JP6261778B2 - Asymmetric dioxime ester compound and its production method and application - Google Patents

Description

  The present invention relates to an asymmetric dioxime ester compound, characterized in that the molecule is an esterified derivative in which a cyclic ketooxime is condensed with arylidene and a chain ketooxime, and the esterified oxime group is a carbonyl group α- It has a use as a photoinitiator in a photocurable composition.

  Oxime ester compounds have long been expressed as photoinitiators, and two patents in US Pat. No. 3,558,309 and US Pat. No. 4,255,513 disclose that oxime ester compounds are photoinitiators. However, some structures of oxime esters have poor thermal stability or low photosensitivity, and have failed to meet the demands of modern electronics industry in terms of performance such as thermal stability and photosensitivity. CN1514845A discloses a series of oxime ester compounds, of which OXE01 and OXE02 are already commercially available. Further products with close performance are oxime esters 305 and 304 disclosed in CN10156472B and CN101508744B.

  The substituted carbazole condensed oxygen heterocyclic ketone oxime ester described in Chinese Patent CN1020466667B has an absorption wavelength reaching 405 nm, which is advantageous for curing with LED lamps and visible light. However, the increase in molecular weight reduces the starting activity of unit mass. Various dioxime ester derivatives based on phenylcarbazole disclosed in Patent WO20080081732 have two oxime ester groups in one molecule, and one of the oxime esters is a phenyl group on the N substitution position. However, experiments have shown that the activity of such oxime esters is very low, cannot make an extra contribution to the photoinitiating activity of the molecule and has no utility.

  In addition, many other oxime ester photoinitiator patents include, for example, WO2006018973, WO2007071497, CN1805955B, CN192222142B, CN19287715A, CN101508744B, and CN1020207727, all of which are in the 3, 6, and 9 position side chains of carbazole. Various modifications were made, and some of them were increased in molecular weight, and the photosensitivity could not be improved.

  The inventor has expressed that a series of asymmetric dioxime ester compounds have very good photoinitiating activity.

  Series 1: Compounds represented by the general formula I.

（Ｉ）

(I)

here,
Ar ₁ is C ₆ -C ₂₀ ortho-arylidene or C ₃ -C ₂₀ ortho-heteroarylidene substituted with X ₁ , wherein C ₆ -C ₂₀ ortho-arylidene or C ₃ -C ₂₀ ortho-hetero In arylidene, two adjacent atoms are connected to Y ₁ and a carbonyl group to form a condensed ring structure, and the substituents on the other atoms are a hydrogen atom; a halogen atom; a C ₁ -C ₁₂ alkyl group; C ₅ -C _{7 naphthenic;} C 5 -C ₇ naphthenes _C 1 -C ₄ alkyl group substituted by _group; C 1 _{-C 12} alkoxyl group; one or more _C 1 _{-C 12} alkoxyl group, _{C 1} -C ₄ alkylbenzyl _{group; R 2 C (O) C} 1 ~C 4 alkoxy group substituted with O; phenyl; optionally one or more _C 1 -C ₄ alkyl group, carboxyl groups, C -C ₁₂ alkyl acyl, aryl acyl, heteroaryl acyl _group, X _{3 R 17,} a phenyl group, a halogen atom, a phenyl group substituted with _CN; C 1 ~C ₄ alkyl benzyl group; _{R 2} C (O C ₁ -C ₄ alkoxyl group substituted with O); C ₁ -C ₃ alkylidenedioxy group; R ₂ C (O) O; C ₁ -C ₁₂ alkylthio group; C ₁ -C ₄ alkylbenzenethio group; CN ; carboxyl _group; C 1 _{-C 12} alkoxycarbonyl group; an aryl group; a heteroaryl _{group; X 3 R 18; C 1} ~C 4 alkyl phenoxy _group; C 1 -C ₈ alkyl acyl phenoxy _group; C 5 -C ₆ naphthenic acyl phenoxy _group; C 5 -C ₆ naphthenic _C 1 -C ₄ alkyl acyl phenoxy group substituted by; C -C ₃ alkylidene group; aryl acyl phenoxy group; a heteroaryl acyl phenoxy _{group; R 2 C (O) O} C 1 is substituted with -C ₄ alkylthio _group; C 1 -C ₄ alkylbenzene thio _{group; C} 1 ~ C ₈ alkyl acyl benzene thio _group; C 5 -C ₆ naphthenic acyl benzene thio group, or a _C 5 _{~C 6 C} 1 _{~C 4} alkyl acyl benzene thio group substituted with naphthenic; aryl acyl benzene thio group; a heteroaryl acyl benzene thio group; or an epoxypropyl group, wherein the epoxy group is optionally _C 1 -C ₄ alkyl group aldehyde, combined ketone and condensed, _{X 3} is O, a S or _{NR 22} Ar ₂ Is C ₆ -C ₂₀ arylidene, C ₃ -C ₂₀ heteroarylidene, and is connected to Ar ₁ via X ₁ Or the Ar ₂ carbon atom in the ortho position of the substituent X ₁ is further connected to Ar ₁ via X ₁ , and Ar is further bonded to Ar ₁ via a single bond, carbon atom, carbonyl group, O, S, NR _18. Connected to ₁ to form an annular structure,
N is 0 or 1,
X ₁ is O, S, NR ₁₈ or Y ₂ -Z ₁ -Y ₂ ,
Y ₁ is met _{(CH 2) m CR 15 R} 16, NR 19, O (CR 15 R 16) m, S (CR 15 R 16) m, (CR 15 R 16) m C = O, S = O M is 0 or 1,
Z ₁ is a C ₁ -C ₁₀ single bond or branched alkylidene, one or more oxygen atoms, a C ₁ -C ₁₀ single bond or branched alkylidene connected to or inserted into a terminal group by a sulfur atom, a no substituents or a substituent a _C 6 _{-C 20} arylidene,
Y ₂ is O, S, NR ₁₈ , O—C (O), where R ₁ is a hydrogen atom; a C ₁ -C ₁₈ alkyl group; optionally one or more C ₃ -C ₇ naphthene groups, phenyl Group, OR ₂₀ , SR ₂₁ , C ₁ -C ₁₈ alkyl group substituted by NR ₂₂ R ₂₃ ; C ₃ -C ₇ Cycloalkylene group, phenylene group, O, S, C inserted by NR _{22 2 to} C ₁₈ alkyl group; C _{3 to} C ₈ naphthene group; CN; NO ₂ ; phenyl group, the above phenyl group is not substituted, and optionally one or more halogen atoms, C _{1 to} C ₄ alkyl _group, C 5 -C ₇ naphthenic, hetero naphthene group, a phenyl group, a heteroaryl group, _CN, C 1 -C ₄ alkane acyl group (alkane acyloxy), substituted with an aryl acyl group,
Or R ₁ is a C ₁ -C ₁₂ alkyl acyl group, a C ₁ -C ₁₂ alkoxylcarbonyl group, wherein the alkyl group is optionally one or more halogen atoms, C ₁ -C ₄ alkyl Substituted with a group, C ₅ or C ₆ naphthene group, phenyl group, CN, OH, X ₃ R ₂₀ , or wherein the alkyl group is optionally inserted with one or more phenylene groups, X ₃ ,
Or R ₁ is a benzoyl group, a phenoxycarbonyl group, wherein the phenyl group is unsubstituted, or optionally one or more halogen atoms, a C ₁ -C ₄ alkyl group, C ₅ Or substituted with a C ₆ naphthene group, a phenyl group, CN, OH, X ₂ R ₂₀ ,
Or R ₁ is a diphenyl-phosphono group or a di (C ₁ -C ₄ alkoxyl group) phosphono group,
R ₂ and R ₃ are each independently a hydrogen atom, a C _{1 to} C ₁₈ alkyl group or a C _{1 to} C ₁₈ alkoxyl group,
Or R ₂ and R ₃ are each independently a C _{2 to} C ₁₈ alkenyl group, optionally having one or more halogen atoms, C _{1 to} C ₄ alkyl groups, C _{5 to} C ₇ naphthene groups, hetero naphthene group, a phenyl group, a heteroaryl group, _CN, C 1 -C ₄ alkane acyl group, substituted with an aryl acyl group, and / _or, C 5 -C ₇ cycloalkylidene group (cycloalkylidene), phenylene, O, S , a _C 2 _{-C 18} alkenyl _{group NR 17} has been inserted,
Or R ₂ and R ₃ are each independently one or more halogen atoms, C ₁ -C ₄ alkyl groups, C ₅ -C ₇ naphthene groups, heteronaphthene groups, phenyl groups, heteroaryl groups, CN , _C 1 -C ₄ alkane acyl group, substituted with an aryl acyl group, and / _or, C 5 -C ₇ cycloalkylidene group, a phenylene _{group, O, S, C 2 ~C} 18 alkyl _{group NR 17} is inserted Because
Or, R ₂ and R ₃ are each independently a C _{5 to} C ₇ naphthene group, and optionally substituted with one or more C _{1 to} C ₄ alkyl groups, a phenyl group, a halogen atom, or CN. a _{5 ~C 7} naphthenic group,
Or R ₂ and R ₃ are each independently a phenyl group, optionally substituted with one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxyl groups, phenyl groups, halogen atoms, CN A substituted phenyl group,
Or R ₂ and R ₃ are each independently a naphthyl group,
Or R ₂ and R ₃ are each independently a benzoyl group, a phenoxycarbonyl group, or a phenyl group therein is not substituted, or optionally, one or more halogen atoms, R ₁₇ , substituted with a C ₅ or C ₆ naphthene group, CN, OH, XR ₁₇ ;
R ₁₅ and R ₁₆ each independently represent a hydrogen atom; a C _{1 to} C ₁₈ alkyl group; a C _{1 to} C ₅ alkyl group substituted with a carboxyl group or a C _{1 to} C ₄ alkoxyl acyl group; R ₂ C (O) _C substituted by O 1 -C ₄ alkyl groups; optionally one or more halogen _atoms, C 1 -C ₄ alkyl _group, C 5 -C ₇ naphthenic, hetero naphthene group, a phenyl group, heteroaryl group, _CN, C 1 -C ₄ alkane acyl group, substituted with an aryl acyl group, _or, C 5 -C ₇ cycloalkylene group, a phenylene group, O, S, _C 2 ~ _{the NR 17} is inserted a C ₁₈ alkyl group, _or, R _{15, R 16} are each _{independently,} C 5 -C ₇ naphthenic or optionally one or more _C 1 -C ₄ alkyl group, a phenyl group, a halo Emissions atom, a _C 5 -C ₇ naphthenic group substituted with CN,
Or R ₁₅ and R ₁₆ are each independently a phenyl group, and optionally one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxyl groups, carboxyl groups, C ₁ -C ₁₂ alkyls acyl _groups, C 5 -C ₆ naphthenic formyl _group, C 5 -C _C 2 substituted by ₆ naphthenic -C ₄ alkyl acyl group, a benzoyl group, _{XR 17,} phenyl group, halogen atom, substituted with CN A phenyl group,
Or, the _{R 15, R 16} constitutes an annular together with them to be connected to a joint carbon atom or silicon atom, the number of atoms constituting the ring is a 4 to 7, or said _{R 15, R 16} is Each of them constitutes a ring with adjacent substituents, and the number of atoms constituting the ring is 4 to 7,
R ₁₇ is a C ₁ -C ₄ alkyl group,
Each R _{18, R 19} are independently a hydrogen _atom; substituted with _{R 2} C (O) O; where C 1 _{-C 18} alkyl _group; C 1 -C ₄ alkoxy _C 1 -C substituted by cyclohexyl acyl group ₅ alkyl group C ₁ -C ₄ alkyl group; optionally one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₃ -C ₇ naphthene group, heteronaphthene group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkane acyl group, arylacyloxy _C 1 _{-C 18} alkyl group substituted with a group; optionally one or more _C 3 -C ₇ cycloalkylene group, a phenylene group, O, S, is _{NR 17} inserted a _C 2 _{-C 18} alkyl group,
Or R ₁₈ and R ₁₉ are each independently a C _{5 to} C ₇ naphthene group, or optionally substituted with one or more C _{1 to} C ₄ alkyl groups, a phenyl group, a halogen atom, or CN. A C ₅ -C ₇ naphthene group,
Or R ₁₈ and R ₁₉ are each independently a phenyl group, and optionally one or more C ₁ -C ₄ alkyl groups, carboxyl groups, C ₁ -C ₁₂ alkyl acyl groups, C ₅ -C ₆ naphthenic formyl _group, a C 5 -C ₆ naphthenes _C 2 -C ₄ alkyl acyl groups substituted with an aryl acyl group, _{XR 17,} a phenyl group, a halogen atom, a phenyl group substituted with CN,
Or R ₁₈ is connected to the aromatic ring in Ar ₁ or Ar ₂ via a single bond, carbon atom, or carbonyl group to form a new ring;
Or R ₁₉ is connected to the aromatic ring in Ar ₁ via a single bond, carbon atom, or carbonyl group to form a new ring;
R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ are each independently a hydrogen atom; a C _{1 to} C ₁₈ alkyl group; a halogen, CN, a C _{1 to} C ₁₈ alkyl group substituted with a C ₁ to C ₄ alkoxyl group; One or more oxygen _atoms, C 5 -C ₇ cycloalkylene group, _C 2 _{-C 18} inserted by a phenylene group alkyl group; a phenyl _{group, C 3 ~C 7 C 1 ~C} 3 alkyl substituted with naphthenic a C 3 -C _{7 naphthenic;} group
Or R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ are each independently a phenyl group, a naphthyl group or a benzoyl group, wherein the phenyl group or naphthyl group is not substituted or is optionally halogenated. , C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxyl group, C ₁ -C ₄ alkylthio group, phenoxy group, benzenethio group, NR ₂₄ R ₂₅ , C ₁ -C ₁₂ alkyl acyl group, substituted with benzoyl group ,
R ₂₄ and R ₂₅ are each a C _{1 to} C ₄ alkyl group, or NR ₂₄ R ₂₅ is morpholine, piperidine, piperazine, N-methylpiperazine, or 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 , R ₁₄ are each independently a hydrogen atom; a halogen atom; a C ₁ -C ₁₂ alkyl group A C ₅ -C ₇ naphthene group; a C ₁ -C ₄ alkyl group substituted with a C ₅ -C ₇ naphthene group; a C ₁ -C ₁₂ alkoxyl group; a phenyl group; optionally one or more C ₁ -C ₄ alkyl group, carboxyl _group, C 1 _{-C 12} alkyl acyl, aryl acyl, heteroaryl acyl _group, X _{3 R 17,} a phenyl group, a halogen atom, a phenyl group substituted with _CN; C 1 -C ₄ alkyl A benzyloxy group; one or more C ₁ -C ₁₂ alkoxyl groups, a C ₁ -C ₄ alkylbenzyloxy group, a C ₁ -C ₄ alkoxyl group substituted with R ₂ C (O) O; R ₂ C ( O) ; CN; a X _{3 R 18,;} carboxyl _group; C 1 _{-C 12} alkoxycarbonyl group; an aryl group; a heteroaryl group
Or R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ are each independently a C ₁ -C ₄ alkylphenoxy group; C ₁ substituted with C 5 -C _{6 naphthenic;} -C ₄ alkylbenzene thio _group; C 1 -C ₈ alkyl acyl phenoxy group; an aryl acyl phenoxy group; a heteroaryl acyl phenoxy _group; C 5 -C ₆ naphthenic acyl phenoxy group C ₁ -C ₄ alkyl acyl phenoxy _group; C 1 -C ₃ alkylidene _group; C 1 _{-C 12} alkylthio _{group; R 2 C (O) C} 1 substituted by O -C ₄ alkylthio groups and _C 1 ~ C ₄ alkylthio _group; C 1 -C ₈ alkyl acyl benzene thio group; aryl acyl benzene thio group; a heteroaryl acyl benzene thio _group; C 5 -C Substituted _C 1 ₆ naphthenic acyl benzene thio group, or a _C 5 -C ₆ naphthenic -C ₄ an alkyl acyl benzene thio group,
Or R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ are each independently an epoxypropyl group, where group is optionally _C 1 -C ₄ alkyl group aldehyde, combined ketone and condensed,
X ₁ is O, S or NR ₁₈ and
X ₂ is O, S, NR ₁₉ ,
Y ₁ is O, S, CR ₁₅ R ₁₆ and
The definitions of other substituents are the same as in Series 1.

