KR102189685B1 - Fluorene-containing oxime ester photoinitiator, its synthesis, photosensitive resin composition containing the same, and its application - Google Patents

Abstract

The present invention discloses a fluorene-containing oxime ester photoinitiator represented by the following formula (I), a synthesis thereof, a photosensitive resin composition containing the same, and an application thereof. Synthesis of the compound is simple, inexpensive, and has good solubility, excellent storage stability and film formation properties when applied to a photocuring field, low exposure requirements, and excellent developability and pattern integrity. The photosensitive resin composition comprises an ultraviolet photosensitive free polymer resin, an active diluent monomer, a fluorene-containing oxime ester photoinitiator of the present application, and an optionally selected colorant and an alkali-soluble resin, and the composition has high photosensitivity and excellent developability, and the resolution is It is highly suitable for manufacturing black matrix, high-precision and high-quality color filters and liquid crystal displays, and has excellent adhesion to substrates, and is also applicable to photo spacers and ribs, photoresists, wet films, and dry films. I can.

Description

Fluorene-containing oxime ester photoinitiator, its synthesis, photosensitive resin composition containing the same, and its application

The present invention belongs to the field of organic chemistry, and specifically relates to a fluorene-containing oxime ester-based photoinitiator, its synthesis, a photosensitive resin composition containing the same, and its application.

In a display device such as a liquid crystal display, a liquid crystal layer is generally installed between two substrates, and electrodes facing each other are disposed on each substrate, and red (R) and green ( A color filter layer formed of each pixel such as G), blue (B), and black is disposed. In general, a matrix is installed to distinguish the darkness of each color of R, G, and B.

Currently, methods of manufacturing color filters mainly include a dyeing method, a printing method, a pigment dispersion method, and an anode method, of which the pigment dispersion method is most widely used. In the pigment dispersion method, after applying a photosensitive resin composition containing a coloring material on a transparent substrate, image exposure, development, and post-curing as necessary are performed, and this process is repeated to form a color filter image. The color filter pixel obtained by the above method has high positioning precision and film thickness precision, has excellent durability (eg, light resistance and heat resistance), and has few pinhole defects.

In color filter manufacturing, BM is generally arranged in a lattice shape, strip shape, or mosaic shape between red, green, and blue patterns to prevent the thin film transistor from failing due to light leakage or to prevent color mixing of each color. Improves the degree. For this reason, BM is required to have high light-shielding property. Therefore, research on forming a high-efficiency BM at low cost using a photosensitive resin in which a light-shielding pigment or dye is dispersed is attracting attention. In general, it is necessary to improve the light-shielding property of BM by increasing the film thickness or by increasing the content of light-shielding pigments or dyes, but if light-shielding properties are all required in the entire light wavelength range, these measures may affect the photosensitive properties of the composition. It is likely to cause a remarkable obstacle, mainly due to the difference in crosslinking density of the exposed part, the non-exposed part, and the exposed bottom part, and the pigment not dissolved in the developer lowers the developability, thereby lowering the linearity of the pattern, or the pattern peeling off, resulting in a residue. Disability appears.

Currently, a photosensitive composition containing an oxime ester-based photoinitiator having carbazole or diphenyl sulfide as its main structure is widely used, but since such photoinitiators have a high cost and their application range is limited to some extent, it is necessary to develop a photoinitiator suitable for the price. .

As photoinitiators, oxime ester compounds are known to those skilled in the art, and have remarkable activity, and are widely applied in high-end photoresist fields such as color filters (RGB), black matrix (BM), photo-spacers, and ribs. Has become.

A typical oxime ester photoinitiator has a carbazole or diphenyl sulfide group as its main group, and its cost is high and its solubility with a resin substrate is insufficient, so under the premise that photosensitivity is not affected, the cost is lower and has good solubility. Developing is the goal to be pursued.

The main object of the present invention is a fluorene-containing oxime ester-based photoinitiator that has a simple synthesis of compounds, low cost, good solubility, and excellent storage stability and film-forming performance when applied to a photocurable composition, its synthesis, and contains It is to provide the said photosensitive resin composition and its application.

In order to achieve the above object, according to one aspect of the present invention, there is provided a fluorene-containing oxime ester-based photoinitiator having a structure represented by the following formula (I):

In the above formula, R ₁ is each independently hydrogen, halogen, a C ₁ -C ₂₀ straight or branched alkyl group, a C ₄ -C ₂₀ cycloalkylalkyl group, a C ₂ -C ₂₀ alkenyl group, and of these groups- CH ₂ -may optionally be substituted by -O-; R ₂ is a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cycloalkylalkyl group or an alkylcycloalkyl group, or is -R ₄ -COO-R ₅ , where R ₄ is a C ₁ -C ₁₀ alkylene group , C ₃ -C ₁₀ cycloalkyl group, a C ₆ -C ₂₀ aryl group or a substituted aryl group, a non-terminal -CH ₂ of that of the arylene group - a cycloalkyl group and -CH ₂ - is optionally -O May be substituted by -, and CH of the aryl group may be optionally substituted by N; R ₅ is a C ₁ -C ₂₀ straight or branched alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ alkylcycloalkyl group or a cycloalkylalkyl group, a C ₆ -C ₃₀ aryl group or a substituted An aryl group, a C ₇ -C ₃₀ aralkyl group, a C ₂ -C ₂₀ alkenyl group, among which -CH ₂ -may be optionally substituted by -O-, -S- or -NH-; R ₃ is a C ₁ -C ₂₀ straight or branched alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ alkylcycloalkyl group or a cycloalkylalkyl group, a C ₆ -C ₃₀ aryl group or a substituted An aryl group, a C ₇ -C ₃₀ aralkyl group, a C ₂ -C ₂₀ alkenyl group; A is hydrogen, halogen, a nitro group, a C ₁ -C ₁₀ straight or branched alkyl group, a C ₄ -C ₁₀ alkylcycloalkyl group or a cycloalkylalkyl group; X is a blank or a carbonyl group, where blank means that the two atoms at both ends of X are directly connected.

Additionally, each of R ₁ is independently hydrogen, halogen, a C ₁ -C ₁₀ straight or branched alkyl group, a C ₄ -C ₁₀ cycloalkylalkyl group, and -CH ₂ -of these groups is optionally -O- Can be substituted by

Additionally, each of R ₁ is independently hydrogen, a C ₁ -C ₆ straight-chain or branched alkyl group, and at least one non-adjacent -CH ₂ -of the alkyl group may be optionally substituted by -O-.

Additionally, R ₂ is a C ₃ -C ₁₀ cycloalkyl group, a C ₄ -C ₁₀ cycloalkylalkyl group or an alkylcycloalkyl group.

In addition, R ₂ is a C ₃ -C ₆ cycloalkyl group, a C ₁ -C ₄ straight or branched alkyl group having a terminal substituted by a C ₃ -C ₆ cycloalkyl group, a C ₁ -C ₄ alkyl group It is a C ₃ -C ₆ cycloalkyl group substituted by.

In addition, R ₄ is a C ₁ -C ₈ alkylene group, a C ₃ -C ₈ cycloalkylene group, a phenylene group, a substituted phenylene group, wherein the non-terminal -CH ₂ -in the alkylene group and -CH in the cycloalkyl group ₂ -may be optionally substituted by -O-, and CH in the phenyl group may be optionally substituted by N.

Additionally, R ₄ is a C ₁ -C ₄ alkylene group, a C ₃ -C ₆ cycloalkylene group, a phenylene group, or a pyridinene group.

Additionally, R ₅ is a C ₁ -C ₁₀ linear or branched alkyl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₄ -C ₁₀ alkylcycloalkyl group or a cycloalkylalkyl group.

Additionally, R ₅ is a C ₁ -C ₆ straight or branched alkyl group, a C ₁ -C ₄ straight or branched alkyl group substituted with a C ₃ -C ₆ cycloalkyl group.

Additionally, R ₃ is a C ₁ -C ₁₀ linear or branched alkyl group, a C ₄ -C ₁₀ cycloalkylalkyl group, a phenyl group, or a C ₂ -C ₈ alkenyl group.

