TW201838968A - Fluorine oxime ester photoinitiator containing polymerisable group, method for preparing the same and the use thereof - Google Patents

Abstract

A fluorine oxime ester photoinitiator containing polymerisable group, a method for preparing the same and the use thereof are disclosed. The fluorine oxime ester photoinitiator has a structure represented by formula (I). The photoinitiator has a relatively large molecular weight, and it also has a polymerisable group. In a photocuring process, the photoinitiator can be polymerized with olefinic double bonds of Polymer monomer to form a polymer having relatively large molecular weight. On the one hand, this makes the photocuring process proceed at a more uniform rate while increasing the photoinitiator activity. On the other hand, since the polymer obtained after photocuring process has relatively large molecular weight, it is difficult to produce a sublimate in a heated state, and thus the above photoinitiator has a low mobility after the photocuring process.

Description

   Perylene oxime ester photoinitiator containing polymerizable group, preparation method and application thereof   

The present invention relates to the field of organic chemistry, and in particular, to a perylene oxime ester photoinitiator containing a polymerizable group, a preparation method and application thereof in the field of photocuring.

UV curing materials have the advantages of fast curing, low solvent volatilization, and energy saving. They are widely used in the field of light curing, especially inks, coatings, adhesives, printed circuit boards, and liquid crystal display manufacturing. Photoinitiators are a key ingredient in the formulation. At present, oxime ester photoinitiators are gradually being developed. The oxime ester photoinitiators with carbazole and diphenyl sulfide as the main structure have been proven to have excellent photosensitivity and have been promoted and applied, especially in the manufacture of liquid crystal displays. Excellent developing performance, but the defects of higher cost and unsatisfactory solubility are also reflected during use. The cost of oxime ester photoinitiators with fluorene as the main structure is low, but the problems of mobility and solubility have not been effectively solved. In practical applications, high-mobility photoinitiators not only have limited application fields (such as food, toys, hygienic packaging materials, etc.), but also adversely affect environmental protection.

The liquid crystal panel includes a black matrix for accentuating the contrast of an image, and a color filter formed with a coloring layer of RGB (which is usually formed of each of red (R), green (G), and blue (B) colors). These black matrices and color filters are formed by repeatedly performing a process in which a photosensitive resin composition (also referred to as a photocurable resin composition) in which coloring agents of black or various colors are dispersed is applied to a substrate and dried. The obtained coating film is exposed and developed to form a desired pattern. For example, publication numbers CN104395824A, CN101923287A, CN103309154A, CN104345559A and other patents disclose the application of different oxime ester compounds in the production of color filters, black matrices, and color photoresists. For example, the patent publication numbers CN105838149A, CN106483764A, and CN106537254A report The application of different oxime ester initiators in color photoresists, color filters, light gaps, and insulating films. These photoinitiators have high photosensitivity, but it is found that there is a risk of migration after long-term use.

In addition, the application of oxime ester photoinitiators in the field of photocuring has been well known. Compared with general photoinitiators, oxime ester photoinitiators have excellent photosensitivity. Quite a variety of oxime ester-based photosensitive resin compositions are used. Developed and applied to the manufacture of liquid crystal displays including color photoresist, black matrix, light spacers and rib walls. However, with the thinning, miniaturization, and high integration of electronic devices, liquid crystal displays are developing in the direction of small size and high definition. This affects the sensitivity, transparency, and adhesion of photosensitive resin compositions in applications. Higher performance is required in terms of pattern developability.

In recent years, when manufacturing liquid crystal displays, people have been trying to improve the light-shielding property of black matrix picture tubes and further improve the contrast of images on liquid crystal displays. In order to solve the above problems, it is generally necessary to add a large amount of a light-shielding agent to a photosensitive resin composition for forming a black matrix picture tube. However, if a large amount of a light-shielding agent is added to the photosensitive resin composition, when the film of the photosensitive resin composition is exposed, it is difficult for the light for curing it to reach the bottom of the film, so that the light-curing resin is combined with the light-curing resin composition. If the sensitivity of the material is drastically reduced, the photosensitive resin composition may cause a problem of poor curing.

When a fluorene ester compound is used as a photopolymerization initiator to form a black matrix picture tube, although it has good sensitivity, it is very easy to over develop and cause the pattern of the black matrix picture tube to be undercut. Generally, when a pattern of a color filter for a liquid crystal display is formed using a photosensitive resin composition, as shown in FIG. 1, a cross section of the pattern in the width direction, that is, a cross section 1 is generally trapezoidal, and the trapezoidal shape is separated from A shape in which the width is wider as the bottom edge 1a is closer and narrower as the bottom edge 1b is closer. At this time, an angle θ formed between the cross section 1 of the pattern and the color filter substrate is an acute angle. However, when the photosensitive resin composition is used to form a black picture tube, it may dissolve with the bottom of a part of the developed pattern formed during the development process. As shown in FIG. 2, the cross section in the pattern width direction is the cross section 2 Undercut edges 21 are generated at both ends of the bottom edge 2a of the sintered edge. At this time, an angle θ formed between the cross section 2 of the pattern and the color filter substrate is an obtuse angle. In this way, if the angle θ is an obtuse angle, when the pixel regions adjacent to the black picture tube are formed, the undercut 21 generates bubbles locally, which seriously damages the display quality of the liquid crystal display device.

In order to solve the technical problems in the prior art as described above, according to one aspect of the present invention, a peroxime ester photoinitiator containing a polymerizable group is provided. By introducing a polymerizable group at the 9-position of the fluorene structure, the formed oxime ester photoinitiator has good solubility, high photo-initiation efficiency, and after curing, it is combined with the matrix resin with almost no migration, and has strong applications. prospect.

In addition, according to another aspect of the present invention, the present invention provides a photocurable resin composition containing the above-described polymerizable group-containing oxime ester photoinitiator and application thereof to solve the existing photocurable composition. It is easy to over develop and cause undercut of the development pattern.

In order to achieve the above object, the present invention provides a oxime ester photoinitiator containing a polymerizable group, which has a structure represented by formula (I):

Wherein, n represents an integer of 1 to 4; R ₁ each independently represents H, nitro, halogen, C ₁ -C ₂₀ linear or branched alkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₄ aralkyl group, C ₃ -C ₅ heterocyclic group containing O, N or S heteroatom and double bond or C ₁ -C ₁₂ alkyl group terminated with the heterocyclic group, or -XC (R ₃ ) = NO-CO-R ₄ , -CH ₂ -in the above group may be optionally substituted by -O-, -S-, -NH-, -CO-, -COO-, or -OCO-.

R ₂ represents a polymerizable group; X represents a direct bond or a carbonyl group (ie, -CO-); R ₃ represents a C ₁ -C ₂₀ straight or branched chain alkyl group, C ₃ -C ₂₀ cycloalkyl group, C ₄ -C ₂₀ cycloalkylalkyl, C ₄ -C ₂₀ alkylcycloalkyl, C ₆ -C ₂₀ aryl, C ₄ -C ₂₀ heteroaryl, containing O, N or S heteroatoms and C ₃ -C ₅ heterocyclic group with double bond or C ₁ -C ₆ alkyl group with the heterocyclic group as cap; R ₄ represents C ₁ -C ₂₀ linear or branched alkyl group, C ₃ -C ₂₀ Cycloalkyl, C ₄ -C ₂₀ cycloalkylalkyl, C ₄ -C ₂₀ alkylcycloalkyl, C ₆ -C ₂₀ aryl, C ₄ -C ₂₀ heteroaryl, or C ₂ -C ₂₀ alkenyl.

In the structure represented by the above formula (I), R _{1 is} preferably H, nitro, halogen, C ₁ -C ₁₀ linear or branched alkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₆ aralkyl group, thienyl group, pyrrolyl group, thiophene group or a pyrrolyl terminated C ₁ -C ₄ alkyl, or _{-XC (R 3) = NO-} CO-R 4, in the aforementioned groups -CH ₂ -can be optionally substituted by -O-, -S-, -NH-, -CO-, -COO-, or -OCO-.

More preferably, n = 1, R ₁ is opposite to the position of -XC (R ₃ ) = NO-CO-R ₄ on the right side of the structure of formula (I), and R _{1 is} selected from H, nitro, C ₁ -C ₄ Linear or branched alkyl, phenyl, benzamidine ( ), 3-thienyl ( ), 3-thienylmethyl ( ), Or -XC (R ₃ ) = NO-CO-R ₄ .

In the structure represented by the formula (I), R ₂ is a polymerizable group containing a double bond, an epoxy group, or a combination thereof.

Preferably, R _{2 is} selected from the following: ───C ₂ -C ₁₂ alkenyl, one or more of the alkenyl -CH ₂ -can be optionally independently selected by -O-,- CO-, -COO-, -OCO- or Substituted; ─── ethylene oxide alkyl or propylene oxide alkyl, one or more of the alkyl groups between the epoxy group and the fluorene structure -CH ₂ -can be optionally independent of each other Is replaced with -O-, -CO-, -COO-, -OCO- or -O-CH ₂ -CH (OH) -CH ₂ -O-.

More preferably, R _{2 is} selected from the group consisting of: C ₃ -C ₈ alkenyl groups, wherein one or more of the alkenyl groups -CH ₂ -can be independently independently selected from -O-, -CO-, -COO-, -OCO- or Substituted; ───C ₁ -C ₈ alkyl groups with ethylene oxide or propylene oxide as the end groups, one or more of the alkyl groups -CH ₂ -can be independently selected independently Substituted by -O-, -CO-, -COO-, -OCO- or -O-CH ₂ -CH (OH) -CH _2- O-, and H in ethylene oxide or propylene oxide It may be substituted by C ₁ -C ₄ alkyl.

