KR102331461B1 - Compound, photosensitive resin composition comprising the same, photo resist, color filter, and display device - Google Patents

Abstract

The present specification provides a compound represented by Formula 1 and a photosensitive resin composition comprising the same, a photosensitive material, a color filter, and a display device.

Description

A compound, a photosensitive resin composition comprising the same, a photosensitive material, a color filter, and a display device

The present specification relates to a compound and a photosensitive resin composition comprising the same. In addition, the present specification relates to a photosensitive material, a color filter, and a display device manufactured using the photosensitive resin composition.

In recent color filters, performance characterized by high luminance and high contrast ratio is required. In addition, one of the main purposes of the development of the display device is to differentiate the performance of the display device through the improvement of color purity and to improve the productivity in the manufacturing process.

Since the pigment type used as a color material for a color filter is present in the color photoresist in a particle-dispersed state, it is difficult to control the luminance and contrast ratio according to the pigment particle size and distribution control. In the case of pigment particles, they are agglomerated in the color filter, resulting in poor dissolution and dispersibility, and multiple scattering of light occurs due to large aggregated particles. The scattering of such polarized light is pointed out as the main factor for lowering the contrast ratio. Efforts to improve luminance and contrast ratio through ultra-fine pigmentation and dispersion stabilization are continuing, but the degree of freedom in selecting color materials for realizing color coordinates for high-color purity display devices is limited. In addition, the previously developed color material, particularly the pigment dispersion method using a pigment, has reached its limit in improving the color purity, luminance, and contrast ratio of a color filter using the same.

Accordingly, there is a demand for the development of a new color material capable of improving color reproduction, luminance, and contrast ratio by increasing color purity.

Korean Patent Publication No. 2001-0009058

The present inventors intend to provide a compound, a photosensitive resin composition comprising the same, a photosensitive material, a color filter, and a display device manufactured using the same.

An exemplary embodiment of the present specification provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

X is O, S, NR', or C=O;

wherein R' is hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; hydroxyl group; sulfonate group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted cycloalkyl group,

When X is C=O, R3 is hydrogen; heavy hydrogen; halogen group; hydroxyl group; sulfonate group; a substituted amine group; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted cycloalkyl group,

r1 and r4 are integers from 0 to 4, and when r1 and r4 are 2 or more, the structures in parentheses ( ) are the same as or different from each other,

r2 is an integer from 0 to 2, and when r2 is 2, R2 are the same as or different from each other,

r3 is an integer of 0 to 3, and when r3 is 2 or more, R3 is the same as or different from each other.

An exemplary embodiment of the present specification includes a compound represented by Formula 1; binder resin; polyfunctional monomers; photoinitiators; And it provides a photosensitive resin composition comprising a solvent.

An exemplary embodiment of the present specification provides a photosensitive material prepared using the photosensitive resin composition.

An exemplary embodiment of the present specification provides a color filter including the photosensitive material.

An exemplary embodiment of the present specification provides a display device including the color filter.

The compound according to an exemplary embodiment of the present specification may be used as a color material in the photosensitive resin composition, and when used as a color material, there is an advantage in that heat resistance and sensitivity are improved.

1 is a view showing the shape of a fine pattern of a color filter substrate according to Example 1. Referring to FIG.
FIG. 2 is a view showing the shape of a fine pattern of a color filter substrate according to Example 2. FIG.
3 is a diagram illustrating a shape of a fine pattern of a color filter substrate according to a comparative example.

Hereinafter, the present specification will be described in more detail.

In the present specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member exists between the two members.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

According to an exemplary embodiment of the present specification, there is provided a compound represented by Formula 1 above. When the compound represented by Formula 1 is used as a color material for the photosensitive resin composition, heat resistance and sensitivity may be improved.

Compared to the case in which R3 of Formula 1 is -NH ₂ , when R3 is hydrogen, the bonding angle is reduced. Accordingly, the intermolecular interaction (π-π stacking) increases, and thus the properties against heat can be improved.

In addition, when UV irradiation to the photosensitive resin composition according to the present specification, the absorption rate at 365 nm, which is the main wavelength, is reduced, and the formation of radicals of the photoinitiator in the photosensitive resin composition according to the present specification may further increase, and thus, to improve the sensitivity can

Examples of the substituents of the compound represented by Formula 1 are described below, but are not limited thereto.