Additionally, R ₃ is a C ₁ -C ₆ linear or branched alkyl group, and a C ₁ -C ₄ linear or branched alkyl group having a terminal substituted by a C ₃ -C ₆ cycloalkyl group.

Additionally, A is a nitro group.

According to another aspect of the present application, (A) a compound having an olefinic unsaturated bond used in a radical polymerization reaction; (B) a photoinitiator which is at least one kind of compounds whose main structure is a fluorene-based compound represented by formula (I); (C) It provides a photosensitive resin composition containing a colorant,

Here, A is hydrogen, halogen, a nitro group, a C ₁ -C ₁₀ straight or branched alkyl group, a C ₃ -C ₁₀ alkylcycloalkyl group, a C ₄ -C ₁₀ alkylcycloalkyl group or a cycloalkylalkyl group, A -CH _2- in may be substituted with O, N, S or C(=O); X is a linker or a carbonyl group; R ₁ is hydrogen, halogen, a C ₁ -C ₂₀ straight or branched alkyl group, a C ₄ -C ₂₀ cycloalkylalkyl group or a C ₂ -C ₂₀ alkenyl group, and -CH ₂ -in R ₁ is O, May be substituted by N, S or C(=O), and between R ₁ may form a ring; R ₂ and R ₃ are independently of each other a C ₁ -C ₂₀ straight or branched alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cycloalkylalkyl group, or a C ₄ -C ₂₀ alkylcycloalkyl group And -CH ₂ -in R ₂ and R ₃ may be substituted by O, N, S or C(=O).

Additionally, based on parts by mass, the photosensitive resin composition contains 0.1 to 100 parts by mass of a compound having an olefinic unsaturated bond, 1 to 5 parts by mass of a photoinitiator and 0 to 50 parts by mass of a colorant, and preferably has an olefinic unsaturated bond. The compound is 30 to 80 parts by mass, more preferably 40 to 70 parts by mass; Preferably, the colorant is more than 0 and 80 parts by mass or less, and more preferably 5 to 40 parts by mass.

Additionally, the structure of a compound having a fluorene-based compound represented by formula (I) as its main structure is as follows,

Here, A is hydrogen, halogen, C ₁ -C ₁₀ straight or branched alkyl group, X is a linker or carbonyl group, R ₁ is hydrogen, halogen, C ₁ -C ₂₀ straight or branched alkyl group or O , A C ₁ -C ₂₀ straight or branched alkyl group substituted by N, S or C (=O); R ₂ and R ₃ are independently of each other a C ₁ -C ₂₀ straight or branched alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cycloalkylalkyl group, or a C ₄ -C ₂₀ alkylcycloalkyl group And -CH ₂ -in R ₂ and R ₃ may be substituted by O, N, S or C(=O).

Additionally, a compound having a fluorene-based compound represented by formula (I) as its main structure includes the following structure.

.

.

Additionally, derivative compounds having a fluorene-based compound represented by formula (I) as a main structure are compounds represented by formulas (III), (IV), and (V);

Where M is R ₁ , R ₂ , R ₃ is a linking group formed by dimerization, M is a blank, a C ₁ -C ₂₄ straight or branched alkylene group, a C ₆ -C ₃₆ straight or branched arylene group or a hetero arylene group , -CH ₂ -in M may be optionally substituted with a sulfur, oxygen, NH or carbonyl group, and a hydrogen atom may be optionally substituted with OH or NO ₂ .

Additionally, a derivative compound having a fluorene-based compound represented by formula (I) as its main structure is a compound having the following structure.

.

.

Additionally, the photosensitive resin composition contains an alkali-soluble resin (D), and preferably the alkali-soluble resin is more than 0 and 80 parts by mass or less, more preferably 20 to 60 parts by mass.

Another object of the present invention is to provide a method for preparing a fluorene-containing oxime ester photoinitiator having the structure of formula (I), wherein R ₂ of formula (I) is a C ₃ -C ₂₀ cycloalkyl group, C _4- In the case of a C ₂₀ cycloalkylalkyl group or an alkylcycloalkyl group, the preparation method,

(1) Synthesis step of intermediate a: raw material a and raw material b are subjected to Friedel-Craft acylation reaction in an organic solvent by catalytic action of aluminum trichloride and zinc chloride to obtain intermediate a;

In the raw material b, R ₂ ′-CO-Cl, R ₂ ′ is R ₂ or R ₂ -CH ₂ -, and specifically, if X is blank in formula (I), R ₂ ′ is R ₂ , and if X is a carbonyl group R ₂ ′ is R ₂ -CH ₂ -;

(2) Synthesis step of intermediate b: When X is blank, intermediate a undergoes oxime reaction by the action of hydroxylamine hydrochloride and sodium acetate to produce intermediate b; When X is a carbonyl group, intermediate a undergoes oxime reaction with nitrite ester or nitrite at room temperature in the presence of an organic solvent and concentrated hydrochloric acid to produce intermediate b;

(3) Synthesis step of the compound of formula (I): Intermediate b is esterified with anhydride (R ₃ -CO) ₂ O or an acyl chloride compound R ₃ -CO-Cl to obtain a target product;

.

.

When R ₂ in Formula (I) is -R ₄ -COO-R ₅ , R ₄ is a C ₁ -C ₁₀ alkylene group, a C ₃ -C ₁₀ cycloalkylene group, a C ₆ -C ₂₀ arylene group or a substituted aryl group, in which non-terminal -CH ₂ in the alkylene group - and a cycloalkyl group of -CH ₂ - may be substituted by -O-, and arbitrary as is, the aryl group of the CH may be substituted by optionally N There is; R ₅ is a C ₁ -C ₂₀ straight or branched alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ alkylcycloalkyl group or a cycloalkylalkyl group, a C ₆ -C ₃₀ aryl group or a substituted An aryl group, a C ₇ -C ₃₀ aralkyl group, a C ₂ -C ₂₀ alkenyl group, wherein -CH ₂ -may be optionally substituted by -O-, -S- or -NH-; including and,

(1) the step of synthesizing intermediate a, the preparation method,

(1') Synthesis step of intermediate a': raw material a and raw material b'are subjected to Friedel-Craft reaction in an organic solvent by the catalytic action of aluminum trichloride and zinc chloride to obtain intermediate a';

"In the structure, R _2" material b is R ₄ or CH ₂ -R _4, and, specifically, where X is a blank in the general formula (I) R ₂ 'is R ₄ and, X is a group R _2' is CH ₂ -R ₄ ;

(2') Synthesis step of intermediate b': Intermediate a'is esterified with alcohol R ₅ OH, which is a raw material c, under conditions in the presence of concentrated sulfuric acid or heteropoly acid to obtain intermediate b';

(3') Synthesis step of intermediate c': When X is blank, intermediate b'undergoes oxime reaction by the action of hydroxylamine hydrochloride and sodium acetate to produce intermediate c'; When X is a carbonyl group, intermediate b'undergoes oxime reaction with nitrite ester or nitrite at room temperature in the presence of an organic solvent and concentrated hydrochloric acid to produce intermediate c';

(4') Synthesis of the compound of formula (I): Intermediate c'is esterified with anhydride (R ₃ -CO) ₂ O or an acyl chloride compound R ₃ -CO-Cl to obtain a target product;

.

.

Includes.

In the above production method, the raw materials used are all compounds already known in the prior art, and are commercially available or can be simply prepared by a known synthetic method.

The relevant reactions in steps (1)-(3) and (1')-(4') are all general reactions to synthesize similar compounds in the field. Upon knowledge of the synthesis idea disclosed in the present invention, a person skilled in the art can easily determine specific reaction conditions based on this.

In the Friedel-Craft reaction of step (1), the reaction temperature is generally -10 to 30°C, and the organic solvent used is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction. For example, dichloromethane, Dichloroethane, benzene, toluene, xylene, and the like.

In the Friedel-Craft reaction of step (1'), the reaction temperature may be room temperature, and the organic solvent used can dissolve the raw material and there is no particular limitation as long as there is no adverse effect on the reaction. For example, dichloromethane, dichloroethane, Benzene, toluene, xylene, and the like. Aluminum trichloride or zinc chloride can enter the reaction system by dropwise addition or divided injection.

