阅读说明：本技术 一种不对称芴肟酯化合物及其制备方法和光敏性组合物 (Asymmetric fluorene oxime ester compound, preparation method thereof and photosensitive composition ) 是由 王康民 于 2019-10-24 设计创作，主要内容包括：本发明提供了一种不对称芴肟酯化合物及其制备方法和光敏性组合物,属于有机合成技术领域。本发明提供的不对称芴肟酯化合物是在9,9-二乙基芴中引入两个侧链形成双酮肟酯结构,可以有效调控不对称芴肟酯化合物的空间位阻,从而增加不对称芴肟酯化合物的溶解度以及与其他材料的相容性；一分子的不对称芴肟酯化合物可以形成两分子的自由基,与其他光引发剂达到相同效果时用量更少,当活性能量射线照射至本发明的制备的不对称肟酯化合物时,产生的自由基的分子量大、移动性小,仅在辐照的区域上发生固化,因而具有优异的图案线性的特性。本发明提供的不对称芴肟酯化合物具有高热稳定性和高相容性,且有对活性能量射线敏感性高。(The invention provides an asymmetric fluorene oxime ester compound, a preparation method thereof and a photosensitive composition, belonging to the technical field of organic synthesis. The asymmetric fluorene oxime ester compound provided by the invention is characterized in that two side chains are introduced into 9, 9-diethylfluorene to form a double-ketoxime ester structure, and the steric hindrance of the asymmetric fluorene oxime ester compound can be effectively regulated and controlled, so that the solubility of the asymmetric fluorene oxime ester compound and the compatibility with other materials are increased; one molecule of asymmetric fluorene oxime ester compound can form two molecules of free radicals, the dosage is less when the same effect is achieved with other photoinitiators, when active energy rays are irradiated to the prepared asymmetric oxime ester compound, the generated free radicals have large molecular weight and small mobility, and curing is only performed on an irradiated area, so that the asymmetric fluorene oxime ester compound has excellent pattern linearity characteristics. The asymmetric fluorenyloxime ester compound provided by the invention has high thermal stability and high compatibility, and has high sensitivity to active energy rays.)

1. An asymmetric fluorenyloxime ester compound characterized by having the structure shown in formula I:

in formula I, R comprises methyl, ethyl, propyl, phenyl or substituted phenyl.

2. The asymmetric fluorenyloxime ester compound of claim 1 wherein said substituted phenyl group comprises a nitrophenyl group.

3. A method for producing an asymmetric fluorenyloxime ester compound according to any one of claims 1 to 2, comprising the steps of:

(1) mixing 9, 9-diethylfluorene, propionyl chloride, butyryl chloride, a metal salt catalyst and a solvent, and carrying out Friedel-crafts reaction to obtain a fluorene acyl compound;

(2) mixing the fluorene acyl compound, nitrite, acid catalyst and solvent, and carrying out nucleophilic substitution reaction to obtain an oxime compound;

(3) mixing the oximino compound, an acylating agent, an alkaline reagent and a solvent, and carrying out an ester forming reaction to obtain an asymmetric fluorene oxime ester compound;

the acylating agent comprises one or more of acetyl chloride, propionyl chloride, butyryl chloride, benzoyl chloride, p-nitrobenzoyl chloride, acetic anhydride, propionic anhydride and benzoic anhydride.

4. The method according to claim 3, wherein in the step (1), the metal salt catalyst comprises aluminum chloride, ferric chloride or zinc chloride;

the molar ratio of the 9, 9-diethylfluorene to the propionyl chloride to the butyryl chloride is 1: (1.05-1.2): (1.05-1.2).

5. The method according to claim 3, wherein in the step (2), the nitrite comprises ethyl nitrite, propyl nitrite or isobutyl nitrite;

the acid catalyst is an inorganic acid solution;

the molar ratio of the fluorene acyl compound to the nitrite is 1: (2.2-2.5).

6. The production method according to claim 3, wherein in the step (3), the alkali agent is an organic base;

the molar ratio of the alkaline reagent to the oxime compound is preferably (2.4-2.6): 1.

7. the preparation method according to claim 1, wherein the Friedel-crafts reaction is carried out at a temperature of-15 to-5 ℃ for 12 to 16 hours;

the temperature of the nucleophilic substitution reaction is 15-35 ℃, and the time is 6-9 h;

the temperature of the ester forming reaction is 0-20 ℃, and the time is 3-5 h.

