KR20210148258A - Photosensitive resin composition for color filter and color filter - Google Patents

Abstract

The present invention discloses a photosensitive resin composition for a color filter, a color filter, and a manufacturing method thereof. The composition includes a photopolymerization initiator, an alkali-soluble resin, a compound having at least one polymerizable unsaturated bond, a colorant, and a hydrogen donor, and when applied to the manufacture of color filters, exhibits excellent photosensitivity and good developability, and has high luminance after curing , excellent adhesion to the substrate.

Description

Photosensitive resin composition for color filter and color filter

The present invention belongs to the field of organic chemistry and photocuring technology, and specifically relates to a photosensitive resin composition used in a color filter, a color filter using the photosensitive resin composition, and a manufacturing method thereof.

A color filter is generally manufactured by forming pigments such as red, green, and blue on a transparent substrate by a method such as a dyeing method, a printing method, and a pigment dispersion method. Currently, the pigment dispersion method is the mainstream in the industry, and after applying a photosensitive resin composition containing a colorant to a transparent substrate, the image is exposed and developed, and if necessary, post-curing is performed to form a color filter through repetition of the above process. . The method has advantages such as high heat resistance and no need for dyeing, and can form a high-precision colored layer.

Recently, demands for chromaticity and contrast aspects of color filters are gradually increasing. In order to achieve high color purity of the display device or high color resolution of the light receiving device, the concentration of the colorant in the composition tends to increase, but this easily generates residues or stains on the non-exposed portion of the substrate or the light-shielding layer during the development process, Adhesion to the substrate is lowered, and problems such as insufficient curing or poor pattern formation of the exposed portion are caused.

Even today, composition/mixing of components in the photosensitive resin composition is still a major means of obtaining a product with better application performance.

In view of the need for the development of the prior art, the main object of the present invention is to provide a photosensitive resin composition for a color filter. The composition has excellent photosensitivity and good developability upon application, high luminance after curing, and excellent adhesion to the substrate.

The specific technical measures adopted to realize the above object are as follows.

As the photosensitive resin composition for color filters, the photosensitive resin composition for color filters comprising the following components:

a photoinitiator (A) comprising a photoinitiator A1 and at least one oxime ester-based photoinitiator A2;

alkali-soluble resin (B);

a compound (C) having at least one polymerizable unsaturated bond;

colorant (D);

hydrogen donor (E).

Here, the photopolymerization initiator A1 is a hexaarylbisimidazole-based (ie, HABI) mixed photoinitiator, and has a structure represented by the general formula (I), wherein the four connection positions 2-1', 2-3', Including 2'-1 and 2'-3 bisimidazole compounds, the total mass percentage content in A1 of the bisimidazole compounds at the four linkage positions is 92% or more.

In Formula (I), Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ may be the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group;

In addition, the molar extinction coefficient of the photoinitiator (A) is 5000-10000 in i-line (365 nm).

Another object of the present invention is to provide a color filter using the photosensitive resin composition and a method for manufacturing the same.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, the photosensitive resin composition of the present invention, a color filter, and a manufacturing method thereof will be described in more detail.

<Photoinitiator (A)>

Photoinitiator A1

As described above, the photopolymerization initiator A1 of the present invention has a structure represented by the general formula (I), wherein the four connection positions 2-1', 2-3', 2'-1, 2'- It is an HABI-based mixed photoinitiator including the bisimidazole compound of 3, wherein the total mass percentage content of the bisimidazole compounds at the four linkage positions in the photopolymerization initiator A1 is 92% or more.

In Formula (I), Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ may be the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group;

In addition, the molar extinction coefficient of the photoinitiator (A) is 5000-10000 in i-line (365 nm).

The bisimidazole compounds satisfying the four linking positions 2-1', 2-3', 2'-1, and 2'-3 of the structure represented by the general formula (I) include the structures specifically listed below. has:

In the general formula (I), the aryl group is preferably a phenyl group.

The substituted aryl group may be mono- or poly-substituted.

Preferably, the substituent of the aryl group may be a halogen, a nitro group, a cyano group, an amino group, a hydroxy group, a C ₁ -C ₂₀ alkyl or alkenyl group, or a C ₁ -C ₈ alkoxy group, where each independent variable ( That is, in each of the substituents), the methylene group may be selectively substituted with oxygen, sulfur, or imino groups.

More preferably, the substituent of the aryl group may be a fluorine, chlorine, bromine, nitro group, cyano group, amino group, hydroxy group, C ₁ -C ₁₀ alkyl group or alkenyl group, or C ₁ -C ₅ alkoxy group, wherein, In each independent variable, the methylene group may be optionally substituted with oxygen, sulfur, or imino groups.

Even more preferably _{, at least one of Ar 1} , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ is an aryl group including a halogen substituent. The halogen substituent enhances the discoloration effect during the curing process, so that the recognition ability of the electronic eye during development (Note: The photosensitive resin layer undergoes exposure and color change occurs to form a color difference from the non-exposed area. The present invention improves the quality of the application by improving the color difference). Particularly preferably, the halogen substituent is chlorine.

Applicants found that the photoinitiation activity of the HABI compound in the study is affected by the electronic effect and steric effect of the aromatic ring substituent, and the substituent of the aromatic ring does not significantly affect the absorption of the HABI compound in the vicinity of 265 nm, but in the vicinity of 365 nm It was found to have a significant effect on the absorption of HABI compounds. When a conjugated system is introduced into the HABI structure, the UV absorption wavelength shifts in the long wavelength direction (ie, causes a redshift phenomenon) and the UV absorption intensity (ie, molar extinction coefficient) increases.

In the photosensitive resin composition of the present invention, the photopolymerization initiator A1 is used as an initiator, and curing of the exposed area can be effectively promoted without inactivation through chain transfer of the generated active radicals by a hydrogen donor. This is advantageous for improving the photosensitivity and luminance of the color filter.

The HABI-based compound represented by the general formula (I), except for the above-mentioned four connection positions 2-1', 2-3', 2'-1, 2'-3, linking positions 1-4', 1-5', 3-4', 3-5', 1-1', 1-3', 3-1', 3-3', 4-1', 4-3', 5-1', 5-3' and the like exist further. However, in the study, the applicant has discovered that it is most preferable to solve the technical problem of the present invention only to have the photopolymerization initiator A1 limited as described above. The performance of a single material at any one connection site is significantly lower than that of the photopolymerization initiator A1, and when the total content of these four connection sites is less than 92%, the performance tends to be significantly inferior.

The photopolymerization initiator A1 used in the present invention preferably satisfies the four connection positions 2-1', 2-3', 2'-1, and 2'-3 of the structure represented by the general formula (I). The total mass percentage content in the photopolymerization initiator A1 of the bisimidazole compound is 95% or more, and particularly preferably, the four linking positions 2-1', 2-3', 2' of the structure represented by the general formula (I) It consists of a bisimidazole compound satisfying -1, 2'-3.

In the study, the applicant found that when the molar extinction coefficient of the photopolymerization initiator is 5000 to 10000 at the i-line (365 nm) point, it has a suitable photosensitivity, the curing speed does not decrease due to lack of photosensitivity, and undercut caused by excessively high photosensitivity does not occur. found that it does not.

The HABI-based photoinitiator is a type of photoinitiator known in the photoresist field, and can be prepared by oxidative coupling of a triarylimidazole-based or substituted triarylimidazole-based compound, and the specific manufacturing process is, for example, US3784557, Reference may be made to prior art descriptions such as US4622286, US4311783, and the like, which are incorporated herein by reference in their entirety. Based on the conventional process, by adding a solvent recrystallization process, the photoinitiator A1 which satisfies the said composition requirement of this invention can be obtained immediately and easily. The solvent may be one of toluene, methanol, ethyl acetate, dichloromethane, water, or a combination of two or more. Without limitation, for the preparation of the photopolymerization initiator A1, reference may be made to the contents described in the applicant's prior application (application number: CN201811451262.4) (which is incorporated herein by reference in its entirety).

Illustratively, the photopolymerization initiator A1 corresponding to the bisimidazole compound of the four connection positions 2-1', 2-3', 2'-1, and 2'-3 is selected from or included in at least one of the following combinations do.