The oxime reaction in step (2) proceeds in a solvent system, and the solvent used is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction.

In the esterification reaction of step (2'), a solvent may or may not be used as necessary. In the case of using a solvent, there is no limitation on the type of solvent as long as it can dissolve the raw material and has no adverse effect on the reaction.

The oxime reaction of step (2) and step (3') proceeds in a solvent system, and there is no particular limitation as long as the solvent used can dissolve the raw material and has no adverse effect on the reaction. When X is a blank, the solvent used may be a mixed solvent of alcohol and water, preferably a mixed solvent of ethanol and water. The reaction proceeds under heating and reflux. When X is a carbonyl group, the organic solvent used may be dichloromethane, benzene, toluene, tetrahydrofuran, etc., and the nitrite ester used may be selected from ethyl nitrite, isopentyl nitrite, isooctyl nitrite, etc. May be selected from sodium nitrite and potassium nitrite.

The esterification reaction of step (3) proceeds in an organic solvent, and there is no particular limitation on the type of solvent, as long as the raw material can be dissolved and there is no adverse effect on the reaction. For example, dichloromethane, dichloroethane, benzene, toluene, xylene Etc.

The esterification reaction of step (4') proceeds in an organic solvent, and there is no particular limitation on the type of solvent as long as the raw material can be dissolved and there is no adverse effect on the reaction, preferably dichloromethane, dichloroethane, benzene, and xylene. .

In the present invention, the fluorene-containing oxime ester-based compound represented by Formula (I) may be polymerized by being connected to each other by R ₁ (one or two), R ₂ or R ₃ to form a dimer. It is known that such a dimerization product can exhibit similar application performance to the fluorene-containing oxime ester photoinitiator represented by the formula (I).

It is also an object of the present invention to apply the fluorene-containing oxime ester photoinitiator represented by the above formula (I) to a photocuring composition (ie, a photosensitive composition). Without limitation, the photoinitiator may be applied to a color photoresist (RGB), a black matrix (BM), a photo spacer, a rib, a dry film, a semiconductor photoresist, and an ink. The photoinitiator has excellent solubility in application, excellent storage stability, low exposure requirements (ie, high photosensitivity), and exhibits very good developability and pattern integrity.

The polymerizable composition of the present invention can be used by mixing with an alkali-soluble resin, and if the alkali-soluble resin (D) acts only as a binder, an alkali-soluble developer is preferable as a developer used in the developing process when forming an image pattern, An alkali-soluble resin as the carbonyl group-containing copolymer is preferable, and a copolymer of an olefinically unsaturated monomer having at least one carbonyl group and other copolymerizable olefinically unsaturated monomers is preferable.

Another object of the present invention is to apply the photosensitive resin composition to the production of a color filter, a black matrix, a photo spacer, a rib, and a photoresist for a dry film.

The photosensitive resin composition of the present invention has a reasonable composition of each component, has a very high photosensitivity, can be crosslinked and cured well even at a very low exposure amount, and has a very good curing effect. The film made of the composition has a smooth edge, no defects, no debris, a completely flawless and clear pattern, and high hardness. The manufactured optical filter has high optical transparency, does not leak light, can be made even at low exposure doses every week, and has excellent precision, flatness, and durability.

It should be noted that, unless contradictory, the embodiments of the present application and features in the embodiments may be combined with each other. Hereinafter, the present invention will be described in detail by combining examples.

According to the analysis in the background art, the oxime ester-based photoinitiator of the prior art has insufficient solubility with the resin substrate, and in order to solve this problem, the present application is a typical implementation method having a structure represented by the following formula (I). Provides a fluorene-containing oxime ester-based photoinitiator,

In the above formula, R ₁ is each independently hydrogen, halogen, a C ₁ -C ₂₀ straight or branched alkyl group, a C ₄ -C ₂₀ cycloalkylalkyl group, a C ₂ -C ₂₀ alkenyl group, and of these groups- CH ₂ -may optionally be substituted by -O-; R ₂ is a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cycloalkylalkyl group or an alkylcycloalkyl group, or is -R ₄ -COO-R ₅ , where R ₄ is a C ₁ -C ₁₀ alkylene group , C ₃ -C ₁₀ cycloalkyl group, a C ₆ -C ₂₀ aryl group or a substituted aryl group, a non-terminal -CH ₂ of that of the arylene group - a cycloalkyl group and -CH ₂ - is optionally -O May be substituted by -, and CH of the aryl group may be optionally substituted by N; R ₅ is a C ₁ -C ₂₀ straight or branched alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ alkylcycloalkyl group or a cycloalkylalkyl group, a C ₆ -C ₃₀ aryl group or a substituted An aryl group, a C ₇ -C ₃₀ aralkyl group, a C ₂ -C ₂₀ alkenyl group, among which -CH ₂ -may be optionally substituted by -O-, -S- or -NH-; R ₃ is a C ₁ -C ₂₀ straight or branched alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ alkylcycloalkyl group or a cycloalkylalkyl group, a C ₆ -C ₃₀ aryl group or a substituted An aryl group, a C ₇ -C ₃₀ aralkyl group, a C ₂ -C ₂₀ alkenyl group; A is hydrogen, halogen, a nitro group, a C ₁ -C ₁₀ straight or branched alkyl group, a C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl group; X is a blank or a carbonyl group, where blank means that the two atoms at both ends of X are directly connected.

The compound is simple to synthesize, has low cost, good solubility, and has excellent storage stability and film formation performance when applied to a photocurable composition.

In another typical embodiment of the present application, (A) a compound having an olefinic unsaturated bond used in a radical polymerization reaction; (B) a photoinitiator which is at least one kind of compounds whose main structure is a fluorene-based compound represented by formula (I); (C) It provides a photosensitive resin composition containing a colorant,

Here, A is hydrogen, halogen, a nitro group, a C ₁ -C ₁₀ straight or branched alkyl group, a C ₃ -C ₁₀ alkylcycloalkyl group, a C ₄ -C ₁₀ alkylcycloalkyl group or a cycloalkylalkyl group, A -CH _2- in may be substituted with O, N, S or C(=O); X is a linker or a carbonyl group; R ₁ is hydrogen, halogen, a C ₁ -C ₂₀ straight or branched alkyl group, a C ₄ -C ₂₀ cycloalkylalkyl group or a C ₂ -C ₂₀ alkenyl group, and -CH ₂ -in R ₁ is O, May be substituted by N, S or C(=O), and between R ₁ may form a ring; R ₂ and R ₃ are independently of each other a C ₁ -C ₂₀ straight or branched alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cycloalkylalkyl group, or a C ₄ -C ₂₀ alkylcycloalkyl group And -CH ₂ -in R ₂ and R ₃ may be substituted by O, N, S or C(=O).

The compound having the formula (I) is simple to synthesize, has low cost, good solubility, and has excellent storage stability and film forming performance when applied to a photocurable composition.

In addition, the photosensitive resin composition has a reasonable composition of each component, has a very high photosensitivity, can be crosslinked well even at a very low exposure amount, and has a very good curing effect. The film made of the composition has a smooth edge, no defects, no debris, a completely flawless and clear pattern, and high hardness. The manufactured optical filter has high optical transparency, does not leak light, can be made even at low exposure doses every week, and has excellent precision, flatness, and durability.

The photosensitive resin composition of the present invention has high photosensitivity and excellent developability, has high resolution, excellent adhesion to the substrate, and is very suitable for manufacturing a black matrix with high light blocking properties, high precision, high quality color filters and liquid crystal displays. Also, it can be applied to photo spacers and ribs.

The photosensitive resin composition of the present invention includes components (A) and (B) and optionally selected components (C) and (D), and detailed descriptions of each component are given below.

<Component (A) radically polymerizable compound>

In the photosensitive resin composition of the present invention, component (A) is a compound or/and an epoxy compound having an olefinic unsaturated bond capable of radical polymerization. The compound having a radically polymerizable olefinic unsaturated bond may be a compound having at least one radically polymerizable olefinic unsaturated bond in the molecule, and the compound may have a chemical form such as a monomer, oligomer, or polymer.

