KR20200101429A - Fluorine-containing fluorene oxime ester photoinitiator, photocurable composition comprising same, and use thereof - Google Patents

Abstract

The present invention provides a fluorine-containing fluorene oxime ester photoinitiator, a photocurable composition comprising the same, and uses thereof. The photoinitiator has a structure represented by general formula (I) or (II). In the fluorine-containing fluorene oxime ester photoinitiator represented by the general formula (I) or (II) provided by the present application, the photoinitiator has the advantage of high initiation efficiency by introducing a fluorine-containing group. In addition, this specificity in the structure allows the photoinitiator to have advantages such as good surface drying properties, good surface curing effects, and not easy to move. Based on this, the above-described photoinitiator has advantages such as not easy to move, high initiation efficiency, good surface drying properties, and good surface curing effect, and has wide applicability.

Description

Fluorine-containing fluorene oxime ester photoinitiator, photocurable composition comprising same, and use thereof

The present invention relates to the field of organic synthesis, in particular to fluorine-containing fluorene oxime ester photoinitiators, photocurable compositions comprising the same, and uses thereof.

The liquid crystal display device has advantages of less energy consumption, less volume, and no radiation than conventional CRT monitors. However, they still have defects such as very narrow viewing angles, image trailing, poor brightness and contrast. In recent years, as the quality of life continues to improve, higher requirements are also proposed for liquid crystal displays. Requirements such as large size, high brightness, wide viewing angle and the like are mentioned, and thus higher requirements are proposed for the materials used in the production of liquid crystal displays.

Color photoresist, black photoresist, and photo-spacer are important components constituting liquid crystal flat panel displays, and are also indispensable materials for next-generation panel displays to achieve large size and high resolution. High sensitivity oxime ester initiators are an important component in the formulation of photoresists and photo-spacers. In recent years, research on high-sensitivity initiators is very popular, but the problems of poor surface drying properties and easy migration for these disclosed photoinitiators are still not effectively solved, which affects the properties of application to other ranges of materials. Crazy.

The main object of the present invention is to provide a fluorine-containing fluorene oxime ester photoinitiator, a photocurable composition comprising the same, and a use thereof in order to solve the problems of poor surface drying properties and easy movement of the existing oxime ester photoinitiator. .

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

In general formula (I), n represents an integer of 1 to 4; m represents an integer from 1 to 4;

에서 선택되고, m'은 1 내지 4의 정수를 나타내고; 여기서 G는 헤테로원자 또는 카르보닐기에서 선택되고, 헤테로원자는 O, N 또는 S이고, M'은 C₁~C₂₀ 선형 또는 분지형 알킬기, C₃~C₈ 시클로알킬기, C₃~C₈ 시클로알킬기로 치환된 C₁~C₁₀ 알킬기, C₆~C₂₀ 아릴기, C₁~C₁₀ 알킬기, 니트로기로 치환된 C₆~C₂₀ 아릴기, 시아노기로 치환된 C₆~C₂₀ 아릴기, C₄~C₂₀ 헤테로아릴기, 니트로기로 치환된 C₆~C₂₀ 헤테로아릴기, 또는 시아노기로 치환된 C₆~C₂₀ 헤테로아릴기에서 선택되거나, 또는 M'에서 하나 이상의 탄소 원자는 헤테로원자로 치환되고, q는 1 또는 2이고;n of R ₁ are each independently -G-(M') _q , hydrogen, nitro group, halogen, or

Is selected from, m'represents an integer of 1 to 4; Where G is selected from a heteroatom or a carbonyl group, the heteroatom is O, N or S, and M'is a C ₁ to C ₂₀ linear or branched alkyl group, a C ₃ to C ₈ cycloalkyl group, a C ₃ to C ₈ cycloalkyl group substituted C ₁ ~ C ₁₀ alkyl group, C ₆ ~ C ₂₀ aryl group, C ₁ ~ C ₁₀ alkyl group, a C ₆ ~ C ₂₀ aryl group substituted with a nitro, a cyano group, a C ₆ ~ C ₂₀ aryl group substituted with, C ₄ ~ C ₂₀ heteroaryl group, a C ₆ ~ C ₂₀ heteroaryl group substituted with a nitro group, or a C ₆ ~ C ₂₀ heteroaryl group substituted with a cyano group, or at least one carbon atom in M'is hetero Substituted by an atom, q is 1 or 2;

R ₂ and R ₂ ′ are each independently selected from polymerizable groups;

Z and Z'are each independently absent or each independently represents a carbonyl group;

m R ₃ and m'R ₅ are each independently selected from fluorine, a linear or branched alkyl group substituted with one or more fluorine, and a linear or branched alkoxy substituted with one or more fluorine;

R ₄ and R ₆ are each independently a C ₁ to C ₂₀ linear or branched alkyl group, a C ₃ to C ₂₀ cycloalkyl group, a C ₁ to C ₁₀ alkyl group substituted with a C ₃ to C ₈ cycloalkyl group, C ₁ to C ₁₀ It is selected from a C ₃ to C ₈ cycloalkyl group, a C ₆ to C ₂₀ aryl group, a C ₄ to C ₂₀ heteroaryl group, or a C ₂ to C ₂₀ alkenyl group substituted with an alkyl group;

In the general formula (II), R ₁ and R ₁ ′ each independently represent a fluorine-containing group;

R ₂ and R ₃ are each independently C ₁ to C ₂₀ linear or branched alkyl group, C ₃ to C ₁₂ cycloalkyl group, C ₄ to C ₁₈ cycloalkylalkyl group, C ₆ to C ₂₀ aryl group, C ₇ to C ₂₄ An arylalkyl group, or a substituted or unsubstituted C ₄ ~C ₂₀ heteroaryl group, or the R ₂ and R ₃ are connected to each other to form a C ₃ ~C ₁₀ cycloalkyl group;

R ₄ represents a hydroxy group, N-morpholinyl group, N-piperidinyl group, N-piperazinyl group, N-pyrrolyl group, or N-secondary amine;

A represents hydrogen, a nitro group, a -CO-CR ₂ R ₃ R ₄ group, or -R ₅ -(R ₆ ) _n , where R ₅ represents O, S, N, or a carbonyl group, and R ₆ is C ₁ to C ₂₀ linear or branched alkyl group, C ₃ to C ₁₂ cycloalkyl group, C ₄ to C ₁₈ cycloalkylalkyl group, substituted or unsubstituted C ₆ to C ₂₀ aryl group, C ₇ to C ₂₄ arylalkyl group, 5- Represents a membered or 6-membered unsaturated heterocyclic group, or a substituted or unsubstituted C ₄ to C ₂₀ heteroaryl group, and n represents 1 or 2.