A1-1:

A1-2:

A1-3:

A1-4:

A1-5:

A1-6:

A1-7:

In the photosensitive resin composition, the content of the photoinitiator A1 is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total composition.

Oxime ester photoinitiator A2

The photopolymerization initiator of the photosensitive resin composition of the present invention further includes at least one oxime ester-based photoinitiator A2 in addition to the photoinitiator A1.

Adding an oxime ester-based photoinitiator to the system is advantageous in improving the photosensitivity and resolution of the composition. In contrast to adding an oxime ester-based photoinitiator or adding other types of photoinitiators (eg, acetophenone-based compounds, triazine-based compounds, etc.) Developability can be remarkably improved, and at the same time, it is advantageous to improve resolution.

The type of the oxime ester-based photoinitiator is not particularly limited, and a conventionally known photoinitiator including an oxime ester group in the structure may be used. Illustratively, 1- (4-phenylthiophenyl) -n-octane-1,2-dione-2-oxime benzoate (1- (4-phenylthiophenyl) -n-octane-1,2-dione-2- benzoic acid oxime ester), 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-ethan-1-one-oxime acetate, 1-[6-(2-methylbenzoyl)- 9-Ethylcarbazol-3-yl]-butan-1-one-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-propan-1-one-oxime Acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-1-cyclohexyl-methane-1-one-oxime acetate, 1-[6-(2-methylbenzoyl) -9-Ethylcarbazol-3-yl]-(3-cyclopentyl)-propan-1-one-oxime acetate, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2 -dione-2-oximebenzoate, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-oximecyclohexylcarboxylate, 1-[6-(2) -Methylbenzoyl)-9-ethylcarbazol-3-yl]-(3-cyclopentyl)-propane-1,2-dione-2-oxime acetate, 1-(6-o-methylbenzoyl-9-ethylcarr Bazol-3-yl)-(3-cyclopentyl)-propane-1,2-dione-2-oxime benzoate, 1-(4-benzoyldiphenylsulfide)-(3-cyclopentylpropanone)-1- Oxime acetate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentylpropanone)-1-oximecyclohexylcarboxylate, 1-(4-benzoyldiphenyl Sulfide)-3-cyclopentylpropanone)-1-oximecyclohexylcarboxylate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane- 1,2-dione-2-oximeo-methylbenzoate (1-(6-orthomethylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1,2-dione-2-orthomethylbenzoic acid oxime ester), 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-oximecyclohexylcarboxylate, 1-(4-tenoyl-diphenylsulfide-4 '-yl)-3-cyclopentyl-propan-1-one-oximea Cetate (1-(4-thiopheneformyl-diphenyl sulfide-4'-yl)-3-cyclopentyl-propane-1-one-acetic acid oxime ester), 1-(4-benzoyldiphenylsulfide)-(3-cyclo Pentyl) -propane-1,2-dione-2-oxime acetate, 1- (6-nitro-9-ethylcarbazol-3-yl) -3-cyclohexyl-propan-1-one-oxime acetate, 1- (6-o-Methylbenzoyl-9-ethylcarbazol-3-yl)-3-cyclohexyl-propan-1-one-oxime acetate, 1-(6-thenoyl-9-ethylcarbazol-3-yl )-(3-cyclohexylpropanone)-1-oxime acetate, 1-(6-furanfuroyl-9-ethylcarbazol-3-yl)-(3-cyclopentylpropanone)-1-oxime acetate; 1,4-diphenylpropane-1,3-dione-2-oxime acetate, 1-(6-furoyl-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane-1,2 -dione-2-oxime acetate, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-oxime acetate, 1-(6-furanfuroyl-9-ethyl Carbazol-3-yl)-(3-cyclohexylpropanone)-1-oxime acetate, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-3-oxime Benzoate, 1-(6-Tenoyl-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane-1,2-dione-2-oxime acetate, 2-[(benzoyloxy)imi No]-1-phenylpropan-1-one, 1-phenyl-1,2-propanedione-2-(oxoacetyl)oxime, 1-(4-phenylthiophenyl)-2-(2-methylphenyl)-ethane -1,2-dione-2-oxime acetate, 1- (9,9-dibutyl-7-nitrofluoren-2-yl) -3-cyclohexyl-propan-1-one-oxime acetate, 1-{ 4-[4-(thiophen-2-formyl)phenylthio]phenyl}-3-cyclopentylpropane-1,2-dione-2-oxime acetate, 1-[9,9-dibutyl-2-yl ]-3-cyclohexylpropylpropane-1,2-dione-2-oxime acetate, 1-[6-(2-benzoyloxyimino)-3-cyclohexylpropyl-9-ethylcarbazol-3-yl]octane -1,2-dione-2-oxime benzoate, 1- (7-nitro-9,9-diallyl fluoren-2-yl) -1- (2-methylphenyl) methanone-oxime acetate, 1 -[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-3-cyclopentyl-propan-1-one-oximebenzoate, 1-[7-(2-methylbenzoyl)-9 ,9-dibutylfluoren-2-yl]-3-cyclohexylpropane-1,2-dione-2-oxime acetate, 1-[6-(furan-2-formyl)-9-ethylcarbazole- At least one may be selected from 3-yl]-3-cyclohexylpropane-1,2-dione-2-ethoxyformyloxime ester and analogs thereof. These oxime ester compounds may be used alone or in combination of two or more.

In consideration of the performance aspect, the mass ratio in the composition of the photoinitiator A1 and the oxime ester-based photoinitiator A2 is 1:5 to 5:5.

In 100 parts by mass of the photosensitive resin composition, the content of the photoinitiator (A) is 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass. If the content is too small, there is a defect that the photosensitivity is lowered; If the content is excessively large, a defect exists in which the photoresist pattern tends to be wider than the line width of the photomask.

<Alkali-soluble resin (B)>

The photosensitive resin composition of this invention WHEREIN: Although the kind in particular of alkali-soluble resin (B) is not restrict|limited, It is preferable to start and select from viewpoints, such as heat resistance, developability, and acquisition easiness. An alkali-soluble resin having an acidic group such as a carboxyl group or a phenolic hydroxyl group is preferable, an alkali-soluble resin of a carboxyl group-containing copolymer is more preferable, an ethylenically unsaturated monomer having a carboxyl group [hereinafter "carboxyl group-containing unsaturated monomer" (P)] and A copolymer of other copolymerizable ethylenically unsaturated monomers [hereinafter "copolymerizable unsaturated monomer" (Q)] [hereinafter "carboxyl group-containing copolymer" (R)] is particularly preferred.

As a carboxyl group-containing unsaturated monomer (P), For example, unsaturated monocarboxylic acid types, such as acrylic acid, methacrylic acid, a crotonic acid, (alpha)-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 higher unsaturated polyhydric carboxylic acid or its anhydride type; Succinic acid mono(2-acryloyloxyethyl) ester, succinic acid mono(2-methacryloyloxyethyl) ester, phthalic acid mono(2-acryloyloxyethyl) ester, phthalic acid mono(2-methacryloyloxy) ester mono(meth)acryloyloxyalkyl esters of divalent or higher polyhydric carboxylic acids such as ethyl) ester; and compounds such as mono(meth)acrylate-based polymers having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. These carboxyl group-containing unsaturated monomers can be used individually or in combination of 2 or more types.

As the copolymerizable unsaturated monomer (Q), for example, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acryl (meth)acrylate-based compounds such as lactate, benzyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl Aromatic vinyl compounds, such as ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; Unsaturated carboxylic acid glycidyl ester types, such as indene types, such as indene and 1-methylindene, glycidyl acrylate, and glycidyl methacrylate; Carboxylic acid vinyl ester types, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, and a 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; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; A monoacryloyl group or monomethacryloyl group at the end of a molecular chain of a polymer such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane and compounds such as macromonomer-based compounds. These copolymerizable unsaturated monomers can be used individually or in combination of 2 or more types.