In the structure represented by the above formula (I), R _{3 is} preferably a C ₁ -C ₁₀ linear or branched alkyl group, a C ₃ -C ₁₀ cycloalkyl group, or a C ₄ -C ₁₀ cycloalkyl alkyl group. Group, C ₄ -C ₁₀ alkylcycloalkyl group, C ₆ -C ₁₀ aryl group, C ₃ -C ₅ heterocyclic group containing O, N or S heteroatom and double bond, or the heterocyclic group is Capped C ₁ -C ₆ alkyl.

More preferably, R _{3 is} selected from C ₂ -C ₆ linear or branched alkyl, C ₃ -C ₈ cycloalkyl, C ₄ -C ₁₀ cycloalkylalkyl, C ₄ -C ₁₀ Alkylcycloalkyl, phenyl (one or more of which H may be optionally substituted by C ₁ -C ₄ alkyl), C ₇ -C ₁₀ phenylalkyl (one or more of phenyl Each H may be optionally substituted with C ₁ -C ₄ alkyl), thienyl, or C ₁ -C ₄ alkyl terminated with thienyl.

In the structure represented by the above formula (I), R _{4 is} preferably a C ₁ -C ₆ linear or branched alkyl group, a C ₃ -C ₁₀ cycloalkyl group, or a C ₄ -C ₁₄ cycloalkyl alkyl group. Radical, C ₄ -C ₁₄ alkylcycloalkyl, or C ₆ -C ₁₂ aryl.

More preferably, R ₄ is a C ₁ -C ₄ linear or branched alkyl group, a C ₃ -C ₈ cycloalkyl group, a C ₄ -C ₁₀ cycloalkylalkyl group, or a phenyl group.

Without limitation, the oxime ester photoinitiator containing a polymerizable group may be selected from the following structures:

According to another aspect of the present invention, the present invention also provides a perylene oxime ester-based photoinitiator containing a polymerizable group, and the perylene oxime ester-based photoinitiator containing a polymerizable group has a structure represented by formula (I):

Wherein, n represents an integer from 1 to 4; X represents a direct bond or a carbonyl group; and R _{1 is} selected from H, a nitro group, a halogen atom, a C ₁ -C ₂₀ straight-chain alkyl group or a branched alkyl group, C ₆ -C ₂₀ aryl, C ₆ -C ₁₄ aryl substituted C ₁ -C ₁₀ alkyl, double bond C ₃ -C ₅ heterocyclyl, double bond C ₃ -C ₅ hetero Cyclyl-terminated C ₁ -C ₁₂ alkyl, or And -CH ₂ -in R ₁ may be substituted with -O-, -S-, -NH-, -CO-, -COO-, or -OCO-; two of said R ₂ are each selected from the group consisting of olefins A double bond-containing substituent, a three-membered epoxy group-containing substituent or a four-membered epoxy group-containing substituent, and two of said R _{2 are the} same or different; said R _{3 is} selected from C ₁ -C ₂₀ linear or branched alkyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₈ cycloalkyl substituted C ₁ -C ₁₀ alkyl, C ₁ -C ₂₀ alkyl substituted C ₃ -C ₈ cycloalkyl, phenyl, a group obtained by substituting at least one hydrogen atom of a phenyl group with a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkoxy group A group obtained by substituting at least one hydrogen atom with a fluorine atom, a thienyl group, or a C ₁ -C ₄ alkyl group terminated with a thienyl group; the R _{4 is} selected from a C ₁ -C ₂₀ linear or branched alkyl group , C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₈ cycloalkyl substituted C ₁ -C ₁₀ alkyl, C ₆ -C ₂₀ aryl, C ₁ -C ₅ alkyl substituted C ₆ -C ₂₀ aryl, C ₄ -C ₂₀ heteroaryl, C ₂ -C ₂₀ alkenyl or C ₁ -C ₅ alkyl substituted C ₆ -C ₂₀ heteroaryl.

Preferably, R ₁ is H, nitro, halogen, C ₁ -C ₁₀ linear or branched alkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₆ aralkyl, thiophene group, pyrrolyl group, thiophene group or a pyrrolyl terminated C ₁ -C ₄ alkyl, or _{-XC (R 3) = NO-} CO-R 4, the R ₁ is a -CH ₂ - may be -O -, -S-, -NH-, -CO-, -COO- or -OCO-.

Preferably, n = 1, the R ₁ is opposite to the position of -XC (R ₃ ) = NO-CO-R ₄ on the right side of the structure of formula (I), and the R _{1 is} selected from H, nitro, C ₁ -C ₄ linear or branched alkyl, phenyl, benzamyl ( ), 3-thienyl ( ), 3-thienylmethyl ( ), Or -XC (R ₃ ) = NO-CO-R ₄ .

Preferably, R ₂ is a polymerizable group containing a double bond, an epoxy group, or a combination thereof.

Preferably, R _{2 is} selected from C ₂ -C ₁₂ alkenyl, ethylene oxide alkyl or propylene oxide alkyl; optionally, when R ₂ is C ₂ -C ₁₂ In the case of an alkenyl group, one or more of -CH ₂ -in R ₂ may be each independently -O-, -CO-, -COO-, -OCO- or Substituted; optionally, when R ₂ is an oxiranyl alkyl group or a propylene oxide alkyl group, one of the alkyl groups between the epoxy group in the R ₂ and the fluorene structure One or more of -CH ₂ -may each be independently replaced by -O-, -CO-, -COO-, -OCO-, or -O-CH ₂ -CH (OH) -CH ₂ -O-.

Preferably, R _{2 is} selected from a C ₃ -C ₈ alkenyl group or a C ₁ -C ₈ alkyl group terminated with ethylene oxide or propylene oxide; optionally, when the When R ₂ is a C ₃ -C ₈ alkenyl group, one or more of -CH ₂ -in R ₂ may be independently selected from -O-, -CO-, -COO-, -OCO- or Substituted; optionally, when R ₂ is a C ₁ -C ₈ alkyl group with ethylene oxide or propylene oxide as the end group, one of the C ₁ -C ₈ alkyl groups Or more -CH ₂ -may each be independently replaced by -O-, -CO-, -COO-, -OCO-, or -O-CH ₂ -CH (OH) -CH ₂ -O-, and said H in the ethylene oxide group or the propylene oxide group may be substituted with a C ₁ -C ₄ alkyl group.

Preferably, R ₃ represents a C ₁ -C ₁₀ linear or branched alkyl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₄ -C ₁₀ cycloalkylalkyl group, or C ₄ -C ₁₀ Alkylcycloalkyl, C ₆ -C ₁₀ aryl, C ₃ -C ₅ heterocyclyl containing O, N or S heteroatoms and double bonds or the C ₃ -C ₅ heterocyclyl as seal end C ₁ -C ₆ alkyl.

Preferably, R _{3 is} selected from C ₂ -C ₆ linear or branched alkyl, C ₃ -C ₈ cycloalkyl, C ₄ -C ₁₀ cycloalkylalkyl, C ₄ -C ₁₀ alkylcycloalkyl, phenyl, C ₇ -C ₁₀ phenylalkyl (one or more H in the phenyl may be optionally substituted by C ₁ -C ₄ alkyl), thienyl, Or C ₁ -C ₄ alkyl terminated with thienyl; optionally, when R ₃ is phenyl, one or more H in the phenyl may be substituted by C ₁ -C ₄ alkyl ; Optionally, when R ₃ is a C ₇ -C ₁₀ phenylalkyl group, one or more H of phenyl groups in the C ₇ -C ₁₀ phenylalkyl group may be C ₁ -C ₄ alkyl.

Preferably, R ₄ is a C ₁ -C ₆ linear or branched alkyl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₄ -C ₁₄ cycloalkylalkyl group, or a C ₄ -C ₁₄ group. Alkylcycloalkyl, or C ₆ -C ₁₂ aryl.

Preferably, R ₄ is a C ₁ -C ₄ linear or branched alkyl group, a C ₃ -C ₈ cycloalkyl group, a C ₄ -C ₁₀ cycloalkylalkyl group, or a phenyl group.

Preferably, the photooxime ester-containing photoinitiator is selected from with One or more of the group.

According to another aspect of the present invention, the present invention also provides a method for preparing a oxime ester photoinitiator containing a polymerizable group represented by the formula (I), including the following steps: (1) a raw material for preparing intermediate a a reacts with raw material b, R ₂ -Y in the presence of a catalyst to form intermediate a; wherein Y represents halogen, preferably F, Cl or Br; (2) preparation of intermediate b, intermediate a and raw materials c is R ₃ '-CO-Cl under the catalysis of aluminum trichloride or zinc chloride in an organic solvent to form a fucosylation reaction to obtain intermediate b; wherein R ₃ ' represents R ₃ or R ₃ -CH _2- , specifically, when X is a direct bond, R ₃ ′ represents R ₃ , when X is a carbonyl group, R ₃ ′ represents R ₃ -CH _2- ; (3) preparation of intermediate c when X is direct When bonded, intermediate b undergoes an oximation reaction under the action of hydroxylamine hydrochloride and sodium acetate to form intermediate c; when X is a carbonyl group, in the presence of concentrated hydrochloric acid, intermediate b is reacted with nitrite or nitrite in oximation reaction carried out at room temperature to produce intermediate c; c preparation of intermediate with an acid anhydride (4) the product of (R ₄ -CO) ₂ O or acyl chloride compound R ₄ -CO-Cl esterification reaction, to give Standard product; reaction scheme is shown below: .

