JP6999039B2 - Fluorine-containing fluorene oxime ester-based photoinitiator, photo-curing composition containing it, and its application - Google Patents

Description

The present invention relates to the field of organic synthesis, and more particularly to a fluorine-containing fluorene oxime ester-based photoinitiator, a photocurable composition containing the same, and its application.

Compared to traditional CRT monitors, LCD displays have the advantages of lower energy consumption, smaller volume, and radiation-free, but have smaller viewing angles, image delay, poor brightness, and poor contrast. ing. In recent years, as people's living standards have improved, people have been demanding higher demands for liquid crystal displays, and demands for large size, high brightness, high contrast and wide viewing angle have been submitted. Therefore, higher demands are placed on the materials used in the manufacture of liquid crystal displays.

Color resists, black resists and photospacers are important components of liquid crystal panel displays and are essential materials for achieving large size and high resolution in next-generation panel displays, and are highly sensitive oximes. Ester initiators are an important component of resist and photospacer compounding formulations, and research into high-sensitivity initiators has been very active in recent years, but the surface drying properties of photoinitiators disclosed so far have been very active. The problem of poor migration and easy migration has not yet been effectively solved, and it will affect the application performance of the material to some extent.

In the present invention, in order to solve the problem that the surface drying property of the conventional oxime ester-based photoinitiator is poor and migration is easy, a fluorine-containing fluorene oxime-based photoinitiator, a photocuring composition containing the same, and its application thereof. The main purpose is to provide.

In order to achieve the above object, the present invention provides a fluorine-containing fluorene oxime ester-based photoinitiator, and the photoinitiator has a structure represented by the general formula (I) or (II):

Here, in the general formula (I), n represents an integer of 1 to 4; m represents an integer of 1 to 4.

_Each of the n R1s is independently -G- (M') _q , hydrogen, nitro group, halogen, or

Selected from, m'indicates an integer of ₁ to 4; where G is selected from a heteroatom or carbonyl group, the heteroatom is O, N or S, and M'is C1 to. C ₂₀ linear or branched alkyl groups, C ₃ to C ₈ cycloalkyl groups, C ₁ to C ₁₀ alkyl groups substituted with C ₃ to C ₈ cycloalkyl groups, C ₆ to C ₂₀ Aryl group, C ₁ to C ₁₀ alkyl group, nitro group substituted C ₆ to C ₂₀ aryl group, cyano group substituted C ₆ to C ₂₀ aryl group, C ₄ to C ₂₀ heteroaryl group, Selected from C ₆ to C ₂₀ heteroaryl groups substituted with nitro groups or C ₆ to C ₂₀ heteroaryl groups substituted with cyano groups, one or more carbon atoms in M'are substituted with heteroatoms. May be good. q is 1 or 2.

R ₂ and R _2'are independently selected from the polymerizable groups.
Z and Z'are independently absent or indicate a carbonyl group.

The m _R3 and _m'R5 are independently fluorine, a linear or branched alkyl group substituted with one or more fluorines, and a direct substituted with one or more fluorines. It is selected from chain or branched chain alkoxy groups.

R ₄ and R ₆ are independently substituted with C ₁ to C ₂₀ linear or branched alkyl groups, C ₃ to C ₂₀ cycloalkyl groups, and C ₃ to C ₈ cycloalkyl groups, respectively. Alkyl groups ₁ to C ₁₀ , cycloalkyl groups C ₃ to C ₈ substituted with alkyl groups C ₁ to C ₁₀ , aryl groups C ₆ to C ₂₀ , heteroaryl groups C ₄ to C ₂₀ or C. It is selected from ₂ to _C20 alkenyl groups.

In the general formula (II), R ₁ and R _{1'independently} represent fluorine-containing groups.
R ₂ and R ₃ are independently C ₁ to C ₂₀ linear or branched alkyl groups, C ₃ to C ₁₂ cycloalkyl groups, C ₄ to C ₁₈ cycloalkyl alkyl groups, and C ₆ to C 18. C ₂₀ aryl groups, C ₇ to C ₂₄ aryl alkyl groups, substituted or unsubstituted C ₄ to C ₂₀ heteroaryl groups, or R ₂ and R ₃ linked together to C ₃ to C ₁₀ Cycloalkyl group is formed.

_R4 represents a hydroxyl group, an N-morpholinyl group, an N-piperidinyl group, an N-piperazinyl group, an N-pyrrolill group or an N-secondary amino group.

A represents a hydrogen, a nitro group, -CO-CR ₂ R ₃ R ₄ groups, or -R _5- (R ₆ ) _n , where R ₅ represents an O, S, N or carbonyl group. R ₆ is a linear or branched alkyl group of C ₁ to C ₂₀ , a cycloalkyl group of C ₃ to C ₁₂ , a cycloalkyl alkyl group of C ₄ to C ₁₈ , and substituted or unsubstituted C ₆ to C ₂₀ . Aryl groups of C7 to _C24 , unsaturated heterocyclic groups of ₅ -membered or 6-membered rings, substituted or unsubstituted _C4 to _C20 heteroaryl groups, where n is 1 or 2 is shown.

If the technical content of the present invention is applied, the fluorine-containing fluorene oxime ester-based photoinitiator represented by the general formula (I) or (II) provided by the present application can be introduced by introducing a fluorine-containing group into the photoinitiator. Will have the advantage of high initiation efficiency. Further, due to the structural peculiarity, the photoinitiator has advantages such as better surface drying characteristics, better surface hardening effect, and less migration. Based on this, the photoinitiator has advantages such as high initiation efficiency, good surface drying characteristics, good surface hardening effect, and difficulty in migration, and is expected to be widely applied.

Embodiments of the Invention If there is no contradiction, the embodiments and the features in the embodiments of the present application can be combined with each other. Hereinafter, the present invention will be described in detail together with embodiments.

As shown in the background art, conventional oxime ester-based photoinitiators have problems of poor surface drying properties and easy migration. In order to solve the above technical problems, the present invention provides a fluorine-containing fluorene oxime ester-based photoinitiator, and the photoinitiator has a structure represented by the general formula (I) or (II).

Here, n represents an integer of 1 to 4. m represents an integer of 1 to 4.
_Each of the n R1s is independently -G- (M') _q , hydrogen, nitro group, halogen, or

Selected from, m'indicates an integer from 1 to 4. Here, G includes, but is not limited to, a heteroatom or a carbonyl group. The hetero atom is O, N or S, where M'is a linear or branched alkyl group of C ₁ to C ₂₀ , a cycloalkyl group of C ₃ to C ₈ , and a cycloalkyl group of C ₃ to C ₈ . C ₁ to C ₁₀ alkyl groups substituted with, C ₆ to C ₂₀ aryl groups, C ₁ to C ₁₀ alkyl groups, nitro group substituted C ₆ to C ₂₀ aryl groups, substituted with cyano groups Includes C ₆ to C ₂₀ aryl groups, C ₄ to C ₂₀ heteroaryl groups, C ₆ to C ₂₀ heteroaryl groups substituted with nitro groups or C ₆ to C ₂₀ heteroaryl groups substituted with cyano groups. Is not limited to these. One or more carbon atoms in M'may be substituted with heteroatoms, where q is 1 or 2.