As a preferable alkali-soluble resin (B), a carboxyl group-containing copolymer (R) is obtained by superposition|polymerization of (P) and (Q). More preferably, (P) contains acrylic acid and/or methacrylic acid as essential components, and depending on the situation, succinic acid mono(2-acryloyloxyethyl) ester, succinic acid mono(2-methacryloyloxyethyl) further comprising at least one compound selected from esters, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like; (Q) is styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate , at least one selected from monomers such as glycerol monoacrylate, glycerol monomethacrylate, N-phenylmaleimide, polystyrene polymer monomer, and polymethyl methacrylate polymer.

Specific examples of the carboxyl group-containing copolymer (R) include (meth)acrylic acid/methyl (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 polymer monomer copolymer, (meth)acrylic acid/methyl(meth)acrylate/polymethylmethacrylate Polymer monomer copolymer, (meth)acrylic acid/benzyl(meth)acrylate/polystyrene polymeric monomer copolymer, (meth)acrylic acid/benzyl(meth)acrylate/polymethylmethacrylate polymeric monomer copolymer, (meth)acrylic acid/ 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene polymer monomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl meth acrylate polymer monomer copolymer, methacrylic acid/styrene/benzyl (meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/succinic acid mono[2-(meth)acryloyloxyethyl]ester/styrene /benzyl (meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/succinic acid mono[2-(meth)acryloyloxyethyl]ester/styrene/allyl (meth)acrylate/N-phenylmalei Mid copolymer, (meth)acrylic acid/styrene/benzyl(meth)acrylate/glycerol mono(meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/ω-carboxypolycaprolactone mono(meth)acryl Late/styrene/benzyl (meth)acrylate/glycerol mono(meth)acrylate/N-phenylmaleimide copolymer etc. are mentioned.

In this invention, alkali-soluble resin (B) can be used individually or in combination of 2 or more types.

The alkali-soluble resin is preferably a polymer having a weight average molecular weight (polystyrene conversion value obtained by measurement by GPC method) of 1,000 to 200,000, more preferably a polymer of 2,000 to 100,000, from the viewpoint of developability and liquid viscosity, etc., 5,000 to A polymer of 50,000 is particularly preferred.

In 100 parts by mass of the photosensitive resin composition, the content of the component (B) is 5 to 60 parts by mass, preferably 10 to 50 parts by mass. If the content of the alkali-soluble resin is excessively small, there is a defect in that the adhesion to the substrate is lowered or the alkali developability of the photocurable part is lowered; When the content of the alkali-soluble resin is excessively large, there is a defect that light-shielding performance is deteriorated.

<Compound (C) having at least one polymerizable unsaturated bond>

The compound (C) having at least one polymerizable unsaturated bond described in the present invention may be in a chemical form such as a monomer, an oligomer or a polymer.

Examples of the compound having at least one or more polymerizable unsaturated bonds include unsaturated carboxylic acids such as acrylate-based, methacrylate-based, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid and salts and esters thereof. and radically polymerizable compounds such as carbamate, amide, acid anhydride, acrylonitrile, styrene, vinyl ether, unsaturated polyester, unsaturated polyether, unsaturated polyamide, and unsaturated polyurethane.

Illustratively, the acrylate-based compound is methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isopentyl 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-hydroxyethyl Acrylate, 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-carboxyethyl acrylate Rate, succinic acid monoacryloyloxyethyl ester, ω-carboxy polycaprolactone 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 tetrabromobisphenol A diacrylate, tricyclodecanedimethylol diacrylate, glycerin PO modified tri Acrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetra acrylates and the like.

Illustratively, the methacrylate-based compound is methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isopentyl methacrylate, hexyl Methacrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate acrylate, 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-tetrafluoropropyl methacrylate , 1H-hexafluoroisopropyl methacrylate, 2-methoxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol methacrylate, Methoxy polyethylene glycol #400 methacrylate, methoxydipropylene glycol methacrylate, methoxytripropylene glycol methacrylate, methoxy polypropylene glycol methacrylate, ethoxydiethylene glycol methacrylate, 2-ethylhexyl carbitol Methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, dipentaerythritol hexamethacrylate, etc. include

Without limitation, the compound (C) having at least one or more polymerizable unsaturated bonds is, for example, allylglycidyl ether, diallyl phthalate, triallyl trimellitate, triallyl isocyanurate, acrylamide, N -Methylolacrylamide (N-methylolacrylamide), diacetone acrylamide, N,N-dimethyl acrylamide, N,N-diethylacrylamide, N-isopropyl acrylamide, acryloylmorpholine, styrene, p- Hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, vinyl acetate, monochlorovinyl acetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate ) and the like are further exemplified.

Compound (C) having at least one or more polymerizable unsaturated bonds of the present invention may be used alone or in combination of two or more in any ratio in order to improve desired properties.

In 100 parts by mass of the photosensitive resin composition, the content of the component (C) is 5 to 50 parts by mass, preferably 10 to 30 parts by mass. If the content of component (C) is too small, there is a defect that the photosensitivity is lowered; When the content of component (C) is excessively large, there is a defect in which the photoresist pattern tends to be wider than the line width of the photomask.

<Colorant (D)>

The type of the colorant (D) of the present invention is not particularly limited, and may include pigments and dyes.

The pigment may include all organic pigments, inorganic pigments, or mixtures thereof generally used in the related art.

The organic pigment is not particularly limited, and may include all common pigments used in printing inks, inkjet inks, and the like. More specifically, water-soluble azo pigments, water-insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, diannes traquinonyl pigments, anthrapyrimidine pigments, ananthrone pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. These organic pigments can be used individually or in combination of 2 or more types.

The inorganic pigment is not particularly limited and may include a metal compound (eg, a metal oxide or a metal complex salt) and carbon black. More specifically, an oxide of at least one metal from among iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony may be selected. These inorganic pigments can be used individually or in combination of 2 or more types.

The organic pigment and the inorganic pigment may further include a compound classified as a pigment according to a color index (published by the British Society of Colorists). More specifically, C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 , 185; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71; C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255, 264; C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, 38; C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, 76; C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58; C.I. Pigment Brown 28; C.I. Pigment Black 1, 7, etc. may be used, wherein C.I. Pigment Yellow 138, 139, 150, 185; C.I. Pigment Orange 38; C.I. Pigment Red 122, 166, 177, 208, 242, 254, 255; C.I. Pigment Violet 23; C.I. Pigment Blue 15:3, 15:6; C.I. It is preferable to use Pigment Green 7, 36, 58 or the like. These pigments can be used individually or in combination of 2 or more types.

Regardless of the inorganic pigment/organic pigment, it is preferable to use a finer pigment as it is considered to have high transmittance, and the average particle diameter of the pigment is preferably 0.01 to 0.1 μm, more preferably 0.01 to 0.05 μm am.

The content of the pigment is not particularly limited, but the content of the pigment is preferably 5 to 95 parts by mass, more preferably 10 to 90 parts by mass, based on 100 parts by mass of the total colorant. When the content of the pigment is within the above range, a color filter manufactured using the pigment may have a sufficient color area and excellent light transmittance, and a desired photosensitivity may be secured.

The dye is not particularly limited, and includes acid dyes having an acid group (eg, sulfonic acid, carboxylic acid, etc.); salts of nitrogen-containing compounds and salts of the above acid dyes; sulfonamides of the acid dyes and derivatives thereof; acid dyes based on azo, xanthene and/or phthalocyanine and derivatives thereof; and the like.

The dye is preferably a compound classified as a dye in the Color Index (published by the British Society of Colorists), or a red dye, a blue dye, or a violet dye among dyes described in the Color Dyeing company.

Illustratively, C.I. It may be a solvent dye, and C.I. yellow dyes such as solvent yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163 and the like; C.I. red dyes such as solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179, and the like; C.I. orange dyes such as solvent orange 2, 7, 11, 15, 26, 41, 45, 56, 62, and the like; C.I. blue dyes such as solvent blue 5, 35, 36, 37, 44, 59, 67, 70, and the like; C.I. violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49 and the like; C.I. green dyes such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, and the like. Here, C.I. Solvent Yellow 14, 16, 21, 56, 151, 79, 93; C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Orange 41, 45, 62; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent Violet 13 and the like are preferred.

