraying, transfer and the like, The thickness is 0.1 micron to 1 millimeter. When the composition contains a solvent composition, the composition is volatilized by a heating method, for example, a drying method at 80 캜, and the solvent is volatilized to form an adhesive layer on the base.

Next, in the exposure step, if the image mask is not directly exposed by the UV laser, the image mask is placed on the adhesive layer, light rays of a certain range of wavelengths are emitted from the ultraviolet or visible light source, The light-receiving portion of the light-emitting device is cured and the blocked portion is not cured.

Next, in the developing step, the protruding pattern is obtained by removing the non-exposed portion. The developing process can be carried out by a person skilled in the art with known parameters, for example, spraying at 30 DEG C and washing. Generally, it is generally developed with an alkaline aqueous solution, for example, a hydroxide of an alkali metal, an aqueous carbonate solution, or ammonium hydroxide, and if necessary, a certain amount of a surfactant such as an organic solvent such as cyclohexanone, acetone, May also be added. A developing method in which the exposed film is immersed in a developing solution or the developing solution is sprayed on the exposed film may be used, and the specific developing temperature and time are determined based on the developing effect. The alkaline solution used in the development is a solution of an alkaline substance in an aqueous solution containing water or a water-soluble organic solvent. Examples of the alkaline substance include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, Triethanolamine, morpholine, and trisodium phosphate, and the weight concentration range is 0.1 to 10%. A surfactant having a weight concentration of 0.05 to 5% may be added to the aqueous solution.

The final heat treatment process can optimize the image fixation degree and generally roasting treatment for 15 to 45 minutes in a heating furnace at 200 to 260 ° C.

According to the composition of the present invention, it is possible to manufacture a light-scattering plate part having a good processing performance, a matrix having a clear matrix, a high light transmittance and a high quality display.

The examples are intended to further illustrate the present invention in detail, and the amounts thereof are all calculated by weight unless otherwise specified.

Example 1: Synthesis of 5-benzenesulfenylindan-1-ketone

(0.2 mol) of 5-chloro-1-indanone was placed in a 50 ml three-necked flask and 30 ml of N, N-dimethylformamide (DMF), 30.0 g (0.27 mol) of thiophenol, Potassium is added and stirred at 40-45 [deg.] C under nitrogen protection for 6 h. The DMF was recovered by decompression, and the residue was taken up in 100 ml of water, extracted twice with 25 ml of 1,2-dichloroethane, the 1,2-dichloroethane solution was combined, washed twice with 10 ml of water and the filter paper was placed on a Buchner funnel The organic phase was filtered, and the filtrate was dried. The residue was crystallized again from methanol and dried to obtain 43.4 g of a thin yellow crystal. The yield was 90.3% and the purity by HPLC analysis reached 98.2%. The melting temperature range is 46.0 ~ 48.0 ℃.

Example 2: Synthesis of 5- (4-octanoylbenzenesulfenyl) indan-1-ketone

24.04 g (0.1 mol) of 5-benzenesulfenylindan-1-ketone, which is the product of Example 1, was dissolved in 120 ml of 1,2-dichloroethane, and the temperature was cooled to 5-10 ° C to obtain 28 g (0.21 mol) After adding dropwise 17.9 g (0.11 mol) of octanoyl chloride with stirring, the reaction solution was treated with diluted hydrochloric acid, and the organic solution was separated, washed once more with water, concentrated, 2-dichloroethane was recovered and the residue was recrystallized again from 100 ml of ethanol to obtain 33.1 g of white crystals. The yield was 90.1%, the melting temperature range was 74.3 to 75.2 ° C, and the product obtained from ¹ H-NMR data was 5- ( Octanoyl group benzenesulfenyl) indan-1-ketone. _{^{1 H-NMR (CDCl 3)}} , δ (ppm) value figures are _{0.8848 (t, 3H, CH 3} ), 1.2892-1.3412 (m, 8H, 4CH 2), 1.7359 (m, 2H, CH 2), 2.7066 ( _{t, 2H, c-CH 2} ), 2.9526 (t, 2H, CH 2), 3.0961 (t, 2H, c-CH 2), 7.2740 / 7.3008 (d, 1H, ArH), 7.3734 (s, 1H, ArH ), 7.4525 / 7.4797 (d, 2H, 2ArH), 7.6677 / 7.6945 (d, 1H, ArH), 7.9221 / 7.9493 (d, 2H, 2ArH).

Example 3: Synthesis of 5- (4-octanoylbenzenesulfenyl) indan-1,2-diketone-2-oxime

(0.05 mol) of the product 5- (4-octanoylbenzenesulfenyl) indan-1-ketone obtained in Example 2 was dissolved in 150 ml of ethanol in a 250 ml three-necked flask, and 2 g of 36% (0.06 mol) of butyl nitrite was added dropwise within 15 min. After stirring at 25 ° C for 5 hours, the reaction solution was cooled to 5 to 10 ° C and filtered to obtain a yellow solid The product was found to have a purity of 98.90% and a melting temperature range of 162.7 to 164.0 ° C. According to ¹ H-NMR data, the product was 5- (4-octanoylbenzenesulfenyl) indane- 1,2-diketone-2-oxime, and the yield was 94.2%. _{^{1 H-NMR (CDCl 3)}} , δ (ppm) value figures are _{0.8866 (t, 3H, CH 3} ), 1.2965-1.3512 (m, 8H, 4CH 2), 1.7493 (m, 2H, CH 2), 2.9737 ( _{t, 2H, CH 2),} 3.7977 (s, 2H, c-CH 2), 7.2674 / 7.2943 (d, 1H, ArH), 7.3320 (s, 1H, ArH), 7.5281 / 7.5558 (d, 2H, 2ArH) , 7.7707 / 7.7977 (d, 1H, 2ArH), 7.9648 / 7.9925 (d, 2H, 2ArH), 12.4460 (s, 1H, NOH).