The raw materials used in the above synthesis are known compounds, which can be obtained commercially or conveniently prepared by known synthesis methods. The synthesis process includes a nucleophilic reaction, a Fockylation reaction, an oximation reaction, and an esterification reaction, which are all conventional reaction types in the field of organic chemical synthesis. After the reaction process is clarified, the specific reaction conditions can be easily determined by those skilled in the art.

In step (1), a raw material a and R ₂ -Y undergo a nucleophilic reaction in the presence of a catalyst to obtain an intermediate a. The catalyst may be selected from sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, potassium methoxide and the like. The reaction is performed in a solvent system, and the type of the solvent used is not particularly limited, as long as it can dissolve the raw materials and does not adversely affect the reaction, DMSO, THF, and DMF are preferred. The reaction temperature is usually room temperature; the reaction time varies slightly depending on the kind of raw materials, and is usually 2-10 hours.

The reaction temperature in step (2) is usually -10-30 ° C. There is no particular limitation on the type of organic solvent used, as long as it can dissolve the raw materials without adversely affecting the reaction, such as dichloromethane, dichloroethane, benzene, toluene, xylene, and the like.

In step (3), the preparation of the intermediate c is performed in a solvent system, and the type of the solvent used is not particularly limited as long as it can dissolve the raw materials and does not adversely affect the reaction. When X is a direct bond, the solvent used may be a mixed solvent of alcohol and water, preferably a mixed solvent of ethanol and water; the reaction is performed under heating and refluxing. When X is a carbonyl group, the solvent used may be dichloromethane, benzene, toluene, tetrahydrofuran, etc. The nitrite may be selected from ethyl nitrite, isoamyl nitrite, isooctyl nitrite, etc. The nitrite may be selected from sodium nitrite, potassium nitrite, and the like.

In step (4), the esterification reaction is performed 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, such as methylene chloride, dichloroethane, benzene, toluene, Xylene and so on.

According to yet another aspect of the present invention, the present invention also provides the use of a polymerizable group-containing oxime ester photoinitiator represented by formula (I) in the field of photocuring, and a photoinitiator containing the oxime ester Light curing resin composition.

The photocurable resin composition according to the present invention may contain a polymerizable compound (that is, a polymer monomer), in addition to a polymerizable group-containing oxime ester-based photoinitiator represented by formula (I), Alkali soluble resin and optionally other components. Preferably, the photo-curable resin composition further includes an alkali-soluble resin and an additive.

As the polymerizable compound (ie, a polymer monomer), those generally used in the field of photocuring can be selected. Preferably, the polymer monomer is a photopolymer monomer compound having an ethylenically unsaturated double bond, for example, (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxy Methyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acryl Amidine, N-hydroxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid , Itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, t-butylacrylamidosulfonic acid, methyl (meth) acrylate, (formaldehyde) (Ethyl) ethyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) propenyloxy phthalate 2-Hydroxypropyl ester, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate Ester, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3 (meth) acrylate -Tetrafluoropropyl ester, (meth) acrylic acid half ester of phthalic acid derivatives, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate , 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12- Dodecanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 2-hydroxy (meth) acrylate -3- (meth) acrylic acid oxypropyl ester, dipentaerythritol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol Di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, poly (ethylene- Propylene) glycol di (meth) acrylate, poly 1,4-butanediol di (meth) acrylate, ethoxylated bisphenol A (Meth) acrylate, propoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, ethylene glycol di (meth) acrylate Ester, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol bis (methyl) Base) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (methyl) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) propenyloxydiethoxyphenyl) propane, 2 , 2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acrylfluorenyloxypropyl (meth) acrylate Ester, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerol Triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., toluene diisocyanate), trimethyl-1,6-hexanediisocyanate, and 1,6 -Reactants of hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, polyol and N-hydroxyl Condensate of methyl (meth) acrylamide, 1,3,5-tripropenylhexahydro-1,3,5-triazine (triacrylformal), 2,4,6-trioxane-1 , 3,5-triazine-1,3,5-triethanol triacrylate, and 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-triethanol Diacrylate and so on. The polymerizable compound may be used singly or in combination of two or more. The content of the polymerizable compound may be 5 to 60 wt%, preferably 10 to 50 wt% based on the solid content of the photocurable resin composition.

The alkali-soluble resin can be appropriately selected from resins that have been used in combination in various photocurable compositions. By using an alkali-soluble resin in the photocurable composition, alkali developability can be further improved. The alkali-soluble resin is preferably a (meth) acrylate copolymer. Based on the solid content of the photocurable resin composition, the content of the alkali-soluble resin may be 0 to 90 weight percent (wt%), preferably 10 to 80 wt%.

According to need, various conventional auxiliaries in the art may also be contained in the photocurable resin composition. Non-limiting examples include solvents, surface conditioners, sensitizers, curing accelerators, photocrosslinkers, photosensitizers, dispersion aids, fillers, adhesion promoters, antioxidants, and ultraviolet absorbers , Anti-flocculant, thermal polymerization inhibitor, defoamer, surfactant, chain transfer agent, etc. All additives can be made of known substances. Examples of the surfactant include anionic compounds, cationic compounds, and nonionic compounds. Examples of the adhesion improving agent include a silane coupling agent. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monoethyl ether, and the like. Examples of the antifoaming agent include a polysiloxane compound and a fluorine compound.

Preferably, the additive is selected from the group consisting of solvents, dyes, pigments, fillers, surface conditioners, defoamers, leveling agents, wetting agents, dispersants, matting agents, curing accelerators, chain transfer agents, antioxidants, One or more selected from the group consisting of an ultraviolet absorber, a deflocculant, a thermal polymerization inhibitor, and an adhesion promoter.

According to another aspect of the present invention, there is provided a color filter including a development pattern, the development pattern being formed using the photocurable resin composition as described above.

According to another aspect of the present invention, there is provided a display device including the color filter as described above.

Practical applications show that the above-mentioned oxime ester photoinitiators of the present invention have the characteristics of high photoinitiation efficiency, good solubility, and no migration, and have good market prospects.

In addition, by applying the technical solution of the present invention, in the photocurable resin composition, the photoinitiator having a structure represented by formula (I) itself has a relatively large molecular weight, and it also has a polymerizable group, so it is photocured. During the process, the photoinitiator can polymerize with the olefinic double bond in the polymer monomer to form a polymer having a larger molecular weight. On the one hand, this is beneficial for curing the above-mentioned photocurable composition at a relatively uniform rate, thereby effectively suppressing the occurrence of undercuts in the pattern during the photocuring process. On the other hand, since the molecular weight of the polymer obtained after curing is relatively large, it is difficult to produce sublimates in a heated state, so the cured product formed by the photocurable composition also has high thermal stability. In summary, even in the case where the photosensitive resin composition contains a light-shielding agent or an insufficient exposure amount, the photocurable composition provided by the present application can suppress the occurrence of undercuts in the pattern after development, and has a relatively high effect after development. High thermal stability.

1, 2‧‧‧ section

1a, 2a‧‧‧Bottom

1b‧‧‧Top edge

21‧‧‧ Undercut

θ‧‧‧ angle

The accompanying drawings, which constitute a part of this application, are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and the descriptions thereof are used to explain the present invention, and do not constitute an improper limitation on the present invention. In the drawings: FIG. 1 shows a schematic diagram of a developing pattern formed using a photocurable composition provided in the present application; and FIG. 2 shows a schematic diagram of a undercut phenomenon occurring in a developing pattern formed using a conventional photocurable composition. .

It should be noted that, in the case of no conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present invention will be described in detail with reference to the following embodiments.

As described in the background art, existing photoinitiators have a problem of easy migration. In order to solve the above technical problem, the present application provides a perylene oxime ester photoinitiator containing a polymerizable group, and the oxime ester photoinitiator containing a polymerizable group has a structure represented by formula (I):

Wherein n represents an integer from 1 to 4; X represents a direct bond or a carbonyl group; R _{1 is} selected from H, a nitro group, a halogen atom, a C ₁ -C ₂₀ linear or branched alkyl group, and C ₆ -C ₂₀ aryl groups, C ₆ -C ₁₄ aryl substituted C ₁ -C ₁₀ alkyl groups, C ₃ -C ₅ heterocyclic groups containing double bonds, C ₃ terminated by C ₃ C ₅ heterocyclic groups containing double bonds _1- C ₁₂ alkyl, or And -CH ₂ -in R ₁ may be substituted with -O-, -S-, -NH-, -CO-, -COO-, or -OCO-; the two R ₂ are each selected from the group consisting of olefinic double bonds A substituent, a substituent containing a three-membered epoxy group, or a substituent containing a four-membered epoxy group, and two R _{2 are the} same or different; R _{3 is} selected from a C ₁ -C ₂₀ linear alkyl group or a branched chain Alkyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₈ cycloalkyl substituted C ₁ -C ₁₀ alkyl, C ₁ -C ₂₀ alkyl substituted C ₃ -C ₈ cycloalkyl, a phenyl group, a phenyl group at least one hydrogen atom is substituted by C ₁ -C ₄ alkyl group obtained, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxy group at least one hydrogen atom is a fluorine atom substituent groups derived, thienyl, thienyl or terminated C ₁ -C ₄ alkyl; R ₄ is selected from C ₁ -C ₂₀ linear or branched alkyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₈ cycloalkyl substituted C ₁ -C ₁₀ alkyl, C ₆ -C ₂₀ aryl, C ₁ -C ₅ alkyl substituted C ₆ -C ₂₀ aryl, C ₄ -C ₂₀ Heteroaryl, C ₂ -C ₂₀ alkenyl or C ₁ -C ₅ alkyl substituted C ₆ -C ₂₀ heteroaryl.