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In this specification,

refers to a site bonded to another substituent or a bonding group.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; sulfonic acid group; sulfonate group; nitrile group; nitro group; hydroxyl group; -COOH; imid; amide group; an alkyl group; cycloalkyl group; amine group; aryl group; heteroaryl group; acryloyl group; acrylate group; It means that it is substituted with one or more substituents selected from the group comprising a heterocyclic group and an anionic group containing at least one of N, O, S or P atoms or does not have any substituents.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In an exemplary embodiment of the present specification, the sulfonate group _{may be represented by -SO 3} M, wherein M may be any one of Group 1 elements of the periodic table, for example, may be Na, but is not limited thereto.

In an exemplary embodiment of the present specification, the amine group is -NH ₂ ; an alkylamine group; cycloalkylamine group; N-alkylarylamine group; arylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but may be 1 to 30. In addition, it may be 1 to 20, it may be 1 to 10. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a cycloalkylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, and 9-methyl -Anthracenylamine group, diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group; N-phenylnaphthylamine group; N-biphenylnaphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; N-biphenylphenanthrenylamine group; N-phenylfluorenylamine group; N-phenylterphenylamine group; N-phenanthrenylfluorenylamine group; There is an N-biphenylfluorenylamine group, and the like, but is not limited thereto.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 30. According to another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-ox There is a tyl group, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, there are a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20, and may be 6 to 10. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, an indenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a triphenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

In the present specification, the acryloyl group means a photopolymerizable unsaturated group, for example, a (meth) acryloyl group may be mentioned, but is not limited thereto.

In the present specification, the acrylate group refers to a photopolymerizable unsaturated group, for example, a (meth)acrylate group, but is not limited thereto.

In this specification, "(meth)acryloyl" represents at least 1 sort(s) chosen from the group which consists of acryloyl and methacryloyl. The notation of '(meth)acrylate' has the same meaning.

In an exemplary embodiment of the present specification, X is O, S, NR', or C=O.

In an exemplary embodiment of the present specification, X is O, NR' or C=O.

In an exemplary embodiment of the present specification, R' is hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group.

In an exemplary embodiment of the present specification, R' is a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group.

In an exemplary embodiment of the present specification, R' is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R' is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In an exemplary embodiment of the present specification, R' is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R' is a substituted or unsubstituted methyl group; a substituted or unsubstituted propyl group; or a substituted or unsubstituted phenyl group.

In an exemplary embodiment of the present specification, R' is a methyl group; Profile group; or a phenyl group.

In an exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; hydroxyl group; sulfonate group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted cycloalkyl group, and when X is C=O, R3 is hydrogen; heavy hydrogen; halogen group; hydroxyl group; sulfonate group; a substituted amine group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted cycloalkyl group.

In an exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; halogen group; hydroxyl group; sulfonate group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted cycloalkyl group, and when X is C=O, R3 is hydrogen; heavy hydrogen; halogen group; hydroxyl group; sulfonate group; a substituted amine group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted cycloalkyl group.

In an exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; bromine; Goat; hydroxyl group; sulfonate group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted cycloalkyl group, and when X is C=O, R3 is hydrogen; heavy hydrogen; halogen group; hydroxyl group; sulfonate group; a substituted amine group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted cycloalkyl group.

In an exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; bromine; Goat; hydroxyl group; sulfonate group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; or a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, and when X is C=O, R3 is hydrogen; heavy hydrogen; halogen group; hydroxyl group; sulfonate group; a substituted amine group; a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; or a substituted or unsubstituted cycloalkyl group.

In an exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; bromine; Goat; hydroxyl group; sulfonate group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; or a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, and when X is C=O, R3 is hydrogen; heavy hydrogen; halogen group; hydroxyl group; sulfonate group; a substituted amine group; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; or a substituted or unsubstituted cycloalkyl group.

In an exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; bromine; Goat; hydroxyl group; sulfonate group; a substituted or unsubstituted amine group; a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; or a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and when X is C=O, R3 is hydrogen; heavy hydrogen; halogen group; hydroxyl group; sulfonate group; a substituted amine group; a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; or a substituted or unsubstituted cycloalkyl group.

In an exemplary embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; bromine; Goat; hydroxyl group; -SO ₃ Na; amine group (—NH ₂ ); a substituted or unsubstituted methyl group; a substituted or unsubstituted ethyl group; a substituted or unsubstituted propyl group; a substituted or unsubstituted butyl group; or a substituted or unsubstituted cyclohexyl group, and when X is C=O, R3 is hydrogen; bromine; hydroxyl group; or a cyclohexylamine group.