Example 4 Synthesis of Dioxime Compound

7.95 g (0.02 mol) of 5- (4-octanoylbenzenesulfenyl) indan-1,2-diketone-2-oxime, which is the product obtained in Example 2, was measured and dissolved in 40 ml of dimethylsulfoxide. (0.03 mol) of butyl nitrite was added dropwise within 15 min. After stirring for 10 hours, the reaction solution was cooled to 5 to 10 ° C and filtered to obtain a yellow solid. After precipitation and drying, 7.72 g was obtained. As a result, the purity was 96.80% and the yield was 90.5%. The melting temperature ranged from 171.0 ° C to 173.0 ° C and the product obtained by ¹ H-NMR data was a dioxime compound. ^{1 H-NMR (DMSO-d} 6), δ (ppm) value figures are _{0.850 (t, 3H, CH 3} ), 1.272-1.492 (m, 8H, 4CH 2), 2.616 (t, 2H, CH 2), 3.738 (s, 2H, c- CH 2), 7.299 / 7.319 (d, 1H, ArH), 7.435 (s, 1H, ArH), 7.557 / 7.578 (d, 2H, 2ArH), 7.719 / 7.739 (d, 1H , 2ArH), 7.847 / 7.867 (d, 2H, 2ArH), 12.446 (s, 1H, NOH), 12.651 (s, 1H, NOH).

Example 5: Synthesis of dioxime ether IIA1

IIA1

IIA1

4.27 g (0.01 mol) of the product of Example 4 was dissolved in 25 ml of 1,2-dichloroethane, 3.1 g (0.03 mol) of anhydrous acetic acid was added dropwise, and the mixture was reacted for 6 hours in a water bath at 20 to 25 ° C. The reaction solution was washed twice with 25 ml of water to separate the water phase. The organic phase was dried with 1.5 g of anhydrous sodium sulfate for 2 hours, filtered to remove the drying agent, and the filtrate was evaporated to dryness under reduced pressure. To the remainder was added 15 ml of ethyl acetate. The mixture was heated until dissolved, and 0.05 g of activated charcoal was added. The reaction mixture was refluxed for 0.5 h, and the charcoal was separated by heat filtration. 15 ml of n-hexane was added to the filtrate. The precipitated crystals were precipitated by suction filtration The filtration cake was vacuum dried to obtain 4.47 g of a yellow crystalline product, the content of which was 98.0% and the yield was 87.8%. The melting temperature range and the values of ¹ H-NMR (CDCl ₃ ) and 隆 (ppm) are shown in Table 1.

Example 6: Synthesis of 5- (4-valeryl group benzenesulfenyl) indan-1-ketone

According to the method of Example 2, 5- (4-valerylbenzenesulfenyl) indan-1-ketone was obtained in the same manner as in Example 2, except that the valerate was used instead of octanoyl chloride. The yield was 93.0%, the melting temperature range was 74.1-75.8 ° C The product obtained by ¹ H-NMR data is 5- [4- (3-cyclopentyl propanoyl) benzenesulfenyl] indan-1-ketone. ^{The values for 1} H-NMR (CDCl ₃ ),? (Ppm) were 0.9590 (t, 3H, CH ₃ ), 1.3533-1.4768 (sextet, 2H, CH ₂ ), 1.7274 (quintet, 2H, CH ₂ ) 2H, c-CH ₂ Ar), 2.9585 (t, 2H, CH ₂ ), 3.0961 (t, 2H, c-CH ₂ CO), 7.2745/7.3030 , ArH), 7.4513 / 7.4791 (d, 2H, 2ArH), 7.6683 / 7.6952 (d, IH, ArH), 7.9213 / 7.9490 (d, 2H, 2ArH).

Example 7: Synthesis of 5- (4-valeryl group benzenesulfenyl) indan-1,2-diketone-2-oxime

According to the oximation reaction method of Example 3, the product of Example 6 was used as a raw material and dimethylsulfoxide was used as a solvent in place of ethanol to effect oxydation reaction. According to HPLC analysis, a single oxigenated product was produced and a single oxigenated product was separated I did not.

Example 8: Synthesis of dioxime compound

Butyl nitrite of the same weight was added dropwise to the reaction solution of Example 7 followed by the second oximation reaction and after 10 hours, the procedure of Example 4 was followed to obtain a yellow solid having a purity of 96.50% The content was 3.30%, the content of the trans isomer was 93.20%, and the yield was 85.0%. The product obtained by ¹ H-NMR data was a bisoxime compound. ^{1 H-NMR (DMSO-d} 6), δ (ppm) value figures are _{0.9073 (t, 3H, CH 3} ), 1.4514-1.5741 (sextet, 2H, CH 2), 2.5879 (t, 2H, CH 2), 3.7380 (s, 2H, c- CH 2), 7.2916 / 7.3192 (d, 1H, ArH), 7.5172 (s, 1H, ArH), 7.5562 / 7.5836 (d, 2H, 2ArH), 7.7166 / 7.7437 (d, 1H , ArH), 7.8505 / 7.8779 (d, 2H, 2ArH), 12.4769 (s, 1H, NOH), 12.6651 (s, 1H, NOH).

Example 9 Synthesis of Dioxime Ether IIA6

According to the reaction method of Example 5, the product of Example 8 was subjected to an esterification reaction to obtain a yellow solid, which had a purity of 98.65%, wherein the content of the cis isomer was 1.25% and the content of the trans isomer Was 97.40% and the yield was 60.3%. ^{According to 1} H-NMR data, the product obtained was IIA6. ¹ H-NMR (CDCl ₃ ), and 隆 (ppm) values are as shown in Table 1.