  Series 3: A compound represented by the general formula II.

here,
R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , 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 a C ₁ -C ₁₂ alkyl group substituted with one or more C ₃ -C ₇ naphthene groups, a phenyl group, OR ₂₀ , SR ₂₁ , NR ₂₂ R _23. Because
R ₂ and R ₃ are each independently a methyl group, an ethyl group, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 2,4,6-trimethylphenyl group, or 2,6-dimethoxybenzene. ,
The definitions of the other groups are the same as the corresponding groups in the general formula II of series 2.

  Series 4: Compounds represented by the general formulas IIIA and IIIB.

here,
X ₂ is NR ₁₉ ,
Y ₁ is O, S, CR ₁₅ R ₁₆ and
_{R 11, R 12, R 13} , R 14 are each independently a hydrogen atom; a halogen _atom; C 1 -C ₄ alkyl _group; C 1 -C ₄ alkoxyl _group; C 1 -C ₄ alkylbenzyl group, _{C 1} a C 1 -C ₄ alkylbenzene thio _group,; -C ₄ alkylthio _group; C 1 -C ₄ alkylphenoxy group
The definitions of the other substituents are the same as the corresponding groups in the general formulas IIIA and IIIB in series 2.

  Series 5: Compounds represented by general formulas IIIA and IIIB.

here,
Y ₁ is CH ₂ or CHCH ₃ and
n = 0,
R ₁ is _C 1 _{-C 12} alkyl group; a optionally a _C 3 -C ₇ naphthene group, a phenyl _group, OR _20, SR _{21, C} substituted with _NR 22 _{R 23 1} ~C ₁₂ alkyl group ,
R ₂ and R ₃ are each independently methyl, ethyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 2,4,6-trimethylphenyl group, or 2,6-dimethoxybenzene, ,
R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ are each independently a hydrogen atom, a C ₁ -C ₄ alkoxyl group,
R ₁₉ is a C ₁ -C ₁₂ alkyl group; a C ₃ -C ₇ naphthene group, a C ₁ -C ₃ alkyl group substituted with a phenyl group,
The definitions of the other groups are the same as the corresponding groups in the general formulas IIIA and IIIB in series 4.

In the above general formulas I, IIA and IIB, R ₂ C (O) or R ₃ C (O) is replaced with (R ₂ ) ₂ P or R ₂ S (O ₂ ), and the corresponding phosphorous acid produced It can also be an ester or a sulfonic acid ester, and has a photofree radical or photocation initiation action.