As a technical solution of the present invention, in the fluorine-containing fluorene oxime ester photoinitiator represented by the general formula (I) or (II) provided by the present application, the photoinitiator has the advantage of high initiation efficiency by introducing a fluorine-containing group. To have. In addition, this specificity in the structure allows the photoinitiator to have advantages such as good surface drying properties, good surface curing effects, and not easy to move. Based on this, the above-described photoinitiator has advantages such as high initiation efficiency, good surface drying properties, good surface hardening effect, and not easy to move, and has wide applicability.

It is indicated that embodiments of the present application and features of the embodiments may be combined with each other without conflict. The invention will be described in detail with reference to the following examples.

As described in the background art, there are problems of poor surface drying properties and easy migration for the existing oxime ester photoinitiators. In order to solve the above technical problem, the present invention provides a fluorine-containing fluorene oxime ester photoinitiator having a structure represented by general formula (I) or (II):

Where n represents an integer of 1 to 4; m represents an integer from 1 to 4;

에서 선택되고, m'은 1 내지 4의 정수를 나타내고; 여기서 G는 헤테로원자 또는 카르보닐기를 비제한적으로 포함하고, 헤테로원자는 O, N 또는 S이고, M'은 비제한적으로 C₁~C₂₀ 선형 또는 분지형 알킬기, C₃~C₈ 시클로알킬기, C₃~C₈ 시클로알킬기로 치환된 C₁~C₁₀ 알킬기, C₆~C₂₀ 아릴기, C₁~C₁₀ 알킬기, 니트로기로 치환된 C₆~C₂₀ 아릴기, 시아노기로 치환된 C₆~C₂₀ 아릴기, C₄~C₂₀ 헤테로아릴기, 니트로기로 치환된 C₆~C₂₀ 헤테로아릴기, 또는 시아노기로 치환된 C₆~C₂₀ 헤테로아릴기를 포함하거나, 또는 M'에서 하나 이상의 탄소 원자는 헤테로원자로 치환되고, q는 1 또는 2이고;n of R ₁ are each independently -G-(M') _q , hydrogen, nitro group, halogen, or

Is selected from, m'represents an integer of 1 to 4; Wherein G includes, but is not limited to, a heteroatom or a carbonyl group, and the heteroatom is O, N or S, and M'is, but is not limited to, a C ₁ to C ₂₀ linear or branched alkyl group, a C ₃ to C ₈ cycloalkyl group, C ₃ ~ C ₈ cycloalkyl group a C ₁ ~ C ₁₀ alkyl group substituted by, C ₆ ~ C ₂₀ aryl group, C ₁ ~ C ₁₀ alkyl group, a C ₆ ~ substituted with a nitro C ₂₀ aryl group, a C ₆ substituted with a cyano group -C ₂₀ aryl group, C ₄ -C ₂₀ heteroaryl group, a C ₆ -C ₂₀ heteroaryl group substituted with a nitro group, or a C ₆ -C ₂₀ heteroaryl group substituted with a cyano group, or one in M' At least one carbon atom is substituted with a heteroatom, and q is 1 or 2;

R ₂ and R ₂ ′ are each independently selected from polymerizable groups; Z and Z'are each independently absent or each independently represents a carbonyl group; m R ₃ and m'R ₅ are each independently selected from fluorine, a linear or branched alkyl group substituted with one or more fluorine, and a linear or branched alkoxy substituted with one or more fluorine; R ₄ and R ₆ are each independently a C ₁ to C ₂₀ linear or branched alkyl group, a C ₃ to C ₂₀ cycloalkyl group, a C ₁ to C ₁₀ alkyl group substituted with a C ₃ to C ₈ cycloalkyl group, C ₁ to C ₁₀ It is selected from a C ₃ to C ₈ cycloalkyl group, a C ₆ to C ₂₀ aryl group, a C ₄ to C ₂₀ heteroaryl group, or a C ₂ to C ₂₀ alkenyl group substituted with an alkyl group;

In the general formula (II), R ₁ and R ₁ ′ each independently represent a fluorine-containing group;

R ₂ and R ₃ are each independently C ₁ to C ₂₀ linear or branched alkyl group, C ₃ to C ₁₂ cycloalkyl group, C ₄ to C ₁₈ cycloalkylalkyl group, C ₆ to C ₂₀ aryl group, C ₇ to C ₂₄ An arylalkyl group, or a substituted or unsubstituted C ₄ ~C ₂₀ heteroaryl group, or the R ₂ and R ₃ are connected to each other to form a C ₃ ~C ₁₀ cycloalkyl group;

R ₄ represents a hydroxy group, N-morpholinyl group, N-piperidinyl group, N-piperazinyl group, N-pyrrolyl group, or N-secondary amine;

A represents hydrogen, a nitro group, a -CO-CR ₂ R ₃ R ₄ group, or -R ₅ -(R ₆ ) _n , where R ₅ represents O, S, N, or a carbonyl group, and R ₆ is C ₁ to C ₂₀ linear or branched alkyl group, C ₃ to C ₁₂ cycloalkyl group, C ₄ to C ₁₈ cycloalkylalkyl group, substituted or unsubstituted C ₆ to C ₂₀ aryl group, C ₇ to C ₂₄ arylalkyl group, 5- Represents a membered or 6-membered unsaturated heterocyclic group, or a substituted or unsubstituted C ₄ to C ₂₀ heteroaryl group, and n represents 1 or 2.

In the fluorine-containing fluorene oxime ester photoinitiator represented by the general formula (I) or (II) provided by the present application, the photoinitiator has the advantage of high initiation efficiency by introducing a fluorine-containing group. To have. In addition, this specificity in the structure allows the photoinitiator to have advantages such as good surface drying properties, good surface curing effects, and not easy to move. Based on this, the above-described photoinitiator has advantages such as high initiation efficiency, good surface drying properties, good surface hardening effect, and not easy to move, and has wide applicability.

In addition, in order to facilitate the further improvement of the property that is not easily moved on the photoinitiator, the photoinitiator represented by the general formula (I) further introduces a polymerizable group at the 9-position of the fluorene structure, thereby obtaining a general formula (I). It allows the photoinitiator to be displayed to be polymerized with the substrate.

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

In order to further reduce the mobility of the above-described fluorine-containing fluorene oxime ester photoinitiator, in General Formula (I), R ₂ and R ₂ ′ are each independently a polymerizable group containing a double bond or an epoxy group. It is preferably selected from.