Example 10: Synthesis of 5- [4- (3-cyclopentylpropanoyl) benzenesulfenyl] indan-1-ketone

5- (4- (3-cyclopentylpropanoyl) benzenesulfenyl] indan-1-yl ketone was obtained in the same manner as in Example 2, except that octanoyl chloride was replaced with 3-cyclopentylpropionyl chloride. The yield was 92.0% 88.5 ~ 90.0 캜, and the product obtained by ¹ H-NMR data was 5- [4- (3-cyclopentyl propanoyl) benzenesulfenyl] indan-1-ketone. _{^{1 H-NMR (CDCl 3)}} , δ (ppm) value figures are _{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, IH, 2ArH), 7.9245 / 7.9517 (d, 2H, 2ArH).

Example 11 Synthesis of 5- [4- (3-cyclopentylpropanoyl) benzenesulfenyl] indan-1,2-diketone-2-oxime

According to the oximation reaction method of Example 3, the product of Example 10 was used as a raw material and oxylation was performed using isoamyl nitrite instead of butyl nitrite to precipitate a yellow solid product and roast the solvent. The purity was 96% ^{According to 1} H-NMR data, the product obtained was 5- [4- (3-cyclopentyl propanoyl) benzenesulfenyl] indan-1,2-diketone-2-oxime, the yield being 95.5%. ^{1 H-NMR (DMSO-d} 6), δ (ppm) value figures are _{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).

Example 12: Synthesis of dioxime compound

According to the reaction method of Example 4, the product of Example 11 was subjected to a second oximization reaction using raw isoquinone instead of butyl nitrite and purification treatment to obtain a yellow solid having a purity of 95.50% , The content of the cis isomer was 5.10%, the content of the trans isomer was 90.40%, and the yield was 88.3%. The product obtained by ¹ H-NMR data was a bisoxime compound. ^{1 H-NMR (DMSO-d} 6), δ (ppm) value levels _{1.1766-1.6286 (m, 8H, 4CH 2} ), 2.1325 (heptet, 1H, CH), 2.6489 / 2.6739 (d, 2H, CH 2) , 3.7410 (s, 2H, c -CH 2), 7.2981 / 7.3249 (d, 1H, ArH), 7.5258 / 7.5529 (d, 2H, 2ArH), 7.5879 (s, 1H, ArH), 7.7188 / 7.7459 (d, 1H, 2ArH), 7.8404 / 7.8680 (d, 2H, 2ArH), 12.4514 (s, 1H, NOH), 12.6649 (s, 1H, NOH).

Example 13: Synthesis of dioxime ether IIA3

IIA3

IIA3

According to the reaction method of Example 5, the product of Example 12 was subjected to an esterification reaction and purification treatment to obtain a yellow solid. The purity was 98.65%, wherein the content of the cis isomer was 1.50% and the content of the trans isomer was 97.15% and the yield was 60.3%. ^{According to 1} H-NMR data, the product obtained was IIA3. ¹ H-NMR (CDCl ₃ ), and δ (ppm) values are as shown in Table 1.

The structures and data of the compounds obtained in Examples 5, 9 and 13 constitutional formula Exterior,
Melting point, ℃ ≪ ¹ > H-NMR, delta ppm

Yellow crystals
125.0-127.0 _{0.879 (s, 3H, CH 3} )
1.272-1.389 (m, 8H, 4CH ₂ )
_{1.531-1.608 (quintet, 2H, CH 2} )
2.275 (s, 3 H, CH ₃ CO)
2.343 (s, 3 H, CH ₃ CO)
_{2.800 (t, 2H, CH 2} )
3.897 (s, 2H, c- CH 2)
7.346 (d, 1 H, ArH)
7.346 / 7.367 (d, 1 H, ArH)
7.532 / 7.554 (d, 2H, 2ArH)
7.815-7.835 (d, 1 H, ArH)
8.102 / 8.124 (d, 2H, 2ArH)

Yellow crystals
98.0-100.0 _{1.0052 (s, 3H, CH 3} )
_{1.5657-1.6922 (sextet, 2H, CH 2} )
2.2787 (s, 3 H, CH ₃ CO)
_{2.3437 (s, 3H, CH 3} CO)
2.7976 (t, 2H, CH ₂ )
3.8990 (s, 2H, c- CH 2)
7.3446 (d, 1 H, ArH)
7.3446 / 7.3710 (d, IH, ArH)
7.5304 / 7.5580 (d, 2H, 2ArH)
7.8114 ~ 7.8392 (d, IH, ArH)
8.1046 / 8.1321 (d, 2H, 2ArH)

Yellow crystals
83.5-85.0 0.8596 / 1.7644 (m, 8H, 4CH ₂ )
2.0991 (heptet, 1H, CH)
_{2.2758 (s, 3H, CH 3} )
_{2.3436 (s, 3H, CH 3} )
2.8670 / 2.8922 (d, 2H, CH 2)
3.9033 (s, 2H, c- CH 2)
7.3535 (s, 1 H, ArH)
7.3495 / 7.3780 (d, IH, ArH)
7.5305 / 7.5582 (d, 2H, 2ArH)
7.8133 / 7.8418 (d, IH, ArH)
8.1052 / 8.1328 (d, 2H, 2ArH)

Example 14: Preparation of alkali-soluble resin

180 g of benzyl methacrylate, 60 g of methacrylic acid, 60 g of hydroxyethyl methacrylic acid, 15 g of azodiisobutyronitrile, 6 g of 1-deuterated canthiol and 1000 ml of toluene are mixed and placed in a static pressure funnel. 1000 ml of toluene is added to a three-necked flask equipped with a stirrer, a static pressure funnel and a thermometer, stirring is started, and the gas in the flask is replaced with nitrogen. The flask is heated to raise the temperature of the solvent to 80 to 85 ° C and warm, and the dropwise addition of the monomer mixture solution is started and completed in about 1 hour. The reaction is continued for 6 h. After naturally cooling and stirring was stopped and the resin was precipitated, the resin filtration cake was washed with 500 ml of toluene by absorbing the upper purification liquid and filtering the resin containing the lower solvent. The filtration cake was roasted under reduced pressure to obtain 250 g of a white powdery solid resin. It was prepared by dissolving it in 20% solution with 1000 g of PMA (propylene glycol monomethyl ether acetic acid).