8. A photosensitive composition comprising a photoinitiator, bisphenol a glycerol diacrylate, dipentaerythritol hexaacrylate, a colorant, and a solvent;

the photoinitiator is the asymmetric fluorenyloxime ester compound as claimed in any one of claims 1 to 3.

9. The photosensitive composition according to claim 8, wherein the mass ratio of the photoinitiator, the bisphenol A glycerol diacrylate, the dipentaerythritol hexaacrylate, the colorant and the solvent is (2-4): (40-60): (5-15): (30-50): (90-110).

Technical Field

The invention relates to the technical field of organic synthesis, in particular to an asymmetric fluorene oxime ester compound, a preparation method thereof and a photosensitive composition.

Background

Photoactive compounds are materials that decompose by absorption of light to produce chemically active atoms or molecules. Among them, the photoinitiator (also called photosensitizer) or photocuring agent (photocuring agent) is a compound that can absorb energy of a certain wavelength in an ultraviolet region (250 to 420nm) or a visible light region (400 to 800nm) to generate radicals, cations, etc. to initiate polymerization, crosslinking and curing of monomers, and is widely used for photocurable adhesives, photocurable inks, photoresists, etc.

The oxime ester compound is a common photoinitiator and has the following advantages: the ultraviolet ray absorption hardly presents color, has high free radical generation rate, and has good compatibility and stability with the photoresist composition material. The prior art such as jp 2008-100955 a, jp 2010-15025 a, CN104684888, WO-2015108386 and CN105198780 disclose some oxime ester compounds, however, the above oxime ester compounds generally have problems of sensitivity to active energy rays, thermal stability or poor compatibility with other compounds when used as photoinitiators, and the application of the oxime ester compounds is limited.

Disclosure of Invention

The invention aims to provide an asymmetric fluorenyloxime ester compound, a preparation method thereof and a photosensitive composition. The asymmetric fluorenyloxime ester compound provided by the invention has high thermal stability, high solubility and high sensitivity to active energy rays.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides an asymmetric fluorene oxime ester compound, which has a structure shown in a formula I:

in formula I, R comprises methyl, ethyl, propyl, phenyl or substituted phenyl.

Preferably, the substituted phenyl group comprises a nitrophenyl group.

The invention provides a preparation method of an asymmetric fluorene oxime ester compound in the technical scheme, which comprises the following steps:

(1) mixing 9, 9-diethylfluorene, propionyl chloride, butyryl chloride, a metal salt catalyst and a solvent, and carrying out Friedel-crafts reaction to obtain a fluorene acyl compound;

(2) mixing the fluorene acyl compound, nitrite, acid catalyst and solvent, and carrying out nucleophilic substitution reaction to obtain an oxime compound;

(3) mixing the oximino compound, an acylating agent, an alkaline reagent and a solvent, and carrying out an ester forming reaction to obtain an asymmetric fluorene oxime ester compound;

the acylating agent comprises one or more of acetyl chloride, propionyl chloride, butyryl chloride, benzoyl chloride, p-nitrobenzoyl chloride, acetic anhydride, propionic anhydride and benzoic anhydride.

Preferably, in step (1), the metal salt catalyst comprises aluminum chloride, ferric chloride or zinc chloride;

the molar ratio of the 9, 9-diethylfluorene to the propionyl chloride to the butyryl chloride is 1: (1.05-1.2): (1.05-1.2).

Preferably, in the step (2), the nitrite comprises ethyl nitrite, propyl nitrite or isobutyl nitrite;

the acid catalyst is an inorganic acid solution;

the molar ratio of the fluorene acyl compound to the nitrite is 1: (2.2-2.5).

Preferably, in the step (3), the alkaline agent is an organic base;

the molar ratio of the alkaline reagent to the oxime compound is preferably (2.4-2.6): 1.

preferably, the temperature of the Friedel-crafts reaction is-15 to-5 ℃, and the time is 12 to 16 hours;

the temperature of the nucleophilic substitution reaction is 15-35 ℃, and the time is 6-9 h;

the temperature of the ester forming reaction is 0-20 ℃, and the time is 3-5 h.

The invention provides application of the asymmetric fluorenyloxime ester compound in the technical scheme as a photoinitiator.

