KR101998729B1 - Novel compound, photosensitive resin composition including the same and color filter - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.)There is provided a compound represented by the following formula (1), a photosensitive resin composition containing the compound, and a color filter manufactured using the photosensitive resin composition.
[Chemical Formula 1]

(Wherein each substituent is as defined in the specification).

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound, a photosensitive resin composition containing the same and a color filter,

The present invention relates to a novel compound, a photosensitive resin composition containing the same, and a color filter.

The liquid crystal display device, which is one of the display devices, has advantages such as lightness, thinness, low cost, low power consumption driving and bonding with an excellent integrated circuit, and its use range is expanding for notebook computers, monitors and TV images. Such a liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and ITO pixel electrodes are formed, and an upper substrate on which an active circuit portion composed of a liquid crystal layer, a thin film transistor, and a capacitor layer and an ITO pixel electrode are formed. The color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate so as to shield the boundary between pixels and a plurality of colors (typically red (R), green (G), blue ) Are arrayed in a predetermined order, and the pixel portions are stacked in this order. In the pigment dispersion method, which is one of the methods of implementing a color filter, a photopolymerizable composition containing a colorant is coated on a transparent substrate provided with a black matrix, a pattern of a pattern to be formed is exposed, And a coloring thin film is formed by repeating a series of processes of thermosetting. The colored photosensitive resin composition used in the production of a color filter according to the pigment dispersion method generally comprises an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a solvent and other additives, and may further contain an epoxy resin or the like. The pigment dispersion method as described above is actively applied to manufacture LCDs for mobile phones, notebooks, monitors, TVs and the like. However, even in a photosensitive resin composition for a color filter using a pigment dispersion method having various advantages in recent years, it is difficult to make the powder finer, and various additives are required because the dispersed state must be stable in the dispersion even when dispersed. And it is difficult to store and transport because the pigment dispersion must maintain an optimal quality state. Further, in a color filter made of a pigment type photosensitive resin composition, there is a limit of brightness and contrast ratio resulting from the pigment particle size. Accordingly, there has been a need to develop dyes having heat resistance and chemical resistance similar to those of pigments instead of pigments.

One embodiment is to provide a novel cyanine-based compound of the zwitter type that is not a salt.

Another embodiment is to provide a photosensitive resin composition comprising the above compound.

Another embodiment is to provide a color filter manufactured using the photosensitive resin composition.

An embodiment provides a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

X ¹ and X ² are each independently * -CR ⁶ R ⁷ - *, * -O- * or * -S- *, and R ⁶ and R ⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 To C10 alkyl group,

R ¹ , R ² and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group,

R ¹ and R ² may be linked to each other to form a ring,

R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an anion or a C1 to C20 alkyl group containing an anion at the terminal thereof,

Provided that any one of R ³ and R ⁴ is an anion or a C1 to C20 alkyl group containing an anion at the terminal thereof and the other is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group.

The anion may be represented by any one of the following formulas A-1 to A-3.

[A-1]

[A-2]

[A-3]

R ³ is a substituted or unsubstituted C 1 to C 20 alkyl group, and R ⁴ may be an anion represented by any one of formulas A-1 to A-3.

The R ⁴ may be an anion represented by the formula (A-2) or (A-3).

The R ⁴ may be an anion represented by the above formula (A-3).

R ³ is a C1 to C20 alkyl group substituted with an anion represented by any one of the above formulas A-1 to A- ³ at the terminal, and R ⁴ may be a hydrogen atom.

The R ³ may be a C1 to C20 alkyl group substituted at the terminal thereof with an anion represented by the above formula (A-2) or (A-3).

The R ³ may be a C1-C20 alkyl group substituted at the terminal thereof with an anion represented by the above formula (A-3).

The compound represented by Formula 1 may be represented by any one of the following Formulas 1-1 to 1-12.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

[Formula 1-11]

[Formula 1-12]

The compound represented by Formula 1 may have a maximum absorbance in a wavelength range of 450 nm to 780 nm.

Another embodiment provides a photosensitive resin composition comprising the compound as a dye in a colorant.

The dye may be a red dye, a violet dye or a yellow dye.

The photosensitive resin composition may further contain a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

The binder resin may include an acrylic binder resin, a cadmium binder resin, or a combination thereof.

The photosensitive resin composition may further comprise a pigment.

The photosensitive resin composition contains 5 to 30% by weight of the colorant, based on the total amount of the photosensitive resin composition; 1% by weight to 10% by weight of the binder resin; 5 wt% to 15 wt% of the photopolymerizable compound; 0.1% by weight to 5% by weight of the photopolymerization initiator, and the balance of the solvent.

The photosensitive resin composition may further include a silane coupling agent comprising malonic acid, 3-amino-1,2-propanediol, a vinyl group or a (meth) acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, .

Another embodiment provides a color filter manufactured using the photosensitive resin composition.

Other aspects of the present invention are included in the following detailed description.