In an exemplary embodiment of the present specification, R1 is hydrogen; bromine; amine group (—NH ₂ ); a methyl group substituted with an epoxy group; or a methyl group substituted with an ethylamine group.

In an exemplary embodiment of the present specification, R2 is hydrogen; -SO ₃ Na; or bromine.

In an exemplary embodiment of the present specification, R3 is hydrogen; bromine; hydroxyl group; or a cyclohexylamine group.

In an exemplary embodiment of the present specification, R4 is hydrogen; bromine; Goat; amine group (—NH ₂ ); a methyl group substituted with an epoxy group; an ethyl group substituted with a hydroxyl group; tert-butyl group; or a cyclohexyl group.

In an exemplary embodiment of the present specification, the methyl group substituted with an epoxy group may be represented by the following substituent, but is not limited thereto.

In the exemplary embodiment of the present specification, the ethyl group substituted with a hydroxyl group may be represented by the following substituents, but is not limited thereto.

In an exemplary embodiment of the present specification, r1 and r4 are integers of 0 to 4, and when r1 and r4 are 2 or more, the structures in parentheses ( ) are the same or different, r2 and r3 are integers of 0 to 2, r2 and when r3 is 2 or more, structures in parentheses ( ) are the same or different.

According to another exemplary embodiment of the present specification, Chemical Formula 1 may be represented by Chemical Formula 2 below.

[Formula 2]

In Formula 2,

R1 to R4 and r1 to r4 are as defined in Formula 1 above.

According to another exemplary embodiment of the present specification, Chemical Formula 1 may be represented by Chemical Formula 3 below.

[Formula 3]

In Formula 3,

R1 to R4 and r1 to r4 are as defined in Formula 1 above.

According to another exemplary embodiment of the present specification, Chemical Formula 1 may be represented by Chemical Formula 4 below.

[Formula 4]

In Formula 4,

R', R1 to R4 and r1 to r4 are as defined in Formula 1 above.

According to another exemplary embodiment of the present specification, Chemical Formula 1 may be represented by any one of the following Chemical Formulas, but is not necessarily limited thereto.

In addition, according to an exemplary embodiment of the present specification, it is possible to provide a color material composition including the compound.

The color material composition may further include at least one of a dye and a pigment in addition to the compound of Formula 1 above. For example, the color material composition may include only the compound of Formula 1, but includes the compound of Formula 1 and one or more dyes, or includes the compound of Formula 1 and one or more pigments, or the compound of Formula 1 , one or more dyes and one or more pigments.

According to an exemplary embodiment of the present specification, a resin composition including the color material composition may be provided.

According to an exemplary embodiment of the present specification, the resin composition may include a compound represented by Formula 1; binder resin; polyfunctional monomers; photoinitiators; and a solvent.

The binder resin is not particularly limited as long as it can exhibit physical properties such as strength and developability of a film made of the resin composition.

The binder resin may use a copolymer resin of a polyfunctional monomer imparting mechanical strength and a monomer imparting alkali solubility, and may further include a binder generally used in the art.

The polyfunctional monomer imparting the mechanical strength of the membrane is an unsaturated carboxylic acid ester; aromatic vinyls; unsaturated ethers; unsaturated imides; and an acid anhydride.

Specific examples of the unsaturated carboxylic acid esters include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl ( meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetra Hydropuffril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl ( Meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxy Cydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, phenoxydiethylene glycol (meth) ) acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, p-nonylphenoxypolypropylene glycol (meth)acrylate, glycidyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, tribromophenyl (meth) ) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate and butyl α-hydroxymethyl acrylate, but only It is not limited.

Specific examples of the aromatic vinyl include styrene, α-methylstyrene, (o,m,p)-vinyl toluene, (o,m,p)-methoxy styrene, and (o,m,p)-chloro styrene. It may be selected from the group consisting of, but is not limited thereto.

Specific examples of the unsaturated ethers may be selected from the group consisting of vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether, but are not limited thereto.

Specific examples of the unsaturated imides are selected from the group consisting of N-phenyl maleimide, N-(4-chlorophenyl) maleimide, N-(4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide. may be, but is not limited thereto.

Examples of the acid anhydride include, but are not limited to, maleic anhydride, methyl maleic anhydride, tetrahydrophthalic anhydride, and the like.

The monomer imparting alkali solubility is not particularly limited as long as it contains an acid group, and for example, (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, 5-norbornene-2-carboxylic acid, mono -2-((meth)acryloyloxy)ethyl phthalate, mono-2-((meth)acryloyloxy)ethyl succinate, ω-carboxy polycaprolactone mono(meth)acrylate selected from the group consisting of It is preferable to use one or more types, but is not limited thereto.