또는

로 치환될 수 있다.In a preferred embodiment, in general formula (I), R ₂ and R ₂ ′ are each independently selected from C ₂ to C ₁₂ alkenyl groups, or at least one -CH ₂ -in R ₂ and R ₂ ′ is each independently to

or

Can be substituted with

또는

로 치환될 수 있다.Preferably, in the general formula (I), R ₂ and R ₂ ′ are each independently selected from a C ₃ to C ₈ alkenyl group, or at least one -CH ₂ -in R ₂ and R ₂ ′ is each independently

or

Can be substituted with

또는 -O-CH₂-CH(OH)-CH₂-O-로 치환된다.In a preferred embodiment, in formula (Ⅰ), R ₂ and R ₂ 'being selected from a C ₁ ~ C ₁₀ alkyl group substituted with a C ₁ ~ C ₁₀ alkyl group or epoxy propyl substituted with an epoxy group, each independently, or At least one -CH ₂ -in the C ₁ to C ₁₀ alkyl group in R ₂ and R ₂ ′ is each independently

Or -O-CH ₂ -CH(OH)-CH ₂ -O-.

또는 -O-CH₂-CH(OH)-CH₂-O-로 치환되거나, 상기 에폭시에틸기 또는 에폭시프로필기에서 H는 C₁~C₄ 알킬기로 치환될 수 있다.In a preferred embodiment, in formula (Ⅰ), R ₂ and R ₂ 'are each independently selected from or selected from an epoxy group or epoxypropyl a C ₁ ~ C ₈ alkyl capping groups, or R ₂ and R _2' in C ₁ At least one -CH ₂ -in the ~C ₈ alkyl group is each independently

Or -O-CH ₂ -CH(OH)-CH ₂ -O-, or H in the epoxyethyl group or the epoxypropyl group may be substituted with a C ₁ ~C ₄ alkyl group.

Preferably, in the general formula (I), m of R ₃ and m'of R ₅ are each independently

에서 선택된다. R₃ 및 R₅로서 상술한 기의 선택은 광개시제의 개시 효율의 추가적인 개선을 용이하게 한다.

Is selected from Selection of the groups described above as R ₃ and R ₅ facilitates further improvement of the initiation efficiency of the photoinitiator.

Preferably, in the general formula (I), R ₄ and R ₆ are each independently C ₁ to C ₆ linear or branched alkyl group, C ₃ to C ₁₀ cycloalkyl group, C ₃ to C ₆ cycloalkyl group substituted C _{It is selected from a 1} to C ₈ alkyl group, a C ₃ to C ₆ cycloalkyl group substituted with a C ₁ to C ₈ alkyl group, or a C ₆ to C ₁₂ aryl group.

More preferably, in the general formula (I), R ₄ and R ₆ are each independently a phenyl group, a C ₁ to C ₄ linear or branched alkyl group, a C ₃ to C ₈ cycloalkyl group, or a C ₃ to C ₆ cycloalkyl group It is selected from C ₁ ~C ₄ alkyl group substituted with.

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

According to another embodiment of the present invention, the present invention further provides a method for preparing a fluorine-containing fluorene oxime ester photoinitiator represented by the above-described general formula (I), comprising the following steps:

(1) Preparation of intermediate a, wherein

Raw material a and raw material b are subjected to Friedel-Craft acylation reaction in an organic solvent under a catalyst of aluminum trichloride or zinc chloride to obtain an intermediate product a; The synthesis scheme is as follows:

,

,

A is absent or is a methylene group.

(2) preparation of intermediate b, wherein

Upon oximation reaction of intermediate b under the action of hydroxylamine hydrochloride and sodium acetate, A is absent and intermediate c is produced; The synthesis scheme is as follows:

.

.

When the intermediate a and the nitrate ester or nitrate salt are subjected to oximation reaction at normal temperature, A is a methylene group, and intermediate c is produced; The synthesis scheme is as follows:

.

.

(3) Preparation of product

또는 산 클로라이드 화합물

을 에스테르화 반응시켜 관심 생성물을 수득하고; 합성 스킴은 다음과 같다:Intermediate b and acid anhydride

Or acid chloride compounds

Esterification reaction to obtain a product of interest; The synthesis scheme is as follows:

,

,

Z is absent or is a carbon group.

All of the raw materials used in the above-described synthesis are commercially available or are known compounds easily produced by known synthesis methods, wherein raw material a can be obtained by the synthesis method disclosed in Chinese Patent Application No. 201710274018.4. The synthesis method sequentially includes a Friedel-Craft acylation reaction, an oxime reaction, and an esterification reaction, all of which are common reaction types in the field of organic chemical synthesis. After clarifying the reaction process flow, the specific reaction conditions will be readily determined by a person skilled in the art.

In step (1), the reaction temperature is typically -10 to 30°C. The type of organic solvent used is not specifically limited as long as it can dissolve the raw material and does not negatively affect the reaction, and is preferably at least one of the group consisting of dichloromethane, dichloroethane, benzene, toluene, and xylene.

In step (2), the preparation of intermediate b is carried out 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. When Z is not present, the solvent used may be a mixed solvent of alcohol and water, preferably a mixed solvent of ethanol and water; The reaction is carried out under heating and reflux. 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 nitrate ester is, without limitation, ethyl nitrate, isopentyl nitrate, And isooctyl nitrate, wherein the nitrate salt includes, but is not limited to, sodium nitrate and/or potassium nitrate.

In step (3), the esterification reaction is carried out in an organic solvent, and the type of solvent is not specifically limited as long as it can dissolve the raw material and does not negatively affect the reaction, preferably dichloromethane, dichloroethane, benzene , Toluene, and at least one of the group consisting of xylene.

In another preferred embodiment, in the fluorine-containing fluorene-based photoinitiator represented by the above-described general formula (II), R ₁ and R ₁ ′ each independently represent a C ₂ to C ₁₀ linear or branched fluorine-containing alkyl group. , Optionally, -CH ₂ -may be substituted with -O- or a phenylene group, and H on the phenylene group may be optionally substituted with a C ₁ to C ₄ alkyl group. Further, preferably, R ₁ and R ₁ ′ are each independently -CF ₃ , -CF ₂ CF ₃ , -CF ₂ -CH ₂ F, or -CF ₂ -CHF ₂ Capped C ₃ ~C ₈ linear Or a branched fluorine-containing alkyl group, optionally -CH ₂ -may be substituted with -O- or 1,4-phenylene group, and H on the 1,4-phenylene group is optionally a C ₁ ~C ₄ alkyl group Can be substituted.

Preferably, in the general formula (II), R ₂ and R ₃ each independently represent a C ₁ to C ₈ linear or branched alkyl group, a C ₄ to C ₁₂ cycloalkylalkyl group, or a C ₇ to C ₁₄ arylalkyl group. Or, or R ₂ and R ₃ are connected to each other to form a C ₃ ~C ₈ cycloalkyl group. More preferably, R ₂ and R ₃ each independently represent a C ₁ to C ₄ linear or branched alkyl group, a C ₄ to C ₁₀ cycloalkylalkyl group, or a C ₇ to C ₁₀ phenylalkyl group, or R ₂ and R ₃ are linked to each other to form a C ₃ ~C ₈ cycloalkyl group.