  Series 6: Compounds represented by the general formulas I, II, IIIA, and IIIB in the above series 1 to 5, and specific structures thereof are as follows (IIA1), (IIA2), (IIA3) , (IIA4), (IIA5), (IIA6), (IIB1), (IIC1), (IIIA1) (IIIA2), (IIIA3), and (IIIB1).

（IIＡ１）

(IIA1)

（IIＡ２）

(IIA2)

（IIＡ３）

(IIA3)

（IIＡ４）

(IIA4)

（IIＡ５）

(IIA5)

（IIＡ６）

(IIA6)

（IIＢ１）

(IIB1)

（IIＣ１）

(IIC1)

（IIIＡ１）

(IIIA1)

（IIIＡ２）

(IIIA2)

（IIIＡ３）

(IIIA3)

（IIIＢ１）

(IIIB1)

The present invention further provides a process for producing a compound represented by the general formula I in the series 1 described above, comprising the following steps:
(1) First step: selective oximation is carried out at the methylene group at the ortho position of the cyclopentanone carbonyl group in the IV compound, and the method involves the conversion of the IV compound and the alkyl nitrite ester into an oxime in an acidic solution. And the corresponding intermediate V is obtained.

（IV）

(IV)

（Ｖ）

(V)

(2) Second step: The intermediate V compound is continuously subjected to the second oximation, and the method A causes the V compound and the nitrite alkyl group ester to undergo an oximation reaction in an acidic solution. In which the corresponding intermediate VI compound is subjected to an oximation reaction of the carbonyl group in the side chain R ₁ CH ₂ CO with a hydroxylamine solution to obtain the corresponding intermediate VII compound. When a cis-trans isomer is present in the oxime group, VI and VII obtained are a mixture of the respective isomers.

（VI）

(VI)

（VII）

(VII)

  (3) Third step: The oximation intermediate VI or VII of the second step is esterified with any of the following acylating agents (1) to (4) or an equivalent acylating agent thereof. When the corresponding general formula I is obtained and there are cis-trans isomers in the oxime group of intermediate VI or VII, the resulting I is a mixture of the respective isomers or Obtain the isomer.

（１）

(1)

（２）

(2)

（３）

(3)

（４）

(4)

  The definitions of all groups in the structure involved in the above reaction are the same as the definitions of the groups in the corresponding structure in Series 1.

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

（IV）

(IV)

here,
The definition of Ar ₁ , Ar ₂ , X ₁ , Y ₁ , R ₁ group is the same as the definition of the corresponding group in the compounds represented by general formula I in series 1.

  The present invention further provides a ketoxime compound represented by the general formula V.

（Ｖ）

(V)

here,
The definition of Ar ₁ , Ar ₂ , X ₁ , Y ₁ , R ₁ group is the same as the definition of the corresponding group in the compounds represented by general formula I in series 1.

  The present invention further provides diketoxime compounds represented by the general formulas VI and VII.

（VI）

(VI)

（VII）

(VII)

here,
The definition of Ar ₁ , Ar ₂ , X ₁ , Y ₁ , R ₁ group is the same as the definition of the corresponding group in the compounds represented by general formula I in series 1.

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

  The present invention further comprises (a) a photoinitiator and (b) at least one carbon-carbon double bond compound capable of performing free radical polymerization, wherein the photoinitiator (a) is at least Provided is a photocurable composition containing one type of the compound represented by the general formula I.

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

  The photocurable composition further contains other additives (d) that are necessary functional components such as developable resins, pigments, antifoaming agents and the like.

  Calculated in parts by weight, the photoinitiator (a) accounts for 0.05 to 25% and preferably 2 to 15% of the entire cured composition, and the other composition is the remaining part of the composition outside the above composition. Occupy.

  Composition (b) is a carbon-carbon double bond compound capable of free radical polymerization, i.e., a photocuring monomer, wherein one carbon-carbon double bond or two and two or more carbon-carbons are included in the molecule. Includes double bonds. The compound containing one carbon-carbon double bond is preferably an acrylate compound or a methacrylate compound. For example, acrylic acid methyl ester, acrylic acid butyl ester, acrylic acid 2-ethylhexyl ester, acrylic acid cyclohexyl ester, acrylic acid Examples include acrylates or methacrylates of monohydric alcohols such as isobornyl ester, hydroxyethyl acrylate, and methacrylic acid methyl ester, and acrylonitrile, N-dialkylacrylamide, N-vinylpyrrolidone, vinylbenzene, acetic acid vinyl ester, and vinyl ether. .

  Examples of the compound containing two and two or more carbon-carbon double bonds include, for example, alkyl group dihydric alcohol, polyhydric alcohol acrylate or methacrylate, polyester polyhydric alcohol, polyether polyhydric alcohol, epoxy resin polyhydric Mention may be made of alcohols, polyurethane polyhydric alcohol acrylates, vinyl ethers and unsaturated dicarboxylic polyhydric alcohol unsaturated polyesters. For example, polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, polyethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, polyester oligomer acrylate, polyurethane oligomer acrylate, aromatic epoxy resin Examples thereof include acrylate and ethylene glycol maleate polyester.

  Such a carbon-carbon double bond compound can be used alone and can be used in combination of two or more, or the mixture is pre-copolymerized to form an oligomer to form a composition. It can also be used for manufacturing. When the polymerization monomer contains an alkali-soluble group such as a carboxylic acid group, a polymer resin having alkali-solubility is obtained and used for the preparation of a photosensitive resist or an aqueous dispersion emulsion.

  Other than using the compound represented by the above general formula I as a photoinitiator, other types of commercially available photoinitiators or auxiliary initiators may be further synthesized in accordance with the demand for the use of the composition. c), α-hydroxy group ketones such as 2-hydroxy group-2-methyl-1-propiophenone and 1-hydroxycyclohexyl phenyl ketone; 2-methyl-2-morpholine group- ( Α-amino group ketones such as 4- (methylthio) phenyl) -1-acetone and 2-dimethylamino group-2-benzenemethyl- (4-morpholinophenyl group) -1-butanone; 2,2-diethoxy-1 , 2-diphenylacetophenone; methyl benzoyl formate, diethylene glycol bisbenzoyl group formic acid, ester polybutylene glycol bisbenzoyl group formate; (2,4, 6-trimethylbenzoyl group) diphenyl group phosphine oxide, di (2,4,6-trimethylbenzoyl group) phenyl group phosphine oxide; benzophenone and substituted derivatives thereof such as benzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4 -Phenylbenzophenone, 2'-chloro-4-phenylbenzophenone, 4-methylthiobenzophenone, 4- (2-hydroxyethyl group thio) benzophenone, 4-hydroxy group benzophenone laurate, benzophenone-4-oxyacetic acid polyethylene glycol ester; Thioxanthone and substituted derivatives thereof such as 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 1-chloro-4-propoxyl thioxanthone, thioxone N-ton-2-formic acid polyethylene glycol ester, thioxanthone-2-oxyacetic acid polyethylene glycol ester; for example 2- (4-methoxy group phenyl group) -4,6-di (trichloromethyl)-[1,3,5] -triazine Halogenated methyltriazines such as hexaarylbiimidazoles (HABI) such as hexaorthochlorophenylbiimidazole; ferrocene compounds; titanocene compounds; coumarins; camphorquinones; acridines such as 9-phenyl group acridines; 4,4′-di (diethyl group amino group) benzophenone, ethyl 4- (dimethylamino) benzoate, triethanolamine, methyldiethanolamine or an addition product of, for example, diethylamine and ethoxylated trimethylolpropane triacrylate There are amines such as active amine compounds; phosphites such as phosphite tribenzene ester and trilauryl phosphite; chain transfer agents such as hexanedithiol and n-octyl mercaptan.

  The composition (d) contains a pigment and a dye, and the pigment is a component necessary for the production of the printing ink and the optical filter, and depending on the demand for use, red, green, blue, black, white, yellow, magenta , Cyan and other specific dedicated colors, and corresponding pigments include commercially available types such as carbon black, phthalocyanine, titanium oxide and the like. The concentration of the pigment usually accounts for 10-30% of the total solid composition weight.

  The composition (d) further comprises phenols and hindered amines polymerization inhibitors such as p-methoxyphenol, nitrosophenylhydroxylamine aluminum complex polymerization inhibitors; such as 2- (2′-hydroxy group phenyl group) -benzotriazoles, Contains light absorbing agents such as salicylic acid esters and triazines; leveling agents such as triethoxyvinylsilane; and necessary additives such as wetting agents and dispersing agents. The amount used thereof is based on reaching the property index of the composition, and is not particularly limited here.

  The composition (d) further contains a developable resin, wherein the alkali-soluble developable resin is, for example, a polyacrylate copolymer containing a carboxylic acid side chain, wherein the comonomer is acrylic acid or methacrylic acid, It is selected from alkyl acrylate ester, alkyl methacrylate ester, styrene, and oligomerized styrene. Examples of the solvent developable resin include general-purpose resins such as cellulose ester, cellulose ether, polyvinyl acetate, polyvinyl butyral, polystyrene, polycarbonate, polyvinyl chloride, polyester, and polyimide. When the developable resin is an alkali-soluble resin, the composition can be used for the production of a photosensitive resist and a color filter for display.

  The composition can further contain a heat-drying resin and a thermosetting resin composition (e), and can contain, for example, a cellulose solution, a polyisocyanate, and a polyimide, which are processed in stages of photocuring and thermosetting. Meet the process requirements of

  A compound having at least one epoxy group and an epoxy group curing accelerator (g) can be further added to the composition as the thermosetting composition (f). As the compound having an epoxy group as the thermosetting composition (f), for example, a well-known thermosetting epoxy compound such as an aliphatic epoxy resin or an aromatic epoxy resin can be used. Bisphenol S-type epoxy resin such as BPS-200, bisphenol A-type epoxy resin, linear novolac epoxy resin, and the like, and partial ester compounds thereof are preferable. The amount of (f) used is 30 to 70 parts by weight.