Example 15: Preparation and development of photosensitive resist

The photocurable composition was prepared according to the ink preparation method in all compositions according to the weight ratio of recipe 15A, 15B, 15C (the photoinitiator was OXE01 as a control) and 15D (photoinitiator was OXE02 as control) shown in Table 2 And was in liquid state with fluidity.

The liquid composition was coated on the glass surface by a winding bar method and roasted at 80 DEG C for 3 minutes to volatilize the solvent PMA. The thickness of the remaining adhesive layer was 2 microns.

A gray scale gradient of 21 was installed on the membrane, and a 2000 W high-pressure mercury lamp was filtered with a 365 nm mesh filter. The distance between the membrane and the lattice was 10 cm and the exposure amount was 800 mJ / cm ² .

And the maximum displayable gradation number was recorded. The larger the value, the stronger the photosensitivity of the measured composition and the higher the photo-curing rate and film-forming performance of the photosensitive resist, and the results are shown in Table 3 Respectively.

The raw material recipe of the composition 15A 15B 15C 15D source Example 9 Photoinitiator 10 Example 9 Example 13 Photoinitiator 10 Example 13 OXE01 10 Commercial OXE02 10 Commercial Alkali soluble resin solution 500 500 500 Example 14 Dipentaerythritol hexaacrylate 100 100 100 Cytec Company

Result of development 15A 15B 15C 15D Maximum number of remaining tones 10 11 6 6

According to the development results shown in Table 3, the photosensitizing compositions prepared using the photoinitiators of Examples 9 and 13 were significantly superior to the photo-curing compositions prepared using OXE01 and OXE02, The curing rate and the film forming performance can be improved.

Example 16: Gel transfer rate test of photocurable composition

The composition obtained from Recipes 15A, 15B, 15C and 15D in Table 2 of Example 15 was applied to the glass surface by a winding bar method and roasted at 80 DEG C for 3 minutes to volatilize the solvent PMA. It was micron.

A 2000-W high-pressure mercury lamp was filtered through a 365-nm grating filter. The distance between the film and the grating was 10 cm and the exposure amounts were 200, 400, and 600 mJ / cm ² , respectively. After curing, the sample was wrapped in stainless steel, and the weight W ₁ was measured. The sample was immersed in acetone for 72 hours and roasted to measure the weight W ₂ of the remaining film. W ₁ / W ₂ was taken as gel transfer ratio gel% Same as.

Test results of gel transfer rate gel% 15A 15B 15C 15D 200 mJ / cm ² 92.8 93.9 78.2 75.7 400 mJ / cm ² 95.3 96.1 83.7 81.1 600 mJ / cm ² 96.5 97.2 85.9 84.0

From Table 4, it can be seen that the photoinitiators of Example 9 and Example 13 in the recipe of the photosensitive resist have a higher polymerization degree of the double bond and clearly higher activity.

Example 17: Curing and curing efficiency test of photosensitive composition by LED light source

The photo-curing compositions 15A, 15B, 15C and 15D in Example 15 were coated on a glass surface by a winding bar method and subjected to a roasting treatment at 80 DEG C for 3 minutes to volatilize the solvent PMA. The thickness of the remaining adhesive films was measured to be 2 microns, And cured by the following method.

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

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

Curing condition: Working distance: 21mm; Time of investigation: 1s

Indication of curing efficiency: After irradiating with a point light source for 1 s, the entire glass was immersed in an acetone solution for 5 s and taken out to measure the diameter of the cured film. The larger the value, the higher the photosensitivity and the higher the curing efficiency, Respectively. When the solder mask ink or the photosensitive composition for the photosensitive resist is cured with the LED light source from the measurement results shown in Table 5, the photosensitive composition provided in the present invention has a higher sensitivity than the conventional composition using OXE01 and OXE02 as photoinitiators .

Result of development Photo-curing composition 15A 15B 15C 15D Diameter mm 16.2 15.5 12.1 10.0

Example 18: Preparation of printing ink and curing by high pressure mercury lamp

10 parts of polyester acrylate ester prepolymer (Jangheung Chemical 6311-10), 30 parts of TPGDA (Jangheung Chemical EM223), 50 parts of carbon black ( Degussa Company P25) and 6 parts of photoinitiator were mixed and polished until the fineness became 2um or less to obtain ink samples 18A to 18D. The gel transfer ratio gel percentage was measured by the method of Example 16 by printing on an aluminum plate with a 420 mesh silk screen and curing with a high-pressure mercury lamp. The measurement results are shown in Table 6. From the measurement results of Table 6, it can be seen that the gel transfer ratio of the compound according to the present invention is clearly higher than that of the control compound.

Printing ink recipe and high pressure mercury lamp curing result Ink number 18A 18B 18C 18D Photoinitiator sample Example 5 Example 9 OXE01 OXE02 gel% 92.3 93.1 62.0 63.0

Example 19: Preparation of printing ink and curing by LED surface light source

Recipe composition ratio: 50 parts of epoxy resin acrylate ester prepolymer, 10 parts of polyester acrylate ester prepolymer, 30 parts of TPGDA, 4 parts of yellow 3G (BASF), 6 parts of photoinitiator. And the mixture was polished until the fineness became 2um or less to obtain ink samples 19A to 19D, which were then applied to a glass plate. Hardened to a 365nm LED plane light source lamp, and dosage is 86mJ / cm ^2. The gel transfer ratio gel% was measured by the method of Example 16. The measurement results are shown in Table 7. From the measurement results of Table 7, it can be seen that the gel transfer ratio of the compound according to the present invention is clearly higher than that of the control compound when the 365 nm LED light source is irradiated.