The compound according to one embodiment is a novel cyanine compound in the form of a zwitter that is not a salt form, and can improve durability and electrical characteristics when used as a colorant in a photosensitive resin composition, and can be usefully used for manufacturing a color filter.

1 is a graph showing the relationship between a room temperature (25 DEG C) and a voltage holding ratio (VHR) at 60 DEG C of a color filter manufactured using the photosensitive resin composition according to Examples 7 to 12 and Comparative Examples 1 to 3, And the results are shown in the graph.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Means that at least one hydrogen atom of the functional group of the present invention is substituted with a halogen atom (F, Br, Cl or I), a hydroxy group, a nitro group, a cyano group, an amino group NH _2, NH (R ^200), or N (R ²⁰¹⁾ (R ^202), wherein R ^200, R ²⁰¹ and R ²⁰² are the same or different, each independently being a C1 to C10 alkyl groups), amidino group, A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, And a substituted or unsubstituted heterocyclic group substituted with at least one substituent selected from the group consisting of a substituted or unsubstituted heterocyclic group.

Unless otherwise specified in the specification, "alkyl group" means C1 to C20 alkyl group, specifically C1 to C15 alkyl group, "cycloalkyl group" means C3 to C20 cycloalkyl group, specifically C3 Refers to a C1 to C20 alkoxy group, specifically, a C1 to C18 alkoxy group, and an "aryl group" means a C6 to C20 aryl group, specifically, a C6 to C20 aryl group, Refers to a C 2 to C 20 alkenyl group, specifically, a C 2 to C 18 alkenyl group, and the "alkylene group" refers to a C 1 to C 20 alkylene group, specifically, a C1 Refers to a C6 to C20 arylene group, and specifically refers to a C6 to C16 arylene group.

(Meth) acrylate "refers to both" acrylic acid "and" methacrylic acid " It means both are possible.

As used herein, unless otherwise defined, "combination" means mixing or copolymerization. "Copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

In the present specification, the cadmium resin means a resin in which at least one functional group selected from the group consisting of the following Chemical Formulas (2-1) to (2-11) is contained in the main backbone of the resin.

In addition, unless otherwise defined herein, "*" means the same or different atom or moiety connected to the formula.

An embodiment provides a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

X ¹ and X ² are each independently * -CR ⁶ R ⁷ - *, * -O- * or * -S- *, and R ⁶ and R ⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 To C10 alkyl group,

R ¹ , R ² and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group,

R ¹ and R ² may be linked to each other to form a ring,

R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an anion or a C1 to C20 alkyl group containing an anion at the terminal thereof,

Provided that any one of R ³ and R ⁴ is an anion or a C1 to C20 alkyl group containing an anion at the terminal thereof and the other is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group.

For example, R ¹ and R ² are each independently present and may not form a ring.

For example, R ¹ and R ² may be bonded to each other to form a ring, such as a benzene ring.

As described above, in a color filter made of a pigment type photosensitive resin composition, there is a limit of luminance and contrast ratio resulting from the pigment particle size. Further, in the case of a color imaging device for an image sensor, a smaller dispersion particle size is required for forming a fine pattern. In order to meet such a demand, attempts have been made to introduce a dye that does not form a particle instead of a pigment to produce a photosensitive resin composition suitable for a dye, thereby realizing a color filter having improved luminance and contrast ratio.

In general, the cyanine compound is separated from the charge and is present in the form of a salt. The photosensitive resin composition containing such a cyanine compound as a colorant has low solubility in an organic solvent such as PGMEA and has durability such as heat resistance and chemical resistance There is a limit to use as a colorant in the photosensitive resin composition. However, the compound according to one embodiment, that is, the compound represented by the formula (1), exists in the form of a zwitter rather than a salt, has an acrylate group at the end, and has a substituent containing an urethane linkage group as an intermediate linking group, It is possible to improve solubility in an organic solvent and is suitable for use as a dye in a photosensitive resin composition. In addition, a photosensitive resin composition using a compound according to one embodiment as a dye can produce a color filter excellent in durability and electrical characteristics.

The anion may be represented by any one of the following formulas A-1 to A-3.

[A-1]

[A-2]

[A-3]

R ³ is a substituted or unsubstituted C 1 to C 20 alkyl group, and R ⁴ may be an anion represented by any one of formulas A-1 to A-3.

For example, R ⁴ may be an anion represented by the formula (A-2) or (A-3). For example, R ⁴ may be an anion represented by the above formula (A-3).

R ³ is a C1 to C20 alkyl group substituted with an anion represented by any one of the above formulas A-1 to A- ³ at the terminal, and R ⁴ may be a hydrogen atom.

For example, R ³ may be a C1-C20 alkyl group substituted at the terminal thereof with an anion represented by the above formula (A-2) or (A-3). For example, R ³ may be a C1 to C20 alkyl group substituted at the terminal thereof with an anion represented by the above formula (A-3).