Examples of compounds having such radically polymerizable olefinic unsaturated bonds include unsaturated carboxylic acids such as acrylate, methacrylate, itaconic acid, crotonic acid, isocrotonic acid and maleic acid, and salts thereof, esters, carbamates, and amides. And radically polymerizable compounds such as anhydride, acrylonitrile, styrene, vinyl ester, and various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated polyurethanes, and the present invention is not limited thereto.

In addition, the acrylate-based compound of the present invention is methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl Acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, benzyl acrylate, 2-hydro Roxyethylacrylate, 2-hydroxypropylacrylate, 2-hydroxy-3-chloropropylacrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-hydroxy-3-allyloxypropylacrylate , 2-acryloyloxyethyl-2-hydroxypropylphthalate, 2,2,2-trifluoroethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butoxyethyl acrylate, β-carboxy Ethyl acrylate, succinic acid monoacryloyloxyethyl ester, ω-carboxypolycaprolactone monoacrylate, trimethylsiloxyethyl acrylate, diphenyl-2-acryloyloxyethyl phosphate, triethylene glycol diacrylate, Tetraethylene glycol diacrylate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate, EO-modified hydrogenated bisphenol A diacrylate, PO-modified hydrogenated bisphenol A Diacrylate, bisphenol F diacrylate, EO-modified bisphenol F diacrylate, PO-modified bisphenol F diacrylate, EO-modified tetrabromo bisphenol A diacrylate, tricyclodecanedimethylol diacrylate, glycerin PO-modified triacrylic Rate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylic It may be a rate or the like.

Additionally, the methacrylate-based compound of the present invention is methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate , Hexyl methacrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, isoboronyl methacrylate , Cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2- Hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoro Propyl methacrylate, 1H-hexafluoroisopropyl methacrylate, 2-methoxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol Methacrylate, methoxypolyethylene glycol #400 methacrylate, methoxydipropylene glycol methacrylate, methoxytripropylene glycol methacrylate, methoxypolypropylene glycol methacrylate, ethoxydiethylene glycol methacrylate, 2- Ethylhexylcarbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, dipentaerythritol hexamethacrylate It may be a acrylate or the like.

Additionally, the compounds of the present invention are allyl glycidyl ether, diallylphthalate, triallyl trimellitate, triallyl isocyanurate, acrylamide, N-hydroxymethylacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N-acryloylmorpholine, styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p -Methylstyrene, vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipic acid, and the like.

Only one radical polymerizable compound (A) of the present invention may be used, and in order to improve desired properties, two or more types may be mixed and used in an arbitrary ratio.

The capacity of the component (A) in the photosensitive resin composition may be 0.1 to 100 parts by mass, preferably 30 to 80 parts by mass, and more preferably 40 to 70 parts by mass.

<Component (B) Photoinitiator>

The component (B) photoinitiator used in the present invention is a fluorene-based compound represented by Formula (I) or Formula (II), and a derivative compound having a compound represented by Formula (I) or Formula (II) as a main structure. It is at least 1 type selected from among. The photoinitiator may be composed of only a fluorene-based compound represented by Formula (I) or Formula (II) or a derivative compound having the same as a main structure, or may be a combination of two compounds.

Additionally, in the compound represented by formula (I) of the present invention,

A is hydrogen, halogen, a nitro group, a C ₁ -C ₁₀ straight or branched alkyl group, a C ₃ -C ₁₀ alkylcycloalkyl group, a C ₄ -C ₁₀ alkylcycloalkyl group or a cycloalkylalkyl group, in A CH ₂ -may be substituted by O, N, S or C (=O), X is a linker or a carbonyl group, R ₁ is hydrogen, halogen, C ₁ -C ₂₀ straight or branched alkyl group, C ₄ is an alkenyl group -C ₂₀ cycloalkyl group or a C ₂ -C _20, R ₁ of the -CH ₂ - is between the O, N, S or C (= O) may be substituted by, R ₁ ring And R ₂ and R ₃ are independently of each other a C ₁ -C ₂₀ straight or branched alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cycloalkylalkyl group or a C ₄ -C ₂₀ is an alkylcycloalkyl group, and -CH ₂ -in R ₂ and R ₃ may be substituted by O, N, S or C (=O), and R ₆ and R ₇ are independently C ₁ -C ₂₀ Is a straight-chain or branched alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cycloalkylalkyl group or a C ₄ -C ₂₀ alkylcycloalkyl group, and -CH ₂ -in R ₆ and R ₇ is O , N, S or C (=O) may be substituted, R ₆ and R ₇ are connected to each other to form a ring, and R ₈ is a photoactive group of a hydroxy group, an N-morpholinyl group or an N-dialkyl group .

As a preferred method, the fluorene-based compound represented by Formula (I) or Formula (II) includes compounds 1'to 30' represented by the following structures.

Derivative compounds having a compound represented by Formula (I) or Formula (II) as the main structure are provided by substitution or linking of branched chains under the premise that the main structure of the compound of Formula (I) or Formula (II) is not changed. It is a derivative obtained. When used as a photoinitiator in the present invention, the derivative compound having the compound represented by Formula (I) or Formula (II) as the main structure is the following Formulas (III), (IV), (V), (VII), (VIII) ) Is a compound represented by:

,

,

Where M is R ₁ , R ₂ , R _3, R ₆ , It is a linking group formed by dimerization of R ₇ and R ₈ , and M is a blank, a C ₁ -C ₂₄ straight or branched akylene group, a C ₆ -C ₃₆ straight or branched arylene group or a hetero arylene group. , -CH ₂ -in M may be optionally substituted with a sulfur, oxygen, NH or carbonyl group, and a hydrogen atom may be optionally substituted with OH or NO ₂ .

Exemplarily, the derivative compound may be a compound having the following structure.

The capacity of the component (B) in the photosensitive resin composition is preferably 1 to 5 parts by mass.

<Component (C) coloring agent>

The photosensitive resin composition of the present invention may further contain a component (C) colorant. Without limitation, by containing the colorant, the composition of the present invention can be used to form a color filter of a liquid crystal display, and when the light shielding agent is a colorant, the composition can form a black matrix image tube in the color filter of the display device. have.

In the present invention, there is no particular limitation on the kind of the colorant as component (c), and may be a compound classified as a pigment in the color index (CI; issued by The Society of Dyers and Colorists), preferably a colorant having the following CI number to be. For example: C.I. Pigment Yellow 1 (hereinafter “CI Pigment Yellow” is the same, so only the number is written), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61 , 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120 , 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185; C.I. Pigment Orange 1 (hereinafter “CI Pigment Orange” is the same, so only the number is written), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55 , 59, 61, 63, 64, 71, 73; C.I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet" is the same, so only the numbers are given), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; C.I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, so only the number is written), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17 , 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2 , 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1 , 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170 , 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220 , 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265; C.I. Pigment Blue 1 (hereinafter "C.I. Pigment Blue" is the same, so only the numbers are given), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66; C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment green 37; C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Pigment Brown 28; C.I. Pigment Black 1, C.I. Pigment Black 7.

When using the light-shielding agent as a colorant, it is preferable to use a black pigment as the light-shielding agent. The black pigment may be, for example, carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, metal oxides such as silver, composite oxides, metal sulfides, metal sulfates or metal carbonates. Among these black pigments, it is preferable to use carbon black having high light-shielding properties, and may be conventional carbon blacks such as channel black, furnace black, pyrolysis black, and lamp black, and channel black having excellent light-shielding properties is used. It is preferred, and it is also possible to apply carbon black using a resin. In addition, in order to adjust the color tone of the carbon black, the organic pigments listed above can be appropriately added as auxiliary pigments. It has been found that even when a black pigment having high light-shielding property is used in the photosensitive resin composition of the present invention, very good developability and pattern integrity can be exhibited.

The capacity of the component (C) in the photosensitive resin composition is 0-50 parts by mass, preferably 5-40 parts by mass.