Printing ink recipe and LED light source curing result Ink number 19A 19B 19C 19D Photoinitiator sample Example 9 Example 13 OXE01 OXE02 gel% 91.5 92.1 80.0 81.5

Example 20: Preparation and exposure of photoresist ink for thin film filter

Recipe composition: 100 parts of an alkali-soluble resin solution (Example 14), dipentaerythritol hexaacrylate (Cytec Corporation DPHA), 100 parts of a photoinitiator, 100 parts of an assistant initiator BCIM (2,2 '- (o- chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole), 500 parts of carbon black (Degussa Company P25) dispersion (containing 20% of carbon black). Uniformly polished according to the ink manufacturing method, and five inks of 20A to 20E were obtained according to the difference of the photoinitiators used.

The pattern mask was covered and exposed to an LED surface light source of 365 nm. The exposure amount was 100 mJ / cm ² , and 30S development was performed with an aqueous solution containing 1% sodium hydroxide and 2% acetone Pattern shape and fixation degree were measured with a stereoscopic microscope. 2: There is no part missing in the exposed part but there is a bent part. 3: The edge of the exposed part does not coincide. 4: The exposed part is complete. No, 5: The exposed part was removed.

The results of the test are as shown in Table 8 and the results in Table 8 show that after exposing and developing the ink containing the compound of the present invention, the edge of the pattern is clear, neat and firm, It can be seen that the performance is significantly better than the control compound.

Exposure assessment of black photosensitive resist ink Ink number 20A 20B 20C 20D 20E Photoinitiator sample Example 5 Example 9 Example 13 OXE01 OXE02 evaluation One One One 4 3

Example 21: Preparation and exposure of photoresist ink for thin film filter

Recipe composition 100 parts of an alkali-soluble resin solution (Example 14), 100 parts of dipentaerythritol hexaacrylate (Cytec company), 100 parts of a photoinitiator and 100 parts of a red pigment L3920 (BASF) Five inks of 21A to 21E were obtained by polishing.

The pattern mask was covered and exposed to 365nm LED surface light source. The exposure amount was 86mJ / cm < ² > and developed with 30S in an aqueous solution containing 1% sodium hydroxide and 2% acetone, The pattern shape and the degree of fixation were measured by a microscope and evaluated in the same manner as in Example 20. The results of the test are shown in Table 9. From the results of Table 9, it can be seen that after exposing and developing the ink containing the compound of the present invention, the edge of the pattern is clear, neat and firm, It can be seen that the performance is significantly better than the control compound.

Exposure assessment of red photosensitive resist ink Ink number 21A 21B 21C 21D 21E Photoinitiator sample Example 5 Example 9 Example 13 OXE01 OXE02 evaluation One One One 3 3

Example 22: Preparation and exposure of photoresist ink for thin film filter

Recipe composition 100 parts of alkali soluble resin solution (Example 14), 100 parts of dipentaerythritol hexaacrylate (Cytec company), 10 parts of photoinitiator and 100 parts of red pigment L3920 (BASF) Five inks of 21A to 21E were obtained by polishing.

The pattern mask was covered and exposed to 365nm LED surface light source. The exposure amount was 86mJ / cm < ² > and developed with 30S in an aqueous solution containing 1% sodium hydroxide and 2% acetone, The pattern shape and the degree of fixation were measured by a microscope and evaluated in the same manner as in Example 20. The evaluation results are shown in Table 10. From the results of Table 10, it can be seen that after exposing and developing the ink containing the compound of the present invention, the edge of the pattern is clear, neat and firm, It can be seen that the performance is significantly better than the control compound.

Exposure assessment of red photosensitive resist ink Ink number 22A 22B 22C 22D 22E Photoinitiator sample Example 5 Example 9 Example 13 OXE01 OXE02 evaluation One One One 5 4

Claims (21)

A compound represented by the general formula (I).