The photoinitiator having the structure represented by the formula (I) has a relatively large molecular weight, and at the same time, it also has a polymerizable group. During the photocuring process, the photoinitiator can react with the olefinic dimer in the polymer monomer. The bonds undergo a polymerization reaction to form a polymer having a larger molecular weight. On the one hand, this allows the photo-curing process to proceed at a more uniform rate while increasing the initiation activity of the photoinitiator. On the other hand, since the molecular weight of the polymer obtained after curing is relatively large, it is difficult to produce sublimates in a heated state. Therefore, after curing, the photoinitiator has lower migration. In summary, the photoinitiator having the above structure has higher photoinitiating activity and lower mobility. The photoinitiator having the above structure has higher photoinitiating activity and lower mobility. In order to further improve the overall performance of the photoinitiator, each group in the photoinitiator may be further optimized.

In a preferred embodiment, R ₁ is H, nitro, halogen, C ₁ -C ₁₀ linear or branched alkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₆ arane , Thienyl, pyrrolyl, C ₁ -C ₄ alkyl terminated with thienyl or pyrrolyl, or -XC (R ₃ ) = NO-CO-R ₄ , -CH _{2 in} R ₁ -may be- O-, -S-, -NH-, -CO-, -COO- or -OCO-.

In a preferred embodiment, n = 1, R ₁ is opposite to the position of -XC (R ₃ ) = NO-CO-R ₄ on the right side of the structure of formula (I), and R _{1 is} selected from H, nitro, and C. _1- C ₄ linear or branched alkyl, phenyl, benzamyl ( ), 3-thienyl ( ), 3-thienylmethyl ( ), Or -XC (R ₃ ) = NO-CO-R ₄ .

In a preferred embodiment, R ₂ is a polymerizable group containing a double bond, an epoxy group, or a combination thereof.

In a preferred embodiment, R _{2 is} selected from C ₂ -C ₁₂ alkenyl, ethylene oxide alkyl, or propylene oxide alkyl; optionally, when R ₂ is C ₂ -C _{In the case} of an alkenyl group of ₁₂ , one or more -CH ₂ -in R ₂ may be each independently -O-, -CO-, -COO-, -OCO- or Substituted; optionally, when R ₂ is an oxiranyl alkyl group or a propylene oxide alkyl group, one or more of the alkyl group between the epoxy group in the R ₂ and the fluorene structure − CH ₂ — may be independently substituted by —O—, —CO—, —COO—, —OCO—, or —O—CH ₂ —CH (OH) —CH ₂ —O—.

In a preferred embodiment, R _{2 is} selected from C ₃ -C ₈ alkenyl or C ₁ -C ₈ alkyl terminated with ethylene oxide or propylene oxide; optionally, When R ₂ is a C ₃ -C ₈ alkenyl group, one or more -CH ₂ -in R ₂ may each be independently replaced by -O-, -CO-, -COO-, -OCO- or Substituted; optionally, when R ₂ is a C ₁ -C ₈ alkyl group terminated with ethylene oxide or propylene oxide group, one or more of C ₁ -C ₈ alkyl groups- CH ₂ -may each be independently substituted with -O-, -CO-, -COO-, -OCO-, or -O-CH ₂ -CH (OH) -CH ₂ -O-, and ethylene oxide or H in propylene oxide may be substituted by C ₁ -C ₄ alkyl.

In a preferred embodiment, R ₃ represents a C ₁ -C ₁₀ linear or branched alkyl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₄ -C ₁₀ cycloalkylalkyl group, C ₄ -C ₁₀ alkylcycloalkyl, C ₆ -C ₁₀ aryl, C ₃ -C ₅ heterocyclyl containing O, N or S heteroatoms and double bonds, or C ₃ -C ₅ heterocyclyl as Capped C ₁ -C ₆ alkyl.

In a preferred embodiment, R _{3 is} selected from C ₂ -C ₆ linear or branched alkyl, C ₃ -C ₈ cycloalkyl, C ₄ -C ₁₀ cycloalkylalkyl, C ₄ -C ₁₀ alkylcycloalkyl, phenyl group, C ₇ -C ₁₀ phenylalkyl (the phenyl group of one or more H optionally substituted with C ₁ -C ₄ alkyl), thienyl, thienyl terminated in thiazol C ₁ -C ₄ alkyl; alternatively, when R ₃ is a phenyl group, a phenyl group or more H can be substituted by C ₁ -C ₄ alkyl group; a Alternatively, when R ₃ is a C ₇ -C ₁₀ phenylalkyl group, one or more H of the phenyl groups in the C ₇ -C ₁₀ phenylalkyl group may be replaced by a C ₁ -C ₄ alkyl group. To replace.

In a preferred embodiment, R ₄ is a C ₁ -C ₆ linear or branched alkyl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₄ -C ₁₄ cycloalkyl alkyl group, C ₄ -C ₁₄ alkylcycloalkyl, or C ₆ -C ₁₂ aryl.

In a preferred embodiment, R ₄ is a C ₁ -C ₄ linear or branched alkyl group, a C ₃ -C ₈ cycloalkyl group, a C ₄ -C ₁₀ cycloalkylalkyl group, or a phenyl group. .

In a preferred embodiment, the photoinitiator containing a oxime ester is selected from with One or more of the group.

One aspect of the present invention provides a method for preparing a polymerizable group-containing oxime ester photoinitiator represented by the above formula (I), including the following steps: (1) a raw material a for preparing an intermediate a and a raw material b, that is, R ₂ -Y reacts in the presence of a catalyst to form intermediate a; wherein Y represents halogen, preferably F, Cl or Br; (2) Preparation of intermediate b, intermediate a and raw material c, ie, R ₃ '- CO-Cl undergoes a fucosylation reaction in an organic solvent under the catalysis of aluminum trichloride or zinc chloride to obtain intermediate b; wherein R ₃ ′ represents R ₃ or R ₃ -CH _2- , specifically, When X is a direct bond, R ₃ ′ represents R ₃ ; when X is a carbonyl group, R ₃ ′ represents R ₃ —CH ₂ —; (3) Preparation of intermediate c. When X is a direct bond, intermediate b is at Perform oximation reaction with hydroxylamine hydrochloride and sodium acetate to produce intermediate c; when X is carbonyl, in the presence of concentrated hydrochloric acid, intermediate b and nitrite or nitrite undergo oximation reaction at normal temperature to produce intermediate c; c preparation of intermediate with an acid anhydride (4) the product of (R ₄ -CO) ₂ O or acyl chloride compound R ₄ -CO-Cl esterification reaction, to give the desired product; the following reaction scheme Shows: .

The raw materials used in the above synthesis are known compounds, which can be obtained commercially or conveniently prepared by known synthesis methods. The synthesis process includes a nucleophilic reaction, a Fockylation reaction, an oximation reaction, and an esterification reaction, which are all conventional reaction types in the field of organic chemical synthesis. After the reaction process is clarified, specific reaction conditions are easy to determine for those skilled in the art.

In step (1), a raw material a and R ₂ -Y undergo a nucleophilic reaction in the presence of a catalyst to obtain an intermediate a. The catalyst may be selected from sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, potassium methoxide and the like. The reaction is performed in a solvent system, and the type of the solvent used is not particularly limited, as long as it can dissolve the raw materials and does not adversely affect the reaction, DMSO, THF, and DMF are preferred. The reaction temperature is usually room temperature; the reaction time varies slightly depending on the kind of raw materials, and is usually 2-10 hours.

The reaction temperature in step (2) is usually -10-30 ° C. There is no particular limitation on the type of organic solvent used, as long as it can dissolve the raw materials without adversely affecting the reaction, such as methylene chloride, dichloroethane, benzene, toluene, xylene, and the like.

In step (3), the preparation of the intermediate c is performed in a solvent system, and the type of the solvent used is not particularly limited as long as it can dissolve the raw materials and does not adversely affect the reaction. When X is a direct bond, the solvent used may be a mixed solvent of alcohol and water, preferably a mixed solvent of ethanol and water; the reaction is performed under heating and refluxing. When X is a carbonyl group, the solvent used may be dichloromethane, benzene, toluene, tetrahydrofuran, etc. The nitrite may be selected from ethyl nitrite, isoamyl nitrite, isooctyl nitrite, etc. The nitrite may be selected from sodium nitrite, potassium nitrite, and the like.

In step (4), the esterification reaction is performed 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, such as methylene chloride, dichloroethane, benzene, toluene, Xylene and so on.

In order to better understand the present invention, another aspect of the present invention provides a photo-curable resin composition. The photo-curable resin composition includes a photoinitiator and a polymer monomer. The polymer monomer contains an olefinic double bond. Photoinitiators include the above-mentioned photoinitiator-containing photoinitiators.

In the photocurable resin composition, the photoinitiator having the structure represented by the formula (I) itself has a relatively large molecular weight, and it also has a polymerizable group. During the photocuring process, the photoinitiator can be polymerized with the polymer. The olefinic double bond in the polymer monomer undergoes a polymerization reaction to form a polymer having a larger molecular weight. On the one hand, this is beneficial for curing the photocurable composition at a relatively uniform rate, thereby effectively suppressing the occurrence of undercuts in the pattern during the photocuring process. On the other hand, since the molecular weight of the polymer obtained after curing is relatively large, it is difficult to produce sublimates in a heated state, so the cured product formed by the photocurable composition also has high thermal stability. In summary, even in the case where the photosensitive resin composition contains a light-shielding agent or an insufficient exposure amount, the photocurable composition provided by the present application can suppress the occurrence of undercuts in the pattern after development, and has a relatively high effect after development. High thermal stability.