The invention provides a photosensitive composition, which comprises a photoinitiator, bisphenol A glycerol diacrylate, dipentaerythritol hexaacrylate, a colorant and a solvent;

the photoinitiator is the asymmetric fluorene oxime ester compound in the technical scheme.

Preferably, the mass ratio of the photoinitiator to the bisphenol A glycerol diacrylate to the dipentaerythritol hexaacrylate to the colorant to the solvent is (2-4): (40-60): (5-15): (30-50): (90-110).

The invention provides an asymmetric fluorene oxime ester compound which has a structure shown in a formula I. The asymmetric fluorene oxime ester compound provided by the invention introduces ester groups at the 2-position and the 7-position of 9, 9-diethylfluorene, and can effectively regulate and control the steric hindrance of the asymmetric fluorene oxime ester compound, thereby effectively reducing the molecular acting force among molecules of the asymmetric fluorene oxime ester compound and increasing the solubility of the asymmetric fluorene oxime ester compound; meanwhile, two side chains are introduced into 9, 9-diethylfluorene to form a diketone oxime ester structure, and when the compound is used as a photoinitiator, one molecule of asymmetric fluorene oxime ester compound can form two molecules of free radicals, so that the same effect as other photoinitiators can be achieved at lower dosage. When active energy rays are irradiated to the asymmetric oxime ester compound provided by the present invention, the generated radicals have a large molecular weight (more than 400) and thus the mobility of the radicals is small, so that curing occurs only on the irradiated region, and thus the asymmetric fluorenyloxime ester compound of the present invention has excellent pattern linearity characteristics. In addition, the asymmetric fluorenyloxime ester compound provided by the invention has high solubility, so that the asymmetric fluorenyloxime ester compound has excellent compatibility with other materials, hardly presents color after absorbing ultraviolet rays, and is very favorable for optical purpose application. The embodiment results show that the prepared photosensitive polymer composition has excellent pattern linearity and can obtain the effect of a more accurate pattern by using the asymmetric fluorene oxime ester compound provided by the invention as a photoinitiator, which indicates that the asymmetric fluorene oxime ester compound provided by the invention has high thermal stability and high sensitivity to active energy rays; and compatibility with other ingredients can be improved by good solubility.

Detailed Description

The invention provides an asymmetric fluorene oxime ester compound, which has a structure shown in a formula I:

in formula I, R comprises methyl, ethyl, propyl, phenyl or substituted phenyl.

In the present invention, the substituted phenyl group is preferably a nitrophenyl group.

In the present invention, the asymmetric fluorenyloxime ester compound preferably has a structure represented by any one of formulas II to V:

the invention provides a preparation method of an asymmetric fluorene oxime ester compound in the technical scheme, which comprises the following steps:

(1) mixing 9, 9-diethylfluorene, propionyl chloride, butyryl chloride, a metal salt catalyst and a solvent, and carrying out Friedel-crafts reaction to obtain a fluorene acyl compound;

(2) mixing the fluorene acyl compound, nitrite, acid catalyst and solvent, and carrying out nucleophilic substitution reaction to obtain an oxime compound;

(3) mixing the oximino compound, acyl chloride or acid anhydride, an alkaline reagent and a solvent, and carrying out an ester forming reaction to obtain an asymmetric fluorene oxime ester compound;

the acylating agent comprises one or more of acetyl chloride, propionyl chloride, butyryl chloride, benzoyl chloride, p-nitrobenzoyl chloride, acetic anhydride, propionic anhydride and benzoic anhydride.

In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.

The invention mixes 9, 9-diethyl fluorene, propionyl chloride, butyryl chloride, metal salt catalyst and solvent to carry out Friedel-crafts reaction to obtain the fluorene acyl compound.

In the present invention, the 9, 9-diethylfluorene is preferably purchased or produced, more preferably produced. In the present invention, the method for preparing 9, 9-diethylfluorene preferably comprises the steps of: mixing fluorene, bromoethane, an alkaline reagent and an organic solvent, and carrying out substitution reaction to obtain 9, 9-diethylfluorene; the reaction route is as follows:

in the present invention, the alkaline agent preferably includes an organic strong base or an inorganic strong base, and more preferably sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide. In the present invention, the molar ratio of the fluorene, bromoethane and alkaline agent is preferably 1: (2.2-2.6): (2.4-2.9), more preferably 1: (2.2-2.5): (2.4-2.8), most preferably 1: (2.3-2.5): (2.5-2.8). In the present invention, the organic solvent preferably includes an aprotic solvent, more preferably includes dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, or toluene; the amount of the organic solvent used in the present invention is not particularly limited, and any organic solvent known in the art may be used.