R ₂ and R _2'are independently selected from the polymerizable groups. Z and Z'are independently absent or indicate a carbonyl group. The m _R3 and _m'R5 are independently fluorine, a linear or branched alkyl group substituted with one or more fluorines, and a direct substituted with one or more fluorines. It is selected from chain or branched chain alkoxy groups. R ₄ and R ₆ are independently substituted with C ₁ to C ₂₀ linear or branched alkyl groups, C ₃ to C ₂₀ cycloalkyl groups, and C ₃ to C ₈ cycloalkyl groups, respectively. Alkyl groups ₁ to C ₁₀ , cycloalkyl groups C ₃ to C ₈ substituted with alkyl groups C ₁ to C ₁₀ , aryl groups C ₆ to C ₂₀ , heteroaryl groups C ₄ to C ₂₀ or C. It is selected from ₂ to _C20 alkenyl groups.

In the general formula (II), R ₁ and R _{1'independently} represent a fluorine ^- containing group.
R ₂ and R ₃ are independently C ₁ to C ₂₀ linear or branched alkyl groups, C ₃ to C ₁₂ cycloalkyl groups, C ₄ to C ₁₈ cycloalkyl alkyl groups, and C ₆ to C 18. C ₂₀ aryl groups, C ₇ to C ₂₄ aryl alkyl groups, substituted or unsubstituted C ₄ to C ₂₀ heteroaryl groups, or R ₂ and R ₃ linked together to C ₃ to C ₁₀ Cycloalkyl group is formed.

_R4 represents a hydroxyl group, an N-morpholinyl group, an N-piperidinyl group, an N-piperazinyl group, an N-pyrrolill group or an N-secondary amino group.

A represents a hydrogen, a nitro group, -CO-CR ₂ R ₃ R ₄ groups, or -R _5- (R ₆ ) _n , where R ₅ represents an O, S, N or carbonyl group. R ₆ is a linear or branched alkyl group of C ₁ to C ₂₀ , a cycloalkyl group of C ₃ to C ₁₂ , a cycloalkyl alkyl group of C ₄ to C ₁₈ , and substituted or unsubstituted C ₆ to C ₂₀ . Aryl groups of C7 to _C24 , unsaturated heterocyclic groups of ₅ -membered or 6-membered rings, substituted or unsubstituted _C4 to _C20 heteroaryl groups, where n is 1 or 2 is shown.

In the fluorine-containing fluorene oxime ester-based photoinitiator represented by the general formula (I) or (II) provided by the present application, by introducing a fluorine-containing group, the photoinitiator has an advantage of high initiation efficiency. become. Further, due to the structural peculiarity, the photoinitiator has advantages such as better surface drying characteristics, better surface hardening effect, and less migration. Based on this, the photoinitiator has advantages such as high initiation efficiency, good surface drying characteristics, good surface hardening effect, and difficulty in migration, and is expected to be widely applied.

Further, in the photoinitiator represented by the general formula (I), by further introducing a polymerizable group at the 9-position of the fluorene structure, the photoinitiator represented by the general formula (I) can be polymerized with the substrate. Therefore, it is advantageous for further improving the migration difficulty of the photoinitiator.

In order to further improve the structural stability of the fluorine-containing fluorene oxime ester-based photoinitiator, preferably, in the general formula (I), M'is a linear or branched alkyl group of C ₁ to C ₁₀ . , C ₃ to C ₆ cycloalkyl groups, C ₁ to C ₅ alkyl groups substituted with C ₃ to C ₆ cycloalkyl groups, C ₆ to C ₁₀ aryl groups, C ₁ to C ₅ alkyl groups. , C ₆ to C ₁₀ aryl groups substituted with nitro groups, C ₆ to C ₁₀ aryl groups substituted with cyano groups, C ₄ to C ₁₀ heteroaryl groups, C ₆ to substituted with nitro groups. Includes, but is not limited to, C ₁₀ heteroaryl groups or C ₆ to C ₁₀ heteroaryl groups substituted with cyano groups.

In order to further reduce the migration property of the fluorine-containing fluorene oxime ester-based photoinitiator, preferably, in the general formula (I), R ₂ and R _{2'independently} have a double bond or an epoxy group. It is selected from the polymerizable groups that it has.

_In one preferred embodiment, in general formula (I), R ₂ and R _2'are independently selected from the alkenyl groups _C2 to C12, respectively. One or more -CH _2- in R ₂ and R _2'are independent of each other.

May be replaced with.
Preferably, in the general formula (I), R ₂ and R _2'are independently selected from the alkenyl groups of C ₃ to C ₈ . One or more -CH _2- in R ₂ are independent of each other.

May be replaced with.
In one preferred embodiment, in general formula (I), R ₂ and R _2'are independently substituted with an oxylanyl group substituted alkyl group of C ₁ to C ₁₀ or an epoxypropyl group. The alkyl groups ₁ to C ₁₀ are shown. One or more -CH _2- in the alkyl groups C ₁ to C ₁₀ in R ₂ and R _2'are independent of each other.

May be replaced with.
In one preferred embodiment, in general formula (I), R ₂ and R _2'are independently selected from the alkyl groups C ₁ to C ₈ in which the oxylanyl group or cyclopropyl group is the blocking group, respectively, and R ₂ And one or more -CH _2- in the alkyl groups of C ₁ to C ₈ in R _2'are independent of each other.

H in the oxylanyl group or the epoxypropyl group may be substituted with _an alkyl group of C1 to _C4 .

Preferably, in the general formula ₍ I), m R3 and _m'R5 are independent of each other.

Is selected from. If the group is selected and used as R ₃ and R ₅ , it is advantageous to further improve the initiation efficiency of the photoinitiator.

Preferably, in general formula (I), R ₄ and R ₆ are independently C ₁ to C ₆ linear or branched alkyl groups, C ₃ to C ₁₀ cycloalkyl groups, C ₃ to C, respectively. Select from C ₁ to C ₈ alkyl groups substituted with ₆ cycloalkyl groups, C ₃ to C ₆ cycloalkyl groups substituted with C ₁ to C ₈ alkyl groups, or C ₆ to C ₁₂ aryl groups. Is done.

More preferably, in the general formula (I), R ₄ and R ₆ are independently phenyl groups, linear or branched alkyl groups C ₁ to C ₄ , and cycloalkyl groups C ₃ to C ₈ , respectively. Alternatively, it is selected from C ₁ to C ₄ alkyl groups substituted with C ₃ to C ₆ cycloalkyl groups.

More preferably, the fluorine-containing fluorene oxime ester-based photoinitiator represented by the general formula (I) is one or more selected from the group consisting of the following.