Even when the photosensitive resin composition contains a light-shielding agent or an insufficient exposure amount, the photocurable composition provided by the present application can suppress the occurrence of undercuts in the pattern after development, and has high thermal stability after development. . In a preferred embodiment, the photo-curable resin composition further includes an alkali-soluble resin and an auxiliary agent. The alkali-soluble resin can be selected from resins commonly used in the art. Adding an alkali-soluble resin to the photocurable composition is beneficial to further improve the alkali developability. Preferably, the alkali-soluble resin is a (meth) acrylate copolymer. More preferably, it is an alkali-soluble resin disclosed in a published patent (CN106397752A).

Preferably, the photo-curable composition includes 0.5 to 10 parts of a oxime ester-containing photoinitiator, 10 to 100 parts of the above-mentioned polymer monomer, 0 to 80 parts of an alkali-soluble resin, and 0 to 100 parts by weight. 500 parts of additive.

More preferably, the photo-curable composition includes 0.5 to 5 parts of a photooxime ester-containing photoinitiator, 10 to 80 parts of the aforementioned polymer monomer, 0 to 60 parts of an alkali-soluble resin, and 0 parts by weight. ~ 200 parts of additives.

In a preferred embodiment, the polymer monomer includes, but is not limited to, (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, Ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (methyl) ) Acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic acid Anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid Butyl ester, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) 2-hydroxybutyl acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) propenyloxy-2-hydroxypropyl phthalate, glycerol mono (methyl Base) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) propylene Esters, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, phthalic acid derivatives (Meth) acrylic acid semi-esters and the like. 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonane Glycol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, ethoxylated hexanediol di (Meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, dipentaerythritol di (methyl) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethoxy Neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, poly (ethylene-propylene) glycol di (meth) acrylate, poly 1,4-butanediol di (Meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di ( (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol five Acrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol pentaerythritol hexa ( (Meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxy) Phenyl) propane, 2-hydroxy-3- (meth) propenyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl Glyceryl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerol triacrylate, glycerol polycondensation Water glyceryl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., toluene diisocyanate), trimethyl-1,6-hexanediisocyanate, 1,6-hexanediisocyanate, Methylbis (meth) acrylamide, (meth) acrylamide methylene ether, polycondensate of polyhydric alcohol and N-methylol (meth) acrylamide, 1,3,5-tripropylene Fluorenylhexahydro-1,3,5-triazine, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-triethanol triacrylate and 2,4 One or more of the group consisting of 1,6-trioxohexahydro-1,3,5-triazine-1,3,5-triethanol diacrylate.

The photocurable resin composition may further include various additives in the art, including, but not limited to, solvents, dyes, pigments, fillers, surface conditioners, defoamers, leveling agents, wetting agents, dispersants, matting agents, One or more of a group consisting of a curing accelerator, a chain transfer agent, an antioxidant, an ultraviolet absorber, a deflocculant, a thermal polymerization inhibitor, and an adhesion promoter.

Preferably, the surfactant includes, but is not limited to, one or more of the group consisting of an anionic compound, a cationic compound, and a nonionic compound.

Preferably, the adhesion improving agent includes, but is not limited to, a silane coupling agent.

Preferably, the thermal polymerization inhibitor includes, but is not limited to, hydroquinone and / or hydroquinone monoethyl ether.

Preferably, the defoaming agent includes, but is not limited to, a polysiloxane compound and / or a fluorine compound.

Preferably, the above photocurable resin composition can also be used in combination with existing photoinitiators or sensitizers in the art.

Preferably, existing photoinitiators in the art include, but are not limited to, benzophenones, thia anthrones, acetophenones, α-hydroxy ketones, α-amino ketones, and benzoic acid formate. And triazines.

Preferably, the sensitizer includes one or more selected from the group consisting of coumarin compounds, anthraquinone compounds, anthracene ester compounds, and acridine compounds.

Another aspect of the present application also provides a method for preparing a photosensitive resin composition. Specifically, the preparation method includes batching according to a desired composition; the above batches are put into a blender and mixed. Preferably, each component of the photocurable composition is filtered by a screening program to make the prepared photosensitive resin composition uniform.

Another aspect of the present application also provides a color filter, which includes a development pattern formed by the photocurable composition provided by the present application.

Preferably, the method for preparing the developing pattern includes the following steps:

1) Apply a photocurable resin composition to a substrate using a roll coater or a coater.

2) The applied photocurable resin composition is dried to form a coating film.

3) The coating film is irradiated with active energy rays such as ultraviolet rays or excimer laser light through a negative mask to expose a part thereof.

4) Developing the coating film after exposure using a developing solution to form a pattern in a desired shape.

5) Post-baking the developed pattern at a certain temperature, preferably 200 ° C to 250 ° C.

Another aspect of the present application provides a display device including the color filter described above.

As described above, by using the photocurable resin composition of the present invention, undercuts in a pattern formed after development can be suppressed. When the photocurable resin composition of the present invention is used to make a development pattern on a color filter, it can prevent air bubbles from entering near the boundary of each pixel, and thus is beneficial to improving the display quality of a liquid crystal display device including the filter.

The present invention is described in further detail below with reference to specific embodiments, which cannot be understood as limiting the scope of protection of the present invention.

Preparation Example

Example 1

(1) Synthesis of intermediate 1a

In a 1000 mL four-necked flask, 135.2 g of raw material 1a, 54.0 g of sodium methoxide, and 100 mL of dichloromethane (DMSO) were added. The mixture was stirred at room temperature for 0.5 hours, and then 120.5 g of raw material 1b was slowly added dropwise. The dropwise addition was controlled for 3 hours. At the end of the reaction, the liquid phase was followed until the starting material no longer changed. The reaction solution was poured into deionized water, stirred, and the product was extracted with n-hexane. The n-hexane product solution was dried over anhydrous magnesium sulfate, and the n-hexane was removed by rotary evaporation. The methanol was recrystallized to obtain 177.6 g of a white solid product, namely, intermediate 1a, with a yield of 81. %, Purity 98%. The structure of intermediate 1a was confirmed by 1H-NMR and mass spectrometry.

¹ H-NMR (CDCl ₃ , 500 MHz): 2.7692 (4H, s), 4.5306-4.8667 (4H, m), 7.2851-7.9904 (14H, m).

MS (m / z): 439 (M + 1) ⁺ .

(2) Synthesis of intermediate 1b

In a 500 mL four-necked flask, 87.7 g of Intermediate 1a, 27 g of aluminum trichloride, and 100 mL of dichloromethane were added. The ice-water bath was lowered to 0 ° C, and a mixed solution of 24.1 g of raw material 1c and 50 mL of dichloromethane was added dropwise. Below 2 ° C, the dropwise addition was completed in about 2 hours, and the stirring was continued for 2 hours after the dropwise addition. The liquid phase was followed to complete the reaction. Then the material was slowly poured into 400 g of ice water and 50 mL of concentrated hydrochloric acid (37%) in dilute hydrochloric acid. Add while stirring, then pour into the separatory funnel, separate the lower dichloromethane layer, and continue to wash the aqueous layer with 50 mL of dichloromethane. Combine the dichloromethane layers and use a 5% aqueous sodium hydrogen carbonate solution (150 mL each time, total 3 times) Wash the dichloromethane layer, then wash the dichloromethane layer with water until the pH is neutral, dry the dichloromethane layer with 80g of anhydrous magnesium sulfate, filter and distill the dichloromethane product solution, recrystallize with methanol, and dry in an oven at 80 ° C In 2 hours, 93.0 g of intermediate 1b was obtained with a yield of 89% and a purity of 98%. MS (m / z): 523 (M + 1) ⁺ .

(3) Synthesis of intermediate 1c

Into a 500 mL four-necked flask, add 53 g of intermediate 1b, 6.0 g of hydroxylamine hydrochloride, 6.4 g of sodium acetate, 100 mL of ethanol, 50 mL of water, and heat and stir at 85 ° C for 5 hours to stop the reaction. Pour the material into a 1000 mL beaker and add 500 mL Stir with water, extract with 100 mL of dichloromethane, add 30 g of anhydrous magnesium sulfate to the extract to dry, suction filter, remove the solvent by rotary evaporation under reduced pressure, spin the bottle to obtain an oily viscous substance, and pour the viscous substance into 100 mL of petroleum ether It was precipitated by stirring and filtered under suction to obtain a white powdery solid, which was dried at 70 ° C. for 5 hours to obtain 41.4 g of intermediate 1c, yield 75%, purity 98%, MS (m / z): 538 (M + 1) ⁺ .

(4) Synthesis of compound 1

Add 26.9g of Intermediate 1c and 100mL of dichloromethane to a 250mL four-necked flask, stir at room temperature for 5 minutes, and then add 5g of propidium chloride dropwise. After the addition is complete in about 30 minutes, continue stirring for 2 hours, and then add 5% carbonic acid The sodium hydrogen solution was adjusted to a neutral pH. The organic layer was separated by a separating funnel, washed twice with 100 mL of water, and dried with 20 g of anhydrous magnesium sulfate. After filtration, the solvent was distilled off to obtain a viscous liquid. The methanol was recrystallized to obtain a white solid powder. After filtration, 26.1 g of compound 1 was obtained in a yield of 88% and a purity of 99%. The structure of compound 1 was confirmed by 1H-NMR and mass spectrometry.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.9554-1.0973 (6H, t), 1.3298-1.3332 (2H, m), 1.4907-1.5163 (2H, m), 2.2631-2.2788 (2H, m), 2.6654-2.8225 (6H, m), 4.5665-4.8826 (4H, d), 7.2806-8.0483 (13H, m).

MS (m / z): 594 (M + 1) ⁺ .

Example 2

(1) Synthesis of intermediate 2a

In a 1000 mL four-necked flask, 83.1 g of raw material 2a, 54.0 g of sodium methoxide, 200 mL of dichloromethane (DMSO) were added, and nitrogen was stirred at room temperature for 0.5 hours. Then 107 g of epichlorochlorobutane was slowly added dropwise and controlled for 3 hours After the dropwise addition, the reaction in the liquid phase was tracked until the raw materials were no longer changed. The reaction solution was poured into deionized water, stirred, and the product was extracted with n-hexane. The n-hexane product solution was dried over anhydrous magnesium sulfate, and the n-hexane was removed by rotary evaporation. The methanol was recrystallized to obtain 134.8 g of a white solid product, that is, intermediate 2a. %, Purity 98%.

The structure of intermediate 2a was confirmed by 1H-NMR and mass spectrometry.

¹ H-NMR (CDCl ₃ , 500 MHz): 1.3695-1.4231 (4H, m), 1.7906-1.8651 (4H, t), 2.4963-2.5678 (6H, m), 7.3853-7.8430 (8H, m).

MS (m / z): 307 (M + 1) ⁺ .

(2) Synthesis of intermediate 2b

In a 500 mL four-necked flask, 61.3 g of intermediate 2a, 27 g of aluminum trichloride, and 100 mL of dichloromethane were added. The ice-water bath was lowered to 0 ° C, and a mixed solution of 34.9 g of raw material 2b and 50 mL of dichloromethane was added dropwise. The temperature was controlled to 10 Below 2 ° C, the dropwise addition was completed in about 2 hours, and the stirring was continued for 2 hours after the dropwise addition. The liquid phase was followed to complete the reaction. Then the material was slowly poured into 400 g of ice water and 50 mL of concentrated hydrochloric acid (37%) in dilute hydrochloric acid. Add while stirring, then pour into the separatory funnel, separate the lower dichloromethane layer, and continue to wash the aqueous layer with 50 mL of dichloromethane. Combine the dichloromethane layers and use a 5% aqueous sodium hydrogen carbonate solution (150 mL each time, total 3 times) Wash the dichloromethane layer, then wash the dichloromethane layer with water until the pH is neutral, dry the dichloromethane layer with 80g of anhydrous magnesium sulfate, filter and distill the dichloromethane product solution, recrystallize with methanol, and dry in an oven at 80 ° C In 2 hours, 76.5 g of intermediate 2b was obtained with a yield of 87% and a purity of 98%. MS (m / z): 445 (M + 1) ⁺ .

(3) Synthesis of intermediate 2c

A 250 mL four-necked flask was charged with 44.5 g of Intermediate 2b, 8.0 g of 37% hydrochloric acid, 7.5 g of isoamyl nitrite, and 100 mL of tetrahydrofuran, and the mixture was stirred at room temperature for 5 hours to stop the reaction. Pour the material into a 1000 mL beaker, add 500 mL of water and stir, extract with 100 mL of dichloromethane, add 30 g of anhydrous magnesium sulfate to the extract to dry, suction filter, and spin off the filtrate under reduced pressure to remove the solvent. Rotate the bottle to obtain an oily substance. Viscous substance, the viscous substance was poured into 100 mL of petroleum ether, stirred and precipitated, and filtered by suction to obtain a white powdery solid, which was dried at 70 ° C for 5 hours to obtain 35.52 g of intermediate 2c, yield 75%, purity 98%, MS (m / m / z): 476 (M + 1) ⁺ .

(4) Synthesis of compound 2

Add 47.4 g of intermediate 2c and 100 mL of dichloromethane to a 250 mL four-necked flask, stir at room temperature for 5 minutes, and then add 13 g of propionic anhydride dropwise. After the addition is complete in about 30 minutes, continue to stir for 2 hours, and then add 5% hydrogen carbonate. The sodium aqueous solution was adjusted to a neutral pH, and the organic layer was separated by a separating funnel, and washed twice with 200 mL of water, dried with 50 g of anhydrous magnesium sulfate, and filtered to spin off the solvent to obtain a viscous liquid. The methanol was recrystallized to obtain a white solid powder. Filtration yielded 45.5 g of product with a yield of 86% and a purity of 99%.

The structure of compound 2 was confirmed by 1H-NMR and mass spectrometry.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.9959-1.1005 (3H, t), 1.3067-1.4432 (17H, m), 1.8668-1.8772 (4H, t), 2.2590-2.2713 (8H, m), 7.2832-8.0122 (7H, m).

MS (m / z): 530 (M + 1) ⁺ .

Example 3

Referring to the methods of Examples 1 and 2, compounds 3-17 having the structures shown were prepared from the corresponding starting materials.

Table 1

Performance characterization

1. By formulating a representative photocurable resin composition, the application performance such as the curing speed, mobility, and solubility of the photoinitiator represented by formula (I) of the present invention is evaluated, and the specific steps are as follows:

(1) A photocurable resin composition having the following composition is prepared:

In the above composition, the photoinitiator is a compound of formula (I) of the present invention or a photoinitiator known in the art (for comparison).

(2) Cure speed

The above composition was stirred under a yellow light, and was taken on a PET template and formed into a film by roll coating, and dried at 90 ° C for 2 minutes to obtain a coating film having a dry film thickness of 2 μm, and then cooled to room temperature. Exposure machine model: RW-UV70201, single exposure 50mJ / cm ² ) irradiation to expose the coating film, and make it solidify into a film.

Based on the evaluation of the number of times that the coating film is cured to form a cured film through the crawler exposure belt, the greater the number of times, the less satisfactory the curing speed.

(3) Migration

Cut the cured film, weigh 0.5g of the cured film sample into a 50mL beaker, add 4.5mL of methanol, and dissolve it with ultrasound for 30 minutes. Move the resulting methanol solution to a 10mL volumetric flask, and continue to wash the sample with methanol twice (2mL × 2), pour into a volumetric flask, transfer 0.1mL toluene as an internal standard with a pipette, add methanol to dissolve, shake evenly, and let stand.

Using Shimadzu LC-20A liquid chromatography (shim pack column, 150 × 6.0nm, detector SPD-20A, detection limit 20ppm, detection wavelength 254nm), use at 25 ℃, flow rate 1.0mL / min, mobile phase (methanol / Water = 90/10), and observe whether the presence of a photoinitiator can be detected. Based on the percentage of the peak area ratio of the liquid phase relative to toluene, the higher the initiator content in the liquid phase, the greater the mobility.

(4) Solubility

The solubility of photoinitiators in reactive diluents and oligomers is an important indicator of the application performance of initiators. The solubility of the photoinitiator in PGMEA is one of the index parameters representing its solubility and measuring the application performance of the photoinitiator.

The compounds of the formula (I) of the present invention and the existing oxime ester photoinitiators as a comparison were used to test their solubility in PGMEA at 25 ° C.

Characterization results are shown in Table 2.

In Table 2, the photoinitiator A is , The photoinitiator B is , Photoinitiator C is .

From the test results in Table 2, it can be seen that the polymerizable group-containing oxime ester photoinitiator represented by formula (I) of the present invention has excellent solubility, and has high initiator efficiency and curing speed in photocuring applications. Fast, without migration, the overall performance is significantly better than the existing oxime ester photoinitiator products.

Application Examples

The photo-initiator prepared in the present application and conventional photo-initiators in the art are used to prepare a photo-curable composition, and the composition of each photo-curable composition is shown in Tables 3 and 4.

Compounds D, E, F, G have the following structures:

The alkali-soluble resin A1 has the following structure:

Performance evaluation:

(1) Sensitivity

The sensitivity of the photosensitive resin compositions in Examples 11 to 29 and Comparative Examples 4 to 9 was evaluated according to the following steps. First, the sample was taken from a PET template and coated with a wire rod, and dried at 90 ° C for 5 minutes to remove the solvent. A coating film having a film thickness of about 2 μm was formed. The substrate on which the coating film was formed was cooled to room temperature, a mask was attached, and a high-pressure mercury lamp 1PCS light source was used to realize long-wavelength radiation through an FWHM filter. Expose the coating film through the gap of the mask at the wavelength of 370 ~ 420nm, then immerse it in 2.5% sodium carbonate solution at 25 ℃ for 20 seconds for development, then wash with ultrapure water, air-dry, and harden at 220 ℃ The pattern was fixed by baking for 30 minutes, and the obtained pattern was evaluated.

At the time of exposure, the minimum exposure amount with a residual film rate of 90% or more after development of the light-irradiated area in the exposure step is evaluated as the exposure required amount. The smaller the amount of exposure required, the higher the sensitivity.

(2) Evaluation of pattern shape

The shapes of the pattern formed by the photosensitive resin compositions of Examples 11 to 29 and Comparative Examples 4 to 9 were evaluated according to the following steps. First, the samples were taken from a PET template, coated with a wire rod, and dried at 90 ° C. 5 The solvent was removed in minutes to form a coating film having a film thickness of about 2 μm. The substrate on which the coating film was formed was cooled to room temperature, a mask was attached, and a high-pressure mercury lamp 1PCS light source was used to realize long-wavelength radiation through an FWHM filter. The coating film was fully exposed through the gap of the mask at a wavelength of 370 to 420 nm (exposure amount 100 mJ / cm ² ), and then immersed in 2.5% sodium carbonate solution at 25 ° C. for 20 seconds for development, and then ultra-pure Washed, air-dried, and hard-baked at 220 ° C for 30 minutes to fix the pattern. The joint angle (cone angle) between the pattern and the substrate was measured with a scanning electron microscope. The cone angle corresponds to the corresponding angle θ in FIG. 1 and FIG. 2 . If the cone angle is an acute angle, it means that there is no undercut in the pattern, and if the cone angle is an obtuse angle, it means that there is an undercut in the pattern. The specific results are shown in Table 5.