In the present invention, the mixing is preferably performed by stirring, and the stirring speed in the present invention is not particularly limited, and a stirring speed known in the art may be used. In the present invention, the order of mixing is preferably such that fluorene, an alkaline agent and an organic solvent are mixed, and bromoethane is added dropwise to the resulting mixture; the dropping rate of the bromoethane is not particularly limited in the present invention, and a dropping rate of bromoethane known in the art may be used.

In the invention, the temperature of the substitution reaction is preferably 10-30 ℃, and more preferably 20-25 ℃; the time of the substitution reaction is preferably 5 to 8 hours, and more preferably 5 to 7 hours.

After the substitution reaction is completed, the invention preferably further comprises the steps of extracting the obtained reaction system, and drying, filtering and concentrating the obtained organic phase by using a drying agent in sequence to obtain the 9, 9-diethylfluorene. In the present invention, the solvent used for the extraction is preferably ethyl acetate. In the present invention, the drying with a drying agent is preferably performed with anhydrous magnesium sulfate or anhydrous sodium sulfate. The filtration and concentration in the present invention are not particularly limited, and filtration and concentration means well known in the art may be used. In the invention, the concentrate obtained after the solvent is removed by concentration is 9, 9-diethylfluorene, and the subsequent reaction can be directly carried out without further purification.

After 9, 9-diethylfluorene is obtained, the 9, 9-diethylfluorene, propionyl chloride, butyryl chloride, a metal salt catalyst and a solvent are mixed for Friedel-crafts reaction to obtain a fluorene acyl compound.

In the present invention, the molar ratio of the 9, 9-diethylfluorene, propionyl chloride and butyryl chloride is preferably 1: (1.05-1.2): (1.05 to 1.2), more preferably 1: (1.1-1.2): (1.1-1.2), most preferably 1: (1.15-1.2): (1.15-1.2).

In the present invention, the metal salt catalyst preferably includes at least one of aluminum chloride, zinc chloride and ferric chloride, and more preferably includes aluminum chloride, zinc chloride or ferric chloride. In the present invention, the molar ratio of the 9, 9-diethylfluorene to the metal salt catalyst is preferably 1: (1.1 to 1.25), more preferably 1: (1.15 to 1.25), most preferably 1: (1.2-1.25).

In the present invention, the solvent preferably includes dichloromethane, trichloromethane, dichloroethane or chlorobenzene, more preferably dichloromethane; the amount of the solvent used in the present invention is not particularly limited, and any organic solvent known in the art may be used.

In the present invention, the mixing is preferably performed by stirring; the stirring and mixing speed is not particularly limited in the present invention, and a stirring speed well known in the art may be used.

In the present invention, the friedel-crafts reaction preferably comprises a first friedel-crafts reaction and a second friedel-crafts reaction twice friedel-crafts reaction process; the first Friedel-crafts reaction is preferably carried out by reacting 9, 9-diethylfluorene with propionyl chloride, and then carrying out the second Friedel-crafts reaction on the obtained fluorenylacyl intermediate product and butyryl chloride. In the present invention, specifically, the friedel-crafts reaction includes the following steps: mixing the 9, 9-diethylfluorene with a solvent, controlling the temperature to the temperature required by the Friedel-crafts reaction, adding a metal salt catalyst, then dropwise adding propionyl chloride into the obtained mixture, and carrying out a first Friedel-crafts reaction to obtain a fluorene acyl intermediate product solution; controlling the temperature to the temperature required by the Friedel-crafts reaction, adding a metal salt catalyst into the fluorenylacyl intermediate product solution, then dropwise adding butyryl chloride into the obtained mixture, and carrying out a second Friedel-crafts reaction to obtain a fluorenylacyl compound, wherein the reaction route is as follows:

the dropping rate of butyryl chloride is not particularly limited in the present invention, and any one known in the art may be used. In the invention, the temperature of the Friedel-crafts reaction is preferably-15 to-5 ℃, and the time is preferably 12 to 16 hours. In the invention, the temperature of the first Friedel-crafts reaction and the temperature of the second Friedel-crafts reaction are independent and are preferably-15 to-5 ℃, and more preferably-15 to-10 ℃; the time of the first Friedel-crafts reaction and the time of the second Friedel-crafts reaction are independent, preferably 6-8 h, and more preferably 6.5-7.5 h.