According to an exemplary embodiment of the present specification, the binder resin has an acid value of 50 to 130 KOH mg/g, and a weight average molecular weight of 1,000 to 50,000.

The polyfunctional monomer is a monomer that forms a photoresist image by light, specifically propylene glycol methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol acrylate, neopentyl glycol di Acrylate, 6-hexanediol diacrylate, 1,6-hexanediol acrylate tetraethylene glycol methacrylate, bisphenoxy ethyl alcohol diacrylate, trishydroxyethyl isocyanurate trimethacrylate, trimethyl 1 selected from the group consisting of propane trimethacrylate, diphenylpentaerythritol hexaacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol hexamethacrylate species or a mixture of two or more species.

The photoinitiator is not particularly limited as long as it is an initiator that triggers crosslinking by generating radicals by light, for example, selected from the group consisting of acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, and oxime-based compounds. There may be more than one type.

The acetophenone-based compound is 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, benzoinmethyl ether, benzoinethyl ether, benzoin isobutyl ether, benzoin Butyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-(4-methylthio)phenyl-2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)-butan-1-one, 2-(4-bromo-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one or 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and the like.

As the biimidazole-based compound, 2,2-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl biimidazole, 2,2'-bis(o-chlorophenyl)-4 ,4',5,5'-tetrakis (3,4,5-trimethoxyphenyl)-1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl)-4, 4',5,5'-tetraphenyl biimidazole, 2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-1,2'-biimidazole, etc. , but not limited thereto.

The triazine-based compound is 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}propionate, ethyl-2-{4-[2,4 -bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 2-epoxyethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6 -yl]phenylthio}acetate, cyclohexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-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-triazine-6 -yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionamide, 2,4-bis(trichloro methyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3,-butadienyl-s -triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like, but are not limited thereto.

The oxime-based compound is 1,2-octadione, -1- (4-phenylthio) phenyl, -2- (o-benzoyloxime) (Ciba Geigisa, SI 124), ethanone, -1- (9 -ethyl)-6-(2-methylbenzoyl-3-yl)-,1-(O-acetyloxime) (CGI 242), N-1919 (Adecas), and the like, but is not limited thereto.

The solvent is acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether , propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1 ,1,2-trichloroethane, 1,1,2-trichloroethene, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, 2 -Ethoxy propanol, 2-methoxy propanol, 3-methoxy butanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxy It may be at least one selected from the group consisting of propionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether, but is not limited thereto.

According to an exemplary embodiment of the present specification, based on the total weight of the solid content in the resin composition, the content of the compound represented by Formula 1 is 5 wt% to 60 wt%, and the content of the binder resin is 1 wt% to 60 wt%, the content of the photoinitiator is 0.1 wt% to 20 wt%, the content of the polyfunctional monomer is 0.1 wt% to 50 wt%.

The total weight of the solid content means the sum of the total weight of the components excluding the solvent in the resin composition. The solid content and the basis of weight % based on the solid content of each component may be measured by general analytical means used in the art, such as liquid chromatography or gas chromatography.

According to an exemplary embodiment of the present specification, the resin composition may further include an antioxidant.

According to an exemplary embodiment of the present specification, the content of the antioxidant is 0.1 wt% to 20 wt% based on the total weight of solids in the resin composition.

According to an exemplary embodiment of the present specification, the resin composition is selected from the group consisting of a photocrosslinking sensitizer, a curing accelerator, an adhesion promoter, a surfactant, a thermal polymerization inhibitor, an ultraviolet absorber, a dispersant, and a leveling agent Add 1 or 2 or more additives include as

According to an exemplary embodiment of the present specification, the content of the additive is 0.1 wt% to 20 wt% based on the total weight of solids in the resin composition.