  When using composition (f), any accelerator (g) can be used as a synergistic composition to achieve good cure accelerating action, such as amine accelerators, imidazole accelerators and other A normally used epoxy resin curing agent can be used, and the amount used is 5% or less of the weight of the composition (f).

  Other than the composition (a), (b), (c), (d), (e), (f), (g), other additives (h) often used in this field in the composition, For example, it can contain inorganic fillers such as barium sulfate, silicon oxide powder, talcum powder, calcium carbonate, and mica powder, which are additives for improving the adhesion and film formation hardness of the composition. Accounts for up to 30% of the total composition.

  The composition can also be used diluted with a solvent, depending on the demand of the application field. Suitable solvents include, for example, ketones such as methyl ethyl ketone and cyclohexanone; hydrocarbons such as toluene, ditoluene, octane, petroleum ether and naphtha; alcohols such as n-butanol and propanediol; propylene glycol monomethyl Examples include ethers, alcohol ethers such as diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate and esters thereof; for example, amides such as N, N-dimethylformamide.

  A mixture diluted in the above composition or solvent is prepared according to the ink production method and then stored in the dark.

  The composition is used for the production of colored or transparent products such as paints, adhesives or inks, photosensitive resists and photoresists, further printing the products, 3D printing, production of display color filters, image copying Used in technology, printed circuit board medium layer, electronic device packaging, optical switch, three-dimensional mold, quartz fiber protective layer, medical product.

  The present invention provides a method for curing a carbon-carbon double bond compound in the photocuring composition in which the composition is coated on a base and irradiated with 190 to 600 nm light to cure the coating layer. The light rays are from the sun, mercury lamp, high pressure mercury lamp or LED lamp. Irradiating the composition with a light wave in the 190-600 nm range or a light wave with a controlled output light wavelength via a grating, and also an LED light source in any constant wavelength range between 360 nm and 410 nm, for example a 365 nm LED It can also be cured by irradiating the coating layer of the composition with a light source. The definition of LED is a light emitting diode semiconductor.

  A method for producing a projection pattern with the photocuring composition is as follows. First, the photocuring composition is diluted with a solvent, and then the diluted photocuring composition is applied to the base, followed by roasting, exposure, and development. Then, an unexposed portion is removed to obtain a projection pattern.

  The 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 a photosensitive resist. It has high photosensitivity, is easily developed with an alkaline aqueous solution, does not swell and deform, and the image forming effect is clear. Suitable for the production of etching photosensitive resist and solder mask photosensitive resist, and can be used for the production of image display and recording material, spray ink cured by LED lamp, LCD, OLED, PDP, and various printed circuit boards It can also be used for the production of and the production of electronic circuit boards or integrated circuits, and it can also be used for barrier coating layers of various electronic components.

  The composition has good enzyme polymerization inhibition resistance and heat processing resistance, meets the requirements of the color filter production process, and is particularly suitable for production of liquid crystal displays and organic semiconductor light emitting displays.

  Using the composition of the present invention as a photoresist, a black, red, green and blue three-color pattern is formed through coating, exposure, development, and heat treatment in order, thereby obtaining a complete color filter. The base of such a color filter can be a glass or organic polymer film and a ceramic sheet.

  The present invention further provides a color filter produced from the above composition.

  The composition is applied to a flat plate or a curved base, and roasted to obtain a film layer. After a mask exposure and development method, an unexposed portion is removed to obtain a projection image. A color filter including black, red, green, and blue pixels includes a compound represented by the general formulas I, II, III, and IV of the present invention, a monomer, an alkali-soluble resin, a corresponding pigment, and an auxiliary substance. It is obtained through coating, exposure, development, and heat treatment of the contained composition. Here, a necessary processing process such as cleaning is also included.

  For example, the composition of the present invention is uniformly applied on a base to be applied by a coating technique method often used in this field such as spin coating, roller coating, spraying, and transfer, and the coating amount is determined as necessary. The typical thickness is 0.1 micron to 1 millimeter. When the composition contains a solvent component, the component is not volatilized by a heating method, for example, an 80 ° C. drying method, and the solvent is volatilized to form an adhesive layer on the base.

  Next, in the exposure process, exposure is performed directly with a UV laser, or an image mask is placed on the adhesive layer, and a range of wavelengths of light is emitted from an ultraviolet or visible light source to transmit the mask with a predetermined energy. The light part is transmitted through the light and exposed, the light receiving part of the adhesive layer is cured, and the blocked part is not cured.

  Next, in a development process, a non-exposed portion is removed to obtain a projection pattern. The development process is performed by parameters known to those skilled in the art, for example, spraying and washing at 30 ° C. Usually, for example, development is performed with an alkaline aqueous solution such as an alkali metal hydroxide, an aqueous carbonate solution, or an aqueous ammonia solution, and if necessary, a fixed amount of a wetting agent such as a surfactant such as cyclohexanone, acetone, An organic solvent such as glycol ether can also be added. A development method in which the exposure film is immersed in the developer or the developer is sprayed onto the exposure film can be used, and the specific development temperature and time are determined according to the development effect. The alkaline solution used for development is obtained by dissolving an alkaline substance in water or an aqueous solution containing a water-soluble organic solvent, and examples of the alkaline substance include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, carbonate Sodium hydrogen, potassium hydrogen carbonate, triethanolamine, morpholine, trisodium phosphate can be mentioned, 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 step can optimize the fixing degree of the image, and is usually roasted for 15 to 45 minutes in a 200 to 260 ° C. heating furnace.

  According to the well-known color filter production process, according to the composition of the present invention, it produces color filter parts with good processing performance, clear matrix, high light transmittance and used for the production of high quality display can do.

  The examples are for explaining the present invention in more detail, and the amounts used are calculated in parts by weight unless otherwise specified.

  Example 1: Synthesis of 5-benzenethio group indan-1-ketone

  33.3 g (0.2 mol) of 5-chloro-1-indanone was weighed into a 50 ml three-necked flask and 30 ml of N, N-dimethylformamide (DMF), 30.0 g (0.27 mol). Benzenethiol and 36 g anhydrous potassium carbonate are added and stirred at 40-45 ° C. for 6 h under nitrogen protection. DMF is recovered by decompression, the remainder is added to 100 ml water, extracted twice with 25 ml 1,2-dichloroethane, combined with 1,2-dichloroethane solution, washed twice with 10 ml water, and Buchner funnel The organic phase is filtered on a filter paper, the filtrate is dried, the residue is recrystallized with methanol, and 43.4 g of pale yellow crystals are obtained after drying. The yield is 90.3% and the purity is determined by HPLC analysis. Reached 98.2%. The melting range is 46.0-48.0 ° C.

  Example 2: Synthesis of 5- (4-octanoyl group benzenethio group) indan-1-ketone

24.04 g (0.1 mol) of 5-benzenethio group indan-1-ketone, which is the product of Example 1, is dissolved in 120 ml of 1,2-dichloroethane, and the temperature is lowered to 5 to 10 ° C. 28 g (0.21 mol) anhydrous aluminum trichloride was added, and 17.9 g (0.11 mol) octanoic acid chloride was added dropwise with stirring. After completion, the mixture was stirred for 4 h, the reaction solution was treated with diluted hydrochloric acid, and the organic solution was dissolved. Separated, washed once with water and concentrated to recover 1,2-dichloroethane, and the rest was recrystallized with 100 ml of ethanol to give 33.1 g of white crystals, yield 90.1% The melting range is 74.3-75.2 ° C., and according to ¹ H-NMR data, the product obtained is 5- (4-octanoyl group benzenethio group) indan-1-ketone. ¹ H-NMR (CDCl ₃ ) and δ (ppm) value data are 0.8848 (t, 3H, CH ₃ ), 1.2892 to 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 / 7.4977 (d, 2H, 2ArH), 7.6777 / 7.6945 (d, 1H, ArH), 7.9221 / 7.9493 (d, 2H, 2ArH).

  Example 3: Synthesis of 5- (4-octanoyl group benzenethio group) indane-1,2-diketone-2-oxime

18.4 g (0.05 mol) of 5- (4-octanoyl group benzenethio group) indan-1-ketone, the product obtained in Example 2, was weighed and dissolved in 150 ml ethanol in a 250 ml three-necked flask. Then, 2 g of 36% concentrated hydrochloric acid was added, and the mixture was kept warm in a water bath at 15 to 20 ° C. and stirred. 6.2 g (0.06 mol) n-butyl nitrite was dropped into 15 min and stirred at 25 ° C. for 5 hours. Thereafter, the temperature of the reaction solution was lowered to 5 to 10 ° C., and a yellow solid was precipitated by filtration. After drying, it was 18.7 g. As a result of analysis, the purity was 98.90% and the melting range was 162.7. According to ¹ H-NMR data at ˜164.0 ° C., the product was 5- (4-octanoyl group benzenethio group) indan-1,2-diketone-2-oxime, and the yield was 94.2%. Reached. ¹ H-NMR (CDCl ₃ ) and δ (ppm) value data are 0.8866 (t, 3H, CH ₃ ), 1.2965 to 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 / 7.7777 (d, 1H, 2ArH), 7.9648 / 7.9925 (d, 2H) , 2ArH), 12.4460 (s, 1H, NOH).