Preferably, in the general formula (II), R ₄ represents a hydroxy group, an N-morpholinyl group, an N-piperidinyl group, or an amino group in which two hydrogens are substituted with a C ₁ to C ₄ alkyl group.

Preferably, in the general formula (II), A represents hydrogen, a nitro group, a -CO-CR ₂ R ₃ R ₄ group, or -R ₅ -(R ₆ ) _n , wherein R ₅ is O, S , N, or a carbonyl group, wherein R ₆ is a C ₁ to C ₈ linear or branched alkyl group, a C ₆ to C ₁₂ aryl group, a C ₆ to C ₁₂ aryl group substituted with a C ₁ to C ₅ alkyl group, a nitro group , Or a cyano group, or a 5-membered unsaturated heterocyclic group, and n represents 1 or 2. More preferably, R ₆ is C ₁ ~ C ₄ linear or branched alkyl group, a furanyl group, a pyrrolyl group, a thienyl group, C ₆ ~ C ₁₀ aryl group, C ₁ ~ C ₄ a C ₆ ~ C ₁₀ substituted alkyl It represents an aryl group, a nitro group, or a cyano group.

Without limitation, the fluorine-containing fluorene-based photoinitiator represented by the general formula (II) may be selected from the following structures:

Accordingly, the present invention also relates to a method for preparing a fluorine-containing fluorene-based photoinitiator represented by the above-described general formula (II), comprising reacting raw materials a and b in the presence of a catalyst, and the reaction formula is as follows: same:

Where M represents H or OH,

When M represents H, R ₀ is R ₁ and R ₀ ′ is R ₁ ′,

When M represents OH, R ₀ and R ₀ ′ respectively correspond to R ₁ and R ₁ ′, R ₁ represents OR ₀ and R ₁ ′ represents OR ₀ ′,

X represents Cl or Br.

All raw materials and agents used in the above-described manufacturing method are compounds known in the art or can be easily prepared by a known method, wherein raw material a is Chinese Invention Patent Application Nos. 201510937328.0, 201710088234.X, 201710530354.0, 201710835527. It can be produced by the synthesis method described in X et al.

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

According to another embodiment of the present invention, the present invention further provides a photocurable composition, wherein the photocurable composition comprises a photoinitiator, and the photoinitiator is the above-described general formula (I) and/or general formula (II). And a fluorine-containing fluorene oxime ester photoinitiator represented by.

In the fluorine-containing fluorene oxime ester photoinitiator represented by the general formula (I) or (II) provided by the present application, by introducing a fluorine-containing group, the photoinitiator has the advantage of high initiation efficiency. In addition, this specificity in the structure allows the photoinitiator to have advantages such as good surface drying properties, good surface curing effects, and not easy to move. Based on this, the above-described photoinitiator has advantages such as not easy to move, high initiation efficiency, good surface drying property, and good surface hardening effect, and has wide applicability.

According to another embodiment of the present invention, the present invention further provides the use of the fluorine-containing fluorene oxime ester photoinitiator represented by the above-described general formula (I) or (II) in the field of photocuring.

In the fluorine-containing fluorene oxime ester photoinitiator represented by the general formula (I) or (II) provided by the present application, by introducing a fluorine-containing group, the photoinitiator has the advantage of high initiation efficiency. In addition, this specificity in the structure allows the photoinitiator to have advantages such as good surface drying properties, good surface curing effects, and not easy to move. Based on this, the above-described photoinitiator has advantages such as not easy to move, high initiation efficiency, good surface drying property, and good surface hardening effect, and has wide applicability.

The present invention also relates to the use of the above-described fluorine-containing fluorene-based photoinitiators in the field of photocuring. Without limitation, this photoinitiator may be used in embodiments such as color photoresist (RGB), black matrix (BM), photo-spacer, rib, dry film, semiconductor photoresist, ink, and the like. This photoinitiator has high initiation efficiency, and can be excellent in surface drying properties and weather resistance.

Hereinafter, the present invention will be described in more detail with reference to specific examples, but it is not understood that the scope of the present invention is limited thereto.

An example of preparing a fluorine-containing fluorene oxime ester photoinitiator represented by the general formula (I) was as follows:

Example 1

(1) Synthesis of intermediate 1a

66.1 g of intermediate 1a, 27.0 g of aluminum trichloride, and 100 ml of dichloromethane were placed in a 500 ml 4-neck flask, and the temperature of the raw material in the 4-neck flask was lowered to 0°C with an ice bath. Thereafter, while stirring, a mixed solution of 57.0 g of raw material 1b and 50 ml of dichloromethane was added dropwise to the above-described raw material, and the temperature of the reaction system was controlled to 10°C or less, and the dropping was completed within 2 hours. Stirring was continued for 2 hours after the dropping was completed, and liquid phase tracking was performed until the reaction was completed. Next, the reaction system was slowly poured into diluted hydrochloric acid formulated with 400 g of ice water and 50 ml of concentrated hydrochloric acid (37%) while stirring, and then poured into a separatory funnel to separate the lower layer, which is a dichloromethane layer. Washing of the aqueous layer was continued with 50 ml of dichloromethane, and the dichloromethane layers were combined. The dichloromethane layer was washed with 5 wt% sodium bicarbonate aqueous solution (150 ml each time, a total of 3 times), and the dichloromethane layer was washed with water until the pH became neutral. The dichloromethane layer was dried with 80 g of anhydrous magnesium sulfate, and after filtration, the dichloromethane solution of the product was evaporated by rotation. After performing recrystallization using methanol as a solvent, drying was performed in an oven at 80° C. for 2 hours to obtain 97.2 g of an intermediate product 1a with a yield of 84 wt% and a purity of 98 wt%. The synthesis scheme was as follows:

.

.

Intermediate 1a was determined by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry:

¹ H-NMR (CDCl ₃ , 500MHz): 1.2885-1.3307 (8H, m), 1.8654-1.9975 (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, 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 hydroxylamine hydrochloride, 8.2 g of sodium acetate, 100 ml of ethanol, and 50 ml of water were placed in a 500 ml four-neck flask. After heating to reflux and stirring at 85° C. for 5 hours, the reaction was stopped. The material was poured into a 1000 ml large beaker, 500 ml of water was added, and then stirred, and 100 ml of dichloromethane was used for extraction. After drying the extract by adding 30 g of anhydrous MgSO ₄ , suction filtration was performed. The solvent was removed by rotary evaporation of the filtrate under reduced pressure, and an oily viscous substance was obtained in a rotary bottle. A viscous substance was poured into 100 ml of petroleum ether, immersed with stirring, and filtered with suction to obtain a white powdery solid, dried at 70° C. for 5 hours, and then 43.7 with a yield of 72 wt% and a purity of 98 wt%. g of intermediate 1b was obtained. MS (m/z): 608 (M+1) ⁺ . The synthesis scheme was as follows:

.