The photocrosslinking sensitizer is benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoyl benzophenone compounds such as benzoate, 3,3-dimethyl-4-methoxybenzophenone, and 3,3,4,4-tetra(t-butylperoxycarbonyl)benzophenone; fluorenone compounds such as 9-fluorenone, 2-chloro-9-prorenone, and 2-methyl-9-fluorenone; Thioxanthone type, such as thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone, diisopropyl thioxanthone compound; xanthone-based compounds such as xanthone and 2-methylxanthone; anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinylpentane), 1,3-bis(9-acridinyl)propane, etc. acridine-based compounds; dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo[2,2,1]heptane-2,3-dione, and 9,10-phenanthrenequinone; phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide; benzoate compounds such as methyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, and 2-n-butoxyethyl-4-(dimethylamino)benzoate; 2,5-bis(4-diethylaminobenzal)cyclopentanone, 2,6-bis(4-diethylaminobenzal)cyclohexanone, 2,6-bis(4-diethylaminobenzal)-4- amino synergists such as methyl-cyclopentanone; 3,3-carbonylvinyl-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-benzoyl-7-(diethylamino)coumarin, 3 -benzoyl-7-methoxy-coumarin, 10,10-carbonylbis[1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-C1]-benzo coumarin-based compounds such as pyrano[6,7,8-ij]-quinolizin-11-one; chalcone compounds such as 4-diethylamino chalcone and 4-azidebenzalacetophenone; At least one selected from the group consisting of 2-benzoylmethylene and 3-methyl-b-naphthothiazoline may be used.

The curing accelerator is used to increase curing and mechanical strength, and specifically, 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 2,5-dimercapto-1,3 ,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol-tetrakis (3-mercaptopropionate), pentaerythritol-tris (3-mercaptopropionate), pentaerythritol Erythritol-tetrakis(2-mercaptoacetate), pentaerythritol-tris(2-mercaptoacetate), trimethylolpropane-tris(2-mercaptoacetate), and trimethylolpropane-tris(3-mercaptopropio) nate) may be used at least one selected from the group consisting of.

The adhesion promoter used herein includes methacryloyloxy propyltrimethoxy silane, methacryloyloxy propyldimethoxy silane, methacryloyloxy propyltriethoxy silane, and methacryloyloxy propyldimethoxysilane. It is possible to select and use at least one type of methacryloyl silane coupling agent such as, and at least one type of octyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, etc. as the alkyl trimethoxysilane. You can choose to use it.

The surfactant is a silicone-based surfactant or a fluorine-based surfactant, and specifically, the silicone-based surfactant is BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307 manufactured by BYK-Chemie. , BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK -354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, etc. can be used. (DaiNippon Ink & Chemicals) F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446 , F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F -486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF , TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc. may be used, but is not limited thereto.

The antioxidant may be at least one selected from the group consisting of hindered phenol antioxidants, amine antioxidants, thio antioxidants, and phosphine antioxidants, but is not limited thereto.

Specific examples of the antioxidant include phosphoric acid-based thermal stabilizers such as phosphoric acid, trimethyl phosphate or triethyl phosphate; 2,6-di-t-butyl-p-cresol, octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, tetrabis[methylene-3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxy benzyl)benzene, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-g, t-Butylphenol 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol) or bis[3 ,3-bis-(4'-hydroxy-3'-tert-butylphenyl)butanoic acid]glycol ester (Bis[3,3-bis-(4'-hydroxy-3'-tert-butylphenyl)butanoicacid]glycol ester), such as a hindered phenol-based primary antioxidant; amines such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, N,N′-diphenyl-p-phenylenediamine or N,N′-di-β-naphthyl-p-phenylenediamine secondary antioxidants; Thio such as dilauryl disulfide, dilauryl thiopropionate, distearyl thiopropionate, mercaptobenzothiazole or tetramethylthiuram disulfide tetrabis[methylene-3-(laurylthio)propionate]methane secondary antioxidants; or triphenyl phosphite, tris (nonylphenyl) phosphite, triisodecyl phosphite, bis (2,4-dibutylphenyl) pentaerythritol diphosphite (Bis (2,4-ditbutylphenyl) Pentaerythritol Diphosphite or (1, 1'-biphenyl) -4,4'-diylbisphosphonoic acid tetrakis [2,4-bis (1,1-dimethylethyl) phenyl] ester ((1,1'-Biphenyl) -4,4' -Diylbisphosphonous acid tetrakis[2,4-bis(1,1-dimethylethyl)phenyl] ester) may be mentioned as a phosphite-based secondary antioxidant.

As the ultraviolet absorber, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chloro-benzotriazole, alkoxy benzophenone, etc. may be used, but the present invention is not limited thereto. All commonly used ones can be used.

Examples of the thermal polymerization inhibitor include p-anisole, hydroquinone, pyrocatechol, t-butyl catechol, N-nitrosophenylhydroxyamine ammonium salt, N-nitrosophenylhydroxy Amine aluminum salt, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, benzoquinone, 4,4-thiobis(3-methyl-6-t-butylphenol), 2,2- Methylenebis (4-methyl-6-t-butylphenol), 2-mercaptoimidazole and may include one or more selected from the group consisting of phenothiazine (phenothiazine), but is not limited thereto. may include those generally known in the art.