Illustratively, C.I. It may be an acid dye, and C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, yellow dyes such as 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, etc.; C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426, and the like; C.I. orange dyes such as acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, and the like; C.I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1, blue dyes such as 335, 340 and the like; C.I. violet dyes such as acid violet 6B, 7, 9, 17, 19, 66 and the like; C.I. green dyes such as acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, and the like. Here, C.I. Acid Yellow 42; C.I. Acid Red 92; C.I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid green 27 and the like are preferable.

Illustratively, C.I. It may be a direct dye, and C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, yellow dyes such as 136, 138, 141 and the like; C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, red dyes such as 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250 and the like; C.I. orange dyes such as direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107 and the like; C.I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, blue dyes such as 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293 and the like; C.I. violet dyes such as direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and the like; C.I. green dyes such as Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, and the like.

Illustratively, C.I. modanto dye, and C.I. yellow dyes such as modanto yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 and the like; C.I. Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95 and the like; C.I. Orange dyes such as Modanto Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc. ; C.I. Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84, and the like; C.I. violet dyes such as modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58, and the like; C.I. green dyes such as modanto green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, and the like.

The above dyes may be used alone or in combination of two or more.

The content of the dye is not particularly limited, but with respect to a total of 100 parts by mass of the colorant, the content of the dye is preferably 5 to 95 parts by mass, more preferably 10 to 90 parts by mass. When the content of the dye is within the above range, it is possible to prevent reliability degradation (elution of the dye by the organic solvent after pattern formation) and at the same time obtain excellent photosensitivity.

The content of the colorant is not particularly limited, but in 100 parts by mass of the photosensitive resin composition, the content of the colorant (D) is generally 5 to 60 parts by mass, preferably 10 to 45 parts by mass. When the content of the colorant is within the above range, the pixel has sufficient color density, and the omission property of the non-pixel portion is not deteriorated during development, thereby reducing the occurrence of residues.

<Hydrogen donor (E)>

The photosensitive resin composition of the present invention further includes a hydrogen donor (E) to improve photosensitivity. The HABI-based compound has a large volume of monoimidazole radicals generated by cleavage after irradiation with light and has low activity due to a steric hindrance effect, making it difficult to initiate monomer polymerization alone. However, the monoimidazole free radical can easily take the active hydrogen of the hydrogen donor to generate a new active free radical to initiate monomer polymerization.

As long as it is a hydrogen donor having the above characteristics, the specific type is not particularly limited, and examples thereof may be an amine-based compound, a carboxylic acid-based compound, an organic sulfur compound containing a mercapto group, or an alcohol-based compound. These compounds can be used individually or in combination of 2 or more types.

Illustratively, the applied amine-based compound may include an aliphatic amine compound such as triethanolamine, methyldiethanolamine, and triisopropanolamine; Methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl- an aromatic amine compound such as p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, or the like.

Illustratively, the applied carboxylic acid-based compound is aromatic heteroacetic acid, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

Illustratively, the applied organic sulfur compound containing a mercapto group is 2-mercaptobenzothiazole (MBO), 2-mercaptobenzimidazole (MBI), dodecylthiol, ethylene glycol bis (3-mercapto) butyrate), 1,2-propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediolbis(3-mercaptobutyrate), octanediolbis(3-mercaptobutyrate) , trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropio) nate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butanediol bis(2-mercaptopropionate), octanediol bis(2-mercaptopropionate) propionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopropionate), Ethylene glycol bis (3-mercaptoisobutyrate), 1,2-propylene glycol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mer) captoisobutyrate), octanediolbis(3-mercaptoisobutyrate), trimethylolpropanetris(3-mercaptoisobutyrate), pentaerythritol tetrakis(3-mercaptoisobutyrate), dipenta Erythritol hexakis (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), 1,2-propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2) -Mercaptoisobutyrate), butanediolbis(2-mercaptoisobutyrate), octanediolbis(2-mercaptoisobutyrate), trimethylolpropanetris(2-mercaptoisobutyrate), pentaerythritol Tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis (2-mercaptoisobutyrate), ethylene glycol bis (4-mercapto valerate), 1,2-propylene glycol bis (4- Mercaptoisovalerate), diethylene glycol bis(4-mercaptovalerate), butanediolbis(4-mercapto) valerate), octanediolbis (4-mercaptovalerate), trimethylolpropanetris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), dipentaerythritol hexakis ( 4-mercapto valerate), ethylene glycol bis (3-mercapto valerate), 1,2-propylene glycol bis (3-mercapto valerate), diethylene glycol bis (3-mercapto valerate), butanediol Bis (3-mercapto valerate), octanediol bis (3-mercapto valerate), trimethylolpropane tris (3-mercapto valerate), pentaerythritol tetrakis (3-mercapto valerate), di Aliphatic secondary polyfunctional thiol compounds, such as pentaerythritol hexakis (3-mercapto valerate); Aromatic secondary such as di(1-mercaptoethyl) phthalate, di(2-mercaptopropyl) phthalate, di(3-mercaptobutyl) phthalate, di(3-mercaptoisobutyl) ester, etc. It may be a polyfunctional thiol compound.

Illustratively, the alcohol-based compound applied is not particularly limited, and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, neopentanol, n-ethanol, cyclohexanol, ethylene glycol, It may be 1,2-propylene glycol, glycerol, benzyl alcohol, phenylethyl alcohol, and the like.

In 100 parts by mass of the photosensitive resin composition, the content of the hydrogen donor (E) is 0.01 to 20 parts by mass, preferably 0.01 to 10 parts by mass. When the content of the hydrogen donor is within the above range, the photosensitivity of the colored photosensitive resin composition may be additionally secured.

<Other optional additives (F)>

The photosensitive resin composition of the present invention optionally comprises other photoinitiators and/or sensitizers, organic solvents, organic carboxylic acids, pigment dispersants, adhesion enhancers, leveling agents, development improvers, antioxidants, thermal polymerization inhibitors, etc. in this area Other commonly used adjuvants may be further added. In addition, depending on the use, surfactants, optical brighteners, plasticizers, flame retardants, ultraviolet absorbers, foaming agents, disinfectants, antistatic agents, magnetic substances, conductive materials, antifungal or antibacterial materials, porous adsorbents, fragrance materials, etc. can be added.

The other photoinitiator and/or sensitizer is different from the photoinitiator A1 and the oxime ester photoinitiator A2. Without limitation, bisimidazole compounds, triazine compounds, coumarin compounds, acridine compounds, oxadiazole compounds, aromatic ketone compounds, benzoin and benzoin alkyl ether compounds, anthraquinone compounds, thioxic acid It may be selected from ton-based compounds and the like. These compounds can be used individually or in combination of 2 or more types.

Illustratively, the bisimidazole-based compound is 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2',5-tris( o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,2',5-tris(2-fluorophenyl )-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5 '-Tetraphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'- Diphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-methoxyphenyl) )-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-chloro-5-nitrophenyl)-4,4'-bis(3,4-dimethoxyphenyl) )-5,5'-bis(o-chlorophenyl)-diimidazole, 2,2'-bis(2-chloro-5-nitrophenyl)-4-(3,4-dimethoxyphenyl)-5- (o-chlorophenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl) -5,5'-bis(o-chlorophenyl)-diimidazole, 2-(2,4-dichlorophenyl)-4-(3,4-dimethoxyphenyl)-,2',5-bis(o -Chlorophenyl)-4',5'-diphenyl-diimidazole, 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetra phenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole and the like. These bisimidazole-based compounds may be used alone or in combination of two or more.

Illustratively, the triazine-based compound is 2-(4-ethylbiphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methyleneoxyphenyl) -4,6-bis(trichloromethyl)-1,3,5-triazine, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio} Propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}prop Cypionate, ethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 2-ethoxyethyl-2-{4-[2, 4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, cyclohexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6- yl]phenylthio}acetate, benzyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 3-{chloro-4-[2, 4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenyl Thio}propionamide, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylamino phenyl)-1,3,-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like. These triazine-based compounds may be used alone or in combination of two or more.

Illustratively, the coumarin-based compound is 3,3'-carbonylbis(7-diethylaminocoumarin), 3-benzoyl-7-diethylaminocoumarin, 3,3'-carbonylbis(7-methoxy coumarin), 7-(diethylamino)-4-methylcoumarin, 3-(2-benzothiazole)-7-(diethylamino)coumarin, 7-(diethylamino)-4-methyl-2H-1 -benzopyran-2-one[7-(diethylamino)-4-methylcoumarin], 3-benzoyl-7-methoxycoumarin and the like. These coumarin-based compounds may be used alone or in combination of two or more.