According to another aspect of the present invention, the present invention further provides a method for producing a fluorine-containing fluorene oxime ester-based photoinitiator represented by the general formula (I), which comprises the following steps.

(1) Preparation of Intermediate a Friedel-Crafts acylation reaction between raw material a and raw material b in an organic solvent is carried out by the catalytic action of aluminum trichloride or zinc chloride to obtain intermediate a. The synthetic route is as follows.

A is absent or is a methylene group.
(2) Preparation of Intermediate b When the intermediate a undergoes an oxime-forming reaction under the action of ammonium hydroxylam chloride and sodium phosphate, A is absent and the intermediate b is obtained. The synthetic route is as follows.

When the intermediate a and the nitrite ester or nitrite undergo an oxime formation reaction at room temperature in the presence of concentrated hydrochloric acid, A is a methylene group and the intermediate b is obtained. The synthetic route is as follows.

(3) Production of product With intermediate b

Esterify with and to obtain the desired product. The synthetic route is as follows.

Z is absent or is a carbon group.
The raw materials used during the synthesis are all known compounds and can be conveniently produced by commercially available or known synthetic methods, of which the raw material a is the synthesis disclosed in Chinese Patent Application No. 201710274018.4. Can be obtained by law. The synthetic process, in turn, includes a Friedel-Crafts acylation reaction, an oximeization reaction and an esterification reaction, all of which are common reaction types in the field of organic chemical synthesis. After clarifying the flow of the reaction, the specific reaction conditions can be easily determined by those skilled in the art.

The reaction temperature in the step (1) is usually −10 to 30 ° C. The type of organic solvent used is not particularly limited as long as it can dissolve the raw material and does not adversely affect the reaction, and is preferably among the group consisting of dichloromethane, dichloroethane, benzene, toluene and xylene. One or more species.

In the step (2), the intermediate b is produced in a solvent system, and the type of solvent used is not particularly limited as long as it can dissolve the raw material and does not adversely affect the reaction. In the absence of Z, the solvent used may be a mixed solvent of alcohol and water, preferably a mixed solvent of ethanol and water; the reaction is under heated reflux. It is done in. When Z is a carbonyl group, the solvent used includes, but is not limited to, one or more of the group consisting of dichloromethane, benzene, toluene and tetrahydrofuran, and the nitrite ester is an ethyl nitrite ester. Includes, but is not limited to, one or more of the group consisting of isoamyl nitrite and isooctyl nitrite, nitrites include, but are not limited to, sodium nitrite and / or potassium nitrite.

In the step (3), the esterification reaction is carried out in an organic solvent, and the type of the solvent is not particularly limited as long as it can dissolve the raw materials and does not adversely affect the reaction, preferably dichloromethane. , Dichloroethane, benzene, toluene and xylene.

In another preferred embodiment, in the fluorine-containing fluorene photoinitiator represented by the general formula (II), R ₁ and R _1'are independently of a linear or branched chain of _C2 to _C10 , respectively. It indicates a fluorine-containing alkyl group, optionally (optionally), of which -CH _2- may be substituted with -O- or a phenylene group, and H on the phenylene group is optionally C ₁ to C ₄ It may be substituted with an alkyl group of. More preferably, R ₁ and R _1'are independently C ₃ to C ₈ having -CF ₃ , -CF ₂ CF ₃ , -CF ₂ -CH ₂ F or -CF ₂ -CHF ₂ as terminal groups, respectively. Represents a linear or branched fluorine-containing alkyl group of, optionally in which _-CH2- may be substituted with an -O- or a 1,4-phenylene group and a 1,4-phenylene group. The above H may be optionally substituted with an alkyl group of C ₁ to C ₄ .

Preferably, in general formula ₍ II), R ₂ and R ₃ are independently C1 to C8 _linear or branched alkyl groups, _C4 to _C12 cycloalkylalkyl groups, _C7 to C7, respectively. It represents an arylalkyl group of _{C14 ,} or _R2 and R3 _are linked together to form a cycloalkyl of C3 to _C8 . More preferably, R ₂ and R ₃ are independently C1 _{- C4 linear} or branched alkyl groups, _C4 to C10 cycloalkylalkyl groups, and _C7 to _C10 phenylalkyl groups, respectively. Or R ₂ and R ₃ are linked to each other to form a cycloalkyl of C ₃ to C ₈ .

Preferably, in general formula (II), R ₄ represents a hydroxyl group, an N-morpholinyl group, an N-piperidinyl group, or an amino group in which _two hydrogens are substituted with C1 to _C4 alkyl groups.

Preferably, in the general formula (II), A represents a hydrogen, a nitro group, -CO-CR ₂ R ₃ R ₄ groups, or -R _5- (R ₆ ) _n , where R ₅ is O. , S, N or carbonyl group, where R ₆ is a linear or branched alkyl group of C ₁ to C ₈ ; aryl group of C ₆ to C ₁₂ ; C ₁ to C ₅ alkyl group, nitro group or cyano group. An aryl group of C ₆ to C ₁₂ substituted with a group; or an unsaturated heterocyclic group having a 5-membered ring, where n represents 1 or 2. More preferably, R ₆ is a linear or branched alkyl group of C ₁ to C ₄ , a furanyl group, a pyrrolyl group, a thienyl group, an aryl group of C ₆ to C ₁₀ ; or a C ₁ to C ₄ alkyl group, The aryl groups of C ₆ to C ₁₀ substituted with a nitro group or a cyano group are shown.

Although not limited, the fluorine-containing fluorene photoinitiator represented by the general formula (II) is selected from the following structures.

Accordingly, the present invention relates to a method for producing a fluorine-containing fluorene photoinitiator represented by the general formula (II), wherein the raw material a and the raw material b are reacted under the action of a catalyst, and the reaction formula is , Shown below.

Here, M represents H or OH.
When M indicates H, R ₀ is i.e. R ₁ and R _0'is i.e. R ₁ '.
When M indicates OH, R ₀ and R _0'correspond to R ₁ and R ₁ ', respectively, and R ₁ indicates OR ₀ and R _1'indicates OR ₀ '.
X indicates Cl or Br.

The raw materials and reagents used in the above-mentioned production method are all known compounds in the prior art or can be conveniently produced by a known process, of which the raw material a is Application No. 2015109373328.0, 20171888234. X, 2017105303540., 2017108355527. It can be manufactured by the synthetic method described in the Chinese invention patent application such as X.

The reaction is carried out in an organic solvent, and the type of the solvent is not particularly limited as long as it can dissolve the raw material and does not adversely affect the reaction, and is preferably a polar solvent, particularly DMF. The catalyst is an alkaline catalyst, preferably at least one of lithium tert-butoxide, sodium tert-butoxide and potassium tert-butoxide. The reaction temperature is 10 to 50 ° C. The reaction time varies slightly depending on the type of raw material, but is usually 1 to 6 hours.