(I)
(here,
Ar ₁ is C ₆ -C ₂₀ o-arylidene substituted by X ₁ or C ₃ -C ₂₀ o -heteroarylidene, and C ₆ -C ₂₀ o-arylidene or C ₃ -C ₂₀ o - the heteroarylidene is connected to Y ₁ and a carbonyl group to form a condensed ring structure, and the substituents on the other atoms are each a hydrogen atom; A halogen atom; A C ₁ -C ₁₂ alkyl group; A C ₅ -C ₇ naphthyl group; A C ₁ -C ₄ alkyl group substituted by a C ₅ -C ₇ naphthyl group; A C ₁ -C ₁₂ alkoxyl group; One or more C ₁ -C ₁₂ alkoxyl groups, C ₁ -C ₄ alkyl group benzyloxy groups, C ₁ -C ₄ alkoxyl groups substituted by R ₂ C (O) O; A phenyl group; Optionally one or more C ₁ -C ₄ alkyl group, a carboxy group, C ₁ -C ₁₂ alkyl group an acyl group, an aryl group, an acyl group, a heteroaryl group, an acyl group, X ₃ R _17, phenyl group, a phenyl group substituted by a halogen atom, CN ; A C ₁ -C ₄ alkyl group, a benzyloxy group; A C ₁ -C ₃ alkylidene diepoxide group; R _{2 is} C (O) O; C ₁ -C ₁₂ alkylsulfinyl; C ₁ -C ₄ alkyl group benzenesulfenyl; CN; A carboxy group; A C ₁ -C ₁₂ alkoxylcarbonyl group; An aryl group carbonyl group; A heteroaryl group carbonyl group; X ₃ R ₁₈ ; A C ₁ -C ₄ alkyl group phenoxy group; C ₁ -C ₈ alkyl group acyl group phenoxy group; A C ₅ -C ₆ naphthyl group, a phenoxy group; A C ₁ -C ₄ alkyl group substituted by a C ₅ -C ₆ naphthyl group, an acyl group phenoxy group; An aryl-acyl group phenoxy group; A heteroaryl group acyl group phenoxy group; C ₁ -C ₄ alkylsulfinyl substituted by R ₂ C (O) O; C ₁ -C ₄ alkyl group benzenesulfenyl; C ₁ -C ₈ alkyl group acyl group benzenesulfenyl; C ₅ -C ₆ naphthyl group, benzenesulfenyl group or C ₁ -C ₄ alkyl group substituted by C ₅ -C ₆ naphthyl group; Aryl-acyl group benzenesulfenyl; A heteroaryl group acyl group, benzenesulfenyl,
Ar ₂ is C ₆ -C ₂₀ O-ylidene, C ₃ -C ₂₀ heteroaryl O-ylidene, and through X ₁ is connected to the Ar _1, or through X ₁ at the same time connected to the Ar ₁ the substituent of the ortho-X ₁ Ar ₂ carbon atoms of the seat is through a straight chain, a carbon atom, a carbonyl group, O, S, NR ₁₈ by one step further connected to the Ar ₁ constitute a cyclic structure,
n is 0 or 1,
X < ₁ > is O, S or NR < ₁₈ &
Y ₁ is (CH ₂ ) _m CR ₁₅ R ₁₆ , NR ₁₉ , O (CR ₁₅ R ₁₆ ) _m , S (CR ₁₅ R ₁₆ ) _m , (CR ₁₅ R ₁₆ ) _m C = O, S = m is 0 or 1,
R ₁ is a hydrogen atom; A C ₁ -C ₁₈ alkyl group; A C ₁ -C ₁₈ alkyl group optionally substituted by one or more C ₃ -C ₇ naphthyl groups, phenyl groups, OR ₂₀ , SR ₂₁ , NR ₂₂ R ₂₃ ; C ₃ -C ₇ cycloalkylene, a phenylene group, a C ₂ -C ₁₈ alkyl group inserted by O, S, NR ₂₂ ; A C ₃ -C ₈ naphthyl group; CN; NO ₂ ; Phenyl group,
Or R ₁ is a C ₁ -C ₁₂ alkyl group acyl group or a C ₁ -C ₁₂ alkoxyl group carbonyl group, wherein the alkyl group is optionally substituted with one or two or more halogen atoms, a C ₁ -C ₄ alkyl group, a C ₅ or C ₆ naphthyl group, Phenyl group, CN, OH, X ₃ R ₂₀ ,
Or R ₁ is a benzoyl group or a phenoxy group carbonyl group, wherein the phenyl group is unsubstituted or optionally substituted with one or two or more halogen atoms, a C ₁ -C ₄ alkyl group, a C ₅ or C ₆ naphthyl group, a phenyl group, CN, OH Lt; / RTI >
Or R ₁ is a diphenyl-phosphono or di (C ₁ -C ₄ alkoxyl group) phosphono group,
R ₂ and R ₃ are each independently a hydrogen atom, a C ₁ -C ₁₈ alkyl group or a C ₁ -C ₁₈ alkoxyl group,
Or R ₂ and R ₃ are each independently a C ₂ -C ₁₈ alkenyl group,
Or R _2, R ₃ are each independently optionally one or a number of halogen atoms, C ₁ -C ₄ alkyl, C ₅ -C ₇ tingi naphthyl, heteroaryl tingi naphthyl, a phenyl group, a heteroaryl group, CN, C ₁ -C ₄ An alkenyl acyloxy group, an aryl acyloxy group and / or a C ₅ -C ₇ cycloalkylidene group, a phenylene group, a C ₂ -C ₁₈ alkyl group inserted by O, S, NR ₁₇ ,
Or R ₂ and R ₃ are each independently a C ₅ -C ₇ naphthyl group, optionally one or more C ₁ -C ₄ alkyl groups, phenyl groups, halogen atoms, C ₅ -C ₇ naphthyl groups substituted by CN,
Or R ₂ and R ₃ are each independently phenyl and are optionally substituted with one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxyl groups, phenyl groups, halogen atoms and CN,
Or R ₂ and R ₃ are each independently a naphthyl group,
Or R ₂ and R ₃ are each independently a benzoyl group or a phenoxy group carbonyl group, or the phenyl group therein is unsubstituted or optionally substituted with one or two or more halogen atoms, R ₁₇ , C ₅ or C ₆ naphthyl groups, CN, OH Lt; / RTI >
R ₁₅ and R ₁₆ each independently represent a hydrogen atom; A C ₁ -C ₁₈ alkyl group; A C ₁ -C ₅ alkyl group substituted by a carboxy group or a C ₁ -C ₄ alkoxyl group acyl group or a C ₁ -C ₄ alkyl group substituted by R ₂ C (O) O,
Or R _15, R ₁₆ are each independently a phenyl group, optionally one or more C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxyl group, carboxyl group, C ₁ -C ₁₂ alkyl group an acyl group, C ₅ -C ₆ naphthyridin A C ₂ -C ₄ alkyl group substituted by a C ₅ -C ₆ naphthyl group, a benzoyl group, a phenyl group, a halogen atom, a phenyl group substituted by CN,
R ₁₇ is a C ₁ -C ₄ alkyl group,
R ₁₈ and R ₁₉ each independently represent a hydrogen atom; A C ₁ -C ₁₈ alkyl group; A C ₁ -C ₅ alkyl group substituted by a C ₁ -C ₄ alkoxyl group acyl group; A C ₁ -C ₄ alkyl group substituted by R ₂ C (O) O; Optionally one or a number of halogen atoms, C ₁ -C ₄ alkyl, C ₃ -C ₇ tingi naphthyl, heteroaryl tingi naphthyl, a phenyl group, a heteroaryl group, CN, C ₁ -C ₄ alkanes one acyloxy group, aryl group acyloxy A substituted C ₁ -C ₁₈ alkyl group; Optionally substituted with one or more C ₃ -C ₇ cycloalkylene groups, phenylene groups, C ₂ -C ₁₈ alkyl groups inserted by O, S, NR ₁₇ ,
Or R _18, R ₁₉ are each independently C ₅ -C ₇ tingi naphthyl, and or optionally one or more C ₁ -C ₄ alkyl group, a phenyl group, a halogen atom, a CN substituted by C ₅ -C ₇ tingi naphthyl and ,
Or R _18, R ₁₉ are each independently a phenyl group, and optionally one or more C ₁ -C ₄ alkyl group, a carboxy group, C ₁ -C ₁₂ alkyl group an acyl group, C ₅ -C ₆ tingi naphthyl formyl group, C ₅ -C _6, the C ₂ -C ₄ alkyl substituted by naphthyl groups tin acyl group, an aryl group, an acyl group, a phenyl group, a phenyl group substituted by a halogen atom, CN,
R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom; A C ₁ -C ₁₈ alkyl group; Halogen, CN, a C ₁ -C ₁₈ alkyl group substituted by a C ₁ -C ₄ alkoxyl group; One or more oxygen atoms, a C ₅ -C ₇ cycloalkylene group, a C ₂ -C ₁₈ alkyl group inserted by a phenylene group; A phenyl group, a C ₁ -C ₃ alkyl group substituted by a C ₃ -C ₇ naphthyl group; C ₃ -C ₇ naphthyl group,
Or _{R 20, R 21, R 22} , R 23 are each independently a phenyl group, a naphthyl group, a benzoyl group, wherein the phenyl and naphthyl groups substituted or not, or respectively optionally halogen, C ₁ -C ₄ alkyl, C ₁ A C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkylsulfinyl group, a phenoxy group, a benzenesulfinyl group, a NR ₂₄ R ₂₅ , a C ₁ -C ₁₂ alkyl group acyl group, a benzoyl group,
R ₂₄ and R ₂₅ are each a C ₁ -C ₄ alkyl group, or NR ₂₄ R ₂₅ is morpholine, piperidine, piperazine, N-methylpiperazine, pyrrole. The method according to claim 1,
Wherein the compound represented by the general formula I is specifically represented by the general formulas II, IIIA and IIIB.