  Example 4: Synthesis of dioxime compounds

7.95 g (0.02 mol) of 5- (4-octanoyl group benzenethio group) indan-1,2-diketone-2-oxime, which was the product obtained in Example 2, was dissolved in 40 ml of dimethyl sulfoxide, After adding 0.5 g of 36% concentrated hydrochloric acid, keeping the temperature in a water bath at 20 to 25 ° C. and stirring, 3.1 g (0.03 mol) of n-butyl nitrite was dropped into 15 min and stirred for 10 hours, and then the reaction solution The temperature was lowered to 5 to 10 ° C., and a yellow solid was precipitated by filtration. After drying, it was 7.72 g. As a result of analysis, the purity was 96.80% and the yield reached 90.5%. did. The melting range is 171.0-173.0 ° C., and according to ¹ H-NMR data, the product obtained is a dioxime compound. ¹ H-NMR (DMSO-d ₆ ), δ (ppm) value data are 0.850 (t, 3H, CH ₃ ), 1.272 to 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 ester IIA1

IIＡ１

IIA1

4.27 g (0.01 mol) of the product of Example 4 was weighed and dissolved in 25 ml of 1,2-dichloroethane, 3.1 g (0.03 mol) of acetic anhydride was added dropwise, and a 20 to 25 ° C. water bath was used for 6 hours. React. The reaction solution is washed twice with 25 ml water, the aqueous phase is separated, the organic phase is dried with 1.5 g anhydrous sodium sulfate for 2 h, filtered to remove the desiccant, and the filtrate is evaporated to dryness under reduced pressure. . Add 15 ml of ethyl acetate to the rest, heat until all are dissolved, add 0.05 g activated carbon and let it flow for 0.5 h, filter by hot filtration to separate the activated carbon, and add 15 ml of n-hexane to the filtrate. The crystals were precipitated, filtered by suction, and the filter cake was vacuum dried to obtain 4.47 g of a yellow crystal product. The content was 98.0% and the yield reached 87.8%. . The melting range, ¹ H-NMR (CDCl ₃ ), and δ (ppm) value data are as shown in Table 1.

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

According to the method of Example 2, 5- (4-valeryl group benzenethio group) indan-1-ketone was obtained by using valeryl chloride instead of octanoic acid chloride, the yield was 93.0%, melting range Is 74.1-75.8 ° C., and according to ¹ H-NMR data, the product obtained is 5- [4- (3-cyclobenzylpropanoyl) benzenethio group] indan-1-ketone. . ¹ H-NMR (CDCl ₃ ) and δ (ppm) value data are 0.9590 (t, 3H, CH ₃ ), 1.3533 to 1.4768 (sextet, 2H, CH ₂ ), 1.7274 (quintet). , 2H, CH ₂ ), 2.7047 (t, 2H, c—CH ₂ Ar), 2.9585 (t, 2H, CH ₂ ), 3.0961 (t, 2H, c—CH ₂ CO), 7 2745 / 7.3030 (d, 1H, ArH), 7.3760 (s, 1H, ArH), 7.4513 / 7.47891 (d, 2H, 2ArH), 7.6683 / 7.6852 (d, 1H, ArH), 7.9213 / 7.9490 (d, 2H, 2ArH).

  Example 7: Synthesis of 5- (4-valeryl group benzenethio group) indane-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 oximeation reaction was carried out using dimethyl sulfoxide as a solvent instead of ethanol, and a monooxime product was generated by HPLC analysis. Not separated.

  Example 8: Synthesis of dioxime compounds

The reaction solution of Example 7 was continuously added dropwise with the same weight of n-butyl nitrite to carry out the second oximation reaction. After 10 hours, the reaction solution was treated according to the method of Example 4 to obtain a yellow solid. The purity was 96.50%, where the cis isomer content was 3.30%, the trans isomer content was 93.20%, and the yield was 85.0%. According to ¹ H-NMR data, the obtained product was a bisoxime compound. ¹ H-NMR (DMSO-d ₆ ), δ (ppm) value data are 0.9073 (t, 3H, CH ₃ ), 1.4514 to 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 / 7.8879 (d, 2H, 2ArH), 12.4769 (s, 1H, NOH), 12.6651 (s, 1H, NOH).

  Example 9: Synthesis of dioxime ester IIA6

IIＡ６

IIA6

According to the reaction method of Example 5, the product of Example 8 was used as a raw material, and an esterification reaction was performed to obtain a yellow solid through purification. The purity was 98.65%, where cis isomerism The content of the product was 1.25%, the content of the trans isomer was 97.40%, and the yield was 60.3%. According to ¹ H-NMR data, the obtained product was IIA6. ¹ H-NMR (CDCl ₃ ) and δ (ppm) value data are as shown in Table 1.

  Example 10: Synthesis of 5- [4- (3-Cyclobenzylpropanoyl) benzenethio group] indan-1-ketone

According to the method of Example 2, substituting 3-cyclobenthylpropionyl chloride for octanoic acid chloride to obtain 5- [4- (3-cyclobenthylpropanoyl) benzenethio group] indan-1-ketone, The yield is 92.0%, the melting range is 88.5-90.0 ° C., and according to ¹ H-NMR data, the product obtained is 5- [4- (3-cyclobenthylpropanoyl) benzenethio Group] Indan-1-ketone. ¹ H-NMR (CDCl ₃ ) and δ (ppm) value data are 1.1072 (m, 2H, CH ₂ ), 1.5328 to 1.8691 (m, 9H, 4CH ₂ + 1CH), 2.7067 (t, 2H, c-CH ₂ ), 2.89689 (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).

  Example 11: Synthesis of 5- [4- (3-Cyclobentopylpropanoyl) benzenethio group] indane-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 an oximation reaction was performed using isoamyl nitrite instead of n-butyl nitrite to precipitate a yellow solid product. And the purity was 96%, and according to ¹ H-NMR data, the product obtained was 5- [4- (3-cyclobenzylpropanoyl) benzenethio group] indan-1,2-diketone-2. -Oxime, the yield was 95.5%. ¹ H-NMR (DMSO-d ₆ ), δ (ppm) value data are 1.1081 (m, 2H, CH ₂ ), 1.4795 to 1.7602 (m, 9H, 4CH ₂ ), 3.0258. (t, 2H, CH ₂ ), 3.7342 (s, 2H, c-CH ₂ ), 7.186 / 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 compounds

According to the reaction method of Example 4, the product of Example 11 was used as a raw material, and the second oximation reaction was performed using isoamyl nitrite instead of n-butyl nitrite, and a yellow solid was obtained after purification. The purity is 95.50%, where the cis isomer content is 5.10%, the trans isomer content is 90.40% and the yield is 88.3%. there were. According to ¹ H-NMR data, the obtained product was a bisoxime compound. ¹ H-NMR (DMSO-d ₆ ), δ (ppm) value data are 1.1766 to 1.6286 (m, 8H, 4CH ₂ ), 2.1325 (heptet, 1H, CH), 2.689 / _{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 / 7.759 (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 ester IIA3

IIＡ３

IIA3

According to the reaction method of Example 5, the esterification reaction was performed using the product of Example 12 as a raw material, and a yellow solid was obtained through a purification treatment. The purity was 98.65%, where the cis isomer The content was 1.50%, the trans isomer content was 97.15%, and the yield was 60.3%. According to ¹ H-NMR data, the obtained product was IIA3. ¹ H-NMR (CDCl ₃ ) and δ (ppm) value data are as shown in Table 1.

Example 14: Preparation of alkali-soluble resin Benzyl methacrylate 180 g, methacrylic acid 60 g, hydroxyethyl methacrylate 60 g, azoisobutyronitrile 15 g, dodecanethiol 6 g, and toluene 1000 ml are mixed and placed in a constant pressure dropping funnel. Place 1000 ml of toluene in a three-necked flask, attach a stirrer, constant pressure dropping funnel and thermometer, start stirring, and replace the gas in the flask with nitrogen. The flask is heated, the solvent temperature is raised to 80-85 ° C., the temperature is kept, and the dropping of the monomer mixed solution is started, and is completed in about 1 h. The reaction is continued for 6 hours. After cooling naturally and stopping the agitation, the resin settles, absorbs the upper clarified solution, filters the resin containing the lower solvent, and wash the resin filter cake with 500 ml of toluene. The filter cake was roasted under reduced pressure to obtain 250 g of a white powdery solid resin. It was prepared by dissolving 1000 g of PMA (1-methoxy-2-provir acetate) in a 20% solution.

Example 15: Preparation and development of photosensitive resist Weight ratios of recipes 15A, 15B and 15C shown in Table 2 (photoinitiator is OXE01 as a control), 15D (photoinitiator is OXE02 as a control) Thus, the photocurable composition was prepared according to the ink preparation method for all the compositions, and was in a fluid liquid state.

  The liquid composition was applied to the glass surface by the wire rod method, roasted at 80 ° C. for 3 minutes, the solvent PMA was volatilized, and the thickness of the remaining adhesive film was measured.

A gray scale meter with 21 gradations was placed on the film, and a 2000 W high pressure mercury lamp beam was filtered with a 365 nm grating filter. The distance between the film and the grating was 10 cm, and the exposure amount reached 800 mJ / cm ² .

  Immerse in a 1% sodium carbonate solution bath at 30 ° C. for 1 min, record the maximum number of remaining gradations that can be displayed, and the higher the value, the stronger the photosensitivity of the measured composition and the photocuring rate of the photosensitive resist The film forming performance is high, and the results are shown in Table 3.

  According to the development results shown in Table 3, the photocuring compositions prepared using the photoinitiators of Example 9 and Example 13 were compared with the photocuring compositions prepared using OXE01 and OXE02. It is remarkably superior, and improves the photocuring rate and film forming performance of the photosensitive resist.

Example 16: Test experiment of gel transition rate of photocured composition The composition obtained in Recipes 15A, 15B, 15C, and 15D in Table 2 of Example 15 above was applied to a glass surface by the wire rod method, and the temperature was 80 ° C. As a result of measuring the thickness of the remaining adhesive film by volatilizing the solvent PMA and measuring the remaining adhesive film thickness, it was 2 microns.

The 2000 W high pressure mercury lamp beam was filtered with a 365 nm grating filter, the distance between the film and the grating was 10 cm, and the exposure amount reached 200, 400, and 600 mJ / cm ² , respectively. After curing, wrap the sample with a stainless steel mesh, weigh W ₁ , soak in acetone for 72 hours, roast, measure the weight W ₂ of the remaining film, and transfer W ₁ / W ₂ to gel The result is as shown in Table 4.

  As can be seen from Table 4, in the photosensitive resist recipe, the photoinitiators of Examples 9 and 13 have a higher degree of polymerization of double bonds and clearly higher activity.

Example 17: Test experiment of curing and curing efficiency of photosensitive composition with LED light source The photocuring compositions 15A, 15B, 15C, and 15D in Example 15 were applied to a glass surface by a wire rod method at 80 ° C. A 3 min loading treatment was performed, the solvent PMA was volatilized, and the thickness of the remaining adhesive film was measured. As a result, it was 2 microns, and was then cured by the following method.

Curing device: LEDUV curing device, Model: UV-101D (Beijing Hiroshi Iwata Science and Technology Co., Ltd.)
Light source: UV-LED point light source, diameter: 10 mm; wavelength: 365 nm, maximum illuminance: 40 mw / cm ²
Curing conditions: Operating distance: 21 mm; Irradiation time: 1 s

  Curing efficiency display method: After irradiating with a point light source for 1 s, the entire glass is immersed in an acetone solution for 5 s and taken out, and the diameter of the figure of the cured film is measured. The larger the numerical value, the higher the photosensitivity and the higher the curing efficiency. Table 5 shows the measurement results. As can be seen from the measurement results in Table 5, when the solder mask ink or the photosensitive resist photosensitive composition is cured with an LED light source, the photosensitive composition provided by the present invention can light existing OXE01 and OXE02. Compared with the composition used as an initiator, it has a higher photosensitivity.

Example 18: Preparation of printing ink and curing with high-pressure mercury lamp Recipe blending ratio: 50 parts of epoxy resin acrylate prepolymer (Changxing Chemical 621-100), 10 parts of polyester acrylate prepolymer (Changxing Chemical 6311-10), TPGDA (Changxing) 30 parts of chemical EM223), 4 parts of carbon black (Degussa company P25) and 6 parts of photoinitiator were mixed and polished to a fineness of 2 μm or less to obtain ink samples 18A to 18D. The aluminum plate was printed with a 420 mesh screen, cured with a high-pressure mercury lamp, the gel transition rate gel% was measured by the method of Example 16, and the measurement results are shown in Table 6. As can be seen from the measurement results in Table 6, as a result of irradiation with the high-pressure mercury lamp, the gel transition rate of the compound according to the present invention is clearly higher than that of the control compound.

Example 19: Preparation of printing ink and curing with LED surface light source Recipe composition ratio: 50 parts epoxy resin acrylate prepolymer, 10 parts polyester acrylate prepolymer, 30 parts TPGDA, 4 parts yellow 3G (BASF company), photoinitiator 6 The parts are mixed and polished to a fineness of 2 μm or less to obtain ink samples 19A to 19D, which are applied to a glass plate. It hardens | cures with a 365 nm LED surface light source lamp, and an exposure amount is 86 mJ / cm < ² >. The gel transition rate gel% was measured by the method of Example 16. Table 7 shows the measurement results. As can be seen from the measurement results in Table 7, as a result of irradiation with a 365 nm LED light source, the gel transition rate by the compound according to the present invention is clearly higher than that of the control compound.

Example 20: Preparation and exposure development of photosensitive resist ink for membrane filter Recipe composition: 500 parts of alkali-soluble resin solution (Example 14), 100 parts of dipentaerythritol hexaacrylate (Cytec company DPHA), 100 parts of photoinitiator, Auxiliary initiator BCIM (2,2′-diortho-chlorphenyl-4,4 ′, 5,5′-tetraphenyl biimidazole) 20 parts, carbon black (Degussa company P25) dispersion 500 parts (containing 20% carbon black) . According to the ink preparation method, it was uniformly polished, and five types of inks 20A to 20E were obtained according to the difference in the photoinitiator used.

Each is coated and roasted under reduced pressure until the thickness becomes 1 um, covered with a pattern mask, exposed with a 365 nm LED surface light source, the exposure amount is 100 mJ / cm ² , 1% sodium hydroxide and 2% acetone. The developed aqueous solution was developed for 30S, and the pattern form and fixing degree were detected with a stereomicroscope. The form and the fixing degree are as follows: 1: the exposed part is complete, no dropout, 2: the exposed part does not drop out, but there is deflection, 3: the edge of the exposed part does not match, 4: the exposed part is not complete 5: Evaluation was performed according to the exposed portion was removed.

  The evaluation of the experimental results is shown in Table 8, and as can be seen from the results in Table 8, after the ink containing the compound of the present invention was exposed and developed, the edge of the pattern was clear and complete, solid and free from dropout. The performance of the compounds according to the invention is clearly superior to the control compound.

Example 21: Preparation and exposure development of photosensitive resist ink for membrane filter Recipe composition: 500 parts of alkali-soluble resin solution (Example 14), 100 parts of dipentaerythritol hexaacrylate (Cytec company), 100 parts of photoinitiator, red 100 parts of pigment L3920 (BASF company). According to the ink preparation method, uniform polishing was performed to obtain five types of inks 21A to 21E.

Coated, under vacuum roasting until a thickness of the 2um, over the pattern mask, exposed with 365nm of LED surface light source, the exposure amount is a 86 mJ / cm ^2, a 1% sodium hydroxide and 2% acetone Development was carried out with an aqueous solution containing 30S, the degree of pattern fixation and the form were detected with a stereomicroscope, and evaluation was carried out in the same manner as in Example 20. The experimental results are shown in Table 9. As can be seen from the results in Table 9, after exposure and development of the ink containing the compound of the present invention, the edge of the pattern is clear and complete, solid and free from dropout. The performance of the compounds according to the invention is clearly superior to the control compound.

Example 22: Preparation and exposure development of photosensitive resist ink for membrane filter Recipe composition: 500 parts of alkali-soluble resin solution (Example 14), 100 parts of dipentaerythritol hexaacrylate (Cytec company), 10 parts of photoinitiator, red 100 parts of pigment L3920 (BASF company). According to the ink preparation method, it was uniformly polished to obtain 5 types of inks 21A to 21E, applied, roasted under reduced pressure until the thickness became 2 μm, covered with a pattern mask, exposed with a 365 nm LED surface light source, The exposure amount is 86 mJ / cm ² , 30S development is performed with an aqueous solution containing 1% sodium hydroxide and 2% acetone, the pattern fixing degree and form are detected with a stereomicroscope, and evaluation is performed in the same manner as in Example 20. did. The evaluation of the experimental results is shown in Table 10, and as can be seen from the results in Table 10, after the ink containing the compound of the present invention was exposed and developed, the edge of the pattern was clear and complete, solid and free from dropout. The performance of the compounds according to the invention is clearly superior to the control compound.

Claims (22)

A compound represented by general formula I.