After the first friedel-crafts reaction is completed, the invention preferably further comprises the steps of dropwise adding ice water into the obtained reaction system, drying the obtained organic phase by adopting anhydrous magnesium sulfate or anhydrous sodium sulfate, and then filtering to obtain the fluorene acyl intermediate product solution. The filtration method of the present invention is not particularly limited, and a filtration method well known in the art may be used. In the present invention, the fluorene acyl intermediate solution can be directly subjected to the subsequent reaction without concentration and purification.

After the second friedel-crafts reaction is completed, the invention preferably further comprises the steps of dropwise adding ice water into the obtained reaction system, and drying, filtering and concentrating the obtained organic phase by using a drying agent in sequence to obtain the fluorene acyl compound. In the present invention, the drying agent used for the drying is preferably dried with anhydrous magnesium sulfate or anhydrous sodium sulfate. The filtration and concentration in the present invention are not particularly limited, and filtration and concentration means well known in the art may be used. In the invention, the concentrate obtained after concentration is the fluorene acyl compound, and the subsequent reaction can be directly carried out without further purification.

After obtaining the fluorene acyl compound, nitrite, acid catalyst and solvent are mixed for nucleophilic substitution reaction to obtain an oxime compound, wherein the reaction route is as follows:

in the present invention, the nitrite preferably includes ethyl nitrite, propyl nitrite, or isobutyl nitrite, and more preferably isobutyl nitrite. In the present invention, the molar ratio of the fluorene acyl compound to the nitrite is preferably 1: (2.2 to 2.5), more preferably 1: (2.3-2.5), most preferably 1: (2.3-2.4).

In the present invention, the acid catalyst is preferably an inorganic acid solution, more preferably comprising hydrochloric acid and/or sulfuric acid, most preferably hydrochloric acid; the amount of the acid catalyst is preferably calculated on the acid in the inorganic acid solution. In the present invention, the molar ratio of the fluorene acyl compound to the acid catalyst is preferably 1: (1.3 to 1.5), more preferably 1: (1.35-1.5), most preferably 1: (1.4-1.5).

In the present invention, the solvent preferably includes toluene, tetrahydrofuran, dimethylsulfoxide or N, N-dimethylformamide, more preferably toluene; the amount of the solvent used in the present invention is not particularly limited, and any organic solvent known in the art may be used.

In the present invention, the mixing is preferably performed by stirring, and the stirring speed in the present invention is not particularly limited, and may be a stirring speed well known in the art. In the present invention, the order of mixing is preferably such that the fluorene acyl compound, the acid catalyst and the solvent are mixed, and after controlling the temperature to a temperature required for the nucleophilic substitution reaction, the nitrite is added dropwise. The dropping speed of the nitrite is not particularly limited in the present invention, and the dropping speed of the nitrite known in the art may be used.

In the invention, the temperature of the nucleophilic substitution reaction is preferably 15-35 ℃, more preferably 15-30 ℃, and most preferably 20-25 ℃; the time of the nucleophilic substitution reaction is preferably 6-9 h, more preferably 7-9 h, and most preferably 7-8 h.

After the nucleophilic substitution reaction is completed, the method preferably further comprises the steps of adding water into the obtained reaction system, washing the obtained organic phase with water, collecting the organic phase, and then sequentially carrying out concentration, crystallization, filtration and drying to obtain the oximino compound. The concentration in the present invention is not particularly limited, and a concentration method known in the art may be used. In the present invention, the solvent used for the crystallization is preferably n-heptane; the crystallization mode is preferably stirring crystallization; the crystallization temperature is preferably 5-10 ℃. The filtration method of the present invention is not particularly limited, and a filtration method well known in the art may be used. The drying mode is not particularly limited in the invention, and the drying mode known in the field can be adopted, such as vacuum drying; the drying temperature is preferably 50-60 ℃, and more preferably 50 ℃; in the present invention, the drying time is not particularly limited, and the drying time may be set to a constant weight.