.

(3) Synthesis of compound 1

30.4 g of intermediate 1b and 100 ml of dichloromethane were placed in a 250 ml 4-neck flask and stirred at room temperature for 5 minutes, and then 5 g of propionyl chloride was added dropwise within about 30 minutes. After continuing to stir for 2 hours, 5% NaHCO ₃ was added to adjust the pH value to be neutral. After separating the organic layer with a separatory funnel, washed twice with 100 ml of water, dried with 20 g of anhydrous MgSO ₄ , filtered, and rotary evaporated to obtain a viscous liquid. A white solid powder was obtained by recrystallization with methanol, which was filtered to give a total of 27.2 g of compound 1 with a yield of 82% and a purity of 99%. The synthesis scheme was as follows:

.

.

The structure of compound 1 was determined by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry:

¹ H-NMR (CDCl ₃ , 500MHz): 0.9869-1.0045 (3H, t), 1.2895-1.3347 (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 product 2a

72.5 g of intermediate 2a, 27.0 g of aluminum trichloride, and 100 ml of dichloromethane were placed in a 500 ml 4-neck flask, and the temperature of the raw material in the 4-neck flask was lowered to 0°C with an ice bath. Thereafter, while stirring, a mixed solution of 54.5 g of raw material 2b and 50 ml of dichloromethane was added dropwise to the above-described raw material, and the temperature of the reaction system was controlled to 10°C or less, and the dropping was completed within 2 hours. Stirring was continued for 2 hours after the dropping was completed, and liquid trace was performed until the reaction was completed. Next, the reaction system was slowly poured into diluted hydrochloric acid formulated with 400 g of ice water and 50 ml of concentrated hydrochloric acid (37%) while stirring, and then poured into a separatory funnel to separate the lower layer, which is a dichloromethane layer. Washing of the aqueous layer was continued with 50 ml of dichloromethane, and the dichloromethane layers were combined. The dichloromethane layer was washed with 5 wt% sodium bicarbonate aqueous solution (150 ml each time, a total of 3 times), and the dichloromethane layer was washed with water until the pH became neutral. The dichloromethane layer was dried with 80 g of anhydrous magnesium sulfate, and after filtration, the dichloromethane solution of the product was evaporated by rotation. After performing recrystallization using methanol as a solvent, drying was performed in an oven at 80° C. for 2 hours to obtain 101.8 g of an intermediate product 2a with a yield of 85 wt% and a purity of 98 wt%. The synthesis scheme was as follows:

.

.

Intermediate 2a was determined by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry:

¹ H-NMR (CDCl ₃ , 500 MHz): 2.1489-2.1673 (4H, t), 2.3507 (3H, s), 4.1043-4.1554 (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 product 2b

59.8 g of intermediate 2a, 10.0 g of 37 wt% hydrochloric acid, 11.8 g of isopentyl nitrate, and 100 ml of tetrahydrofuran were placed in a 250 ml 4-neck flask. After stirring at room temperature for 5 hours, the reaction was stopped. The material was poured into a 1000 ml large beaker, 500 ml of water was added, and then stirred, and 100 ml of dichloromethane was used for extraction. After drying the extract by adding 30 g of anhydrous MgSO ₄ , it was filtered with suction. The solvent was removed by rotary evaporation of the filtrate under reduced pressure, and an oily viscous substance was obtained in a rotary bottle. A viscous substance was poured into 100 ml of petroleum ether, immersed with stirring, and filtered with suction to obtain a white powdery solid, dried at 70° C. for 5 hours, and then 44.8 g in a yield of 75% and a purity of 98%. Intermediate product 2b was obtained. MS (m/z): 614 (M+1) ⁺ . The synthesis scheme was as follows:

.

.

(3) Synthesis of compound 2

30.7 g of intermediate 2b and 100 ml of dichloromethane were placed in a 250 ml 4-neck flask and stirred at room temperature for 5 minutes, and then 6.5 g of propionic anhydride was added dropwise within about 30 minutes. After continuing to stir for 2 hours, 5% NaHCO ₃ was added to adjust the pH value to be neutral. The organic layer was separated with a separatory funnel, washed twice with 200 ml of water, dried over 50 g of anhydrous MgSO ₄ , filtered, and rotary evaporated to give a viscous liquid. A white solid powder was obtained by recrystallization with methanol, which was filtered to give 28.5 g of product with a yield of 85% and a purity of 99%.

The synthesis scheme was as follows:

.

.

The structure of compound 2 was determined by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry:

¹ H-NMR (CDCl ₃ , 500MHz): 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

Compound 3-13 having the structure shown in Table 1 was prepared by using the corresponding raw materials with reference to the methods of Examples 1 and 2.

rescue MS (m/z) Compound 3

604 Compound 4

670 Compound 5

812 Compound 6

634 Compound 7

597 Compound 8

638 Compound 9

724 Compound 10

714 Compound 11

724 Compound 12

1086 Compound 13

782

Evaluation of the properties of photoinitiators

By formulating a representative photocurable resin composition, application characteristics such as curing speed, mobility, and surface drying characteristics of the photoinitiator represented by Formula (I) of the present invention were evaluated, and specific steps are as follows.

(1) As shown in Table 2, a photocurable resin composition having the following composition was formulated (parts by weight).

Example Comparative example One 2 3 4 5 6 One 2 3 4 A 20 20 20 20 20 20 20 20 20 20 B 57 57 57 57 57 57 57 57 57 57 C1 3 C2 3 C3 3 C4 3 C5 3 C6 3 C7 3 C8 3 C9 3 C10 3 D1 20 20 20 20 20 20 20 20 20 20

In Table 2 above,

A: 1,6-hexanediol diacrylate;

B: Acrylate 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 speed.

The above-described composition was stirred under a yellow light lamp. Thereafter, the material was taken on the PET template, a film was formed by roll coating, and dried at 90° C. for 2 minutes to obtain a coated film having a dry film thickness of 2 μm. Thereafter, the above-described coating film was cooled to room temperature, and the above-described coating film was exposed by irradiating with a high-pressure mercury lamp (exposure device model: RW-UV70201, single exposure amount: 50 mJ/cm ² ) and cured to form a film. I did.

The number of passes through the track-type exposure tape required to cure the coating film to form the cured film was used for evaluation. The higher the number, the undesirable cure rate was indicated.

(3) Mobility.