<Component (D) alkali-soluble resin>

The polymerizable composition of the present invention can be used by mixing with an alkali-soluble resin, and if the alkali-soluble resin (D) acts only as a binder, an alkali-soluble developer is preferable as a developer used in the developing process when forming an image pattern, Alkali-soluble resin as a carbonyl group-containing copolymer is preferred. In particular, an olefinically unsaturated monomer having at least one carbonyl group (hereinafter abbreviated as “carbonyl group-containing unsaturated monomer” (P)) and other copolymerizable olefinically unsaturated monomers (hereinafter “copolymeric A copolymer (abbreviated as "carbonyl group-containing copolymer" (R)) of synthetic unsaturated monomer" (Q)) is preferred.

Examples of the carbonyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid, or anhydrides thereof; Trivalent or more unsaturated polyhydric carboxylic acids or anhydrides thereof; Mono succinate (2-acryloyloxyethyl), mono succinate (2-methacryloyloxyethyl), phthalic acid monophthalate mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) ) Mono[(methyl)acryloyloxyalkyl]esters of polyhydric carboxylic acids such as divalent or higher; and mono (meth)acrylates, which are polymers having carboxyl groups and hydroxy groups at both ends, such as ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.

In addition, copolymerizable unsaturated monomers are styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxy Styrene, o-vinylbenzyl methyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. Aromatic vinyl compounds; Unsaturated carboxylic acid glycidyl esters such as indene-based glycidyl acrylate and glycidyl methacrylate such as indene and 1-methylindene; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; Acrylamide, methacrylamide, unsaturated acrylamide systems such as α-chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; Maleimide, N-phenylmaleimide, Unsaturated imide systems such as N-cyclohexylmaleimide; Aliphatic conjugated diene systems such as 1,3-butadiene, isoprene, and chloroprene; polystyrene, A monoacryloyl group or a monomethacryloyl group at the end of a polymer molecular chain such as polymethyl acrylate, polymethyl methacrylate, poly (n-butyl acrylate), poly (n-butyl methacrylate), and polysiloxane The large molecular monomer system which has, etc. are mentioned. These copolymerizable unsaturated monomers may be used alone or in combination of two or more.

The carbonyl group-containing copolymer (hereinafter referred to as "carbonyl group-containing copolymer (R)") preferably used in the present invention is obtained by polymerizing (P) and (Q); The (P) contains acrylic acid and/or methacrylic acid as necessary components, and additionally, succinate mono (2-acryloyloxyethyl), succinate mono (2-methacryloyloxyethyl), ω- Carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate and at least one compound selected from a carbonyl group-containing unsaturated monomer component, wherein (Q) is styrene, methyl acrylate, methyl methacrylate , 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-phenyl It is at least one member selected from maleimide, polystyrene macromolecular monomers, and polymethylmethacrylate macromolecular monomers.

Specific examples of the carbonyl group-containing copolymer (R) include (meth)acrylic acid/(meth)acrylate copolymer, (meth)acrylic acid/benzyl (meth)acrylate copolymer, (meth)acrylic acid/2-hydroxyethyl (meth) )Acrylate/benzyl(meth)acrylate copolymer, (meth)acrylic acid/methyl(meth)acrylate/polystyrene macromolecular monomer copolymer, (meth)acrylic acid/methyl(meth)acrylate/polymethylmethacrylate Copolymer of large molecular monomer, copolymer of (meth)acrylic acid/benzyl (meth)acrylate/polystyrene large molecular monomer, (meth)acrylic acid)/benzyl (meth)acrylate/polymethylmethacrylate copolymer of large molecular monomer Copolymer, (meth)acrylic acid/2-hydroxyethyl (meth)acrylate/benzyl (meth)acrylate/polystyrene macromolecular monomer copolymer, (meth)acrylic acid/2-hydroxyethyl (meth)acrylate/benzyl Copolymer of (meth)acrylate/polymethylmethacrylate macromolecular monomer, (meth)acrylic acid/styrene/benzyl (meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/succinic acid mono[2- (Meth)acryloyloxyethyl]/styrene/benzyl(meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/succinic acid mono(2-(meth)acryloyloxyethyl)/styrene/allyl (Meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/styrene/benzyl (meth)acrylate/glycerol mono(meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/ω -Carboxypolycaprolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, etc., and the like, present in the carbonyl group-containing copolymer molecule. The substituent may be modified by other materials.

In the present invention, the alkali-soluble resin (D) can be used alone or in combination of two or more.

Component (D) has a capacity in the photosensitive resin composition of 0 to 80 parts by mass, preferably 20 to 60 parts by mass.

<Other components that can be selected arbitrarily>

Depending on the application requirements of the product, at least one large molecule or polymer compound may be added to the composition as necessary to improve the application performance in the process of using the composition, and such a large molecule or polymer compound is a polyol or polyester polyol In addition, a polymer that does not contain a reactive functional group may be optionally added, and such a polymer is generally a resin containing an acidic functional group such as a phenolic hydroxy group or a hydroxy group, and may be used together with other photoinitiators.

In addition, to the photosensitive resin composition of the present invention, other general auxiliary agents in the field may be optionally added, and other auxiliary agents include, but are not limited to, a sensitizer, a dispersant, a surfactant, a solvent, and the like.

The polymerizable composition of the present invention can be polymerized through energy generated by an electron beam, such as ultraviolet rays, visible rays, near infrared rays, or the like during the polymerization reaction, to obtain a target polymer. The light source that imparts energy is preferably a light source having a dominant wavelength that emits light in a wavelength range of 250 nm to 450 nm. Examples of light sources having a dominant wavelength that emit light in the wavelength range of 250nm to 450nm, including high-pressure mercury lamps, medium-pressure mercury lamps, mercury xenon lamps, metal halide lamps, high power metal halide lamps, pulsed xenon lamps, deuterium lamps, LED lamps, fluorescent lamps. There are various light sources such as lamp, Nd-YAG triple wave laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser and semiconductor excitation laser.

<Production and application>

When each component is weighed according to the amount and then uniformly mixed, the photosensitive resin composition of the present invention can be obtained, which belongs to a conventional technique known to those skilled in the art.

It is an object of the present invention to provide a use of a photosensitive resin composition in the manufacture of a color filter, a black matrix, a photo spacer, a rib, and a photoresist for a dry film.

Techniques for producing RGB, BM, photospacer, etc. by photocuring and photolithographic processes using a photosensitive resin composition are well known to those skilled in the art, and generally i) dissolve the photosensitive resin composition in an appropriate organic solvent and uniformly Mixing to obtain a liquid composition; ii) uniformly coating the liquid composition on the substrate using a coater such as a spin coater, a wire bar coater, a roll coater or a spray coater; iii) performing prebaking and drying to remove the solvent; iv) attaching a mask to the sample to expose it, and then developing to remove the unexposed area; v) performing post-baking to obtain a photoresist dry film having a desired shape.

The photoresist film comprising the black pigment is a black matrix (BM), and the photoresist film comprising the red, green and blue pigment is the corresponding R, G, B photoresist.

Hereinafter, the present invention will be described in detail by combining specific examples, but this should not be understood as limiting the scope of the present invention.

Manufacturing Example

(1) 중간체 1a의 제조

(1) Preparation of intermediate 1a

120 g of raw material 1a, 67 g of aluminum trichloride, and 100 ml of dichloromethane were added to a 500 mL four-necked flask, and after lowering the temperature to 0°C with an ice bath, a mixed solution of 80 g of raw material b and 50 mL of dichloromethane was added dropwise. Was added dropwise within about 2 hours while being controlled at 10° C. or lower, followed by liquid chromatography while stirring for 2 hours and carried out until the reaction was completed, and 800 g of ice water and 100 mL of concentrated hydrochloric acid (37%) The dichloromethane layer of the lower layer was separated by stirring while slowly adding to the diluted hydrochloric acid prepared with, and then the dichloromethane layer of the lower layer was separated by putting it in a separating funnel, and the aqueous layer was continuously washed with 50 mL of dichloromethane, combined with the dichloromethane layer, and then 5% hydrogen carbonate. Wash the dichloromethane layer using an aqueous sodium solution (300 mL each time, a total of 3 times), and then wash the dichloromethane layer with water until the pH becomes neutral, and dry the dichloromethane layer with 150 g of anhydrous magnesium sulfate and filter. , The dichloromethane product solution was evaporated while rotating, recrystallized with methanol, and dried in an oven at 70° C. for 2 hours to obtain 141 g of intermediate 1a. Yield: 78%, purity: 98%, MS (m/z): 364 (M+1) ⁺ .