The compound according to one embodiment containing an anion represented by the above formula (A-2) is more excellent in durability (such as heat resistance) and electrical characteristics than the anion represented by the above formula (A-1) Compounds according to one embodiment containing an anion represented by the above formula (A-3) rather than an anion may have excellent durability (e.g., heat resistance) and electrical characteristics.

It is preferable that the anion or an alkyl substituent including an anion at a terminal thereof is connected to a nitrogen atom having a positive charge more than when the alkyl substituent including an anion at the anion or the terminal is connected to a carbon atom constituting the benzene ring ) And electrical characteristics.

The compound represented by Formula 1 may be represented by any one of the following Formulas 1-1 to 1-12, but is not limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

[Formula 1-11]

[Formula 1-12]

The compound represented by Formula 1 may have a maximum absorbance in a wavelength range of 450 nm to 780 nm.

Another embodiment provides a photosensitive resin composition comprising the compound as a dye in a colorant.

The dye may be a red dye, a violet dye or a yellow dye.

The photosensitive resin composition may further contain a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

Hereinafter, the components will be described in detail.

coloring agent

The colorant comprises a dye, and the dye may comprise a compound according to one embodiment. For example, the dye may be a compound according to one embodiment.

The dye may be a red dye, a violet dye or a yellow dye.

The colorant may further comprise, in addition to the compound, an organic solvent-soluble dye.

Examples of the organic solvent soluble dye include a triarylmethane compound, an anthraquinone compound, a benzylidene compound, a xanthene compound, a phthalocyanine compound, an azapphyrin compound, and an indigo compound.

The colorant may further include a pigment in addition to the above-mentioned compounds.

The pigment may include a blue pigment, a violet pigment, a red pigment, a green pigment, a yellow pigment and the like.

Examples of the blue pigments include C.I. Blue pigment 15: 6, C.I. Blue pigment 15, C.I. Blue pigment 15: 1, C.I. Blue pigment 15: 2, C.I. Blue pigment 15: 3, C.I. Blue pigment 15: 4, C.I. Blue pigment 15: 5, C.I. Blue pigment 16, C.I. Blue pigment 22, C.I. Blue pigment 60, C.I. Blue pigment 64, C.I. Blue pigment 80, or a combination thereof.

Examples of the violet pigment include C.I. Violet pigment 1, C.I. Violet pigment 19, C.I. Violet pigment 23, C.I. Violet pigment 27, C.I. Violet pigment 28, C.I. Violet pigment 29, C.I. Violet pigment 30, C.I. Violet pigment 32, C.I. Violet pigment 37, C.I. Violet pigment 40, C.I. Violet pigment 42, C.I. Violet pigment 50, or a combination thereof.

Examples of the red pigment include C.I. Red pigment 254, C.I. Red pigment 255, C.I. Red pigment 264, C.I. Red pigment 270, C.I. Red pigment 272, C.I. Red pigment 177, C.I. Red pigment 179, C.I. Red pigment 89 and the like.

Examples of the green pigment include C.I. Green pigment 7, C.I. Green pigment 36, C.I. Pigment green 58, C.I. And halogenated phthalocyanine pigments such as Pigment Green 59 and the like.

Examples of the yellow pigments include C.I. Pigment yellow 139, C.I. Pigment yellow 138, C.I. Pigment yellow 150, etc. These may be used alone or in combination of two or more.

The pigment may be included in the photosensitive resin composition in the form of a pigment dispersion.

The pigment dispersion may include a solid pigment, a solvent, and a dispersant for uniformly dispersing the pigment in the solvent.

The solid pigment may be present in the pigment dispersion in an amount ranging from 1% to 20%, such as 8% to 20%, such as 8% to 15%, such as 10% to 20% 15% by weight.

As the dispersing agent, a nonionic dispersing agent, an anionic dispersing agent, a cationic dispersing agent and the like can be used. Specific examples of the dispersing agent include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid Salts, alkylamide alkylene oxide adducts, and alkylamines. These may be used singly or in combination of two or more.

DISPERBYK-161, DISPERBYK-160, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-160, DISPERBYK-130, DISPERBYK- -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400 and EFKA-450 of EFKA Chemical Co., Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or Ajinomoto's PB711 and PB821.

The dispersing agent may be contained in an amount of 1 to 20% by weight based on the total amount of the pigment dispersion. When the dispersing agent is contained within the above range, the dispersibility of the photosensitive resin composition can be maintained because an appropriate viscosity can be maintained, so that optical, physical and chemical quality can be maintained when the product is applied.

As the solvent for forming the pigment dispersion, ethylene glycol acetate, ethyl cellosolve, propylene glycol (mono) methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether and the like can be used.

The colorant may be included in an amount of 5% by weight to 30% by weight, for example, 5% by weight to 25% by weight based on the total amount of the photosensitive resin composition. When the colorant is contained within the above range, the color reproducibility is excellent and the pattern is excellent in curability and adhesion.

Binder resin

The binder resin may include an acrylic binder resin, a cadmium binder resin, or a combination thereof. For example, the binder resin may be an acrylic binder resin.