(I)
(here,
Ar ₁ is C ₆ -C ₂₀ ortho-arylidene or C ₃ -C ₂₀ ortho-heteroarylidene substituted with X ₁ , wherein C ₆ -C ₂₀ ortho-arylidene or C ₃ -C ₂₀ ortho-hetero In arylidene, two adjacent atoms are connected to Y ₁ and a carbonyl group to form a condensed ring structure, and the substituents on the other atoms are a hydrogen atom; a halogen atom; a C ₁ -C ₁₂ alkyl group; C ₅ -C _{7 naphthenic;} C 5 -C ₇ naphthenes _C 1 -C ₄ alkyl group substituted by _group; C 1 _{-C 12} alkoxyl group; one or more _C 1 _{-C 12} alkoxyl group, _{C 1} -C ₄ alkyl group a benzyl _{group, R 2 C (O) C} 1 ~C 4 alkoxy group substituted with O; phenyl; optionally one or more _C 1 -C ₄ alkyl group, carboxyl groups, C _{1 to} C ₁₂ alkyl acyl group, aryl acyl group, heteroaryl acyl group, X ₃ R ₁₇ , phenyl group, halogen atom, phenyl group substituted with CN; C _{1 to} C ₄ alkyl benzyloxy group; C _{1 to} C ₃ alkylidene dioxy groups; R ₂ C (O) O; C _{1 to} C ₁₂ alkylthio groups; C _{1 to} C ₄ alkylbenzenethio groups; CN; carboxyl groups; C _{1 to} C ₁₂ alkoxylcarbonyl groups; arylcarbonyl groups; X ₃ R ₁₈ ; C ₁ -C ₄ alkylphenoxy group; C ₁ -C ₈ alkylacylphenoxy group; C ₅ -C ₆ naphthene acylphenoxy group; C substituted with C ₅ -C ₆ naphthene group ₁ -C ₄ alkyl acyl phenoxy group; an aryl acyl phenoxy group; a heteroaryl acyl phenoxide Groups _{R 2 C} (O) C substituted by O 1 -C ₄ alkylthio groups and _C 1 -C ₄ alkylbenzene thio _group; C 1 -C ₈ alkyl acyl benzene thio _group; C 5 -C ₆ naphthenic acyl benzenethiolate A C ₁ -C ₄ alkylacylbenzenethio group substituted with a group or a C ₅ -C ₆ naphthene group; an arylacylbenzenethio group; a heteroarylacylbenzenethio group; or an epoxypropyl group, wherein group is optionally _C 1 -C ₄ alkyl aldehyde, combined ketone and condensed, _{X 3} is O, a S or _{NR 22} Ar ₂ is _C 6 _{-C 20 arylidene,} a C 3 _{-C 20} heteroaryl arylidene , via _{X 1} is connected to the Ar _1, or, through a _{X 1} is connected to the Ar _1, is Ar ₂ carbon atoms ortho of the substituents _{X 1} Furthermore, it is connected to Ar ₁ via a single bond, carbon atom, carbonyl group, O, S, NR ₁₈ to form 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 met _{(CH 2) m CR 15 R} 16, NR 19, O (CR 15 R 16) m, S (CR 15 R 16) m, (CR 15 R 16) m C = O, S = O M is 0 or 1,
Z ₁ is a C ₁ -C ₁₀ single bond or branched alkylidene, one or more oxygen atoms, a C ₁ -C ₁₀ single bond or branched alkylidene connected to or inserted into a terminal group by a sulfur atom, a no substituents or a substituent a _C 6 _{-C 20} arylidene,
Y ₂ is O, S, NR ₁₈ , O—C (O), where R ₁ is a hydrogen atom; a C ₁ -C ₁₈ alkyl group; optionally one or more C ₃ -C ₇ naphthene groups, phenyl Group, OR ₂₀ , SR ₂₁ , C ₁ -C ₁₈ alkyl group substituted by NR ₂₂ R ₂₃ ; C ₃ -C ₇ Cycloalkylene group, phenylene group, O, S, C inserted by NR _{22 2} -C ₁₈ alkyl _radical; C 3 -C ₈ naphthenic; CN; NO _2; a phenyl group, or a phenyl group is not substituted, optionally one or more halogen _{atoms, C} 1 ~ C ₄ alkyl _group, C 5 -C ₇ naphthenic, hetero naphthene group, a phenyl group, a heteroaryl group, _CN, C 1 -C ₄ alkane acyl group, substituted with an aryl acyl group,
Or R ₁ is a C ₁ -C ₁₂ alkyl acyl group, a C ₁ -C ₁₂ alkoxylcarbonyl group, wherein the alkyl group is optionally one or more halogen atoms, C ₁ -C ₄ alkyl Substituted with a group, C ₅ or C ₆ naphthene group, phenyl group, CN, OH, X ₃ R ₂₀ , or wherein the alkyl group is optionally inserted with one or more phenylene groups, X ₃ ,
Or R ₁ is a benzoyl group, a phenoxycarbonyl group, wherein the phenyl group is unsubstituted, or optionally one or more halogen atoms, a C ₁ -C ₄ alkyl group, C ₅ Or substituted with a C ₆ naphthene group, a phenyl group, CN, OH, X ₂ R ₂₀ ,
Or R ₁ is a diphenylphosphono group or a di (C ₁ -C ₄ alkoxyl group) phosphono group,
R ₂ and R ₃ are each independently a hydrogen atom, a C _{1 to} C ₁₈ alkyl group or a C _{1 to} C ₁₈ alkoxyl group,
Or R ₂ and R ₃ are each independently a C _{2 to} C ₁₈ alkenyl group, optionally having one or more halogen atoms, C _{1 to} C ₄ alkyl groups, C _{5 to} C ₇ naphthene groups, hetero naphthene group, a phenyl group, a heteroaryl group, _CN, C 1 -C ₄ alkane acyl group, substituted with an aryl acyl group, and / _or, C 5 -C ₇ cycloalkylidene group, a phenylene group, O, S, _{NR 17} there a inserted _C 2 _{-C 18} alkenyl group,
Or R ₂ and R ₃ are each independently one or more halogen atoms, C ₁ -C ₄ alkyl groups, C ₅ -C ₇ naphthene groups, heteronaphthene groups, phenyl groups, heteroaryl groups, CN , _C 1 -C ₄ alkane acyl group, substituted with an aryl acyl group, and / _or, C 5 -C ₇ cycloalkylidene group, a phenylene _{group, O, S, C 2 ~C} 18 alkyl _{group NR 17} is inserted Because
Or, R ₂ and R ₃ are each independently a C _{5 to} C ₇ naphthene group, and optionally substituted with one or more C _{1 to} C ₄ alkyl groups, a phenyl group, a halogen atom, or CN. a _{5 ~C 7} naphthenic group,
Or R ₂ and R ₃ are each independently a phenyl group, optionally substituted with one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxyl groups, phenyl groups, halogen atoms, CN A substituted phenyl group,
Or R ₂ and R ₃ are each independently a naphthyl group,
Or R ₂ and R ₃ are each independently a benzoyl group, a phenoxycarbonyl group, or a phenyl group therein is not substituted, or optionally, one or more halogen atoms, R ₁₇ , substituted with a C ₅ or C ₆ naphthene group, CN, OH, XR ₁₇ ;
R ₁₅ and R ₁₆ each independently represent a hydrogen atom; a C _{1 to} C ₁₈ alkyl group; a C _{1 to} C ₅ alkyl group substituted with a carboxyl group or a C _{1 to} C ₄ alkoxyl acyl group; R ₂ C (O) _C substituted by O 1 -C ₄ alkyl groups; optionally one or more halogen _atoms, C 1 -C ₄ alkyl _group, C 5 -C ₇ naphthenic, hetero naphthene group, a phenyl group, heteroaryl group, _CN, C 1 -C ₄ alkane acyl group, substituted with an aryl acyl group, _or, C 5 -C ₇ cycloalkylene group, a phenylene group, O, S, _C 2 ~ _{the NR 17} is inserted a C ₁₈ alkyl group, _or, R _{15, R 16} are each _{independently,} C 5 -C ₇ naphthenic or optionally one or more _C 1 -C ₄ alkyl group, a phenyl group, a halo Emissions atom, a _C 5 -C ₇ naphthenic group substituted with CN,
Or R ₁₅ and R ₁₆ are each independently a phenyl group, and optionally one or more C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxyl groups, carboxyl groups, C ₁ -C ₁₂ alkyls acyl _groups, C 5 -C ₆ naphthenic formyl _group, C 5 -C _C 2 substituted by ₆ naphthenic -C ₄ alkyl acyl group, a benzoyl group, _{XR 17,} phenyl group, halogen atom, substituted with CN A phenyl group,
Or, the _{R 15, R 16} constitutes an annular together with them to be connected to a joint carbon atom or silicon atom, the number of atoms constituting the ring is a 4 to 7, or said _{R 15, R 16} is Each of them constitutes a ring with adjacent substituents, and the number of atoms constituting the ring is 4 to 7,
R ₁₇ is a C ₁ -C ₄ alkyl group,
Each R _{18, R 19} are independently a hydrogen _atom; substituted with _{R 2} C (O) O; where C 1 _{-C 18} alkyl _group; C 1 -C ₄ alkoxy _C 1 -C substituted by cyclohexyl acyl group ₅ alkyl group C ₁ -C ₄ alkyl group; optionally one or more halogen atoms, C ₁ -C ₄ alkyl group, C ₃ -C ₇ naphthene group, heteronaphthene group, phenyl group, heteroaryl group, CN, C ₁ -C ₄ alkane acyl group, arylacyloxy _C 1 _{-C 18} alkyl group substituted with a group; optionally one or more _C 3 -C ₇ cycloalkylene group, a phenylene group, O, S, is _{NR 17} inserted a _C 2 _{-C 18} alkyl group,
Or R ₁₈ and R ₁₉ are each independently a C _{5 to} C ₇ naphthene group, or optionally substituted with one or more C _{1 to} C ₄ alkyl groups, a phenyl group, a halogen atom, or CN. A C ₅ -C ₇ naphthene group,
Or R ₁₈ and R ₁₉ are each independently a phenyl group, and optionally one or more C ₁ -C ₄ alkyl groups, carboxyl groups, C ₁ -C ₁₂ alkyl acyl groups, C ₅ -C ₆ naphthenic formyl _group, a C 5 -C ₆ naphthenes _C 2 -C ₄ alkyl acyl groups substituted with an aryl acyl group, _{XR 17,} a phenyl group, a halogen atom, a phenyl group substituted with CN,
Or R ₁₈ is connected to the aromatic ring in Ar ₁ or Ar ₂ via a single bond, carbon atom, or carbonyl group to form a new ring;
Or R ₁₉ is connected to the aromatic ring in Ar ₁ via a single bond, carbon atom, or carbonyl group to form a new ring;
R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ are each independently a hydrogen atom; a C _{1 to} C ₁₈ alkyl group; a halogen, CN, a C _{1 to} C ₁₈ alkyl group substituted with a C ₁ to C ₄ alkoxyl group; One or more oxygen _atoms, C 5 -C ₇ cycloalkylene group, _C 2 _{-C 18} inserted by a phenylene group alkyl group; a phenyl _{group, C 3 ~C 7 C 1 ~C} 3 alkyl substituted with naphthenic a C 3 -C _{7 naphthenic;} group
Or R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ are each independently a phenyl group, a naphthyl group or a benzoyl group, wherein the phenyl group or naphthyl group is not substituted or is optionally halogenated. , C ₁ -C ₄ alkyl group, C ₁ -C ₄ alkoxyl group, C ₁ -C ₄ alkylthio group, phenoxy group, benzenethio group, NR ₂₄ R ₂₅ , C ₁ -C ₁₂ alkyl acyl group, substituted with benzoyl group ,
R ₂₄ and R ₂₅ are each a C _{1 to} C ₄ alkyl group, or NR ₂₄ R ₂₅ is morpholine, piperidine, piperazine, N-methylpiperazine, or pyrrole. ) A compound of general formula I according to claim 1,
More specifically, a compound represented by any one of 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 , R ₁₄ are each independently a hydrogen atom; a halogen atom; a C ₁ -C ₁₂ alkyl group A C ₅ -C ₇ naphthene group; a C ₁ -C ₄ alkyl group substituted with a C ₅ -C ₇ naphthene group; a C ₁ -C ₁₂ alkoxyl group; a phenyl group; optionally one or more C ₁ -C ₄ alkyl group, carboxyl _group, C 1 _{-C 12} alkyl acyl, aryl acyl, heteroaryl acyl _group, X _{3 R 17,} a phenyl group, a halogen atom, a phenyl group substituted with _CN; C 1 -C ₄ alkyl A benzyloxy group; one or more C ₁ -C ₁₂ alkoxyl groups, a C ₁ -C ₄ alkylbenzyloxy group, a C ₁ -C ₄ alkoxyl group substituted with R ₂ C (O) O; R ₂ C ( O) ; CN; a X _{3 R 18,;} carboxyl _group; C 1 _{-C 12} alkoxycarbonyl group; an aryl group; a heteroaryl group
Or R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ are each independently a C ₁ -C ₄ alkylphenoxy group; C ₁ -C ₄ alkylbenzene thio _group; C 1 -C ₈ alkyl acyl phenoxy group; an aryl acyl phenoxy group; a heteroaryl acyl phenoxy _group; C 5 -C ₆ naphthenate acyl phenoxy _group; C 5 -C ₆ C substituted with naphthenic ₁ -C ₄ alkyl acyl phenoxy _group; C 1 -C ₃ alkylidene _group; C 1 _{-C 12} alkylthio _{group; R 2 C (O) C} 1 substituted by O -C ₄ alkylthio groups and _C 1 -C ₄ alkyl group benzenethio group; C ₁ -C ₈ alkyl acyl benzene thio group; aryl acyl benzene thio group; a heteroaryl acyl benzene thio group; C ₅ A -C ₆ naphthenic acyl benzene thio group, or a _C 5 -C ₆ naphthenic _C 1 -C ₄ alkyl acyl benzene thio group substituted by, _{or, R 4, R 5, R} 6, R 7, R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ are each independently an epoxypropyl group, where the epoxy group is optionally a C ₁ -C ₄ alkyl group aldehyde, ketone Condensed with
X ₁ is O, S or NR ₁₈ and
X ₂ is O, S, NR ₁₉ ,
Y ₁ is O, S, CR ₁₅ R ₁₆ and
The definition of other substituents is the same as that of claim 1. ) A compound of the general formula I according to claim 2,
In the compound represented by the general formula II,
R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , 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 a C ₁ -C ₁₂ alkyl group substituted with one or more C ₃ -C ₇ naphthene groups, a phenyl group, OR ₂₀ , SR ₂₁ , NR ₂₂ R _23. Because
R ₂ and R ₃ are each independently a methyl group, an ethyl group, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 2,4,6-trimethylphenyl group, or 2,6-dimethoxybenzene. ,
The definition of the other groups is the same as in claim 2. A compound of the general formula I according to 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 and
R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ are each independently 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 benzyloxy group; a C 1 -C ₄ alkylbenzene thio _{group,; 1} -C ₄ alkylthio _group; C 1 -C ₄ alkylphenoxy group
The other substituents are the same as defined in claim 2. A compound represented by the general formula I according to claim 4,
Y ₁ is CH ₂ or CHCH ₃ and
n = 0,
R ₁ is a C _{1 to} C ₁₂ alkyl group, optionally a C _{3 to} C ₇ naphthene group, a phenyl group, a C _{1 to} C ₁₂ alkyl group substituted with OR ₂₀ , SR ₂₁ , NR ₂₂ R ₂₃ , ,
R ₂ and R ₃ are each independently methyl, ethyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 2,4,6-trimethylphenyl group or 2,6-dimethoxybenzene group. And
R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ are each independently a hydrogen atom, a C ₁ -C ₄ alkoxyl group,
R ₁₉ is a C ₁ -C ₁₂ alkyl group; a C ₃ -C ₇ naphthene group, a C ₁ -C ₃ alkyl group substituted with a phenyl group,
The definition of other groups is the same as that of Claim 4. A compound of general formula I according to claim 1,
The specific structures are the following (IIA1), (IIA2), (IIA3), (IIA4), (IIA5), (IIA6), (IIB1), (IIC1), (IIIA1) (IIIA2), (IIIA3), And (IIIB1).