The dispersant may be used as a method of internally adding the pigment to the pigment in the form of surface-treating the pigment in advance, or a method of externally adding the pigment to the pigment. As the dispersant, a compound type, nonionic, anionic or cationic dispersant may be used, and fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants may be mentioned. These may be used individually or in combination of 2 or more types.

Specifically, the dispersant is polyalkylene glycol and its esters, polyoxyalkylene polyhydric alcohols, ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylate esters, carboxylates, There is at least one selected from the group consisting of an alkylamide alkylene oxide adduct and an alkylamine, but is not limited thereto.

The leveling agent may be polymeric or non-polymeric. Specific examples of the polymeric leveling agent include polyethyleneimine, polyamideamine, and reaction products of amines and epoxides, and specific examples of the nonpolymeric leveling agent include non-polymeric sulfur-containing and non-polymeric nitrogen-containing The compounds include, but are not limited to, those commonly used in the art may be used.

According to an exemplary embodiment of the present specification, there is provided a photosensitive material manufactured using the resin composition.

More specifically, the resin composition of the present specification is applied on a substrate by an appropriate method to form a thin film or patterned photosensitive material.

The coating method is not particularly limited, but a spray method, a roll coating method, a spin coating method, etc. may be used, and in general, a spin coating method is widely used. In addition, after forming the coating film, in some cases, the residual solvent may be partially removed under reduced pressure.

The light source for curing the resin composition according to the present specification includes, for example, a mercury vapor arc emitting light having a wavelength of 250 nm to 450 nm, a carbon arc, an Xe arc, and the like, but is not necessarily limited thereto.

The resin composition according to the present specification is a pigment-dispersed photosensitive material for manufacturing a thin film transistor liquid crystal display (TFT LCD) color filter, a thin film transistor liquid crystal display (TFT LCD) or a photosensitive material for forming a black matrix of an organic light emitting diode, It can be used for photosensitive material for forming overcoat layer, column spacer photosensitive material, photocurable paint, photocurable ink, photocurable adhesive, printing plate, photosensitive material for printed wiring board, photosensitive material for plasma display panel (PDP), etc., and its use is limited do not specifically place

According to an exemplary embodiment of the present specification, there is provided a color filter including the photosensitive material.

The color filter may be manufactured using a resin composition including the compound represented by Formula 1 above. A color filter may be formed by coating the resin composition on a substrate to form a coating film, and exposing, developing and curing the coating film.

The resin composition according to an exemplary embodiment of the present specification has excellent heat resistance, and has little color change due to heat treatment, so that it is possible to provide a color filter having high color reproducibility and excellent sensitivity even by a curing process during the manufacture of a color filter.

The substrate may be a glass plate, a silicon wafer, and a plate made of a plastic substrate such as polyethersulfone (PES) or polycarbonate (PC), and the type is not particularly limited.

The color filter may include a red pattern, a green pattern, a blue pattern, and a black matrix.

According to another exemplary embodiment, the color filter may further include an overcoat layer.

A grid-like black pattern called a black matrix may be disposed between the color pixels of the color filter for the purpose of improving contrast. Chromium can be used as the material of the black matrix. In this case, a method of depositing chromium on the entire glass substrate and forming a pattern by etching may be used. However, in consideration of the high cost in the process, the high reflectivity of chromium, and environmental pollution caused by the chromium waste solution, a resin black matrix by a pigment dispersion method capable of fine processing may be used.

The black matrix according to the exemplary embodiment of the present specification may use a black pigment or a black dye as a color material. For example, carbon black alone or a mixture of carbon black and a colored pigment can be used. At this time, since a colored pigment lacking in light-shielding property is mixed, the strength of the film or adhesion to the substrate decreases even if the amount of the color material is relatively increased. There are advantages to not being.

A display device including a color filter according to the present specification is provided.

The display device includes a plasma display panel (PDP), a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display (LCD), and a thin film transistor. It may be any one of a liquid crystal display device (Thin FIlm Transistor-Liquid Crystal Display, LCD-TFT) and a cathode ray tube (CRT).

Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art.