The above-described cured film was cut out and used as a sample, and 0.5 g of a sample of the cured film was weighed and placed in a 50 ml beaker. 4.5 ml of methanol was added, and sonication was performed by ultrasonication for 30 minutes. The resulting solution was transferred to a 10 ml volumetric flask, and the sample was washed twice with methanol (2 ml×2), and then poured into a volumetric flask. 0.1 ml of toluene was taken as an internal standard with a dedicated pipette, and methanol was added until a predetermined volume was reached, followed by uniform shaking and standing.

LC-20A liquid chromatography (Sim Pack column, 150 × 6.0 nm, detector: SPD-20A, detection limit: 20 ppm, detection wavelength: 254 nm) from Shimadzu, Japan was used at 25° C. to obtain a photoinitiator. It was observed if the presence could be detected, where the flow rate was 1.0 ml/min and the mobile phase had a volume ratio of methanol/water = 90/10. In terms of the percentage of the peak area ratio of liquid to toluene, the higher the content of the liquid phase in the initiator, the greater the mobility.

(4) Measurement of surface drying

Using the cotton ball blowing method (GB/T 1728-1979 (1989)), carefully place a 1 cm ² loose absorbent cotton ball on the surface of the cured film, and put the cotton ball into your mouth at a distance of 15 cm in the transverse direction from the cotton ball. Gently blown.

If the cotton ball can be blown away and no cotton filaments remain on the film surface, it is marked as A;

If the cotton ball can be blown away, but the cotton filament remains on the film surface, it is marked as B;

If the cotton ball can or cannot be blown away, it is marked C;

If the cotton balls can be blown away and no cotton filaments remain on the film surface, the surface is dry, indicating that the film has good surface drying properties.

The characterization results are shown in Table 3.

Curing rate,
Number of passes Mobility Surface drying test Example 1 One Not detected A Example 2 One Not detected A Example 3 One Not detected A Example 4 One Not detected A Example 5 One Not detected A Example 6 One Not detected A Comparative Example 1 One 1.94 C Comparative Example 2 2 2.26 C Comparative Example 3 3 3.41 B Comparative Example 4 One Not detected C

As can be seen from the test results in Table 3, the fluorene oxime ester photoinitiator containing a polymerizable group represented by the general formula (I) of the present invention has excellent surface drying properties, high initiation efficiency in photocuring applications, and high curing speed. Has, there is no migration, and its overall properties are considerably superior to the existing oxime ester photoinitiator products.

An example of preparation of a fluorine-containing fluorene oxime ester photoinitiator represented by the general formula (II) was as follows:

Example 1

Synthesis of compound 1

36.8 g of raw material 1a, 10.6 g of sodium tert-butoxide, and 50 mL of DMF were placed in a 250 mL 4-neck flask and stirred at room temperature (about 25°C), and 26.6 g of raw material 1b was added dropwise within about 1 hour. I did. Stirring was continued for 3 hours after the dropping was completed, and liquid phase trace was performed until the reaction was completed. The raw material was slowly poured into 200 g of water, and extraction was performed with dichloromethane (50 ml each time, a total of 2 times). The dichloromethane layer was washed with 5% sodium bicarbonate aqueous solution (100 ml each time, a total of 3 times), and the dichloromethane layer was washed with water until the pH became neutral. The dichloromethane layer was dried with 80 g of anhydrous magnesium sulfate, and after filtration, the dichloromethane solution of the product was evaporated by rotation. Recrystallization was performed with methanol and drying in an oven at 70° C. for 2 hours to obtain 41.9 g of compound 1 with a yield of 75% and a purity of 98%.

The structure of compound 1 was determined by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry:

¹ H-NMR (CDCl ₃ , 500MHz): 1.3662-1.3772 (6H, s), 1.8068-1.8925 (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, 10.6 g of potassium tert-butoxide, and 50 mL of DMF were placed in a 250 mL 4-neck flask and stirred at room temperature (about 25° C.), and 27,3 g of raw material 2b within about 1 hour Was dripped. Stirring was continued for 3 hours after the dropping was completed, and liquid phase trace was performed until the reaction was completed. The material was slowly poured into 200 g of water, and extraction was performed with dichloromethane (50 ml each time, a total of 2 times). The dichloromethane layer was washed with 5% sodium bicarbonate aqueous solution (100 ml each time, a total of 3 times), and the dichloromethane layer was washed with water until the pH became neutral. The dichloromethane layer was dried with 80 g of anhydrous magnesium sulfate, and after filtration, the dichloromethane solution of the product was evaporated by rotation. Recrystallization was performed with methanol, and dried in an oven at 70° C. for 2 hours to obtain 51.4 g of compound 2 with a yield of 68% and a purity of 98%.

The structure of compound 1 was determined by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry:

¹ H-NMR (CDCl ₃ , 500 MHz): 0.9556-0.9918 (3H,t), 1.5208-1.5476 (2H, m), 2.2675-2.2807 (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, a compound having the structure shown in Table 4 was prepared using the corresponding raw material.

rescue MS (m/z) Compound 3

514 Compound 4

559 Compound 5

624 Compound 6

646 Compound 7

666 Compound 8

605 Compound 9

666 Compound 10

654 Compound 11

577 Compound 12

589 Compound 13

689 Compound 14

733 Compound 15

559 Compound 16

669 Compound 17

666 Compound 18

666 Compound 19

593 Compound 20

768

Characterization of characteristics

By formulating an exemplary photocurable resin composition, the main application properties of the photoinitiator represented by the general formula (II) of the present invention were evaluated.

1. Formulation of photocurable resin composition

The photocurable resin composition was composed of the following components:

20 parts by weight of 1,6-hexanediol diacrylate

Acrylate copolymer [benzyl methacrylate/methacrylic acid/hydroxyethyl methacrylate (molar ratio: 70/10/20) copolymer, Mv: 10000] 57 parts by weight

3 parts by weight of photoinitiator

20 parts by weight of butanone (solvent).

The constituents were uniformly mixed to obtain a photocurable resin composition used to evaluate properties. The photoinitiator was a fluorine-containing fluorene-based photoinitiator represented by the general formula (II) of the present invention or (as a comparison) a representative fluorene-based photoinitiator known in the prior art.

2. Evaluation of characteristics

The evaluation of the properties of the photocurable resin composition included curing speed, surface drying properties, and weather resistance.

(1) curing speed

The photocurable resin composition was stirred under a yellow light lamp. The material was taken on the PET template, a film was formed by roll coating and dried at 90° C. for 2 minutes to obtain a coated film having a dry film thickness of 2 μm. Thereafter, this was cooled to room temperature, and the coating film was exposed by irradiation with a high-pressure mercury lamp (exposure device model: RW-UV70201, single exposure amount: 50 mJ/cm ² ) and cured to form a film.