The acrylic resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer, and is a resin containing at least one acrylic repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and combinations thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5% by weight to 50% by weight, for example, 10% by weight to 40% by weight based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These may be used singly or in combination of two or more.

Specific examples of the acrylic binder resin include (meth) acrylic acid / benzyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene copolymer, (meth) acrylic acid / benzyl methacrylate / 2- Acrylate copolymer, a (meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but not limited thereto, and they may be used alone or in combination have.

The weight average molecular weight of the acrylic binder resin may be from 3,000 g / mol to 150,000 g / mol, such as from 5,000 g / mol to 50,000 g / mol, such as from 20,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the photosensitive resin composition is excellent in physical and chemical properties, has an appropriate viscosity, and is excellent in adhesion to a substrate during the production of a color filter.

The acid value of the acrylic binder resin may be from 15 mgKOH / g to 60 mgKOH / g, such as from 20 mgKOH / g to 50 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.

The cadmium binder resin may include a repeating unit represented by the following formula (2).

(2)

In Formula 2,

R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,

R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

Z ¹ is a single bond, O, CO, SO ₂ , CR ¹⁵ R ¹⁶ , SiR ¹⁷ R ¹⁸ (wherein R ¹⁵ to R ¹⁸ are each independently a hydrogen atom or a substituted or unsubstituted C 1 to C 20 alkyl group) Is any one of the linking groups represented by formulas (2-1) to (2-11)

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

[Chemical Formula 2-5]

(In the above Formula 2-5,

R ^a is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH = CH ₂ or a phenyl group.

[Chemical Formula 2-6]

[Chemical Formula 2-7]

[Chemical Formula 2-8]

[Chemical Formula 2-9]

[Chemical Formula 2-10]

[Chemical Formula 2-11]

Z ² is an acid anhydride residue,

m1 and m2 are each independently an integer of 0 to 4;

The cadmium-based binder resin may include a functional group represented by the following formula (3) on at least one of both terminals.

(3)

In Formula 3,

Z ³ can be represented by the following formulas (3-1) to (3-7).

[Formula 3-1]

(Wherein R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group or an ether group)

[Formula 3-2]

[Formula 3-3]

[Chemical Formula 3-4]

[Formula 3-5]

(Wherein R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 alkenylamine group).

[Chemical Formula 3-6]

[Chemical Formula 3-7]

Examples of the cationic binder resin include fluorene-containing compounds such as 9,9-bis (4-oxiranylmethoxyphenyl) fluorene; Benzene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride , Tetrahydrofuran tetracarboxylic acid dianhydride, tetrahydrophthalic anhydride and the like; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; Propylene glycol methyl ethyl acetate, and N-methyl pyrrolidone; Phosphorus compounds such as triphenylphosphine; And an amine or an ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, or the like.

When the cationic binder resin is used together with the acrylic binder resin described above, a photosensitive resin composition having excellent adhesion and high resolution and high brightness characteristics can be obtained.

The weight average molecular weight of the cationic binder resin may be from 500 g / mol to 50,000 g / mol, such as from 3,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the cationic binder resin is within the above range, pattern formation is good without residue in the production of a color filter, no loss of film thickness during development, and good patterns can be obtained.

The cadmium binder resin may have an acid value of from 100 mgKOH / g to 140 mgKOH / g.

The binder resin may be contained in an amount of 1 wt% to 10 wt%, for example, 1 wt% to 7 wt% with respect to the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, excellent sensitivity, developability and adhesiveness can be obtained.

Photopolymerization  compound

The photopolymerizable compound may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond.

By having the ethylenically unsaturated double bond, the photopolymerizable compound can form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern formation step.

Specific examples of the photopolymerizable compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethacrylate (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate and the like.

Examples of commercially available products of photopolymerizable compounds are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®; KAYARAD TC-110S ^® and TC-120S ^{® from} Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; KAYARAD HDDA ^® , HX-220 ^® and R-604 ^{® from} Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of ^{社V-260 ®, V-} 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -710 ^® , copper M-8030 ^® , copper M-8060 ^® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. These products may be used alone or in combination of two or more.

The photopolymerizable compound may be treated with an acid anhydride so as to give better developing properties.

The photopolymerizable compound may be included in an amount of 5 wt% to 15 wt%, for example, 5 wt% to 10 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerizable compound is contained within the above range, the pattern is formed with sufficient curing during exposure in the pattern formation process, and therefore, the pattern is excellent in heat resistance, light resistance and chemical resistance, and resolution and adhesion are excellent.

Light curing Initiator

The photopolymerization initiator is an initiator generally used in a photosensitive resin composition, for example, an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, a oxime compound, Can be used.

Examples of the acetophenone compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt Dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) (Trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like.

Examples of the oxime compounds include O-acyloxime compounds, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- ) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl- Etc. may be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione -1-one oxime-O-acetate, 1- (4-phenylsulfanylphenyl) -butan-1-one oxime- O-acetate, and the like.

The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a nonimidazole compound, or a fluorene compound in addition to the above compounds.