<Production Example>

Preparation Example 1: Synthesis of Compound A

(1) Synthesis of compound A-1

1-amino-4-bromoanthraquinone-2-sulfonate sodium salt (10 g, 24.7 mmol) with bis(pinacolato)diborane (9.42 g, 37.05 mmol), potassium acetic acid ( 7.27 g, 74.1 mmol), Pd(dba) ₂ (0.28 g, 0.98 mmol), PCy ₃ (0.28 g, 0.49 mmol) were added, 1,4-dioxane (400 ml) was added, and the mixture was stirred under reflux for about 12 hours. did it After the reaction was completed, it was cooled to room temperature and filtered. The organic layer was separated from the filtrate, and the organic layer was distilled under reduced pressure and recrystallized from EA/Hexane to obtain Compound A-1 (7.91 g, 71 %).: MS[M] = 451.09

(2) Synthesis of compound A

Compound A-1 (10 g, 22.2 mmol), 2-bromo-9H-xanthene-9-one (5.1 g, 18.5 mmol), Pd(t-Bu ₃ P) ₂ (0.045 g, 0.089 mmol) was mixed with 2M K ₂ CO ₃ Aqueous solution (60 mL) and THF (200 mL) were added, and the mixture was stirred under reflux for about 4 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, distilled under reduced pressure, and recrystallized from Tol/EA to obtain Compound A (8.45 g, 88%): MS [M] = 519.0

Preparation Example 2: Synthesis of Compound B

(1) Synthesis of compound B-1

After dissolving 2-hydroxyanthraquinone (10 g, 44.63 mmol) in dimethylformamide (100 mL), NBS (8.34 g, 46.85 mmol) was dissolved in dimethylformamide (100 ml), layered at room temperature, and stirred for 4 hours . After completion of the reaction, the solid produced during the reaction was filtered, washed with distilled water, and dried to obtain Compound B-1 (9.62 g, 68%): MS [M] = 301.96

(2) Synthesis of compound B-2

Compound B-1 (10 g, 33.12 mmol) with Bis(pinacolato)diborane (12.63 g, 49.68 mmol), potassium acetic acid (9.75 g, 99.36 mmol), Pd(dba) ₂ (0.37 g, 1.32 mmol), PCy ₃ (0.38 g, 0.66 mmol) was added, 1,4-dioxane (300 ml) was added, and the mixture was stirred under reflux for about 12 hours. After the reaction was completed, it was cooled to room temperature and filtered. The organic layer was separated from the filtrate, and the organic layer was distilled under reduced pressure and recrystallized from EA/Hexane to obtain Compound B-2 (9.39 g, 81 %): MS[M] = 350.13

(3) Synthesis of compound B

Compound B-2 (10 g, 28.56 mmol), 4-bromo-1-aminoanthraquinone (7.16 g, 23.8 mmol), Pd(t-Bu ₃ P) ₂ (0.049 g, 0.095 mmol) was mixed with 2M K ₂ CO ₃ Aqueous solution (20 mL) and THF (200 mL) were added, and the mixture was stirred under reflux for about 4 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, the organic layer was dried over magnesium sulfate, distilled under reduced pressure, and recrystallized from Tol/EA to obtain Compound B (8.69 g, 82 %): MS [M] = 445.10

Comparative Example compound

Pigment Red177

<Example of Preparation of Resin Composition>

Example 1

4.000 g of compound A, a copolymer of benzyl methacrylate and methacrylic acid as a binder resin (molar ratio 60:40, acid value 100 KOH mg/g, weight average molecular weight measured by GPC 15,000), molecular weight distribution (PDI) 2.0 g, solid content (SC) 25%, solvent propylene glycol monomethyl ether acetate (PGMEA, Propylene glycol monomethyl ether acetate) 28.680 g, Samyang Corporation-03 2.000 g as a photoinitiator, DPHA as a photopolymerizable compound as a polyfunctional monomer (Japan) 7.170 g of gunpowder), 18.250 g of PGMEA (propylene glycol monomethyl ether acetate) and 40.000 g of MBDG (diethylene glycol butyl methyl ether) as a solvent, and DIC's F-475, 0.5 g as an additive to prepare a photosensitive resin composition did.

Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that Compound A was changed to Compound B in Example 1.

comparative example

A photosensitive resin composition was prepared in the same manner as in Example 1, except that Compound A was changed to Pigment Red177, a compound of Comparative Example 1 in Example 1.

<Experimental example>

Substrate fabrication and heat resistance evaluation

The photosensitive resin compositions according to Examples 1 and 2 and Comparative Examples were respectively used to prepare the substrate. Specifically, the photosensitive resin compositions according to Examples 1 and 2 and Comparative Examples were ^{spin-coated on glass (5 X 5 cm 2} ), and prebake: PrB) was performed at 100° C. for 100 seconds. A film was formed.