The number of passes through the track-type exposure tape required to cure the coating film to form the cured film was used for evaluation. The higher the number, the undesirable cure rate was indicated.

(2) weather resistance

With reference to GB/T-1740-2007, a method of measuring the resistance of paint films to heat and humidity was used. A sufficiently cured cured film was placed in a pre-adjusted temperature- and humidity-adjustable tank (temperature 50±1° C., relative humidity 96±2%) and left for 240 hours, followed by bubbling of the surface of the cured film, Fracture phenomena such as cracking and yellowing were evaluated.

If there was no change, it was marked as A;

If there is any fracture phenomenon such as bubbling, cracking, yellowing, etc., it is marked as B.

(3) Surface drying characteristics

With reference to GB/T 1728-1979 (1989), it was measured using the cotton ball blowing method. A loose absorbent cotton ball of about 1 cm ² was carefully placed on the surface of the cured film, and the cotton ball was gently blown into the mouth at a distance of 15 cm in the transverse direction from the cotton ball.

If the cotton ball can be blown away and no cotton filaments remain on the film surface, it is marked as A;

If the cotton ball can be blown away, but the cotton filament remains on the film surface, it is marked as B;

If the cotton ball cannot be blown out, it is marked C.

If the cotton balls can be blown away and no cotton filaments remain on the film surface, the surface is dry, indicating that the film has good surface drying properties.

Table 5 shows the characterization results of the properties.

Photoinitiator Curing speed Weather resistance Surface drying properties Example Compound 1 One A A Compound 2 One A A Compound 3 One A A Compound 4 One A A Compound 5 One A A Compound 6 One A A Compound 7 One A A Compound 8 One A A Compound 9 One A A Compound 10 One A A Compound 11 One A A Compound 12 One A A Compound 13 One A A Compound 14 One A A Compound 15 One A A Compound 16 One A A Compound 17 One A A Compound 18 One A A Compound 19 One A A Compound 20 One A A Comparative example Comparative compound 1 3 B B Comparative compound 2 2 B B

In Table 5, the structures of Comparative Compounds 1 and 2 are shown below:

As can be seen from the test results in Table 5, the photocurable resin composition using the fluorine-containing fluorene-based photoinitiator represented by the general formula (II) of the present invention can be sufficiently cured with a single exposure capacity of 50 mJ/cm ² . And exhibited significantly higher initiation efficiency, and had significantly better weatherability and surface drying properties than samples with conventional fluorene-based photoinitiators.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention. Various modifications and variations of the present invention may be made by those skilled in the art. All modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the scope protected by the present invention.

Claims (22)

A fluorine-containing fluorene oxime ester photoinitiator, wherein the photoinitiator has a structure represented by general formula (I) or (II):

In the general formula (I), n represents an integer of 1 to 4; M represents an integer of 1 to 4;
n of R ₁ are each independently -G-(M') _q , hydrogen, nitro group, halogen, or

It is selected from, and m'represents an integer of 1 to 4; Wherein G is selected from a heteroatom or a carbonyl group, the heteroatom is O, N or S, and M'is a C ₁ ~ C ₂₀ linear or branched alkyl group, C ₃ ~ C ₈ cycloalkyl group, C ₃ ~ C ₈ a C ₁ is substituted by a cycloalkyl group ~ C ₁₀ alkyl group, C ₆ ~ C ₂₀ aryl group, C ₁ ~ C ₁₀ alkyl group, with the nitro group substituted C ₆ ~ C ₂₀ aryl group, substituted with a cyano group C ₆ ~ C ₂₀ aryl Group, a C ₄ ~ C ₂₀ heteroaryl group, a C ₆ ~ C ₂₀ heteroaryl group substituted with a nitro group, or a C ₆ ~ C ₂₀ heteroaryl group substituted with a cyano group, or at least one carbon in the M′ The atom is substituted with a heteroatom and q is 1 or 2;
R ₂ and R ₂ ′ are each independently selected from a polymerizable group;
Z and Z'are each independently absent or each independently represents a carbonyl group;
m of R ₃ and m'of R ₅ are each independently selected from fluorine, a linear or branched alkyl group substituted with one or more fluorine, and a linear or branched alkoxy substituted with one or more fluorine;
The R ₄ and R ₆ are each independently a C ₁ to C ₂₀ linear or branched alkyl group, a C ₃ to C ₂₀ cycloalkyl group, a C ₁ to C ₁₀ alkyl group substituted with a C ₃ to C ₈ cycloalkyl group, C ₁ to C ₁₀ alkyl substituted by C ₃ ~ C ₈ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, a C ₄ ~ C ₂₀ heteroaryl group, or a C ₂ ~ C ₂₀ alkenyl group is selected from;
In the general formula (II), R ₁ and R ₁ ′ each independently represent a fluorine-containing group;
The R ₂ and R ₃ are each independently a C ₁ to C ₂₀ linear or branched alkyl group, a C ₃ to C ₁₂ cycloalkyl group, a C ₄ to C ₁₈ cycloalkylalkyl group, a C ₆ to C ₂₀ aryl group, C ₇ to C ₂₄ arylalkyl group, or a substituted or unsubstituted C ₄ ~C ₂₀ heteroaryl group, or the R ₂ and R ₃ are connected to each other to form a C ₃ ~C ₁₀ cycloalkyl group;
R ₄ represents a hydroxy group, N-morpholinyl group, N-piperidinyl group, N-piperazinyl group, N-pyrrolyl group, or N-secondary amine;
Wherein A represents hydrogen, a nitro group, -CO-CR ₂ R ₃ R ₄ group, or -R ₅ -(R ₆ ) _n , wherein R ₅ represents O, S, N, or a carbonyl group, and R ₆ Is a C ₁ to C ₂₀ linear or branched alkyl group, a C ₃ to C ₁₂ cycloalkyl group, a C ₄ to C ₁₈ cycloalkylalkyl group, a substituted or unsubstituted C ₆ to C ₂₀ aryl group, a C ₇ to C ₂₄ arylalkyl group, Represents a 5-membered or 6-membered unsaturated heterocyclic group, or a substituted or unsubstituted C ₄ to C ₂₀ heteroaryl group, and n represents 1 or 2. The method according to claim 1,
In the general formula (I), M'is a C ₁ to C ₁₀ linear or branched alkyl group, a C ₃ to C ₆ cycloalkyl group, a C ₁ to C ₅ alkyl group substituted with a C ₃ to C ₆ cycloalkyl group, C ₆ ~ C ₁₀ aryl group, C ₁ ~ C ₅ alkyl group, a C ₆ ~ C ₁₀ aryl group substituted with substituted with a nitro-C ₆ ~ C ₁₀ aryl group, a cyano group, C ₄ ~ C ₁₀ heteroaryl group, substituted with nitro a C ₆ ~ C ₁₀ heteroaryl group, a cyano group or a C ₆ ~ C _10, characterized in that the fluorine is selected from the heteroaryl group substituted with-containing fluorene oxime ester photoinitiator. The method according to claim 1,
In the general formula (I), R ₂ and R ₂ ′ are each independently selected from a polymerizable group containing a double bond or an epoxy group. A fluorine-containing fluorene oxime ester photoinitiator. The method of claim 3,
In the general formula (I), R ₂ and R ₂ ′ are each independently selected from a C ₂ to C ₁₂ alkenyl group, or at least one -CH ₂ -in R ₂ and R ₂ ′ is each independently to