It can be seen from Table 5 that the bonding angle between the shape of the pattern formed by the photocurable compositions prepared in Examples 11 to 29 of the present application and the substrate is an acute angle, as shown in FIG. 1; The bonding angle between the shape of the photocurable composition pattern and the substrate is an obtuse angle. Therefore, the polymerizable fluorene-based photoinitiator of the present invention has excellent photosensitivity, and can be used to effectively solve the undercut problem whether it is used alone or in combination with other photoinitiators.

(3) Evaluation of sublimation

The sublimation product of the initiator in the composition after the exposure was detected. Under the conditions of 100 mJ / cm ² , 80 films were prepared for the formulations of Examples 11, 19, 20, 24 and Comparative Examples 4, 9 respectively for exposure. After exposure, the mask was cleaned with the same amount of tetrahydrofuran, and the Shimadzu liquid chromatography (LC-200) was used to quantitatively analyze the mask attachments. The peak area and peak height were recorded at the peak position of the initiator. The higher the area and peak height, the more obvious the sublimation. The results are shown in Table 6.

It can be seen from Table 6 that the use of the photosensitive composition of the present invention exhibits a characteristic of suppressing the generation of sublimates.

In summary, the photosensitive resin composition according to the present invention can suppress the formation of undercuts in the pattern after development, and rarely generates sublimation during heating after development.

The above descriptions are merely preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (32)