The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate and the like .

The photopolymerization initiator may be included in an amount of 0.1 wt% to 5 wt%, for example, 0.1 wt% to 3 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, it is possible to obtain sufficient reliability due to sufficient curing during exposure in the pattern formation step, to have excellent heat resistance, light resistance and chemical resistance, excellent resolution and adhesion, It is possible to prevent the transmittance from being lowered.

menstruum

The solvent may be a compound having compatibility with a compound according to one embodiment, a pigment, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and the like but not reacting with the solvent.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and the like, and also include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, And high boiling solvents such as ethyl acetate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among them, glycol ethers such as ethylene glycol monoethyl ether and the like are preferably used in consideration of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be contained in an amount of from about 40% by weight to about 80% by weight based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity, and hence the processability in the production of the photosensitive resin film in the color filter is excellent.

Other additives

The above-mentioned photosensitive resin composition may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid, in order to prevent spots and spots upon application, to improve the leveling performance, 3-amino-1,2-propanediol; A silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group or an epoxy group; Leveling agents; Fluorine surfactants; A radical polymerization initiator, and the like.

Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanate propyltriethoxysilane,? -Glycine (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. These may be used singly or in combination of two or more.

The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is contained within the above range, the adhesion and storage stability are excellent.

The photosensitive resin composition may further include an epoxy compound to improve adhesion with the substrate.

Examples of the epoxy compound include a phenol novolak epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.

The epoxy compound may be contained in an amount of 0.01 to 20 parts by weight, for example, 0.1 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is contained within the above range, the adhesiveness and storage stability are excellent.

The above-mentioned photosensitive resin composition may further contain a surfactant for improving coatability and preventing defect formation if necessary.

Examples of the fluorine-based surfactant include F-482, F-484, F-478 and F-554 manufactured by DIC Corporation, but the present invention is not limited thereto.

The surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is contained within the above range, uniformity of coating is ensured, no staining occurs, and wetting of the glass substrate is excellent.

The photosensitive resin composition may contain a certain amount of other additives such as an antioxidant and a stabilizer within a range that does not impair the physical properties.

According to another embodiment, there is provided a color filter manufactured using the photosensitive resin composition.

The pattern forming process in the color filter is as follows.

Applying the photosensitive resin composition on a support substrate by spin coating, slit coating, inkjet printing or the like; Drying the applied photosensitive resin composition to form a photosensitive resin composition film; Exposing the photosensitive resin composition film; Developing the exposed photosensitive resin composition film with an aqueous alkali solution to produce a photosensitive resin film; And a step of heat-treating the photosensitive resin film. The process conditions and the like are well known in the art, and therefore, detailed description thereof will be omitted herein.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are only the preferred embodiments of the present invention, and the present invention is not limited to the following Examples.

(Synthesis of Compound)

Synthetic example  1: Synthesis of Compound Represented by Formula 1-1

1.5 equivalents of 2-iodoethanol was added to 2,3,3-trimethylindolenine and refluxed for 18 hours in toluene solvent to obtain intermediate 1. One equivalent of N, N'-diphenylformamidine and one equivalent of triethyl orthoformate was added to Intermediate 1 obtained and refluxed for 16 hours in an ethanol solvent to obtain Intermediate 2.

1.5 equivalents of 1-iodobutane are added to 2,3,3-trimethyl-3H-indole-5-carboxylic acid, and the reaction is carried out in the same manner as in the preparation of Intermediate 2 to obtain Intermediate 3.

10 equivalents of pyridine and 10 equivalents of acetic anhydride were added to the intermediate 2 and 2 equivalents of the intermediate 3 to obtain a cyanine intermediate 4, which was reacted with cyanoethyl methacrylate to give a total yield of 30% (Maldi-tof MS: 627.8 m / z) was obtained.

Synthetic example  2: Synthesis of Compound Represented by Formula 1-2

In the same manner as in Synthesis Example 1 except that 2,3,3-trimethylindolenine and 4-bromobutanoic acid were used instead of 2,3,3-trimethyl-3H-indole-5-carboxylic acid and 1-iodobutane in Synthesis Example 1 Thereby obtaining a compound represented by the following formula (1-2) in a total yield of 34%.

[Formula 1-2]

Mald-tof MS: 613.8 m / z

Synthetic example  3: Synthesis of Compound Represented by Formula 1-3

A compound represented by the following Formula 1-3 was obtained in a total yield of 39% in the same manner as in Synthesis Example 1 except that 5-bromovaleric acid was used instead of 4-bromobutanoic acid in Synthesis Example 1.

[Formula 1-3]

Mald-tof MS: 627.8 m / z

Synthetic example  4: Synthesis of Compound Represented by Formula 1-4

In the same manner as in Synthesis Example 1 except that potassium 2,3,3-trimethyl-3H-indole-5-sulfonate was used instead of 2,3,3-trimethyl-3H-indole-5-carboxylic acid in Synthesis Example 1 To obtain a compound represented by the following formula (1-4) in a total yield of 41%.