Illustratively, the acridine-based compound is 9-phenylacridine, 9-p-methylphenylacridine, 9-m-methylphenylacridine, 9-o-chlorophenylacridine, 9-o-fluoro Lophenylacridine, 1,7-bis(9-acridinyl)heptane, 9-ethylacridine, 9-(4-bromophenyl)acridine, 9-(3-chlorophenyl)acridine din, 1,7-bis(9-acridine)heptane, 1,5-bis(9-acridinepentane), 1,3-bis(9-acridine)propane and the like. These acridine-based compounds may be used alone or in combination of two or more.

Illustratively, the oxadiazole-based compound is 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(cyanostyryl)-1,3,4 -oxadiazole, 2-trichloromethyl-5- (naphthoyl-1-yl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-styryl) styryl-1 ,3,4-oxadiazole and the like. These oxadiazole-based compounds may be used alone or in combination of two or more.

Illustratively, the aromatic ketone-based compound is acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, benzophenone, 4-benzoyldiphenylsulfide, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl-4'-ethyldiphenylsulfide, 4-benzoyl-4'-propyldiphenylsulfide, 4,4'-bis( Diethylamino)benzophenone, 4-p-toluenemercaptobenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4' -bis(methyl, ethylamino)benzophenone, acetophenone dimethyl ketal, benzil dimethyl ketal, α,α'-dimethylbenzyl ketal, α,α'-diethoxyacetophenone, 2-hydroxy-2 -Methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-p-hydroxyethyl etherphenylpropanone, 2-methyl-1-(4-methylthio Phenyl)-2-morpholine1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinephenyl)1-butanone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide , 2,4,6 (trimethylbenzoyl)diphenylphosphine oxide, 2-hydroxy-1-{3-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1,1, 3-Trimethyl-inden-5-yl}-2-methylpropanone, 2-hydroxy-1-{1-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1,3 ,3-Trimethyl-inden-5-yl}-2-methylpropanone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxye toxy)-phenyl-(2-hydroxy-2-propyl)ketone and analogs thereof. These aromatic ketone-based compounds may be used alone or in combination of two or more.

Illustratively, the benzoin and benzoin alkyl ether-based compounds include benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, and the like. These benzoin and benzoin alkyl ether compounds may be used alone or in combination of two or more.

Illustratively, the anthraquinone-based compound is 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthracene- 9,10-diethyl ester, 1,2,3-trimethylanthracene-9,10-dioctyl ester, 2-ethylanthracene-9,10-di(methyl 4-chlorobutyrate), 2-{3-[( 3-ethyloxetan-3-yl)methoxy]-3-oxopropyl)anthracene-9,10-diethyl ester, 9,10-dibutoxyanthracene, 9,10-diethoxy-2-ethylanthracene, 9 , including 10-bis(3-chloropropoxy)anthracene, 9,10-bis(2-hydroxyethylthio)anthracene, 9,10-bis(3-hydroxy-1-propylthio)anthracene and the like do. These anthraquinone-based compounds may be used alone or in combination of two or more.

Illustratively, the thioxanthone-based compound is thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chlorothiok xanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diisopropylthioxanthone and the like. These thioxanthone-based compounds may be used alone or in combination of two or more.

Illustratively, the organic solvent may dissolve each component described above, and is not particularly limited. For example, a glycol ether-based solvent, an alcohol-based solvent, an ester-based solvent, a ketone-based solvent, an amide-based solvent, and chlorine-containing solvents and the like. In particular, it is preferable to select the colorant in consideration of factors such as solubility, coating property, and safety of the alkali-soluble resin. Ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methyl methoxybutanol (3-methyl-3-methoxybutanol) ), butylcarbitol (diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol mono-tert-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2- propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monoethyl ether acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether acetate), Methoxybutyl acetate (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate (EEP), methyl lactate, ethyl lactate, propyl lactate, butylac Tate, 2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), isophorone (3, 5,5-trimethyl-2-cyclohexen-1-one), diisobutylketone (2,6-dimethyl-4-heptanone), N-methylpyrrolidone (4-methylaminolactam or NMP), methanol , ethanol, isopropanol, n-propanol, isobutanol, n-butanol and the like are preferable. These solvents can be used individually or in combination of 2 or more types.

Illustratively, the type of the organic carboxylic acid is not particularly limited, and for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, hexanoic acid, diethyl acetic acid, heptanoic acid, aliphatic mono acids such as octanoic acid carboxylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl aliphatic dicarboxylic acids such as succinic acid, tetramethylsuccinic acid, and citraconic acid; aliphatic tricarboxylic acids such as tricarballylic acid (1,2,3-propanetricarboxylic acid), aconitic acid, and camphoronic acid (norbornanetricarboxylic acid); aromatic monocarboxylic acids such as benzoic acid, toluic acid, isopropylbenzoic acid, 2,3-dimethylbenzoic acid, and 3,5-dimethylbenzoic acid; Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, mellophanic acid (1,2,3,5-benzene tetracarboxylic acid), pyromellitic acid (1,2,4,5) -benzene tetracarboxylic acid) such as aromatic polycarboxylic acids; Phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamic acid methyl ester, cinnamic acid benzyl ester, cinnamylidene acetic acid, coumaric acid, umbelic acid ( umbellic acid) and other carboxylic acids. Organic carboxylic acids can be used individually or in combination of 2 or more types.

Illustratively, the type of dispersant is not particularly limited, and for example, polyamide amines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly( Polymer dispersants such as meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formaldehyde condensate, polyoxyethylenealkylphosphate, polyoxyethylenealkylamine, alcanolamine, pigment derivatives, etc. may be included. . These dispersants can be used individually or in combination of 2 or more types.

Illustratively, the type of the adhesive strengthening agent is not particularly limited, and for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl) -3-Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane (3- glycidyloxypropyltrimethoxysilane), 3-glycidoxypropyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3- metacroyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like. These adhesive enhancers may be used alone or in combination of two or more.

Illustratively, the thermal polymerization inhibitor may include, for example, p-methoxyphenol, hydroquinone, catechol, tert-butylcatechol, phenothiazine, and p-methoxyphenol. These thermal polymerization inhibitors can be used individually or in combination of 2 or more type.

Illustratively, the type of surfactant is not particularly limited, and may include, for example, a fluorine surfactant, a silicone surfactant, or a mixture thereof. These surfactants can be used individually or in combination of 2 or more types.

Illustratively, the type of the plasticizer is not particularly limited, and for example, dioctyl phthalate, di (dodecyl) phthalate, triethylene glycol dicaprylate, dimethyl ethylene glycol phthalate, tricresyl phosphate, di octyl adipate, dibutyl sebacate, triacetyl glycerol, and the like. These plasticizers can be used individually or in combination of 2 or more types.

<Color filter and manufacturing method thereof>

As described above, the present invention also relates to a color filter using the photosensitive resin composition and a method for manufacturing the same.

The color filter of this invention contains the coloring pattern formed from the said photosensitive resin composition in a support body, It is characterized by the above-mentioned.

Techniques for producing RGB, BM, photospacers, etc. through photocuring and photolithography processes using the photosensitive resin composition are already known to those skilled in the art, and typically, by applying the photosensitive resin composition on a support, a process step of forming a photosensitive resin layer (abbreviated as "forming process"); a process step of exposing the photosensitive resin layer to light through a mask (abbreviated as "exposure process"); and a process step of forming a colored pattern by developing the exposed photosensitive resin layer (abbreviated as "developing process").

Specifically, the photosensitive resin composition of the present invention is applied directly or indirectly on a support (substrate) through another layer to form a photosensitive resin layer; curing only the portion of the coating film irradiated with light by performing exposure through a predetermined mask pattern; By developing using a developing solution, a pattern-like film composed of pixels of each color (three or four colors) is formed to manufacture the color filter of the present invention.