(II)

(IIIA)

(IIIB)
(here,
R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom; A halogen atom; A C ₁ -C ₁₂ alkyl group; A C ₅ -C ₇ naphthyl group; A C ₁ -C ₄ alkyl group substituted by a C ₅ -C ₇ naphthyl group; A C ₁ -C ₁₂ alkoxyl group; A phenyl group; Optionally one or more C ₁ -C ₄ alkyl group, a carboxy group, C ₁ -C ₁₂ alkyl group an acyl group, an aryl group, an acyl group, a heteroaryl group, an acyl group, X ₃ R _17, phenyl group, a phenyl group substituted by a halogen atom, CN ; A C ₁ -C ₄ alkyl group, a benzyloxy group; One or more C ₁ -C ₁₂ alkoxyl groups, C ₁ -C ₄ alkyl group benzyloxy groups, C ₁ -C ₄ alkoxyl groups substituted by R ₂ C (O) O; R _{2 is} C (O) O; CN; A carboxy group; A C ₁ -C ₁₂ alkoxylcarbonyl group; An aryl group carbonyl group; A heteroaryl group carbonyl group; X ₃ R ₁₈ ,
Or R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a C ₁ -C ₄ alkyl group phenoxy group; C ₁ -C ₄ alkyl group benzenesulfenyl; C ₁ -C ₈ alkyl group acyl group phenoxy group; An aryl-acyl group phenoxy group; A heteroaryl group acyl group phenoxy group; A C ₅ -C ₆ naphthyl group, a phenoxy group; A C ₁ -C ₄ alkyl group substituted by a C ₅ -C ₆ naphthyl group, an acyl group phenoxy group; A C ₁ -C ₃ alkylidene diepoxide group; C ₁ -C ₁₂ alkylsulfinyl; C ₁ -C ₄ alkylsulfenyl substituted by R ₂ C (O) O and benzenesulfenyl C ₁ -C ₄ alkyl group; C ₁ -C ₈ alkyl group acyl group benzenesulfenyl; Aryl-acyl group benzenesulfenyl; Heteroaryl group acyl group benzenesulfenyl; C ₅ -C ₆ naphthyl group, benzenesulfenyl group or C ₁ -C ₄ alkyl group substituted by a C ₅ -C ₆ naphthyl group,
Or _{R 4, R 5, R 6} , R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14 is a group-glycidyl each alone, wherein the epoxy group is an optionally C ₁ - C ₄ alkyl group aldehyde, condensed with ketone,
X < ₁ > is O, S or NR < ₁₈ &
X ₂ is O, S, NR ₁₉ ,
Y ₁ is O, S, CR ₁₅ R ₁₆ ,
The definition of other substituents is the same as in paragraph 1.) 3. The method of claim 2,
In the compound represented by the general formula II,
R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are all hydrogen atoms,
X < ₁ > is O or S,
Y ₁ is CH ₂ , CHCH ₃ or C (CH ₃ ) ₂ ,
n = 1,
R ₁ is a C ₁ -C ₁₂ alkyl group, optionally one or more C ₃ -C ₇ naphthyl groups, phenyl group, a C ₁ -C ₁₂ alkyl group substituted by OR ₂₀ , SR ₂₁ , NR ₂₂ R ₂₃ ,
R ₂ and R ₃ are each independently methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylphenyl or 2,6-
And the other groups are as defined in claim 2. 3. The method of claim 2,
In the compounds represented by the general formulas IIIA and IIIB,
X ₂ is NR ₁₉ ,
Y ₁ is O, S, CR ₁₅ R ₁₆ ,
R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom; A halogen atom; A C ₁ -C ₄ alkyl group; A C ₁ -C ₄ alkoxyl group; A C ₁ -C ₄ alkyl group, a benzyloxy group; C ₁ -C ₄ alkylsulfenyl; A C ₁ -C ₄ alkyl group phenoxy group; C ₁ -C ₄ alkyl group, benzenesulfenyl,
Other substituents are the same as defined in claim 2. 5. The method of claim 4,
Y ₁ is CH ₂ or CHCH ₃ ,
n = 0,
R ₁ is a C ₁ -C ₁₂ alkyl group, optionally a C ₃ -C ₇ naphthyl group, a phenyl group, a C ₁ -C ₁₂ alkyl group substituted by OR ₂₀ , SR ₂₁ , NR ₂₂ R ₂₃ ,
R ₂ and R ₃ are each independently methyl, ethyl, phenyl, 2-methylphenyl, 3-methylphenyl, 2,4,6-trimethylphenyl or 2,6-dimethoxybenzene,
R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydrogen atom or a C ₁ -C ₄ alkoxyl group,
R ₁₉ is a C ₁ -C ₁₂ alkyl group, a C ₃ -C ₇ naphthyl group, a C ₁ -C ₃ alkyl group substituted by a phenyl group,
And the other groups are the same as defined in claim 4. The method according to claim 1,
The concrete structure