A peroxime ester photoinitiator containing a polymerizable group, and has a structure represented by formula (I): Wherein, n represents an integer of 1 to 4; each of R ₁ independently represents H, nitro, halogen, C ₁ -C ₂₀ linear or branched alkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₄ aralkyl, C ₃ -C ₅ heterocyclic group containing O, N or S heteroatom and double bond, or C ₁ -C ₁₂ alkyl group terminated with the heterocyclic group, or -XC (R ₃ ) = NO-CO-R ₄ , -CH ₂ -in the above group can be optionally replaced by -O-, -S-, -NH-, -CO-, -COO- or -OCO- Substitution; said R ₂ represents a polymerizable group; said X represents a direct bond or a carbonyl group; said R ₃ represents a C ₁ -C ₂₀ straight or branched chain alkyl group, a C ₃ -C ₂₀ cycloalkyl group, C ₄ -C ₂₀ cycloalkylalkyl, C ₄ -C ₂₀ alkylcycloalkyl, C ₆ -C ₂₀ aryl, C ₄ -C ₂₀ heteroaryl, containing O, N or S hetero Atom and double bond C ₃ -C ₅ heterocyclic group or C ₁ -C ₆ alkyl group with the heterocyclic group as cap; the R ₄ represents C ₁ -C ₂₀ straight or branched alkyl group, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ cycloalkylalkyl, C ₄ -C ₂₀ alkylcycloalkyl, C ₆ -C ₂₀ aryl, C ₄ -C ₂₀ heteroaryl Or C ₂ -C ₂₀ alkenyl. The oxime ester photoinitiator according to item 1 of the scope of the patent application, wherein R ₁ is H, nitro, halogen, C ₁ -C ₁₀ linear or branched alkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₆ aralkyl, thienyl, pyrrolyl, C ₁ -C ₄ alkyl terminated with thienyl or pyrrolyl, or -XC (R ₃ ) = NO-CO-R ₄ , -CH ₂ -in the above group may be optionally substituted with -O-, -S-, -NH-, -CO-, -COO- or -OCO-. The oxime ester photoinitiator according to item 1 or 2 of the scope of the patent application, wherein n = 1, R ₁ and the right side of the structure of formula (I) -XC (R ₃ ) = NO-CO- The positions of R ₄ are opposite, and R _{1 is} selected from the group consisting of H, nitro, C ₁ -C ₄ linear or branched alkyl, phenyl, benzamyl ( ), 3-thienyl ( ), 3-thienylmethyl ( ), Or -XC (R ₃ ) = NO-CO-R ₄ . The oxime ester photoinitiator according to item 1 of the scope of the patent application, wherein R ₂ is a polymerizable group containing a double bond, an epoxy group, or a combination structure thereof. The oxime ester photoinitiator according to item 1 or 4 of the scope of the patent application, wherein R _{2 is} selected from the group consisting of: C ₂ -C ₁₂ alkenyl groups, and one or more of the alkenyl groups -CH ₂ -can be optionally independently selected by -O-, -CO-, -COO-, -OCO- or Substituted; ethylene oxide alkyl or propylene oxide alkyl, one or more of -CH ₂ -in the alkyl group between the epoxy group and the fluorene structure may be optionally each independently -O-, -CO-, -COO-, -OCO- or -O-CH ₂ -CH (OH) -CH ₂ -O-. The oxime ester photoinitiator according to item 1 or 4 of the scope of the patent application, wherein R _{2 is} selected from the group consisting of C ₃ -C ₈ alkenyl groups, and one or more of the alkenyl groups -CH ₂ -can be optionally independently selected by -O-, -CO-, -COO-, -OCO- or Substituted; C ₁ -C ₈ alkyl groups terminated with ethylene oxide or propylene oxide, one or more of -CH ₂ -in the alkyl group may be optionally each independently -O -, -CO-, -COO-, -OCO- or -O-CH ₂ -CH (OH) -CH ₂ -O-, and H in ethylene oxide or propylene oxide can be replaced by C _1- C ₄ alkyl. The oxime ester photoinitiator according to item 1 in the scope of the patent application, wherein R ₃ represents a C ₁ -C ₁₀ linear or branched alkyl group, C ₃ -C ₁₀ cycloalkyl group, C _4- C ₁₀ cycloalkylalkyl, C ₄ -C ₁₀ alkylcycloalkyl, C ₆ -C ₁₀ aryl, C ₃ -C ₅ hetero containing O, N or S heteroatoms and double bonds A cyclic group or a C ₁ -C ₆ alkyl group terminated with the heterocyclic group. The oxime ester photoinitiator according to item 1 or 7 of the scope of the patent application, wherein R _{3 is} selected from a C ₂ -C ₆ linear or branched alkyl group, and a C ₃ -C ₈ cycloalkane Radical, C ₄ -C ₁₀ cycloalkylalkyl, C ₄ -C ₁₀ alkylcycloalkyl, phenyl, C ₇ -C ₁₀ phenylalkyl, thienyl, or thienyl-terminated C _1- C ₄ alkyl, wherein one or more H in the phenyl group can be optionally substituted by C ₁ -C ₄ alkyl, and benzene in the C ₇ -C ₁₀ phenyl alkyl group One or more H in the group may be optionally substituted by C ₁ -C ₄ alkyl. The oxime ester photoinitiator according to item 1 in the scope of the patent application, wherein R ₄ is a C ₁ -C ₆ linear or branched alkyl group, C ₃ -C ₁₀ cycloalkyl group, C cycloalkylalkyl of ₄ -C ₁₄ alkyl group C ₄ -C ₁₄ cycloalkyl or C ₆ -C ₁₂ aryl group is. The oxime ester photoinitiator according to item 1 or 9 of the scope of the patent application, wherein R ₄ is a C ₁ -C ₄ linear or branched alkyl group, or C ₃ -C ₈ cycloalkyl group. , C ₄ -C ₁₀ cycloalkylalkyl, or phenyl. An oxime ester photoinitiator containing a polymerizable group, wherein the oxime ester photoinitiator containing a polymerizable group has a structure represented by formula (I): Wherein, n represents an integer from 1 to 4; X represents a direct bond or a carbonyl group; and R _{1 is} selected from H, a nitro group, a halogen atom, a C ₁ -C ₂₀ straight-chain alkyl group or a branched alkyl group, C ₆ -C ₂₀ aryl, C ₆ -C ₁₄ aryl substituted C1-C ₁₀ alkyl, double bond C ₃ -C ₅ heterocyclyl, double bond C ₃ -C ₅ heterocyclic Alkyl-terminated C ₁ -C ₁₂ alkyl, or And -CH ₂ -in the R ₁ may be substituted with -O-, -S-, -NH-, -CO-, -COO-, or -OCO-; the two R ₂ are each selected from A double bond-containing substituent, a three-membered epoxy group-containing substituent or a four-membered epoxy group-containing substituent, and two of said R _{2 are the} same or different; said R _{3 is} selected from C ₁ -C ₂₀ linear or branched alkyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₈ cycloalkyl substituted C ₁ -C ₁₀ alkyl, C ₁ -C ₂₀ alkyl substituted C ₃ -C ₈ cycloalkyl, phenyl, a group obtained by substituting at least one hydrogen atom of a phenyl group with a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkoxy group A group obtained by substituting at least one hydrogen atom with a fluorine atom, a thienyl group, or a C ₁ -C ₄ alkyl group terminated with a thienyl group; the R _{4 is} selected from a C ₁ -C ₂₀ linear or branched alkyl group , C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₈ cycloalkyl substituted C ₁ -C ₁₀ alkyl, C ₆ -C ₂₀ aryl, C ₁ -C ₅ alkyl substituted C ₆ -C ₂₀ aryl, C ₄ -C ₂₀ heteroaryl, C ₂ -C ₂₀ alkenyl or C ₁ -C ₅ alkyl substituted C ₆ -C ₂₀ heteroaryl. The oxime ester photoinitiator according to item 11 in the scope of application patent, wherein R ₁ is H, nitro, halogen, C ₁ -C ₁₀ linear or branched alkyl, C ₆ -C ₁₂ aryl, C ₇ -C ₁₆ aralkyl, thienyl, pyrrolyl, C ₁ -C ₄ alkyl terminated with thienyl or pyrrolyl, or -XC (R ₃ ) = NO-CO-R ₄ , -CH ₂ -in R ₁ may be substituted with -O-, -S-, -NH-, -CO-, -COO-, or -OCO-. The oxime ester photoinitiator according to item 11 or 12 of the scope of the patent application, wherein n = 1, R ₁ and the position on the right side of the structure of formula (I) -XC (R ₃ ) = NO-CO-R ₄ In contrast, and R _{1 is} selected from H, nitro, C ₁ -C ₄ linear or branched alkyl, phenyl, benzamyl ( ), 3-thienyl ( ), 3-thienylmethyl ( ), Or -XC (R ₃ ) = NO-CO-R ₄ . The oxime ester photoinitiator according to item 11 in the scope of application patent, wherein R ₂ is a polymerizable group containing a double bond, an epoxy group, or a combination structure thereof. The oxime ester photoinitiator according to item 11 or 14 of the scope of application patent, wherein the R _{2 is} selected from C ₂ -C ₁₂ alkenyl, ethylene oxide alkyl, or propylene oxide alkyl. Alkyl; optionally, when R ₂ is a C ₂ -C ₁₂ alkenyl, one or more -CH ₂ -in R ₂ may each be independently -O-, -CO- , -COO-, -OCO- or Substituted; optionally, when R ₂ is an oxiranyl alkyl group or a propylene oxide alkyl group, one of the alkyl groups between the epoxy group in the R ₂ and the fluorene structure One or more of -CH ₂ -may each be independently replaced by -O-, -CO-, -COO-, -OCO-, or -O-CH2-CH (OH) -CH2-O-. The oxime ester photoinitiator according to item 11 or 14 of the scope of the patent application, wherein R _{2 is} selected from C ₃ -C ₈ alkenyl or ethylene oxide or propylene oxide as Capped C ₁ -C ₈ alkyl; optionally, when R ₂ is C ₃ -C ₈ alkenyl, one or more -CH ₂ -in R ₂ may be each independently By -O-, -CO-, -COO-, -OCO- or Substituted; optionally, when R ₂ is a C ₁ -C ₈ alkyl group with ethylene oxide or propylene oxide as the end group, one of the C ₁ -C ₈ alkyl groups Or -CH ₂ -may each be independently substituted with -O-, -CO-, -COO-, -OCO-, or -O-CH2-CH (OH) -CH2-O-, and the epoxy H in the ethane group or the propylene oxide group may be substituted by a C ₁ -C ₄ alkyl group. The oxime ester photoinitiator according to item 11 in the scope of the patent application, wherein R ₃ represents a C ₁ -C ₁₀ linear or branched alkyl group, C ₃ -C ₁₀ cycloalkyl group, C _4- C ₁₀ cycloalkylalkyl, C ₄ -C ₁₀ alkylcycloalkyl, C ₆ -C ₁₀ aryl, C ₃ -C ₅ hetero containing O, N or S heteroatoms and double bonds A cyclic group or a C ₁ -C ₆ alkyl group with the C ₃ -C ₅ heterocyclic group as a cap. The oxime ester photoinitiator according to claim 11 or claim 17, wherein R _{3 is} selected from a C ₂ -C ₆ linear or branched alkyl group, and a C ₃ -C ₈ cycloalkane Radical, C ₄ -C ₁₀ cycloalkylalkyl, C ₄ -C ₁₀ alkylcycloalkyl, phenyl, C ₇ -C ₁₀ phenylalkyl, thienyl, or thienyl-terminated C _1- C ₄ alkyl, wherein one or more H of phenyl in the C ₇ -C ₁₀ phenylalkyl may be optionally substituted by C ₁ -C ₄ alkyl; When R ₃ is phenyl, one or more H in the phenyl may be substituted by C ₁ -C ₄ alkyl; optionally, when R ₃ is C ₇ -C ₁₀ In the case of a phenylalkyl group, one or more H of the phenyl groups in the C ₇ -C ₁₀ phenylalkyl group may be substituted by a C ₁ -C ₄ alkyl group. The oxime ester photoinitiator according to item 11 in the scope of the patent application, wherein R ₄ is a C ₁ -C ₆ linear or branched alkyl group, C ₃ -C ₁₀ cycloalkyl group, C cycloalkylalkyl of ₄ -C ₁₄ alkyl group C ₄ -C ₁₄ cycloalkyl or C ₆ -C ₁₂ aryl group is. The oxime ester photoinitiator according to claim 11 or claim 19, wherein R ₄ is a C ₁ -C ₄ linear or branched alkyl group, or C ₃ -C ₈ cycloalkyl group. , C ₄ -C ₁₀ cycloalkylalkyl or phenyl. The oxime ester photoinitiator according to item 11 in the scope of application patent, wherein the oxime ester-containing photoinitiator is selected from the group consisting of with One or more of the group. The method for preparing an oxime ester photoinitiator containing a polymerizable group according to any one of claims 1 to 21 of the scope of the patent application, comprising the following steps: (1) preparation of intermediate a and raw material a and raw material b That is, R ₂ -Y reacts in the presence of a catalyst to form intermediate a; wherein Y represents halogen; (2) Preparation of intermediate b and intermediate a and raw material c, namely R ₃ '-CO-Cl in aluminum trichloride Or zinc chloride catalyzed in a organic solvent to obtain a fucosylation reaction to obtain intermediate b; wherein R ₃ ′ represents R ₃ or R ₃ -CH _2- , specifically, when X is a direct bond, R ₃ ′ represents R ₃ , when X is a carbonyl group, R ₃ ′ represents R ₃ -CH _2- ; (3) Preparation of intermediate c, when X is a direct bond, the role of intermediate b in hydroxylamine hydrochloride and sodium acetate The oximation reaction is carried out to produce intermediate c; when X is a carbonyl group, the intermediate b and the nitrite or nitrite are subjected to the oximation reaction at normal temperature to produce intermediate c; (4) Preparation of the product Intermediate c is subjected to an esterification reaction with an acid anhydride (R ₄ -CO) ₂ O or a chloride compound R ₄ -CO-Cl to obtain the target product; the reaction formula is as follows: The preparation method according to item 22 of the scope of patent application, wherein in the step (1), a raw material a and R ₂ -Y undergo a nucleophilic reaction in the presence of a catalyst, the catalyst is selected from sodium methoxide and t-butanol Sodium, potassium tert-butoxide and potassium methoxide.     The preparation method according to item 22 of the scope of application for a patent, wherein in the step (3), the nitrite is selected from ethyl nitrite, isoamyl nitrite and isooctyl nitrite, and The nitrite is selected from sodium nitrite and potassium nitrite.         Application of the photooxime ester photoinitiator containing a polymerizable group according to any one of the scope of application patents 1 to 21 in the field of photocuring.         A photocurable resin composition, wherein the photocurable resin composition includes a photoinitiator and a polymer monomer, the polymer monomer contains an olefinic double bond, and the photoinitiator includes a sulfoxime ester-containing A photoinitiator. The photoinitiator-containing photoinitiator is a photooxime ester-based photoinitiator containing a polymerizable group according to any one of claims 1 to 21.         The photocurable resin composition according to item 26 of the scope of application for a patent, wherein the photocurable resin composition further includes an alkali-soluble resin and an additive.         The photocurable resin composition according to item 27 of the scope of application for a patent, wherein the polymer monomer is selected from (meth) acrylamide, hydroxymethyl (meth) acrylamide, and methoxymethyl (Meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic acid Anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth) acrylate, (meth) acrylic acid Ethyl ester, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acrylate 2- Hydroxypropyl ester, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acrylfluorenyloxy-2- Hydroxypropyl ester, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Methylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoro (meth) acrylate Propyl ester, (meth) acrylic acid half ester of phthalic acid derivative, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecane Glycol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 2-hydroxy-3- (meth) acrylate (Meth) acryloxypropyl propyl, dipentaerythritol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (methyl) Base) acrylate, tripropylene glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, poly (ethylene-propylene) di Alcohol di (meth) acrylate, poly 1,4-butanediol di (meth) acrylate, ethoxylated bisphenol A bis (methyl) ) Acrylate, propoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, ethylene glycol di (meth) acrylate, di Ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate Ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) propenyloxydiethoxyphenyl) propane, 2,2- Bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acrylfluorenyloxypropyl (meth) acrylate, Diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, triglyceride , Glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate, trimethyl-1,6-hexanediisocyanate, 1,6-hexanediisocyanate, methylenebis ( (Meth) acrylamide, (meth) acrylamide methylene ether, polycondensate of polyhydric alcohol and N-hydroxymethyl (meth) acrylamide, 1,3,5-triacrylfluorene hexahydro -1,3,5-triazine, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-triethanol triacrylate and 2,4,6-tri One or more of the group consisting of oxohexahydro-1,3,5-triazine-1,3,5-triethanol diacrylate.         The photocurable resin composition according to item 27 of the scope of application for a patent, wherein the alkali-soluble resin is a (meth) acrylate copolymer.         The photocurable resin composition according to item 27 of the scope of application for a patent, wherein the additive is selected from the group consisting of a solvent, a dye, a pigment, a filler, a surface conditioner, a defoamer, a leveling agent, a wetting agent, a dispersant, One or more of a matting agent, a curing accelerator, a chain transfer agent, an antioxidant, an ultraviolet absorber, a deflocculant, a thermal polymerization inhibitor, and an adhesion promoter.         A color filter includes a development pattern, wherein the development pattern is formed using the photocurable resin composition according to any one of claims 26 to 30 of the scope of application for a patent.         A display device, wherein the display device includes a color filter according to item 31 of the scope of patent application.