After an oxime compound is obtained, the oxime compound, an acylating agent, an alkaline reagent and a solvent are mixed for ester forming reaction to obtain an asymmetric fluorene oxime ester compound; the acylating agent preferably comprises one or more of acetyl chloride, propionyl chloride, butyryl chloride, benzoyl chloride, p-nitrobenzoyl chloride, acetic anhydride, propionic anhydride and benzoic anhydride; the reaction route is as follows:

in the present invention, the molar ratio of the oximino compound to the acylating agent is preferably 1: (2.2 to 2.4), more preferably 1: (2.25-2.4), most preferably 1: (2.3-2.4). In the present invention, the basic agent is preferably an organic base, more preferably includes triethylamine and/or pyridine, more preferably triethylamine; the molar ratio of the alkaline reagent to the oxime compound is preferably (2.4-2.6): 1, more preferably (2.4 to 2.5): 1.

in the present invention, the solvent preferably includes ethyl acetate, dichloromethane, dichloroethane or chloroform, more preferably ethyl acetate; the amount of the solvent used in the present invention is not particularly limited, and any organic solvent known in the art may be used.

In the present invention, the mixing is preferably performed by stirring, and the stirring speed in the present invention is not particularly limited, and a stirring speed known in the art may be used. In the present invention, the order of mixing is preferably to mix the oxime compound and the solvent, add the basic reagent, control the temperature to the temperature required for the ester-forming reaction, and then drop the acylating agent; in the present invention, the dropping rate of the acylating agent is not particularly limited, and a dropping rate of the acylating agent known in the art may be used.

In the invention, the temperature of the ester forming reaction is preferably 0-20 ℃, more preferably 0-15 ℃, and most preferably 5-10 ℃; the time of the ester forming reaction is preferably 3-5 h, more preferably 3.5-5 h, and most preferably 3-4 h.

After the ester forming reaction is completed, the invention preferably further comprises the steps of adding water into the obtained reaction system, washing the obtained organic phase with water, collecting the organic phase, and then sequentially carrying out concentration, crystallization, filtration and drying to obtain the asymmetric fluorene oxime ester compound. The concentration in the present invention is not particularly limited, and a concentration method known in the art may be used. In the present invention, the solvent used for the crystallization is preferably ethanol; the crystallization mode is preferably stirring crystallization; the crystallization temperature is preferably 5-10 ℃. The filtration method of the present invention is not particularly limited, and a filtration method well known in the art may be used. The drying mode is not particularly limited in the invention, and the drying mode known in the field can be adopted, such as vacuum drying; the drying temperature is preferably 50-60 ℃, and more preferably 50 ℃; in the present invention, the drying time is not particularly limited, and the drying time may be set to a constant weight.

The invention provides a photosensitive composition, which comprises a photoinitiator, bisphenol A glycerol diacrylate, dipentaerythritol hexaacrylate, a colorant and a solvent; the photoinitiator is the asymmetric fluorene oxime ester compound in the technical scheme.

In the present invention, the colorant is preferably carbon black. In the present invention, the solvent preferably includes propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and more preferably propylene glycol monomethyl ether acetate.

In the invention, the mass ratio of the photoinitiator, the bisphenol A glycerol diacrylate, the dipentaerythritol hexaacrylate, the colorant and the solvent is preferably (2-4): (40-60): (5-15): (30-50): (90-110), more preferably (2-3.5): (45-60): (8-15): (35-50): (95-110), most preferably (2-3): (50-55): (10-12): (40-45): (100 to 105).

The photosensitive composition provided by the invention takes the asymmetric fluorenyloxime ester compound with excellent photoinitiation characteristics as the photoinitiator, has excellent pattern linearity and can obtain the effect of more accurate pattern.

In the present invention, the method for preparing the photosensitive composition comprises the steps of: bisphenol A glycerol diacrylate, dipentaerythritol hexaacrylate, a colorant asymmetric fluorexime ester compound and a solvent are mixed to obtain the photosensitive composition.

In the present invention, the mixing mode is preferably stirring mixing, and the rotation speed of the stirring mixing is not particularly limited in the present invention, and a stirring speed well known in the art may be adopted; the stirring and mixing time is preferably 20-40 min, more preferably 25-35 min, and most preferably 30 min; in the present invention, the temperature for the stirring and mixing is not particularly limited, and is specifically room temperature. The preparation method provided by the invention is simple to operate and suitable for industrial production.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.