(2) Preparation of intermediate 1b

In a 500 mL four-necked flask, 73 g of intermediate 1a, 14 g of hydroxylamine hydrochloride, 16 g of sodium acetate, 150 mL of ethanol, and 50 mL of water were added, followed by stirring while heating to reflux at 85° C. for 5 hours, and the reaction was stopped. , Put in a 2000 mL beaker, add 1000 mL of water, stir, extract with 200 mL of dichloromethane, add 50 g of anhydrous MgSO ₄ to the extract, dry, filter, and then reduce the pressure to remove the solvent by rotary evaporation. Then, an oily viscous material is obtained in a rotating flask, and the viscous material is added to 150 mL of petroleum ether, stirred to precipitate, and filtered to obtain a white powdery solid, and dried at 60° C. for 5 hours to obtain 57 g of intermediate 1b To obtain. Yield: 75%, purity: 98%, MS (m/z): 379 (M+1) ⁺ .

(3) Synthesis of compound 1

To a 250 mL four-neck flask, 38 g of intermediate 1b and 100 mL of dichloromethane were added, and after stirring at room temperature for 5 minutes, 11 g of acetic anhydride was all added dropwise within about 30 minutes, followed by stirring for 2 hours, and then pH Add 5% NaHCO ₃ aqueous solution until the value becomes neutral, separate the organic layer with a separatory funnel, wash twice with 200 mL of water, dry with 50 g of anhydrous MgSO ₄ , filter, and spin evaporate to solvent Removal of the to give a viscous liquid, recrystallization with methanol to give a white solid powder, and filtered to give a product of 36g. Yield: 85%, purity: 99%.

The structure of the product was confirmed by hydrogen nuclear magnetic resonance spectroscopy and mass spectroscopy.

¹ H-NMR (CDCl ₃ , 500MHz): 1.0023-1.1128(3H,d), 1.409-1.4511(7H,m), 1.6157-1.6832(10H,m), 2.0824(3H,s), 8.0121-8.4465(6H) ,m). MS(m/z):421(M+1) ⁺ .

(1) Preparation of intermediate 2a

105 g of raw material 2a, 67 g of aluminum trichloride, and 100 mL of dichloromethane were added to a 500 mL four-neck flask, and after lowering the temperature to 0°C with an ice bath, a mixed solution of 74 g of raw material 2b and 50 mL of dichloromethane was added dropwise. With the temperature controlled to 10℃ or less, all dropwise additions were made within about 2 hours, followed by stirring for 2 hours until the liquid phase reaction was completed, prepared with 800 g of ice water and 100 mL of concentrated hydrochloric acid (37%). After stirring while slowly adding to dilute hydrochloric acid, it was put into a separatory funnel to separate the dichloromethane layer of the lower layer, and the aqueous layer was continuously washed with 50 mL of dichloromethane, combined with the dichloromethane layer, and then 5% aqueous sodium hydrogen carbonate solution. Wash the dichloromethane layer using (300 mL each time, total 3 times), and then wash the dichloromethane layer with water until the pH becomes neutral, and dry the dichloromethane layer with 150 g of anhydrous magnesium sulfate, filter, and dichloromethane. The methane product solution was evaporated while rotating, recrystallized with methanol, and dried in an oven at 70° C. for 2 hours to obtain 127 g of intermediate 2a. Yield: 79%, purity: 98%, MS (m/z):322 (M+1) ⁺ .

(2) Preparation of intermediate 2b

To a 250 mL four-neck flask, 64 g of intermediate 2a, 20 g of 37% hydrochloric acid, 23 g of isopentyl nitrite, and 100 mL of tetrahydrofuran were added, stirred at room temperature for 5 hours, and then the reaction was stopped and placed in a 2000 mL beaker. , 1000 mL of water was added and stirred, extracted with 200 mL of dichloromethane, dried by adding 50 g of anhydrous MgSO ₄ to the extract, filtered, and then rotary evaporated under reduced pressure to remove the solvent. A daily viscous material is obtained, and the viscous material is added to 150 mL of petroleum ether, stirred to settle, and then filtered to obtain a white powdery solid, which is dried at 60° C. for 5 hours to obtain 57 g of intermediate 1b. Yield: 78%, purity: 98%, MS (m/z):351 (M+1) ⁺ .

(3) Synthesis of compound 2

35 g of intermediate 2b and 100 mL of dichloromethane were added to a 250 mL four-necked flask, and after stirring at room temperature for 5 minutes, 10 g of propionyl chloride was all added dropwise within about 30 minutes, followed by stirring for 2 hours. Add to 5% NaHCO ₃ aqueous solution until the pH value becomes neutral, separate the organic layer with a separatory funnel, wash twice with 200 mL of water, dry with 50 g of anhydrous MgSO ₄ , filter, and rotate evaporation. Removal of the solvent yields a viscous liquid, recrystallization with methanol yields a white solid powder, and filtration yields 35 g of product. Yield: 86%, purity: 99%.

The structure of the product was confirmed by hydrogen nuclear magnetic resonance spectroscopy and mass spectroscopy.

¹ H-NMR (CDCl ₃ , 500MHz): 1.0162-1.1057 (3H, t), 1.5069-1.5161 (5H, m), 1.6755-1.6992 (4H, m), 2.2624-2.3004 (2H, m), 3.8774 (2H ,s) 7.9151-8.3325 (6H,m). MS(m/z):407(M+1) ⁺ .

Example 3

With reference to the methods of Examples 1 and 2, compounds 3 to 12 shown in Table 1 below were synthesized using corresponding raw materials.

Example 13

(1) Preparation of intermediate 13a

120 g of raw material 13a, 43 g of raw material 13b (i.e., malonic anhydride) and 150 mL of dichloromethane were added to a 1 L four-neck flask, stirred at room temperature, and 67 g of aluminum trichloride were added in portions within 1 hour, and then continued. After completing the liquid phase trace reaction while stirring for 2 hours, stirring while slowly adding to dilute hydrochloric acid prepared with 1200 g of ice water and 100 mL of concentrated hydrochloric acid (37%), and then put in a separating funnel to separate the dichloromethane layer of the lower layer, 50 mL The aqueous layer was continuously washed with dichloromethane of, and then combined with the dichloromethane layer, the dichloromethane layer was washed with 5% aqueous sodium hydrogen carbonate solution (300 mL each time, a total of 3 times), and then the pH was neutral. Wash the dichloromethane layer with water until the temperature is reached, dry the dichloromethane layer with 150 g of anhydrous magnesium sulfate, filter, and evaporate while rotating the dichloromethane product solution to recrystallize with methanol, and dry in an oven at 70° C. for 2 hours Upon request, 143 g of intermediate 13a are obtained. Yield: 87%, purity: 99%, MS (m/z): 326 (M+1) ⁺ .

(2) Preparation of intermediate 13b

130 g of intermediate 13a, 5 g of 98% concentrated sulfuric acid, and 100 ml of ethanol were added to a 500 mL four-necked flask, connected to a distillation apparatus, heated to reflux at 80°C, and collected water produced by the reaction while heating, and a change occurred. The reaction was stopped by performing a liquid phase trace reaction until no reaction, and the reaction solution was added to 500 mL of deionized water, extracted with dichloromethane (100 mL each time, 3 times in total), the dichloromethane layer was combined, washed with water, and rotary evaporation. 110 g of intermediate 13b is obtained. Yield: 78%, purity: 98%, MS (m/z): 354 (M+1) ⁺ .