(IIA1) (IIA2)

(IIA3) (IIA4)

(IIA5) (IIA6)

(IIB1) (IIC1)

(IIIA1) (IIIA2)

(IIIA3) (IIIB1)
Lt; RTI ID = 0.0 > I. ≪ / RTI > (1) First step: Oxidation is selectively carried out at the ortho-methylene group of the cyclopentanone carbonyl group in the IV compound, and the method is an oxime-oxidation reaction of the IV compound and the alkyl nitrogen ester in an acidic solution, V,

(IV)

(V)

(2) Step 2: The intermediate V compound is subjected to secondary oximation, which is a method of obtaining the corresponding intermediate VI compound by oximating the V compound and the alkyl nitrite ester in an acidic solution, Method B is a method of obtaining the corresponding intermediate VII compound by performing the oximation reaction of the carbonyl group in the side chain R < ₁ > CH < ₂ > CO in a hydroxylamine solution,

(VI)

(VII)
(3) Third step: Oxidizing intermediate VI or VII of the second step is reacted with the following acylating agent

,

,

,

(Wherein the definitions of the groups in the above structural formulas are the same as those of the corresponding groups in the above-mentioned formula (1)) to obtain the corresponding compounds represented by the general formula I by esterification reaction with an acylating agent,
Lt; RTI ID = 0.0 > I < / RTI > An asymmetric diketone compound represented by the general formula IV.

(IV)
(here,
The definitions of Ar ₁ , Ar ₂ , X ₁ , Y ₁ and R ₁ groups are the same as those of the corresponding groups in the above formula). A ketooxime compound represented by the general formula V:

(V)
(here,
The definitions of Ar ₁ , Ar ₂ , X ₁ , Y ₁ and R ₁ groups are the same as those of the corresponding groups in paragraph 8). A diketooxime compound represented by the general formula VI or VII.

(VI)

(VII)
(here,
The definitions of Ar ₁ , Ar ₂ , X ₁ , Y ₁ and R ₁ groups are the same as those of the corresponding groups in the paragraph 9). 1. A photocurable composition comprising a photoinitiator and a carbon double bond compound capable of performing at least one free radical polymerization, wherein the photoinitiator contains at least one compound represented by the general formula (I) 12. The method of claim 11,
The photo-curable composition contains an additive. 13. The method of claim 12,
Wherein the photoinitiator accounts for 0.05 to 25% of the total composition, and the carbon double bond compound and additives thereof occupy the rest of the composition. 13. The method according to claim 11 or 12,
Wherein the carbon double bond compound is selected from an acrylic acid ester compound and a methacrylic acid ester compound. 13. The method of claim 12,
Wherein the additive comprises a developable resin and a pigment or dye. 13. A method of curing a photo-curable composition, comprising applying the photo-curable composition of claim 11 or 12 to a base and curing the coating layer by irradiating a light beam having a wavelength of 190 to 600 nm. 17. The method of claim 16,
Wherein said light is provided from the sun, mercury lamp, high pressure mercury lamp or LED lamp. First, a photo-curing composition is prepared by diluting the photo-curing composition of claim 11 or 12 in a solvent, then applying the diluted photo-curable composition to a base, and removing the unexposed portion through roasting, To form a protrusion pattern. And at least one compound containing a black, red, green and blue pixels and at least one compound represented by the general formula I of claim 1, a photo-curing monomer, an alkali-soluble resin, a pigment, and an additive And is obtained by successively applying, exposing, developing and heat-treating the composition. A method for producing a light guide plate comprising black, red, green and blue pixels, comprising the steps of: mixing at least one compound represented by the general formula I of claim 1 or 6, a photo-curable monomer, an alkali- Applying, exposing, developing, and heat-treating the composition consisting of the additive in order, finally obtaining the light guide plate. delete