According to yet another aspect of the invention, the invention further provides a photoinitiator, wherein the photoinitiator comprises a photoinitiator, wherein the photoinitiator is the general formula (I). And / or contains a fluorine-containing fluorene oxime ester-based photoinitiator represented by the general formula (II).

In the fluorine-containing fluorene oxime ester-based photoinitiator represented by the general formula (I) or (II) provided by the present application, by introducing a fluorine-containing group, the photoinitiator has an advantage of high initiation efficiency. become. Further, due to the structural peculiarity, the photoinitiator has advantages such as better surface drying property, better surface hardening effect, and less migration. Based on this, the photoinitiator has advantages such as difficulty in migration, high initiation efficiency, good surface drying property, and good surface hardening effect, and is expected to be widely applied.

According to yet another aspect of the present invention, the present invention further provides application of the fluorine-containing fluorene oxime ester-based photoinitiator represented by the general formula (I) or (II) to the photocuring field. ..

In the fluorine-containing fluorene oxime ester-based photoinitiator represented by the general formula (I) or (II) provided by the present application, by introducing a fluorine-containing group, the photoinitiator has an advantage of high initiation efficiency. become. Further, due to the structural peculiarity, the photoinitiator has advantages such as good surface drying property, good surface hardening effect, and difficulty in migration. Based on this, the photoinitiator has advantages such as difficulty in migration, high initiation efficiency, good surface drying property, and good surface hardening effect, and is expected to be widely applied.

The present invention further relates to the application of the fluorine-containing fluorene photoinitiator to the photocuring field. Although not limiting, the photoinitiator can be applied in color resists (RGB), black matrices (BM), photospacers (photo-scapers), ribs, dry films, semiconductor photoresists and inks. The photoinitiator has high initiation efficiency and can provide excellent surface drying properties and weather resistance.

Examples The present invention will be described in more detail below together with specific examples, but should not be understood as a limitation on the scope of protection of the present invention.

Examples of production of the fluorine-containing fluorene oxime ester-based photoinitiator represented by the general formula (I) are shown below.

Example 1
(1) Synthesis of Intermediate 1a 66.1 g of Intermediate 1a, 27.0 g of aluminum trichloride, and 100 mL of dichloromethane are added to a 500 mL four-necked flask, and the four-necked flask is filled with an ice water bath. The temperature of the raw material was lowered to 0 ° C. Then, while stirring, a mixed solution of 57.0 g of the raw material 1b and 50 mL of dichloromethane was dropped into the raw material, and at the same time, the temperature of the reaction system was controlled to 10 ° C. or lower, and the dropping was completed over 2 hours. After completion of the dropping, stirring was continued for 2 hours, and tracking was performed by liquid phase chromatography until the reaction was completed. Subsequently, the reaction system was slowly poured into dilute hydrochloric acid containing 400 g of ice water and 50 mL of concentrated hydrochloric acid (37%), stirred while adding, and then poured into a separating funnel to form a lower dichloromethane layer. Was separated and the aqueous layer was subsequently washed with 50 mL dichloromethane and combined with the dichloromethane layer. The dichloromethane layer was washed with 5 wt% aqueous sodium hydrogen carbonate solution (150 mL each, 3 times in total), then the dichloromethane layer was washed with water until the pH became neutral, and the dichloromethane layer was washed with 80 g of anhydrous magnesium sulfate. After drying, the product's dichloromethane solution was rotary-evaporated, recrystallized using methanol as a solvent, and then dried in an oven at 80 ° C. for 2 hours to obtain 97.2 g of intermediate 1a with a yield of 84 wt%. Yes, the purity was 98 wt%. The synthetic route is as follows.

Intermediate 1a is confirmed by proton nuclear magnetic resonance spectra and mass spectrometry.
^{1 1} H-NMR (CDCl ₃ , 500 MHz): 1.2885-1.307 (8H, m) 1.8564-1.9975 (8H, m) 2.3506 (3H, s), 3.8098 ( 2H, s), 4.9657-5.0342 (4H, m), 5.6786-5.7153 (2H, t), 6.1976 (1H, s), 6.4672-6.8400 (3H, 3H,) m), 7.2813-7. 9503 (7H, m).

MS (m / z): 579 (M + 1) ⁺ .
(2) Synthesis of Intermediate 1b 57.9 g of Intermediate 1a, 7.0 g of hydroxylammonium chloride, 8.2 g of sodium phosphate, 100 mL of ethanol, and 50 mL of water were placed in a 500 mL four-necked flask and heated at 85 ° C. After stirring for 5 hours while refluxing, turn off the reaction, pour the contents into a 1000 mL large beaker, add 500 mL of water and stir, extract with 100 mL dichloromethane and add 30 g anhydrous ו ₄ to the extract. Dry, suction filter, rotate and evaporate the filtrate under reduced pressure to remove the solvent, obtain an oily viscous in a rotating bottle, pour the viscous into 100 mL petroleum ether and stir. The solid was obtained by suction filtration to obtain a white powdery solid, which was baked at 70 ° C. for 5 hours to obtain 43.7 g of the intermediate 1b, the yield was 72 wt%, the purity was 98 wt%, and MS (m). / Z): 608 (M + 1) ⁺ . The synthetic route is shown below.

(3) Synthesis of compound 1 30.4 g of intermediate 1b and 100 mL of dichloromethane are added to a 250 mL four-necked flask, and the mixture is stirred at room temperature for 5 min, and then 5 g of propionyl chloride is added dropwise over about 30 min. After the dropping is completed, stirring is continued for 2 hours, then a 5% NaHCO ₃ aqueous solution is added to adjust the pH value to be neutral, the organic layer is separated with a liquid separation funnel, and the mixture is further twice with 100 mL of water. Washed, dried in 20 g anhydrous dichloromethane ₄ , filtered, rotated and evaporated to remove solvent, viscous liquid obtained, recrystallized from methanol to obtain white solid powder, filtered and compound 1 total. 27.2 g was obtained, the yield was 82%, and the purity was 99%. The synthetic route is as follows.

The structure of compound 1 is confirmed by proton nuclear magnetic resonance spectra and mass spectrometry.
^{1 1} H-NMR (CDCl ₃ , 500 MHz): 0.9869-1.0045 (3H, t), 1.285-1.3347 (8H, m), 1.8678-1.9668 (8H, m), 2.2678-2.3567 (5H, m), 4.9678-5.0546 (4H, m), 5.6695-5.7206 (2H, m), 6.1996 (1H, s), 6. 7846-8. 0331 (10H, m).