(3) Preparation of intermediate 13c

To a 250 mL four-necked flask, 71 g of intermediate 13b, 14 g of hydroxylamine hydrochloride, 15 g of sodium acetate, 100 mL of ethanol, and 30 mL of water were added, heated to reflux at 85° C. for 5 hours, and placed in a 2000 mL beaker, When 1000 mL of water was added and stirred, a large amount of solid precipitated, filtered and washed with water, and recrystallized with methanol to obtain a white powdery solid, and dried at 60° C. for 5 hours to obtain 70 g of intermediate 13c. Yield: 95%, purity: 98%, MS(m/z):369(M+1) ⁺ .

(4) Synthesis of compound 13

To a 250 mL four-neck flask, 37 g of intermediate 13c and 100 mL of dichloromethane were added, and after stirring at room temperature for 5 minutes, 11 g of acetic anhydride was all added dropwise within about 30 minutes, followed by stirring for 2 hours, and then pH Add to 5% NaHCO ₃ aqueous solution until the value becomes neutral, separate the organic layer with a separatory funnel, wash twice with 200 mL of water, dry with 50 g of anhydrous MgSO ₄ , filter, and spin evaporate to remove the solvent. When removed, a viscous liquid is obtained, recrystallization with methanol yields a white solid powder, and filtration yields 36 g of product. Yield: 89%, purity: 99%.

The structure of the product was confirmed by hydrogen nuclear magnetic resonance spectroscopy and mass spectroscopy.

¹ H-NMR (CDCl ₃ , 500MHz): 1.2892-1.3061 (3H,t), 1.6849 (6H,s), 2.0812 (3H,s), 3.6832 (2H,s), 4.1168-4.2000 (2H,m), 7.8121-8.7466 (6H, m). MS(m/z):411(M+1) ⁺ .

(1) Preparation of intermediate 14a

106 g of raw material 14a, 50 g of raw material 14b (i.e., malonic anhydride) and 150 mL of dichloromethane were added to a 1 L four-necked flask, stirred at room temperature, and 67 g of aluminum trichloride were added in portions within 1 hour, and then continued. After completing the liquid phase trace reaction while stirring for 2 hours, stirring while slowly adding to dilute hydrochloric acid prepared with 1200 g of ice water and 100 mL of concentrated hydrochloric acid (37%), and then put in a separating funnel to separate the dichloromethane layer of the lower layer, 50 mL The aqueous layer was continuously washed with dichloromethane of, and then combined with the dichloromethane layer, the dichloromethane layer was washed with 5% aqueous sodium hydrogen carbonate solution (300 mL each time, a total of 3 times), and then the pH was neutral. Wash the dichloromethane layer with water until the temperature is reached, dry the dichloromethane layer with 150 g of anhydrous magnesium sulfate, filter, and evaporate while rotating the dichloromethane product solution to recrystallize methanol, and dry it in an oven at 70° C. for 2 hours Upon request, 134 g of intermediate 14a are obtained. Yield: 86%, purity: 99%, MS (m/z): 312 (M+1) ⁺ .

(2) Preparation of intermediate 14b

124 g of intermediate 14a, 5 g of 98% concentrated sulfuric acid, and 100 mL of cyclobutyl methanol were added to a 500 mL four-necked flask, connected to a distillation apparatus, heated to reflux at 140° C., and collected the water produced by the reaction while heating, and changed. The reaction was stopped by following the liquid phase reaction until there was no occurrence, and the reaction solution was added to 500 mL of deionized water, extracted with dichloromethane (100 mL each time, 3 times in total), the dichloromethane layer was combined, washed with water, and rotated. Evaporation yields 117 g of intermediate 14b. Yield: 77%, purity: 98%, MS (m/z):380 (M+1) ⁺ .

(3) Preparation of intermediate 14c

76 g of intermediate 14b, 24 g of isopentyl nitrite, 10 g of 37% hydrochloric acid, and 50 mL of tetrahydrofuran were added to a 250 mL four-necked flask, stirred at room temperature for 5 hours, and then the reaction was stopped and placed in a 2000 mL beaker. , 1000 mL of water was added and stirred, extracted with 200 mL of dichloromethane, dried by adding 50 g of anhydrous MgSO ₄ to the extract, filtered, and then rotary evaporated under reduced pressure to remove the solvent. A daily viscous substance is obtained, and the viscous substance is added to 150 mL of petroleum ether, stirred to settle, and then filtered to obtain a white powdery solid, which is dried at 60° C. for 5 hours to obtain 78 g of intermediate 14c. Yield: 95%, purity: 98%, MS (m/z):409 (M+1) ⁺ .

(4) Synthesis of compound 14

41 g of intermediate 14c and 100 mL of dichloromethane were added to a 250 mL four-necked flask, and after stirring at room temperature for 5 minutes, 11 g of butyryl chloride were all added dropwise within about 30 minutes, followed by stirring for 2 hours. Add to 5% NaHCO ₃ aqueous solution until the pH value becomes neutral, separate the organic layer with a separatory funnel, wash twice with 200 mL of water, dry with 50 g of anhydrous MgSO ₄ , filter, and rotate evaporation. Removal of the solvent yields a viscous liquid, recrystallization with methanol yields a white solid powder, and filtration yields 43 g of product. Yield: 90%, purity: 99%.

The structure of the product was confirmed by hydrogen nuclear magnetic resonance spectroscopy and mass spectroscopy.

¹ H-NMR(CDCl ₃ , 500MHz): 1.0001-1.1102(3H,t), 1.5981-1.6002 (2H,m), 1.9167-2.1621(6H,m), 2.3346-2.5842(5H,m), 3.8813(2H) ,s), 3.9768-4.0130 (2H, m), 7.8046-8.7573 (6H, m). MS (m/z):479 (M+1) ⁺ .

Example 15

With reference to the methods of Examples 13 and 14, compounds 15 to 30 shown in Table 1 below were synthesized using corresponding raw materials.

Property evaluation

1. Solubility test

The solubility size of a photoinitiator in PGMEA is one of the index coefficients for evaluating its solubility and applicability to the photoinitiator. The solubility in PGMEA was measured at 25° C. using a conventional nitro group-containing carbazole oxime ester photoinitiator as a comparison target with the compound of formula (I) of the present invention, and the results are as shown in Table 2.

As can be seen from the table, the two conventional nitro group-containing carbazole oxime ester photoinitiators are not basically dissolved in PGMEA, but the compounds of the present invention have very good solubility in PGMEA and are industrialized. The application meets the need for solubility of 8% by weight or more.

2. Storage stability and film formation characteristics experiment

An exemplary photocurable composition was prepared and evaluated for storage stability and film forming properties of the photoinitiator represented by formula (I) of the present invention.

(1) Preparation of a photocurable composition of the following composition

200 parts by mass of acrylate copolymer

[Benzyl methacrylate/methacrylic acid/hydroxyethyl methacrylate (molar ratio 70/10/20) copolymer (Mv:10000)]

100 parts by mass of dipentaerythritol hexaacrylate

5 parts by mass of photoinitiator

900 parts by mass of butanone (solvent)

In the above composition, the photoinitiator is a fluorene-containing oxime ester compound represented by the formula (I) disclosed in the present invention or a photoinitiator known in the prior art (to be compared).

(2) storage stability

After storing the liquid photocurable composition at room temperature for 1 month, the degree of precipitation of the material was visually evaluated according to the following criteria.

A: No precipitation was observed; B: Slight precipitation was observed; C: Significant precipitation was observed.

(3) film formation properties

After stirring the exemplary photocurable composition having the above composition under a yellow lamp condition, a film is formed by roll coating on a PET template, and then dried at 90°C for 2 minutes to obtain a coating film having a thickness of 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 perform long-wavelength emission through an FWHM color filter. After exposing the coating film under UV light with a wavelength of 370-420 nm through the gap in the mask, immerse in 2.5% sodium carbonate solution at 25°C and develop for 20 seconds, then wash with ultrapure water, air dry, and at 220°C for 30 minutes During hard baking, the pattern was fixed, and the obtained pattern was evaluated.

① Light sensitivity

At the time of exposure, the minimum exposure amount in which the residual film ratio after development of the light irradiated area in the exposure step was 90% or more was evaluated as the exposure required amount. The smaller the exposure requirement, the higher the sensitivity.