Hereinafter, each process of the manufacturing method of the present invention will be described in more detail.

forming process

In the photosensitive resin layer forming process, the photosensitive resin composition of this invention is apply|coated on a support body, and the photosensitive resin layer is formed.

As the applied support, for example, sodalime glass, non-alkali glass, pyrex glass, quartz glass, plastic substrate used for liquid crystal display devices and the like, and a transparent conductive film on the support A photoelectric conversion element substrate used for an image pickup device such as an attached support, a silicon substrate, etc., and an auxiliary metal oxide film semiconductor (CMOS), etc. are mentioned. In some cases, a black matrix separating each pixel is formed on the substrate.

In addition, if necessary, a lower coating layer may be formed on the support to improve adhesion with the upper layer, prevent material diffusion, or planarize the surface of the substrate.

As a method of applying the photosensitive resin composition of the present invention to the support, various coating methods such as slit coating, inkjet, spin coating, roll coating, and screen printing may be applied.

As a coating film thickness of the photosensitive resin composition, Preferably it is 0.1-10 micrometers, More preferably, it is 0.5-3 micrometers.

The photosensitive resin composition applied to the support is generally dried at 70 to 110° C. for 2 to 4 minutes to form a photosensitive resin layer.

exposure process

In the exposure process, the photosensitive resin layer formed in the photosensitive resin layer forming process is exposed through a mask. During the process, only the portion of the coating film irradiated with light is cured.

The exposure is preferably carried out by irradiation with radiation. As the radiation usable during exposure, it is particularly preferable to use ultraviolet rays such as g-rays and i-rays, and it is more preferable to use a high-pressure mercury lamp. Irradiation intensity becomes like this. Preferably it is 5-1500 mJ/cm<^2> , More preferably, it is 10-500 mJ/cm<^2> .

development process

After the exposure process, an alkali developing treatment (development process) is performed to dissolve the unexposed part in the aqueous alkali solution during the exposure process, leaving only the photocured part.

Developing temperature is 20-30 degreeC normally, and developing time is 20 to 90 second.

In the manufacturing method of the present invention, after the forming process of the photosensitive resin layer, the exposure process, and the developing process are performed, a post-curing process of further curing the formed coloring pattern through heating and/or exposure if necessary may be added. can

Depending on the desired number of color tones, a color filter having a desired color tone may be manufactured by repeating the photosensitive resin layer forming process, exposure process, and developing process (and a post-curing process added as necessary).

The photosensitive resin composition of the present invention has excellent photosensitivity and good developability, high luminance after curing, and excellent adhesion to a substrate. The manufacturing method can manufacture a high-performance color filter with high production efficiency.

1 is a high performance liquid chromatography (HPLC) graph of product a1.
2 is a high-performance liquid chromatography graph of T1.
3 is a high performance liquid chromatography graph of T2.
4 is a high-performance liquid chromatography graph of T3.
5 is a structure spectrum of T1 obtained by single crystal diffraction.

The present invention will be described in more detail below with specific examples, but should not be construed as limiting the protection scope of the present invention.

1. Preparation of HABI-based mixed photoinitiators

1.1 Preparation of HABI-based mixed photoinitiator a1

31.8 g of 2-(o-chlorophenyl)-4,5-diphenyl-imidazole (M1, 2-(o-Chlorophenyl)-4,5-diphenyl-imidazole) in a 1L 4-neck flask under nitrogen atmosphere, 2,5-bis(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazole (M2, 2,5-Bis(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)- imidazole) 51.3g, 30% liquefied caustic soda 4.2g, tetrabutylammonium bromide 4.0g, toluene 300g, heat and stir at 60 ~ 65℃, sodium hypochlorite (Sodium hypochlorite, 11% aqueous solution) 85 g was added dropwise. After completion of the dropwise addition, the reaction was carried out by heating, and the sampling was controlled through HPLC until the reaction was completed with M1 and M2 of less than 1%, and the reaction was completed, and the heating was terminated. After completion of the warming reaction, the mixture was washed 4 times with 100 g of pure water, then the aqueous layer was extracted once with 20 g of toluene, and the organic layer was distilled under reduced pressure. 70 g of methanol was added to the substance obtained by distillation and stirred until dissolved, then the solution was added dropwise to a solution of 30 g of methanol and 50 g of pure water, and after completion of the dropping, 79.1 g of product a1 was obtained by filtration, washing and baking. obtained.

The product a1 was analyzed using high performance liquid chromatography, and the results are shown in FIG. 1 . The analysis result shows that the peak total content of the products of the four linkages 2-1', 2-3', 2'-1, and 2'-3 is 92.5%. Product a1 is a mixture obtained by homo and cross coupling of two different mono imidazoles (ie, M1 and M2), comprising T1, T2 and T3.

In order to accurately verify the composition of the structure of the product, validation analysis was performed on components T1, T2, and T3, respectively. Pure T1, T2, and T3 were obtained through methods such as homo-coupling of monoimidazole, column chromatography, and chromatographic separation, respectively, and structure confirmation was performed, respectively.

2 to 4 are high performance liquid chromatography graphs of T1, T2, and T3, respectively.

Referring to FIG. 5 , in T1, only one peak exists in the liquid phase, but two peak shapes are obtained according to single crystal diffraction. Combining the structural properties, it can be confirmed that the main product by the coupling of two monoimidazoles is a mixture formed by connecting hydrogen-containing N of one imidazole and C at 2-position of the other imidazole, This clearly indicates that the structure of T1 is the two linkage positions 2'-1 and 2'-3 described in the present invention.

Since M1, a monoimidazole synthesizing T1, belongs to a symmetric imidazole, the polarities of 2'-1 and 2'-3 obtained by coupling are similar and liquid phase separation is difficult. Due to the structural symmetry of M1, the structures of 2'-1 and 2-1' among the structures of the product obtained by homo-coupling are the same, and the structures of 2'-3 and 2-3' are also the same. Therefore, the main structure of T1 is the product of two linkages 2'-1 and 2'-3, respectively, T1-1: 2,2'-bis(o-chlorophenyl)-4,4',5,5'- tetraphenyl-1,2'-diimidazole (2,2'-Bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazol); T1-2: 2,2'-bis (o-chlorophenyl) -4,4',5,5'-tetraphenyl-2'-3-diimidazole (2,2'-Bis (o-chlorophenyl) -4,4',5,5'-tetraphenyl-2'-3-diimidazol), and the structural formula is shown as follows:

Mono imidazole M2 synthesizing T2 belongs to asymmetric mono imidazole, there are two structures of M2-1 and M2-2, and the structural formula is shown as follows:

The isolated pure T2 was analyzed. The main structure was confirmed by performing LCMS with the product of the four linkages. In mass spectrometry, fragment peaks of 849 and 850 were obtained through software provided in the equipment, and the molecular weight of the product was 848, which was consistent with T+1 and T+2. This proves that the four products are similar in structure and have the same molecular weight. T2 is synthesized by asymmetric monoimidazole coupling, and theoretically, there are eight main structures connected to the linkages of 1-2 and 2-3. However, in the case of homo-coupled monoimidazole, among the structures Since the structures of 2'-1 and 2-1' are the same, and the structures of 2'-3 and 2-3' are also the same, T2 is actually connected to the four main structures connected to the connecting positions of 1-2 and 2-3. is present, and the composition is as follows: T2-1: 2,2',5,5'-tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)- 2'-3-diimidazole (2,2',5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole), T2- 2: 2,2',4,5'-tetra (o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1-2'-diimidazole (2,2', 4,5'-Tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1-2'-diimidazole), T2-3: 2,2',5,5'-tetra ( o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole (2,2',5,5'-Tetra(o-chlorophenyl)-4, 4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole), T2-4: 2,2',4,5'-tetra(o-chlorophenyl)-4',5-bis(3 ,4-dimethoxyphenyl)-2',3-diimidazole (2,2',4,5'-Tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-2' ,3-diimidazole), the structure is shown below:

T3 is formed by the coupling of M1 and M2, and the main structure in the liquid phase of pure T3 obtained by separation was confirmed by LCMS with the product at the four linkages. In mass spectrometry, molecular fragment peaks of 755 and 756 were obtained through software provided in the equipment, and the molecular weight of the product was 754, which was consistent with T+1 and T+2. This proves that the four products are similar in structure and have the same molecular weight. T3 is formed by bonding of symmetric imidazole M1 and asymmetric imidazole M2, and there are four main structures connected to the linkages of 1-2 and 2-3, and the composition is as follows: T3-1 : 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-diimidazole (2,2' ,5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-diimidazole), T3-2: 2,2',5-tris(o -Chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2',3-diimidazole (2,2',5-Tris(o-chlorophenyl)-4 -(3,4-dimethoxyphenyl)-4',5'-diphenyl-2',3-diimidazole), T3-3: 2,2',5-tris(o-chlorophenyl)-4-(3,4 -dimethoxyphenyl)-4',5'-diphenyl-2,3'-diimidazole (2,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4' ,5'-diphenyl-2,3'-diimidazole), T3-4: 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5' -diphenyl-1',2-diimidazole (2,2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1',2- diimidazole), the structural formula is shown as

Summarizing the above experimental analysis, product a1 is T1(T1-1, T1-2), T2(T2-1, T2-2, T2-3, T2-4), T3(T3-1, T3-2) , T3-3, T3-4), wherein a1 of the bisimidazole compound consisting of four connection positions 2-1', 2-3', 2'-1, 2'-3 My content is 92.5%.

A2 to a8 were respectively prepared with reference to the above-described process, and the status of each product is as shown in Table 1-1 below.

[Table 1-1]

Remark: In order to prevent the occurrence of intermolecular association phenomenon, adopt acetonitrile as a solvent ^{to prepare a solution with a solubility of 1×10 -4} mol/L, measure the ultraviolet absorption spectrum of the solution at 25°C, and then ε =A/CL (molar extinction coefficient unit L×mol ^-1 ×cm ^-1 ) The molar extinction coefficient at 365 nm (i-line) wavelength was calculated according to the formula.

1.2 Preparation of HABI-based mixed photoinitiator a9

In a nitrogen atmosphere, 2- (4-chlorophenyl) -5- (6-chlorophenyl) -4- (3,4-dimethoxyphenyl) -imidazole (M3, 2- (4- Chlorophenyl)-5-(6-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazole) 50 g, 2,5-bis(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imid Dazole (M2, 2,5-Bis(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-imidazole) 51g, 30% liquid caustic soda 5.6g, Tetrabutylammonium bromide 4.0g, toluene 300g was added, heated and stirred, and 90 g of sodium hypochlorite (11% aqueous solution) was added dropwise at 60 to 65°C. After completion of the dropwise addition, the reaction was carried out by heating, and sampling was controlled through HPLC until the reaction was completed with both M2 and M3 of less than 1%, and the heating was terminated. After completion of the warming reaction, the mixture was washed 4 times with 100 g of pure water, then the aqueous layer was extracted once with 20 g of toluene, and the organic layer was distilled under reduced pressure. 70 g of methanol was added to the substance obtained by distillation and stirred until dissolved, and then the solution was added dropwise to a solution of 30 g of methanol and 50 g of pure water, washed, dried and baked after completion of the dropping to obtain 98 g of product a9 did

The analysis result shows that the peak total content of the products of the four linking positions 2-1', 2-3', 2'-1, and 2'-3 is 93.2%.

Product a9 is a mixture obtained by homo and cross coupling of two different mono imidazoles (ie, M2 and M3), comprising T2, T4 and T5. In order to accurately verify the structure and composition of the product, validation analysis was performed on components T2, T4, and T5, respectively. T2, T4, and T5 were respectively obtained through methods such as homo-coupling of monoimidazole, column chromatography, and chromatographic separation, and structure confirmation was performed, respectively.

T2 was consistent with the T2 structure of compound a1.

T4 is formed by homocoupling of the asymmetric monoimidazole M3, and there are four main structures connected to the linkages of 1-2 and 2-3, and the composition is as follows, respectively: T4-1: 2 ,2'-bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole ( 2,2'-Bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole), T4-2: 2,2'-bis(4-chlorophenyl)-4,5'-bis(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole (2,2'-Bis(4-chlorophenyl)-4,5'-bis(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole), T4-3 : 2,2'-bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimi Dazole (2,2'-Bis(4-chlorophenyl)-5,5'-bis(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole), T4- 4: 2,2'-bis(4-chlorophenyl)-4',5-bis(o-chlorophenyl)-4,5'-bis(3,4-dimethoxyphenyl)-2,3'-di Imidazole (2,2'-Bis(4-chlorophenyl)-4',5-bis(o-chlorophenyl)-4,5'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole), structural formula is denoted as:

LCMS was performed to confirm the structure, and the spectra of the four structures were consistent. In mass spectrometry, fragment peaks of 849 and 850 were obtained through software provided in the equipment, and the molecular weight of the product was 848, which was consistent with T+1 and T+2. This proves that the four products are similar in structure and have the same molecular weight.

T5 is formed by the coupling of asymmetric M2 and asymmetric M3, and there are four main structures connected to the connection positions of 1-2 and 2-3, and the composition is as follows: T5-1: 2- (4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole (2- (4-chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2,3'-diimidazole), T5-2: 2'- (4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole (2'- (4-chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole), T5-3: 2-(4 -Chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole (2-(4) -chlorophenyl)-2',5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole), T5-4: 2'-(4 -Chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1',2-diimidazole (2'-(4) -chlorophenyl)-2,5,5'-tris(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1',2-diimidazole), the structural formula is shown as follows:

LCMS was performed to confirm the structure, and the spectra of the four structures were consistent. In mass spectrometry, fragment peaks of 849 and 850 were obtained through software provided in the equipment, and the molecular weight of the product was 848, which was consistent with T+1 and T+2. This proves that the four products are similar in structure and have the same molecular weight.

Summarizing the above experimental analysis, product a9 is T2(T2-1, T2-2, T2-3, T2-4), T4(T4-1, T4-2, T4-3, T4-4), T5( T5-1, T5-2, T5-3, T5-4) can be seen, and here, it is composed of four connection positions 2-1', 2-3', 2'-1, 2'-3 The content in a9 of the used bisimidazole compound is 93.2%.

A10 to a16 were respectively prepared with reference to the above-described process, and the status of each product is as shown in Table 1-2 below.

[Table 1-2]

Remark: In order to prevent the occurrence of intermolecular association phenomenon, adopt acetonitrile as a solvent ^{to prepare a solution with a solubility of 1×10 -4} mol/L, measure the ultraviolet absorption spectrum of the solution at 25°C, and then ε =A/CL (molar extinction coefficient unit L×mol ^-1 ×cm ^-1 ) The molar extinction coefficient at 365 nm (i-line) wavelength was calculated according to the formula.

1.3 Preparation of HABI-based mixed photoinitiator a17

a17 is BCIM produced by Changzhou Tronly New Electronic Materials Co., Ltd., among them, it contains bismidazole compounds at four connection positions 2-1', 2-3', 2'-1, and 2'-3 and (since it belongs to a symmetrical structure, the structures of 2-1' and 2'-1 are the same, and the structures of 2-3' and 2'-3 are also the same), and in A1 of the bisimidazole compound at the four connection positions The total mass percentage content is 99%, and the molar extinction coefficient at a wavelength of 365 nm (i-line) is 26 L×mol ⁻¹ ×cm ⁻¹ . The structural formula is shown as:

2. Preparation of photosensitive resin composition

According to the composition shown in Tables 2-1 and 2-2, each component was uniformly mixed to prepare a photosensitive resin composition. Unless otherwise specified, all numbers indicated in tables are parts by mass.

[Table 2-1]

[Table 2-2]

Here, the meaning represented by each component in Tables 2-1 and 2-2 is as shown in Table 2-3.

[Table 2-3]

Table 2-4 shows the molar extinction coefficients of the photopolymerization initiators of Examples 1 to 10 and Comparative Examples 1 to 12 at the wavelength of 365 nm (i-line) with reference to the above-described test method for the molar extinction coefficient.

[Table 2-4]

3. Performance evaluation

3.1 Luminance

For the photosensitive resin composition prepared in each Example and Comparative Example, the photosensitive resin composition obtained above was applied to glass (#1737, manufactured by Corning Incorporated) using a spin coating method, and then volatile components at 100° C. for 3 minutes was volatilized to form a photosensitive resin layer. After cooling, the photosensitive resin layer was exposed using an ultra-high pressure mercury lamp by setting the amount of irradiation light to 100 mJ/cm ^{2 .} Then, it was post-baked at 230 DEG C for 20 minutes to obtain a glass substrate having a colored layer having a film thickness of 2 mu m. The chromaticity of a glass substrate having a colored layer was measured using a microspectroscopic measuring apparatus OSP-SP200 manufactured by Olympus, and the Y value at chromaticity x=0.29, y=0.59 was measured with a C light source. A higher Y value indicates better performance as a color filter for a liquid crystal display device.

The Y value was determined according to the following criteria.

○: Y value of 57 or more

◎: Y value 55 or more and less than 57

●: Y value less than 55

3.2 Photosensitivity

For the photosensitive resin compositions prepared in each of Examples and Comparative Examples, the photosensitive resin composition obtained above was applied to glass (#1737, manufactured by Corning Incorporated) using a spin coating method, and then volatile components at 100° C. for 3 minutes was volatilized to form a photosensitive resin layer. After cooling, using an i-line reduction projection exposure apparatus, the coating film was irradiated with a wavelength of 365 nm through a mask having a length of 20 μm and a width of 20 μm at an exposure amount of 50 mJ/cm ^{2 .} After irradiation, the coating film was developed at 23° C. for 60 seconds using a developer (product name: CD-2000, 60%, manufactured by Fujifilm Electronic Materials Co., Ltd.). Then, after washing with running water for 20 seconds, spray drying was performed to obtain a pattern image. Image formation was confirmed using an optical microscope. It is preferable that the width of the fabricated pixel pattern is large because the photosensitivity is high.

The width of the fabricated pixel pattern is determined according to the following criteria:

○: 35 μm or more

◎: 20 μm or more, less than 35 μm

●: less than 20μm

3.3 Developability

For the photosensitive resin composition prepared in each Example and Comparative Example, the liquid composition was applied to a glass substrate using a spin coater, and then dried at 100° C. for 5 minutes to remove the solvent, and a coating film having a thickness of 10 μm was formed. ; In order to obtain a coating film having the above-described thickness, the application process may be performed once or divided into several times; The amount of energy around and cooling the substrate with the coating film to ambient temperature, by attaching the mask to receive the copy wavelength 250 ~ 450nm, 1 times an exposure through an exposure device equipped with a RW-UV.70201 track-type high-pressure mercury lamp 80mJ / cm ² As a result, the coating film was exposed by irradiating ultraviolet rays through the gaps in the mask; It was developed at 25° C. with a 1% aqueous NaOH solution, then washed with ultrapure water and air-dried; Finally, the pattern transferred from the mask was obtained by post-baking in an oven at 240° C. for 30 minutes.

Developability was evaluated by observing the pattern of the substrate with a scanning electron microscope (SEM). The judging criteria are as follows:

○: No residue was observed in the non-exposed part

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

●: Residues are clearly observed in unexposed areas

3.4 Adhesion evaluation

With reference to GB9286-88 <Paints and varnishes-Cross cut test for films>, the adhesion of the coating film was evaluated by the cross cut test method for the pattern obtained in 3.3. According to the degree of damage, it was divided into 0-5 grades (total of 6 grades), where the highest grade 0 was the absence of any microlattice on the membrane surface; Severe peeling of the surface of the membrane occurs in the lowest grade of 5.

The evaluation results are as shown in Table 3.

[Table 3]

As can be seen from the results of Table 3, when the composition of Examples is applied to filter manufacturing, it exhibits excellent photosensitivity and good developability, high luminance after curing, and excellent adhesion to the substrate. The present invention is significantly superior to the photosensitive resin composition of Comparative Example in overall application performance.

The above-described embodiment is a preferred embodiment of the present invention, but the implementation method of the present invention is not limited to the above-described embodiment. All other changes, modifications, substitutions, combinations and simplifications made within the spirit and principle of the present invention are included within the protection scope of the present invention in the manner of equivalent substitution.

Claims (14)

A photosensitive resin composition for a color filter comprising the following components:
a photoinitiator (A) comprising a photoinitiator A1 and at least one oxime ester-based photoinitiator A2;
alkali-soluble resin (B);
a compound (C) having at least one polymerizable unsaturated bond;
colorant (D);
hydrogen donor (E).
Here, the photopolymerization initiator A1 is a hexaarylbisimidazole-based mixed photoinitiator, and has a structure represented by the general formula (I), wherein the four connection positions 2-1', 2-3', 2'-1, 2'-3 bisimidazole compounds are included, and the total mass percentage content in A1 of the bisimidazole compounds at the four linkage positions is 92% or more.

In Formula (I), Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , Ar ₆ may be the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group;
In addition, the molar extinction coefficient of the photoinitiator (A) is 5000-10000 in the i-line (365 nm). According to claim 1,
The photosensitive resin composition for a color filter, characterized in that the mass ratio of the photoinitiator A1 and the oxime ester-based photoinitiator A2 in the composition is 1:5 to 5:5. According to claim 1,
Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , Ar ₆ may be the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group, wherein the aryl group is a phenyl group. A photosensitive resin composition. 4. The method according to any one of claims 1 to 3,
The substituent of the aryl group is halogen, nitro group, cyano group, amino group, hydroxyl group, C ₁ -C ₂₀ alkyl or alkenyl group, C ₁ -C ₈ alkoxy group, where each independent variable (ie, each substituent) A photosensitive resin composition for a color filter, characterized in that the methylene group may be selectively substituted with oxygen, sulfur, or imino groups. 4. The method according to any one of claims 1 to 3,
The substituent of the aryl group is fluorine, chlorine, bromine, nitro group, cyano group, amino group, hydroxy group, C ₁ -C ₁₀ alkyl or alkenyl group, C ₁ -C ₅ alkoxy group, where methylene of each independent variable The photosensitive resin composition for a color filter, characterized in that the group can be selectively substituted with oxygen, sulfur, or imino groups. 4. The method according to any one of claims 1 to 3,
At least one of Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , and Ar ₆ is an aryl group including a halogen substituent; Preferably, the photosensitive resin composition for a color filter, characterized in that the halogen substituent is chlorine. 4. The method according to any one of claims 1 to 3,
In the photopolymerization initiator A1 of the bisimidazole compound satisfying the four linkage positions 2-1', 2-3', 2'-1, and 2'-3 of the structure represented by the general formula (I) in the photoinitiator A1 The total mass percentage content is 95% or more, and preferably, the four connection positions 2-1', 2-3', 2'-1, 2'-3 of the structure represented by the general formula (I) are satisfied. A photosensitive resin composition for color filters, comprising a bisimidazole compound. According to claim 1,
The alkali-soluble resin (B) is an alkali-soluble resin of a carboxyl group-containing copolymer, preferably a copolymer of an ethylenically unsaturated monomer having a carboxyl group and other copolymerizable ethylenically unsaturated monomers. Photosensitive resin composition for color filters. According to claim 1,
The compound (C) having at least one polymerizable unsaturated bond is a photosensitive resin composition for a color filter, characterized in that at least one is selected from an acrylate-based compound and a methacrylate-based compound. According to claim 1,
The colorant (D) is a photosensitive resin composition for a color filter, characterized in that it is selected from pigments and/or dyes. According to claim 1,
The hydrogen donor (E) is at least one selected from an amine-based compound, a carboxylic acid-based compound, an organic sulfur compound containing a mercapto group, and an alcohol-based compound. The support body is equipped with the coloring pattern formed from the said photosensitive resin composition in any one of Claims 1-11, The color filter characterized by the above-mentioned. A method for manufacturing a color filter, comprising:
A process step of forming a photosensitive resin layer by applying the photosensitive resin composition according to any one of claims 1 to 11 on a support; a process step of exposing the photosensitive resin layer through a mask; and developing the exposed photosensitive resin layer to form a colored pattern. 14. The method of claim 13,
The method of manufacturing a color filter, characterized in that it further comprises a post-curing process of further curing the colored pattern formed through heating and/or exposure.

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