MS (m / z): 664 (M + 1) ⁺ .
Example 2
(1) Synthesis of Intermediate 2a 72.5 g of Intermediate 2a, 27.0 g of aluminum trichloride and 100 mL of dichloromethane are charged in a 500 mL four-necked flask, and the temperature of the raw material in the four-necked flask is set using an ice water bath. Was cooled to 0 ° C. Then, while stirring, a mixed solution of 54.5 g of the raw material 2b and 50 mL of dichloromethane was added dropwise, and at the same time, the temperature of the reaction system was controlled to 10 ° C. or lower, and the addition was completed over 2 hours. After completion of the dropping, stirring was continued for 2 hours, and tracking was performed by liquid phase chromatography until the reaction was completed. Subsequently, the reaction system is slowly poured into dilute hydrochloric acid containing 400 g of ice water and 50 mL of concentrated hydrochloric acid (37%), stirred while adding, and then poured into a liquid separation funnel to pour it into the lower dichloromethane. The layers were separated, and the water layer was subsequently washed with 50 mL of dichloromethane, combined with the dichloromethane layer, and the dichloromethane layer was washed with 5 wt% aqueous sodium hydrogen carbonate solution (150 mL each, 3 times in total), followed by. The dichloromethane layer is washed with water until the pH becomes neutral, the dichloromethane layer is dried with 80 g of anhydrous magnesium sulfate, and after filtration, the dichloromethane solution of the product is rotationally evaporated to recrystallize using methanol as a solvent, and then recrystallized. It was dried in an oven at 80 ° C. for 2 hours to obtain 101.8 g of intermediate 2a, which had a yield of 85 wt% and a purity of 98 wt%. The synthetic route is as follows.

Intermediate 2a is confirmed by proton nuclear magnetic resonance spectra and mass spectrometry.
^{1 1} H-NMR (CDCl ₃ , 500 MHz): 2.1489-2.673 (4H, t), 2.3507 (3H, s), 4.143-4.1554 (4H, t), 5.7986- 6.0521 (4H, m), 6.4207-6.4332 (2H, d), 7.1105-7. 8023 (10H, m).

MS (m / z): 599 (M + 1) ⁺ .
(2) Synthesis of Intermediate 2b To a 250 mL four-necked flask, add 59.8 g of Intermediate 2a, 37 wt% hydrochloric acid 10.0 g, nitrite isoamyl ester 11.8 g, and 100 mL tetrahydrofuran, and stir at room temperature for 5 hours. And turned off the reaction. The contents are poured into a large 1000 mL beaker, 500 mL of water is added and stirred, extracted with 100 mL of dichloromethane, 30 g of anhydrous _regsvr4 is added to the extract, dried, suction filtered and the filtrate is depressurized. Rotate underneath to remove solvent and obtain an oily viscous in a rotating bottle, pour the viscous into 100 mL petroleum ether, stir and precipitate, suction filter and white powder solid. The mixture was baked at 70 ° C. for 5 hours to obtain 44.8 g of the intermediate 2b, the yield was 75%, the purity was 98%, and MS (m / z): 614 (M + 1) ⁺ . The synthetic route is as follows.

(3) Synthesis of compound 2 30.7 g of intermediate 2b and 100 mL of dichloromethane are added to a 250 mL four-necked flask, and the mixture is stirred at room temperature for 5 min, and then 6.5 g of propionic anhydride is added dropwise to about 30 min. The dropping is completed, and the mixture is continuously stirred for 2 hours. Then, a 5% aqueous solution of NaHCO ₃ is added to adjust the pH value to be neutral, the organic layer is separated by a liquid separation funnel, and 200 mL of water is used. Washed twice with, dried with 50 g of anhydrous _regsvr4 , filtered and then rotated to remove solvent to give a viscous liquid, recrystallized with methanol to give a white solid powder, filtered and filtered to product. 28.5 g was obtained, the yield was 85%, and the purity was 99%.

The synthetic route is as follows:

The structure of compound 2 is confirmed by proton nuclear magnetic resonance spectra and mass spectrometry.
^{1 1} H-NMR (CDCl ₃ , 500 MHz): 1.0004-1.1049 (3H, t), 2.1497-2.2732 (6H, m), 4.1003-4.1666 (4H, t), 5.8006-6.1056 (4H, m), 6.4275-6.4365 (2H, d), 7.2809-8. 0603 (7H, m).

MS (m / z): 670 (M + 1) ⁺ .
Example 3
With reference to the methods of Examples 1 and 2, compounds 3 to 13 having the structures shown in Table 1 are prepared from the corresponding raw materials.

Performance Evaluation of Photoinitiator By preparing a typical photocurable resin composition, the applicable performance of the photoinitiator represented by the formula (I) of the present invention, such as curing speed, migration property, and surface drying, is evaluated. The specific procedure is shown below.

(1) A photocurable resin composition (part by weight) having the following composition is prepared and shown in Table 2.

Here, in Table 2, A: 1,6-hexanediol diacrylate.
B: Acrylic acid ester copolymer [benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate (molar ratio 70/10/20) copolymer (Mv: 10000)].

C1: Compound 1, C2: Compound 2, C3: Compound 4, C4: Compound 7, C5: Compound 11, C6: Compound 12.

D1 is butanone (solvent).
(2) Curing rate.

The composition is stirred under a yellow light lamp, then collected, coated on a PET substrate by roll coating to form a film, and dried at 90 ° C. for 2 min to obtain a coating film having a dry film thickness of 2 μm. .. After that, the coating film is cooled to room temperature and irradiated with a high-pressure mercury lamp (exposure machine model number: RW-UV70201, exposure amount of 50 mJ / cm ² each time) to expose the coating film and cure the film. Let me.

The evaluation is made based on the number of times the coating film is passed through the belt-type exposure machine until the coating film is cured to form a cured film, and the larger the number of times the coating film is passed, the more unfavorable the curing speed is.

(3) Migration.
The cured film is cut into pieces and used as a sample. A 0.5 g cured membrane sample is weighed and placed in a 50 mL beaker, 4.5 mL of methanol is added and ultrasonically dissolved for 30 min. The resulting solution is transferred to a 10 mL volumetric flask, the sample is subsequently washed twice with methanol (2 mL x 2), poured into the volumetric flask, 0.1 mL of toluene is collected with a pipette and added as an internal standard, and methanol is used. To the specified amount of volume, shake until uniform, and let stand.

Japan Shimadzu LC-20A liquid chromatography (sim pack column, 150 × 6.0 nm, detector SPD-20A, detection limit 20 ppm, detection wavelength 254 nm) is adopted, and the flow rate is 1.0 mL / min at 25 ° C., fluid phase. (Volume ratio methanol / water = 90/10) is used to observe whether the presence of the photoinitiator can be detected. The percentage of the peak area ratio of liquid phase chromatography to toluene indicates that the higher the content of the initiator in the liquid phase, the greater the migration property.

(4) Surface dryness measurement Using the cotton ball blowing method (GB / T 1728-1979 (1989)), while lightly placing one 1 cm ² fluffy degreased cotton ball on the surface of the cured film, the cotton ball Blow a cotton pad lightly along the horizontal direction with your mouth at a distance of 15 cm from.