The distance between the substrate on which the film was formed and the photomask was set to 350 μm, and an exposure ^{amount of 40 mJ/cm 2} was irradiated to the entire surface of the substrate using an exposure machine.

Thereafter, the exposed substrate was developed in a developer (KOH, 0.05%) for 60 seconds. Then, using a spectrophotometer, the L value, a value, and b value were measured for chromaticity with a C light source and a 2 degree viewing angle.

After the measurement, the substrate was postbake (PB) at 230° C. for 20 minutes, and the L value, a value, and b value were measured with a C light source and a 2 degree viewing angle using a spectrophotometer.

In addition, after the measurement, postbake (PB360) for 360 minutes at 230°C was performed, and the L value, a value, and b value were measured using a spectrophotometer with a C light source and a 2 degree viewing angle.

The color difference was calculated using the measured value and the following equation. The smaller the color difference, the smaller the change in production, meaning that it has excellent heat resistance.

[formula]

Color difference-1(ΔE _ab )= [(L value of PB - L value of PrB) ² + (a value of PB - a value of PrB) ² + (b value of PB - b value of PrB) ² ] ^{1/ 2}

Color difference-2(ΔE _ab )= [(L value of PB360 - L value of PB) ² + (a value of PB360 - a value of PB) ² + (b value of PB360 - b value of PB) ² ] ^{1/ 2}

The values obtained by the above formula are shown in Table 1 below.

Color difference-1 (ΔE _ab ) Color difference-2 (ΔE _ab ) Example 1 16.9 21.3 Example 2 19.2 23.8 comparative example 23.4 38.5

According to Table 1, it was confirmed that the color filter substrates formed using the photosensitive resin compositions of Examples 1 and 2 of the present invention had a smaller color difference than the color filter substrates according to Comparative Examples and had excellent heat resistance.

Sensitivity (micropattern) evaluation

After one time of post heat treatment (PB), the micropatterns prepared on the substrate were measured for resolution using an optical microscope. The initial thickness of the fine pattern of the color filter substrates prepared in Examples 1 and 2 and Comparative Examples was measured and shown in Table 2 below.

fine pattern
first thickness Example 1 9 um Example 2 8 um comparative example 17 um

The thinner the formation of the fine pattern when irradiated with the same exposure energy, the better the sensitivity of the photosensitive resin composition.

According to Table 2, the thickness of the fine pattern of the color filter substrate formed using the photosensitive resin composition of Examples 1 and 2 of the present invention is greater than the thickness of the fine pattern of the color filter substrate formed using the photosensitive resin composition of Comparative Example. It was confirmed that it was thin. From this, it was confirmed that the sensitivity of the photosensitive resin composition according to Examples 1 and 2 of the present invention is better than the sensitivity of the photosensitive resin composition according to Comparative Example.

Claims (10)

delete delete A compound represented by the following formula (3):
[Formula 3]

In Formula 3,
R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; hydroxyl group; sulfonate group; an amine group unsubstituted or substituted with cyclohexane; an alkyl group unsubstituted or substituted with an epoxy group, an ethylamine group, or a hydroxyl group; or a cycloalkyl group,
r1 and r4 are integers from 0 to 4,
When r1 is 2 or more, R1 are the same as or different from each other,
When r4 is 2 or more, R4 is the same as or different from each other,
r2 is an integer from 0 to 2, and when r2 is 2, R2 are the same as or different from each other,
r3 is an integer of 0 to 3, and when r3 is 2 or more, R3 is the same as or different from each other. delete 4. The method according to claim 3,
The compound represented by Formula 3 is a compound represented by any one of the following Formulas:

. a compound of claim 3 or 5; binder resin; polyfunctional monomers; photoinitiators; And a photosensitive resin composition comprising a solvent. 7. The method of claim 6,
Based on the total weight of the solid content in the photosensitive resin composition, the content of the compound represented by Formula 3 is 5 wt% to 60 wt%,
The content of the binder resin is 1% to 60% by weight,
The content of the photoinitiator is 0.1 wt% to 20 wt%,
The content of the polyfunctional monomer is 0.1% to 50% by weight of the photosensitive resin composition. A photosensitive material manufactured using the photosensitive resin composition according to claim 6. A color filter comprising the photosensitive material according to claim 8 . A display device comprising the color filter according to claim 9 .

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