[Formula 1-4]

Mald-tof MS: 663.8 m / z

Synthetic example  5: Synthesis of Compound Represented by Formula 1-5

2-methylbenzoxazole was used instead of 2,3,3-trimethylindolenine in Synthesis Example 1 and 2-methyl-1,3-benzoxazole-6-carboxylic acid was used instead of 2,3,3-trimethyl-3H- sulfonic acid was used in the same manner as in Synthesis Example 1, the compound represented by the following Formula 1-5 was obtained in a total yield of 34%.

[Formula 1-5]

Mald-tof MS: 611.7 m / z

Synthetic example  6: Synthesis of Compound Represented by Formula 1-6

2-methylbenzothiazole was used instead of 2,3,3-trimethylindolenine in Synthesis Example 1, and 2-methyl-1,3-benzothiazole-6-carboxylic acid was used instead of 2,3,3-trimethyl-3H- sulfonic acid was used in the same manner as in Synthesis Example 1, the compound represented by the following Formula 1-6 was obtained in a total yield of 31%.

[Chemical Formula 1-6]

Mald-tof MS: 643.8 m / z

Synthetic example  7: Synthesis of Compound Represented by Formula 1-7

In the same manner as in Synthesis Example 2 except that 1,3-propanesultone was used instead of 4-bromobutanoic acid in Synthesis Example 2, a compound represented by the following Formula 1-7 was obtained in a total yield of 42%.

[Chemical Formula 1-7]

Mald-tof MS: 649.8 m / z

Synthetic example  8: Synthesis of Compound Represented by Formula 1-8

In the same manner as in Synthesis Example 7 except that 2-methylbenzoxazole was used instead of 2,3,3-trimethyl-3H-indolenine in Synthesis Example 7, the compound represented by the following Formula 1-8 was obtained in a total yield of 37% .

[Chemical Formula 1-8]

Mald-tof MS: 623.7 m / z

Synthetic example  9: Synthesis of Compound Represented by Formula 1-9

In the same manner as in Synthesis Example 7, except that 2-methylbenzothiazole was used instead of 2,3,3-trimethyl-3H-indolenine in Synthesis Example 7, the compound represented by the following Formula 1-9 was obtained in a total yield of 35% .

[Chemical Formula 1-9]

Mald-tof MS: 639.8 m / z

Synthetic example  10: Synthesis of Compound Represented by Formula 1-10

Synthesis Example 7 was repeated except that 2,3,3,5-Tetramethylindolenine was used instead of 2,3,3-trimethyl-3H-indolenine in Synthesis 7 to obtain the compound represented by Formula 1- 10 was obtained.

[Chemical Formula 1-10]

Mald-tof MS: 663.8 m / z

Synthetic example  11: Synthesis of Compound Represented by Formula 1-11

In the same manner as in Synthesis Example 7 except that 1,1,2-trimethyl-1H-benz [e] indole was used instead of 2,3,3-trimethyl-3H-indolenine in Synthesis Example 7, a total of 27% The compound represented by the following formula 1-11 was obtained in the yield.

[Formula 1-11]

Maldi-tof MS: 699.9 m / z

Synthetic example  12: Synthesis of Compound Represented by Formula 1-12

4.0 g of dimethylformamide and 70 g of chloroform were placed in a reactor and the mixture was cooled and stirred at 0 ° C. 5.0 g of thionyl chloride was added dropwise so that the temperature of the liquid of the mixture did not exceed 12 캜, and the mixture was stirred at 0 캜 for 30 minutes. 10 g of the compound of the formula 1-7 in Synthesis Example 7 was slowly added at room temperature, and the mixture was stirred at 35 캜 for 3 hours. 0.6 g of thionyl chloride was added thereto, and the mixture was stirred at 35 DEG C for 1.5 hours. The reaction solution was cooled again, and 7.3 g of trifluoromethanesulfonamide was slowly added thereto so that the temperature did not exceed 12 ° C. Then, 12.3 g of triethylamine was added dropwise thereto, followed by stirring at room temperature for 14 hours. Insolubles were removed by filtration and the reaction solvent was removed under reduced pressure. 100 g of water was added, and 15% aqueous sodium carbonate solution was added dropwise thereto, and the suspension was stirred for 1 hour while maintaining the pH at 7.0 to 7.5. The compound represented by the following formula 1-12 was extracted using 100 g of dichloromethane and subjected to column purification using a dichloromethane / methanol (15/1) mixed solution. The organic solvent was removed and dried to obtain 6.1 g of a compound represented by the following formula 1-12.

[Formula 1-12]

Mald-tof MS: 780.9 m / z

compare Synthetic example  1: A compound represented by the formula C-1

1,1'-Diethyl-3,3,3 ', 3'-tetramethylindocarbocyanine Iodide (CAS No. 14696-39-0) / TCI / product code A2684

[Chemical formula C-1]

compare Synthetic example  2: Synthesis of the compound represented by the formula C-2

Synthesis was carried out in the same manner as in Synthesis Example 1, 1.5-equivalent of 1-iodobutane was added to 2,3,3-trimethylindolenine and refluxed in a toluene solvent for 18 hours to obtain Intermediate 1. To the obtained intermediate 1, an equivalent amount of N, N'-diphenylformamidine and an equivalent amount of triethyl orthoformate are added, and reflux is carried out in an ethanol solvent for 16 hours to obtain intermediate 2.

1.5 equivalent of 1,3-propanesultone was added to 2,3,3-trimethylindolenine and the reaction was carried out in the same manner as in the preparation of Intermediate 2 to obtain Intermediate 3.

Intermediate 2 and 2 equivalents of Intermediate 3 were charged with 10 times pyridine and 10 equivalents of acetic anhydride and reacted to give the compound represented by the formula C-2 in a total yield of 41%.

[Chemical formula C-2]

Mald-tof MS: 506.2 m / z

compare Synthetic example  3: Synthesis of the compound represented by the formula C-3

Except that potassium 2,3,3-trimethyl-3H-indole-5-sulfonate was used in place of 2,3,3-trimethylindolenine in Comparative Synthesis Example 2, the same procedure as in Comparative Synthesis Example 2 was conducted to give a total yield of 21% To obtain a compound represented by the following formula (C-3).

[Formula C-3]

Mald-tof MS: 520.2 m / z

(Synthesis of photosensitive resin composition)

Example  One

The photosensitive resin composition according to Example 1 was prepared by mixing the following components in the compositions shown in Table 1 below.

Specifically, a photopolymerization initiator was dissolved in a solvent and stirred at room temperature for 2 hours. Then, an acrylic binder resin and a photopolymerizable compound were added thereto, followed by stirring at room temperature for 2 hours. Subsequently, a compound (dye) represented by the formula (1-1) and a pigment (in the form of a pigment dispersion) were added to the obtained reaction product as a colorant and stirred at room temperature for 1 hour. Then, the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(Unit: wt%) Ingredients content coloring agent dyes The compound represented by Formula 1-1 5.0 Pigment dispersion Pigment Y138 pigment dispersion 15.0 Alkali-soluble resin (A) / (B) = 15/85 (w / w),
Molecular weight (Mw) = 22,000 g / mol
(A): methacrylic acid
(B): benzyl methacrylate 3.5 Photopolymerizable compound Dipentaerythritol hexaacrylate (DPHA) 8.0 Photopolymerization initiator 1,2-octanedione 1.0 2- (4-methyl-benzyl) -l- (4-morpholin-4-yl-phenyl) -butan- 0.5 menstruum Cyclohexanone 37.0 PGMEA (Propylene Glycol Monomethyl Ether Acetate) 30.0 Total 100.00

Example  2

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound represented by the general formula (1-2) was used in place of the compound represented by the general formula (1-1).

Example  3

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by Formula 1-3 was used instead of the compound represented by Formula 1-1.

Example  4

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound represented by Formula 1-4 was used in place of the compound represented by Formula 1-1.

Example  5

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound represented by Formula (1-5) was used in place of the compound represented by Formula (1-1).

Example  6

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by Formula 1-6 was used instead of the compound represented by Formula 1-1.

Example  7

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound represented by Formula 1-7 was used instead of the compound represented by Formula 1-1.

Example  8

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by the general formula (1-8) was used instead of the compound represented by the general formula (1-1).

Example  9

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by the general formula (1-9) was used instead of the compound represented by the general formula (1-1).

Example  10

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by Formula 1-10 was used in place of the compound represented by Formula 1-1.

Example  11

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by the formula (1-11) was used in place of the compound represented by the formula (1-1).

Example  12

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound represented by Formula 1-12 was used instead of the compound represented by Formula 1-1.

Comparative Example  One

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the compound represented by the formula (C-1) was used in place of the compound represented by the formula (1-1).

Comparative Example  2

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound represented by the formula C-2 was used instead of the compound represented by the formula 1-1.

Comparative Example  3

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the compound represented by the formula C-3 was used instead of the compound represented by the formula 1-1.

Evaluation 1: Measurement of Voltage Conservation Rate

Cells were fabricated to measure voltage preservation rate (VHR). Specifically, the photosensitive resin compositions according to Examples 7 to 12 and Comparative Examples 1 to 3 were coated on a glass plate on which ITO was patterned, exposed, developed and baked, and then a glass plate on which ITO was patterned And then covered and sealed. Then, the gap between the glass plates was filled with liquid crystal to prepare a cell.

The results were confirmed by applying a direct current voltage of 0.5 V to 3 V to the two electrodes of the cell. The voltage was maintained at 1 V and the frequency was changed from 60 Hz to 120 Hz by alternating current. The voltage was maintained at room temperature (25 ° C) ) Were measured, and the results are shown in Table 2 and Fig.

VHR (1V) Room temperature 60 ° C Example 7 96.8 88.7 Example 8 97.1 89.5 Example 9 96.3 89.1 Example 10 97.9 89.2 Example 11 96.9 88.5 Example 12 97.3 89.0 Comparative Example 1 29.8 31.2 Comparative Example 2 97.9 89.6 Comparative Example 3 97.2 88.9

From Table 2 and FIG. 1, it can be seen that Examples 7 through 12, which include the compounds according to one embodiment as dyes, have higher voltage holding ratios than Comparative Examples 1 through 3, (VHR).

Evaluation 2: Heat resistance measurement

The photosensitive resin composition prepared in Examples 1 to 12 and Comparative Examples 1 to 3 was coated on a glass substrate having a thickness of 1 mm to a thickness of 1 m to 3 m using a spin coater After coating at 250 rpm to 350 rpm, pre-baking was carried out on a hot plate at 90 ° C. Then, the entire exposure was carried out under the condition of 50 mJ / cm ² in the exposure machine, and development was carried out in a development machine using a 111-fold KOH developer under the condition of washing solution / developing solution = 1 / 0.8 for 60 seconds and 60 seconds, . After development, post-baking was performed in an oven at 230 ° C for 20 minutes to prepare a color chip. The prepared color sample was further treated at 230 DEG C for 60 minutes using a convection oven, and the color change before and after the treatment was evaluated using the MCPD (Otsuka) Was calculated, and the results are shown in Table 3 below.

Heat resistance Example 1 15.1 Example 2 3.1 Example 3 8.5 Example 4 11.2 Example 5 31.3 Example 6 34.2 Example 7 2.9 Example 8 3.2 Example 9 2.5 Example 10 2.8 Example 11 3.0 Example 12 2.7 Comparative Example 1 36.0 Comparative Example 2 3.5 Comparative Example 3 12.4

From the above Table 3, it can be seen that the photosensitive resin compositions of Examples 1 to 12 containing the compound according to one embodiment as a dye have better heat resistance than those of the photosensitive resin compositions of Comparative Examples 1 to 3, As shown in Fig.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, And it goes without saying that the invention belongs to the scope of the invention.

Claims (18)

A compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
X ¹ and X ² are each independently * -CR ⁶ R ⁷ - *, * -O- * or * -S- *, and R ⁶ and R ⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 To C10 alkyl group,
R ¹ , R ² and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group,
R ¹ and R ² may be linked to each other to form a ring,
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an anion or a C1 to C20 alkyl group containing an anion at the terminal thereof,
Provided that any one of R ³ and R ⁴ is an anion or a C1 to C20 alkyl group containing an anion at the terminal thereof and the other is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group.
The method according to claim 1,
Wherein the anion is represented by any one of the following formulas (A-1) to (A-3).
[A-1]

[A-2]

[A-3]

3. The method of claim 2,
R ³ is a substituted or unsubstituted C1 to C20 alkyl group,
Wherein R ⁴ is an anion represented by any one of formulas A-1 to A-3.
The method of claim 3,
Wherein R < ⁴ > is an anion represented by the above formula (A-2) or (A-3).
5. The method of claim 4,
And R < ⁴ > is an anion represented by the above formula (A-3).
3. The method of claim 2,
R ³ is an anion-substituted C 1 to C 20 alkyl group represented by any one of the above-mentioned formulas A-1 to A- ³ at the terminal,
Wherein R < ⁴ > is a hydrogen atom.
The method according to claim 6,
And R ³ is a C1 to C20 alkyl group substituted at the terminal thereof with an anion represented by the above formula (A-2) or (A-3).
8. The method of claim 7,
And R ³ is a C1 to C20 alkyl group substituted with an anion represented by the above formula (A-3) at the terminal.
The method according to claim 1,
The compound represented by the formula (1) is represented by any one of the following formulas (1-1) to (1-12).
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

[Formula 1-11]

[Formula 1-12]

The method according to claim 1,
Wherein the compound represented by Formula 1 has a maximum absorbance in a wavelength range of 450 nm to 780 nm.
A photosensitive resin composition comprising the compound of any one of claims 1 to 10 as a dye in a colorant.
12. The method of claim 11,
Wherein the dye is a red dye, a violet dye or a yellow dye.
12. The method of claim 11,
The photosensitive resin composition further comprises a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
14. The method of claim 13,
Wherein the binder resin comprises an acrylic binder resin, a carcass binder resin or a combination thereof.
14. The method of claim 13,
Wherein the coloring agent further comprises a pigment.
16. The method of claim 15,
The photosensitive resin composition preferably contains, relative to the total amount of the photosensitive resin composition,
5% to 30% by weight of the colorant;
1% by weight to 10% by weight of the binder resin;
5 wt% to 15 wt% of the photopolymerizable compound;
0.1% to 5% by weight of the photopolymerization initiator and
The solvent balance
.
14. The method of claim 13,
The photosensitive resin composition may further include a silane coupling agent comprising malonic acid, 3-amino-1,2-propanediol, a vinyl group or a (meth) acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, .
A color filter produced by using the photosensitive resin composition of claim 11.

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