If the cotton ball can be blown off and no cotton fiber remains on the surface of the membrane, it is designated as A;
B if the cotton ball can be blown off but cotton fibers remain on the surface of the membrane;
C if the cotton ball cannot be blown off;
If the cotton balls can be blown off and no cotton fibers remain on the surface of the film, that is, the surface is dry, indicating that the surface drying property of the film is excellent.

The evaluation results are shown in Table 3.

As can be seen from the measurement results in Table 3, the polymerizable group-containing fluorene oxime ester-based photoinitiator represented by the general formula (I) of the present invention has excellent surface drying properties and an initiator efficiency in application to photocuring. High, fast cure, no migration, and clearly superior to traditional oxime ester-based photoinitiator products in terms of overall performance.

Examples of production of the fluorine-containing fluorene oxime ester-based photoinitiator represented by the general formula (II) are shown below.

Example 1
Synthesis of compound 1

36.8 g of raw material 1a, sodium tert-butoxide 10.6 g and DMF 50 mL are charged in a 250 mL four-necked flask, stirred at room temperature (about 25 ° C.), 26.6 g of raw material 1b is added dropwise, and about 1h is added. After the dropping was completed, stirring was continued for 3 hours, and tracking was performed by liquid phase chromatography until the reaction was completed. The contents are slowly poured into 200 g of water, extracted with dichloromethane (50 mL each time, 2 times in total), and the dichloromethane layer is washed with 5% aqueous sodium hydrogen carbonate solution (100 mL each time, 3 times in total). Subsequently, the dichloromethane layer was washed with water until the pH became neutral, the dichloromethane layer was dried with 80 g of anhydrous magnesium sulfate, filtered, and then the dichloromethane solution of the product was rotationally evaporated and recrystallized from methanol. It was opened at 70 ° C. and dried for 2 hours to obtain 41.9 g of compound 1, having a yield of 75% and a purity of 98%.

The structure of compound 1 is confirmed by proton nuclear magnetic resonance spectra and mass spectrometry.
^{1 1} H-NMR (CDCl ₃ , 500 MHz): 1.3662-1.3772 (6H, s), 1.80681-1.8925 (8H, m), 2.3675-2.4704 (7H, m), 3.6523-3.6744 (4H, t), 7.3027-8.1823 (6H, m).

MS (m / z): 560 (M + 1) ⁺ .
Example 2
Synthesis of compound 2

50.5 g of raw material 2a, potassium tert-butoxide and 50 mL of DMF are charged in a 250 mL four-necked flask, stirred at room temperature (about 25 ° C.), 27.3 g of raw material 2b is added dropwise, and about 1 h is added. After the dropping was completed, stirring was continued for 3 hours, and tracking was performed by liquid phase chromatography until the reaction was completed. The contents are slowly poured into 200 g of water, extracted with dichloromethane (50 mL each time, 2 times in total), and the dichloromethane layer is washed with 5% aqueous sodium hydrogen carbonate solution (100 mL each time, 3 times in total). Subsequently, the dichloromethane layer was washed with water until the pH became neutral, the dichloromethane layer was dried with 80 g of anhydrous magnesium sulfate, filtered, and then the dichloromethane solution of the product was rotationally evaporated and recrystallized from methanol to 70. It was dried for 2 hours at an open temperature of ° C. to obtain 51.4 g of compound 2, having a yield of 68% and a purity of 98%.

The structure of compound 1 is confirmed by proton nuclear magnetic resonance spectra and mass spectrometry.
^{1 1} H-NMR (CDCl ₃ , 500 MHz): 0.9556-0.9918 (3H, t), 1.5208-1.5476 (2H, m), 2.2675-2.2787 (6H, s), 2.7598-2.7604 (2H, s), 5.9989-6.0387 (2H, d), 7.1225-8.1783 (16H, m).

MS (m / z): 706 (M + 1) ⁺ .
Example 3-20
With reference to the method of Example 1, compounds having the structures shown in Table 4 are prepared from the corresponding raw materials.

Performance Evaluation A representative photocurable resin composition is prepared, and the essential application performance of the photoinitiator represented by the general formula (II) of the present invention is evaluated.

1. 1. Preparation of photo-curing resin composition The photo-curing resin composition is composed of the following components.

1,6-Hexanediol Diacrylate 20 parts by weight acrylic acid ester copolymer [benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate (molar ratio 70/10/20) copolymer, Mv = 10000]
57 parts by weight Photoinitiator 3 parts by weight Butanone (solvent) 20 parts by weight.

If each component is uniformly mixed, a photocurable resin composition for performance evaluation can be obtained. Here, the photoinitiator is a fluorine-containing fluorene photoinitiator represented by the general formula (II) of the present invention or a typical fluorene photoinitiator known in the prior art as a inverse proportion.

2. 2. Performance evaluation Performance evaluation for a photocurable resin composition includes curing speed, surface drying characteristics and weather resistance.

(1) Curing rate The photo-curing resin composition is stirred under a yellow light lamp, then collected, coated on a PET substrate by roll coating to form a film, and dried at 90 ° C. for 2 min to increase the thickness of the dried film. A coating film of 2 μm is obtained, then cooled to room temperature, and irradiated with a high-pressure mercury lamp (exposure machine model number: RW-UV70201, exposure amount of 50 mJ / cm ² each time) to expose the coating film and cure. Form a film.

The evaluation is made based on the number of times the coating film is passed through the belt-type exposure machine until the coating film is cured to form a cured film, and the larger the number of times the coating film is passed, the more unfavorable the curing speed is.

(2) Weather resistance With reference to GB / T-1740-2007, a method for measuring the moisture and heat resistance of the coating film is adopted. A fully cured cured film is placed in a pre-adjusted temperature / humidity control box (temperature 50 ± 1 ° C., relative humidity 96 ± 2%) and left for 240 hours, after which foaming, cracking, and yellowing of the surface of the cured film occur. Evaluate the destructive phenomenon such as.

If there is no change, it is A;
When there is a destructive phenomenon such as foaming, cracking, and yellowing, it is designated as B.

(3) Surface drying characteristics With reference to GB / T 1728-1979 (1989), the measurement is carried out by adopting the cotton ball blowing method. Lightly place one 1 cm ² fluffy degreased cotton ball on the surface of the cured film, and lightly blow the cotton ball along the horizontal direction with your mouth at a distance of 15 cm from the cotton ball.

If the cotton ball can be blown off and no cotton fiber remains on the surface of the membrane, it is designated as A;
B if the cotton ball can be blown off but cotton fibers remain on the surface of the membrane;
C if the cotton ball cannot be blown off;
If the cotton balls can be blown off and no cotton fibers remain on the surface of the film, that is, the surface is dry, indicating that the surface drying property of the film is excellent.

The evaluation results are shown in Table 5.

The structures of Comparative Compounds 1 and 2 in Table 5 are shown below.

As can be seen from the measurement results in Table 5, the photocurable resin composition using the fluorine-containing fluorene photoinitiator represented by the general formula (II) of the present invention has an exposure amount of 50 mJ / cm ² at a time. It can be fully cured with, clearly shows higher initiation efficiency, and is also clearly superior to samples using conventional fluorene photoinitiators in weather resistance and surface drying properties.

The above are merely preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, various changes and changes can be made to the present invention. As long as it is within the spirit and gist of the present invention, any modifications, equivalent substitutions, improvements, etc. made should be included within the scope of protection of the present invention.

Claims (25)

A fluorine-containing fluorene oxime ester-based photoinitiator having a structure represented by the general formula (I ) .

Here , in the general formula (I), the n represents an integer of 1 to 4. The m represents an integer of 1 to 4.
The n _R1s are each independently of -G- (M') _q , hydrogen, nitro group, halogen, or.

Is selected from. The m'represents an integer of 1 to 4. Here, G is selected from a hetero atom or a carbonyl group, the hetero atom is O, N or S, and M'is a linear or branched alkyl group of C ₁ to C ₂₀ , C. ₃ to C ₈ cycloalkyl groups, C ₁ to C ₁₀ alkyl groups substituted with C ₃ to C ₈ cycloalkyl groups, C ₆ to C ₂₀ aryl groups, C ₁ to C ₁₀ alkyl groups, nitro C ₆ to C ₂₀ aryl groups substituted with groups, C ₆ to C ₂₀ aryl groups substituted with cyano groups, heteroaryl groups C ₄ to C ₂₀ substituted, C ₆ to C ₂₀ substituted with nitro groups. It is selected from the heteroaryl group of _C6 to _C20 substituted with a cyano group. One or more carbon atoms in the M'may be substituted with the heteroatom. q is 1 or 2.
The R ₂ and the R _2'are independently selected from the polymerizable groups.
The Z and the Z'are independently absent or indicate a carbonyl group.
The m of the R ₃ and the m'of the R ₅ are independently substituted with fluorine, a linear or branched alkyl group substituted with one or more fluorines, and one or more fluorines, respectively. It is selected from straight-chain or branched-chain alkoxy groups.
The R ₄ and R ₆ are independently substituted with a linear or branched alkyl group of C ₁ to C ₂₀ , a cycloalkyl group of C ₃ to C ₂₀ , and a cycloalkyl group of C ₃ to C ₈ , respectively. Alkyl groups of C ₁ to C ₁₀ , cycloalkyl groups of C ₃ to C ₈ substituted with alkyl groups of C ₁ to C ₁₀ , aryl groups of C ₆ to C ₂₀ , and heteroaryl groups of C ₄ to C ₂₀ . Alternatively, it is selected from C ₂ to C ₂₀ alkenyl groups . In the general formula (I), the M'is substituted with a linear or branched alkyl group of C ₁ to C ₁₀ , a cycloalkyl group of C ₃ to C ₆ , and a cycloalkyl group of C ₃ to C ₆ . C ₁ to C ₅ alkyl groups, C ₆ to C ₁₀ aryl groups, C ₁ to C ₅ alkyl groups, nitro group substituted C ₆ to C ₁₀ aryl groups, and cyano groups substituted C ₆ Choose from C ₁₀ aryl groups, C ₄ to C ₁₀ heteroaryl groups, nitro group substituted C ₆ to C ₁₀ heteroaryl groups or cyano groups substituted C ₆ to C ₁₀ heteroaryl groups. The fluorine-containing fluorene oxime ester-based photoinitiator according to claim 1, wherein the light initiator is characterized by the above. The fluorine-containing according to claim 1, wherein in the general formula (I), the R ₂ and the R _2'are independently selected from a polymerizable group containing a double bond or an epoxy group. Fluorene oxime ester-based photoinitiator. In the general formula (I), the R ₂ and the R _2'are independently selected from the alkenyl groups of C ₂ to C ₁₂ , and one or more of the R ₂ and the R ₂ '. CH ₂ -is independent of each other

The fluorine-containing fluorene oxime ester-based photoinitiator according to claim 3, which may be substituted with. In the general formula (I), the R ₂ And the above R ₂ ’Is C independently ₃ ~ C ₈ Selected from the alkenyl groups of the above R ₂ And the above R ₂ ’One or more -CHs in ₂ -Is independent of each other

The fluorine-containing fluorene oxime ester-based photoinitiator according to claim 3, which may be substituted with. In the general formula (I), the R ₂ and the R _2'are independently substituted with an alkyl group of C ₁ to C ₁₀ substituted with an oxylanyl group or an epoxypropyl group of C ₁ to C ₁₀ . Selected from the alkyl groups, one or more -CH ₂ -s in the alkyl groups C ₁ to C ₁₀ in the R ₂ and the R _2'are independent of each other.

The fluorine-containing fluorene oxime ester-based photoinitiator according to claim 3, which may be substituted with. In the general formula (I), the R ₂ and the R _2'are independently selected from the alkyl groups C ₁ to C ₈ having an oxylanyl group or an epoxypropyl group as a terminal group , respectively, and the R ₂ and the above. One or more -CH _2- in the alkyl groups C ₁ to C ₈ in R _2'are independent of each other.

The fluorine-containing fluorene oxime according to claim 6 , wherein H in the oxylanyl group or the epoxypropyl group may be substituted with an alkyl group of C ₁ to C ₄ . Ester-based photoinitiator. _In the general formula (I), the m R3 and the _m'R5 are independent of each other.

The fluorine-containing fluorene oxime ester-based photoinitiator according to any one of claims 1 to 4, which is characterized by being selected from. In the general formula (I), the R ₄ and the R ₆ are independently a linear or branched alkyl group of C ₁ to C ₆ , a cycloalkyl group of C ₃ to C ₁₀ , and C ₃ to C, respectively. From C _{1 to C 8 alkyl groups substituted with 6 cycloalkyl groups, C 3 to C 6 cycloalkyl groups substituted with C 1 to C 8 alkyl groups , or C 6} to C ₁₂ aryl groups. The fluorine-containing fluorene oxime ester-based photoinitiator according to any one of claims 1 to 4, characterized in that it is selected. In the general formula (I), the R ₄ and the R ₆ are independently a phenyl group, a linear or branched alkyl group of C ₁ to C ₄ , a cycloalkyl group of C ₃ to C ₈ , or a cycloalkyl group of C 3 to C 8. The fluorine-containing fluorene oxime ester-based photoinitiator according to claim 9 , which is selected from C ₁ to C ₄ alkyl groups substituted with C ₃ to C ₆ cycloalkyl groups. The fluorine-containing fluorene according to claim 1, wherein the fluorine-containing fluorene oxime ester-based photoinitiator represented by the general formula (I) is one or more selected from the group consisting of the following. Oxime ester-based photoinitiator.

A fluorine-containing fluorene photoinitiator having a structure represented by the general formula (II).

In the general formula (II), the R ₁ And the above R ₁ ’Independently indicate a fluorine-containing group.
The R ₂ And the above R ₃ Are independent of each other, C ₁ ~ C ₂₀ Linear or branched alkyl group, C ₃ ~ C ₁₂ Cycloalkyl group, C ₄ ~ C ₁₈ Cycloalkylalkyl group, C ₆ ~ C ₂₀ Aryl group, C ₇ ~ C ₂₄ Arylalkyl groups of, substituted or unsubstituted C ₄ ~ C ₂₀ Shows a heteroaryl group of or R ₂ And R ₃ Are connected to each other and C ₃ ~ C ₁₀ Cycloalkyl group is formed.
The R ₄ Indicates a hydroxyl group, an N-morpholinyl group, an N-piperidinyl group, an N-piperazinyl group, an N-pyrrolill group or an N-tertiary amino group.
A is hydrogen, nitro group, -CO-CR. ₂ R ₃ R ₄ Group or -R ₅ -(R ₆ ) _n And here, R ₂ , R ₃ And R ₄ Is synonymous with the general formula (II), and is R. ₅ Indicates an O, S, N or carbonyl group, said R ₆ Is C ₁ ~ C ₂₀ Linear or branched alkyl group, C ₃ ~ C ₁₂ Cycloalkyl group, C ₄ ~ C ₁₈ Cycloalkylalkyl group, substituted or unsubstituted C ₆ ~ C ₂₀ Aryl group, C ₇ ~ C ₂₄ Arylalkyl group, 5-membered or 6-membered unsaturated heterocyclic group, or substituted or unsubstituted C ₄ ~ C ₂₀ Indicates a heteroaryl group of, where n represents 1 or 2. In the general formula (II), the R ₁ and the R _1'are independently selected from the linear or branched fluorine-containing alkyl groups of C ₂ to C ₁₀ , and optionally, -CH in the group. ₂ − may be substituted with —O— or a phenylene group, and H on the phenylene group may be optionally substituted with _an alkyl group of C1 to _C4 . 12. The fluorine-containing fluorene photoinitiator according to 12. In the general formula (II), the R ₁ and the R _{1'independently} have -CF ₃ , -CF ₂ CF ₃ , -CF ₂ -CH ₂ F or -CF ₂ -CHF ₂ as a terminal group, respectively. C ₃ to C ₈ linear or branched fluorine-containing alkyl groups, optionally in which -CH _2- may be substituted with an -O- or a 1,4-phenylene group, and may also be substituted. The fluorine-containing fluorene photoinitiator according to claim 12 , wherein H on the 1,4-phenylene group may be optionally substituted with an alkyl group of C ₁ to C ₄ . In the general formula (II), the R ₂ and the R ₃ are independently a linear or branched alkyl group of C ₁ to C ₈ , a cycloalkyl alkyl group of C ₄ to C ₁₂ , and C ₇ to C 12. The fluorine-containing fluorene according to claim 12 , wherein the arylalkyl group of C ₁₄ is shown, or R ₂ and R ₃ are linked to each other to form a cycloalkyl group of C ₃ to C ₈ . Alkane initiator. In the general formula (II), the R ₂ and the R ₃ are independently a linear or branched alkyl group of C ₁ to C ₄ , a cycloalkyl alkyl group of C ₄ to C ₁₀ , and C ₇ to C 10. The fluorine-containing fluorene according to claim ₁₅ , which exhibits a phenylalkyl group of C10 or is characterized _in that _R2 and R3 _are linked to _each other to form a cycloalkyl group of C3 to C8. Alkane initiator. In the general formula (II), the R ₄ is characterized by exhibiting a hydroxyl group, an N-morpholinyl group, an N-piperidinyl group, or an amino group in which two hydrogens are substituted with an alkyl group of C ₁ to C ₄ . The fluorine-containing fluorene photoinitiator according to claim 12 . In the general formula (II), the A represents a hydrogen, a nitro group, -CO-CR ₂ R ₃ R ₄ groups, or -R _5- (R ₆ ) _n , where R ₂ and R ₃ are. , C1 to _{C8 linear} or branched alkyl groups, C4 _to C12 _{cycloalkylalkyl} groups, C7 _to C14 _arylalkyl groups, or R2 _and R3 _, respectively. Are linked together to form C ₃ to C ₈ cycloalkyl groups; the R ₄ is a hydroxyl group, an N-morpholinyl group, an N-piperidinyl group, or two hydrogens are C ₁ to C ₄ alkyl. An amino group substituted with a group; R ₅ indicates an O, S, N or carbonyl group, and R ₆ is a linear or branched alkyl group of C ₁ to C ₈ ; of C ₆ to C ₁₂ . Aryl groups; C ₆ to C ₁₂ aryl groups substituted with C ₁ to C ₅ alkyl groups, nitro groups or cyano groups; or 5-membered unsaturated heterocyclic groups, where n is 1 or 2. The fluorine-containing fluorene photoinitiator according to claim 12 , which is characterized by showing. In the general formula (II), the R ₆ is a linear or branched alkyl group of C ₁ to C ₄ , a furanyl group, a pyrrolyl group, a thienyl group, an aryl group of C ₆ to C ₁₀ ; C ₁ to C. The fluorine-containing fluorene photoinitiator according to claim 18 , wherein the aryl group of C ₆ to C ₁₀ is substituted with an alkyl group, a nitro group or a cyano group of ₄ . A method for producing a fluorine-containing fluorene photoinitiator represented by the general formula (II) according to any one of claims 12 to 19 , wherein the raw material a and the raw material b are reacted under the action of a catalyst. The reaction formula is a method for producing a fluorine-containing fluorene photoinitiator, which is shown below.

Here, in the general formula (II), the M represents H or OH.
When M indicates H, R ₀ is, that is, R ₁ , and R _0'is , that is, R ₁ '.
When the M indicates OH, the R ₀ and the R _0'correspond to R ₁ and R ₁ ', respectively, and the R ₁ indicates OR ₀ , and the R _1'is OR. Indicates ₀ '.
The X indicates Cl or Br. The production method according to claim 20 , wherein the catalyst is an alkaline catalyst. The production method according to claim 20, wherein the catalyst is at least one of lithium tert-butoxide, sodium tert-butoxide and potassium tert-butoxide. A photocurable composition, wherein the photoinitiator contains a photoinitiator, and the photoinitiator is the fluorine-containing fluorene oxime ester-based photoinitiator according to any one of claims 1 to 11 . A photocuring composition comprising the fluorine-containing fluorene photoinitiator according to any one of Items 12 to 19 . The fluorine-containing fluorene oxime ester system according to any one of claims 1 to 11 , which is applied to the production of a color resist, a black matrix, a photo spacer, a rib, a dry film, a semiconductor photoresist or an ink. Photoinitiator. The fluorine-containing fluorene light according to any one of claims 12 to 19, which is applied to the production of a color resist, a black matrix, a photo spacer, a rib, a dry film, a semiconductor photoresist or an ink. Ink .