(IIA1)

(IIA2)

(IIA3)

(IIA4)

(IIA5)

(IIA6)

(IIB1)

(IIC1)

(IIIA1)

(IIIA2)

(IIIA3)

(IIIB1) The manufacturing method of the compound represented by the general formula I of Claim 1 including the following processes.
(1) First step: selective oximation is carried out at the methylene group at the ortho position of the cyclopentanone carbonyl group in the IV compound, and the method involves the conversion of the IV compound and the alkyl nitrite ester into an oxime in an acidic solution. And the corresponding intermediate V is obtained.

(IV)

(V)
(2) Second step: The intermediate V compound is continuously subjected to the second oximation, and the method A causes the V compound and the nitrite alkyl group ester to undergo an oximation reaction in an acidic solution. In which the corresponding intermediate VI compound is subjected to an oximation reaction of the carbonyl group in the side chain R ₁ CH ₂ CO with a hydroxylamine solution to obtain the corresponding intermediate VII compound. obtain.

(VI)

(VII)
(3) Third step: The oximation intermediate VI or VII of the second step is esterified with any of the following acylating agents (1) to (4) or an equivalent acylating agent thereof. The corresponding compound of general formula I is obtained.

(1)

(2)

(3)

(4)
In addition, the definition of the group in the said structural formula is the same as the definition of the corresponding group in Claim 1. An asymmetric diketone compound represented by the general formula IV.

(IV)
(Here, the definitions of Ar ₁ , Ar ₂ , X ₁ , Y ₁ , R ₁ groups are the same as the corresponding groups in claim 1). A ketoxime compound represented by the general formula V:

(V)
(Here, the definition of Ar ₁ , Ar ₂ , X ₁ , Y ₁ , R ₁ group is the same as the definition of the corresponding group in claim 8). A diketoxime compound represented by the general formula VI or VII.

(VI)

(VII)
(Wherein the definitions of Ar ₁ , Ar ₂ , X ₁ , Y ₁ , R ₁ groups are the same as the corresponding groups in claim 9).   A photoinitiator and a carbon-carbon double bond compound capable of performing at least one free radical polymerization, wherein the photoinitiator is represented by the general formula I according to claim 1. A photocurable composition containing the compound to be prepared. The photocurable composition according to claim 11,
A photocuring composition further containing an additive. The photocurable composition according to claim 12, wherein
Calculated in parts by weight, the photoinitiator accounts for 0.05-25% of the total composition, and the photocuring where the carbon-carbon double bond compound and the additive occupy the remaining part of the composition. Composition. The photocurable composition according to claim 11 or 12,
The carbon-carbon double bond compound is a photocuring composition selected from an acrylate compound and a methacrylate compound. The photocurable composition according to claim 12, wherein
The photocurable composition in which the additive contains a developable resin and a pigment or dye. Colored or transparent paints, inks, adhesives, photosensitive resist, or photo registry utilizing photocurable composition according to claim 11 or 12 in the manufacture of, application method of the photocurable composition.   A method for curing a photocurable composition comprising applying the photocurable composition according to claim 11 or 12 to a base and irradiating a light beam having a wavelength of 190 to 600 nm to cure the coating layer. A method for curing a photocurable composition according to claim 17,
A curing method wherein the light is from the sun, mercury lamp, high pressure mercury lamp or LED lamp.   First, the photocuring composition according to claim 11 or 12 is diluted with a solvent, and then the diluted photocuring composition is applied to a base, followed by roasting, exposure, and development methods. A method of producing a projection pattern with a photocurable composition that removes an exposed portion to obtain a projection pattern.   Black, red, green, and blue pixels are included, and at least one kind of the compound represented by the general formula I according to claim 1 or 6, a photocurable monomer, an alkali-soluble resin, a pigment, and an additive, A color filter obtained by sequentially coating, exposing, developing, and heat-treating a composition comprising   A method for producing a color filter comprising black, red, green, and blue pixels, comprising at least one compound represented by formula I according to claim 1 or 6, a photocurable monomer, and an alkali-soluble resin And a composition containing a pigment and an additive, in order, coating, exposing, developing and heat-treating, and finally obtaining the color filter. Printing a color or transparent paint, ink, adhesive, photosensitive resist, or photoresist produced using the photocurable composition according to claim 11 or 12, printing, 3D printing, production of a display color filter A method for applying a photocurable composition, used for packaging electronic devices or forming printed circuit board media layers.