or

Substituted with;
Preferably, in the general formula (I), the R ₂ and the R ₂ ′ are each independently selected from a C ₃ to C ₈ alkenyl group, or at least one -CH ₂ in the R ₂ and the R ₂ ′ -Each independently

or

Fluorine-containing fluorene oxime ester photoinitiator, characterized in that it is substituted with. The method of claim 3,
Wherein in formula (Ⅰ), wherein R ₂ and wherein R ₂ 'is selected from a C ₁ ~ C ₁₀ alkyl group or epoxypropyl a C ₁ ~ C ₁₀ alkyl group substituted with substituted with an epoxy group are each independently of the other, is, or the R ₂ and at least one -CH ₂ -in the C ₁ ~C ₁₀ alkyl group in R ₂ ′ are each independently

Or -O-CH ₂ -CH(OH)-CH ₂ -O-, characterized in that the substituted fluorine-containing fluorene oxime ester photoinitiator. The method of claim 5,
In the general formula (I), R ₂ and R ₂ ′ are each independently selected from a C ₁ to C ₈ alkyl group capped with an epoxy ethyl group or an epoxy propyl group, or C ₁ in the R ₂ and R ₂ ′ At least one -CH ₂ -in the ~C ₈ alkyl group is each independently

Or -O-CH ₂ -CH(OH)-CH ₂ -O-, or in the epoxyethyl group or the epoxypropyl group, H is substituted with a C ₁ to C ₄ alkyl group. Oxime ester photoinitiator. The method according to any one of claims 1 to 4,
In the general formula (I), m of R ₃ and m'of R ₅ are each independently

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

The method according to claim 1,
In the general formula (II), R ₁ and R ₁ ′ each independently represent a C ₂ to C ₁₀ linear or branched fluorine-containing alkyl group, and optionally -CH ₂ -is -O- or a phenylene group. Fluorine-containing fluorene-based photoinitiator, characterized in that it may be substituted, and H on the phenylene group may be optionally substituted with a C ₁ to C ₄ alkyl group. The method according to claim 1 or 11,
In the general formula (II), R ₁ and R ₁ ′ are each independently -CF ₃ , -CF ₂ CF ₃ , -CF ₂ -CH ₂ F, or -CF ₂ -CHF ₂ Capped C ₃ ~ C _{8 represents a} linear or branched fluorine-containing alkyl group, optionally -CH ₂ -may be substituted with -O- or 1,4-phenylene group, and H on the 1,4-phenylene group is optionally C ₁ Fluorine-containing fluorene-based photoinitiator, characterized in that it can be substituted with a ~C ₄ alkyl group. The method according to claim 1,
In the general formula (II), R ₂ and R ₃ each independently represent a C ₁ to C ₈ linear or branched alkyl group, a C ₄ to C ₁₂ cycloalkylalkyl group, or a C ₇ to C ₁₄ arylalkyl group, or , Or R ₂ and R ₃ are linked to each other to form a C ₃ to C ₈ cycloalkyl group. A fluorine-containing fluorene-based photoinitiator. The method according to claim 1 or 13,
In the general formula (II), R ₂ and R ₃ each independently represent a C ₁ to C ₄ linear or branched alkyl group, a C ₄ to C ₁₀ cycloalkylalkyl group, or a C ₇ to C ₁₀ phenylalkyl group, or , Or R ₂ and R ₃ are linked to each other to form a C ₃ to C ₈ cycloalkyl group. A fluorine-containing fluorene-based photoinitiator. The method according to claim 1,
In the general formula (II), R ₄ represents a hydroxy group, an N-morpholinyl group, an N-piperidinyl group, or an amino group in which two hydrogens are substituted with a C ₁ to C ₄ alkyl group. Fluorene-based photoinitiator. The method according to claim 1,
In the general formula (II), A is hydrogen, a nitro group, -CO-CR ₂ R ₃ R ₄ group, or -R ₅ -(R ₆ ) _n , wherein R ₅ is O, S, N, Or a carbonyl group, wherein R ₆ is a C ₁ to C ₈ linear or branched alkyl group, a C ₆ to C ₁₂ aryl group, a C ₆ to C ₁₂ aryl group substituted with a C ₁ to C ₅ alkyl group, a nitro group, or a cyanide group. A fluorine-containing fluorene-based photoinitiator, characterized in that it represents no group or a 5-membered unsaturated heterocyclic group, and n represents 1 or 2. The method according to claim 1 or 16,
In the general formula (II), R ₆ is C ₁ to C ₄ linear or branched alkyl group, furanyl group, pyrrolyl group, thienyl group, C ₆ to C ₁₀ aryl group, C ₁ to C ₄ alkyl group substituted ₆ to C ₁₀ A fluorine-containing fluorene-based photoinitiator, characterized in that it represents an aryl group, a nitro group, or a cyano group. A method for preparing a fluorine-containing fluorene-based photoinitiator represented by the general formula (II) of any one of claims 1 to 17, comprising reacting raw materials a and b in the presence of a catalyst, wherein the reaction formula is as follows: Same manufacturing method:

In the general formula (II), M represents H or OH,
When M represents H, R ₀ is R ₁ and R ₀ ′ is R ₁ ′,
When M represents OH, the R ₀ and R ₀ ′ respectively correspond to R ₁ and R ₁ ′, the R ₁ represents OR ₀ and the R ₁ ′ represents OR ₀ ′,
X represents Cl or Br. The method of claim 18,
The process, characterized in that the catalyst is a basic catalyst, preferably at least one lithium tert-butoxide, sodium tert-butoxide, and potassium tert-butoxide. A photocurable composition, wherein the photocurable composition comprises a photoinitiator, and the photoinitiator comprises the fluorine-containing fluorene oxime ester photoinitiator of any one of claims 1 to 19. Use of the fluorine-containing fluorene oxime ester photoinitiator of any one of claims 1 to 19 in the field of photocuring. The method of claim 21,
The photoinitiator, characterized in that it is used to prepare color photoresist, black matrix, photo-spacer, rib, dry film, semiconductor photoresist, and ink.