② Developability and pattern integrity

The pattern on the substrate was observed with a scanning electron microscope (SEM) to evaluate developability and pattern integrity.

Developability was evaluated according to the following criteria:

○: No residue was observed in the non-exposed portion;

◎: A small amount of residue was observed in the non-exposed part, but it is acceptable;

●: Significant residue was observed in the unexposed part.

Pattern integrity was evaluated according to the following criteria:

◇: No pattern defect was observed;

□: Some defects were observed in some parts of the pattern;

◆: A number of defects are clearly observed in the pattern.

Table 3 shows the evaluation results.

As can be seen from Table 3, compared to the conventional nitro group-containing carbazole oxime ester-based photoinitiator, the photocurable composition containing the fluorene-containing oxime ester-based photoinitiator of the present invention has good storage stability, and the exposure requirements are all 60 mJ/ It is as low as less than cm ² , and also has excellent developing effect and pattern integrity, and has very excellent film forming properties. In summary, since the fluorene-containing oxime ester-based photoinitiator represented by the formula (I) disclosed in the present invention has excellent applicability, and has low raw material and manufacturing cost, there is a very good application prospect.

Related experiments of the composition

According to the blending ratio shown in Table 4, the photosensitive resin compositions of Examples 53-60 and Comparative Examples 5-8 were prepared. The structures of the photoinitiators A1 to A4 of Comparative Examples 5 to 9 are as follows.

.

.

Note: All above are parts by mass

The photosensitive resin composition prepared according to the blending ratio shown in Table 4 is uniformly mixed in 100 parts by mass of a solvent in propylene glycol monomethyl ether acetate (PGMEA) to form a liquid composition.

After coating the liquid composition on a glass substrate using a spin coater, drying at 100° C. for 5 minutes to remove the solvent, a coating film having a thickness of 10 μm is formed, and in order to obtain a coating film of the thickness The process can be divided into one or several times.

Cooling the substrate with the coating film to room temperature, attaching the mask, and using an LED light source (Uvata LED UV curing irradiation device, maximum irradiation intensity 400Mw/cm ² ), through the gap of the mask, the coating film under ultraviolet rays of 370 ~ 420nm wavelength To perform exposure.

At a temperature of 25°C, it was developed with 1% NaOH aqueous solution, washed with ultrapure water, and air dried.

Finally, baking in an oven at 240° C. for 30 minutes to obtain a pattern with the mask removed.

Property evaluation

1. Evaluation of exposure sensitivity

In the exposure step, the minimum exposure amount in which the residual film ratio after development of the light irradiation area was 90% or more was evaluated as the required exposure amount. The smaller the exposure requirement, the higher the sensitivity.

2. Developability and pattern integrity

The pattern on the substrate was observed with a scanning electron microscope (SEM) to evaluate developability and pattern integrity.

Developability was evaluated according to the following criteria.

○: No residue was observed in the non-exposed portion;

◎: A small amount of residue was observed in the non-exposed part, but it is acceptable;

●: Significant residue was observed in the unexposed part.

Pattern integrity was evaluated according to the following criteria.

◇: No pattern defect was observed;

□: Some defects were observed in some parts of the pattern;

◆: A number of defects are clearly observed in the pattern.

3. Hardness evaluation

The evaluation was conducted with reference to GB/T 6739-1996 <Coating film hardness pencil measurement method>. Using a coating film pencil scratch hardness tester, the coating film scratch trace is observed, and a pencil in which no scratch is observed is taken as the pencil hardness of the coating film.

4. Adhesion evaluation

Refer to GB9286-88 <Paints and varnishes--Cross cut test for films>, and evaluate the adhesion state of the coating film through the cross cut test method. Divided into 0-5 levels (6 levels in total) according to the degree of destruction, the best is 0 level, meaning that there is no peeling off the surface of the film, and level 5 is the worst, meaning severe peeling occurs on the surface of the film do.

The evaluation results are shown in Table 5.

As can be seen from the results of Table 5, the color filter photoresist prepared with the composition of Examples 53 to 60 has very good developability and pattern integrity, and is very excellent in adhesion and hardness, but Comparative Examples 5 to 8 There is certainly a lack of The exposure doses of Examples 53 to 60 were all 70 mJ/cm ² It should be noted that it is less than, and is much lower than the exposure amount of Comparative Examples 5 to 8, and shows very good photosensitivity. In summary, the photosensitive resin composition of the present invention exhibits very excellent applicability and has a broad application prospect.

The above is only a preferred embodiment of the present invention, the present invention is not limited thereto, and those skilled in the art can change and correct the present invention. Any corrections, equivalent substitutions, and improvements made within the spirit and principle of the present invention are all included within the scope of protection of the present invention.

Claims (24)

(A) a compound having an olefinic unsaturated bond used in a radical polymerization reaction;
(B) a photoinitiator which is at least one kind of compounds whose main structure is a fluorene-based compound represented by the general formula (I); And
(C) As a photosensitive resin composition containing a colorant,

In the above formula (I), A is hydrogen, halogen, nitro group, C ₁ -C ₁₀ straight or branched alkyl group, C ₃ -C ₁₀ alkylcycloalkyl group, C ₄ -C ₁₀ alkylcycloalkyl group or cyclo alkyl group, a is of -CH _2- O, N, or S may be substituted by a C (= O), and;
X is a linker or a carbonyl group;
R ₁ is hydrogen, halogen, a C ₁ -C ₂₀ straight or branched alkyl group, a C ₄ -C ₂₀ cycloalkylalkyl group or a C ₂ -C ₂₀ alkenyl group, and -CH ₂ -in R ₁ is O, May be substituted by N, S or C(=O), and between R ₁ may form a ring;
R ₂ is a C ₁ -C ₂₀ straight or branched alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cycloalkylalkyl group or a C ₄ -C ₂₀ alkylcycloalkyl group, and in R _2- CH ₂ -may be substituted by O, N, S or C(=O);
R ₃ is a C ₁ -C ₄ linear or branched alkyl group having a terminal substituted by a C ₃ -C ₆ cycloalkyl group, a photosensitive resin composition. The method of claim 1,
A is hydrogen, a nitro group, a C ₁ -C ₁₀ straight or branched alkyl group;
X is a linker or a carbonyl group;
R ₁ is hydrogen, a C ₁ -C ₂₀ straight or branched alkyl group or a C ₁ -C ₂₀ straight or branched alkyl group substituted by O, N, S or C(=O);
R ₂ is a C ₁ -C ₂₀ straight or branched alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cycloalkylalkyl group or a C ₄ -C ₂₀ alkylcycloalkyl group, and in R _2- CH ₂ -may be substituted by O, N, S or C(=O);
R ₃ is a C ₁ -C ₄ linear or branched alkyl group having a terminal substituted by a C ₃ -C ₆ cycloalkyl group, a photosensitive resin composition. The method according to claim 1 or 2,
The compound having a fluorene-based compound represented by the general formula (I) as its main structure includes a photosensitive resin composition having the following structure;

,

,

,

. The method of claim 1,
A derivative compound having a fluorene-based compound represented by formula (I) as its main structure is a compound represented by formulas (III), (IV), and (V),

In the above formulas, M is R ₁ , Is a linking group formed by dimerization of R ₂ and R ₃ , and M is a blank, a C ₁ -C ₂₄ straight or branched alkylene group, or a C ₆ -C ₃₆ straight or branched arylene group or a hetero arylene group And -CH ₂ -in M is optionally substituted with a sulfur, oxygen, NH or carbonyl group, and a hydrogen atom is optionally substituted with OH or NO ₂ , a photosensitive resin composition. The method of claim 1 or 4,
The derivative compound having a fluorene-based compound represented by formula (I) as its main structure is a compound having the following structure, a photosensitive resin composition:

,

,

. The method of claim 1,
The photosensitive resin composition further comprises an alkali-soluble resin (D), and a mass part of the alkali-soluble resin is more than 0 and 80 parts by mass or less, or 20 to 60 parts by mass. A method for producing a color filter, photolithography, black matrix, photo spacer, rib, wet film, or dry film by using the photosensitive resin composition according to claim 1 or 2. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete