KR102018236B1 - Novel compound, photosensitive resin composition including the same and color filter - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.)Provided is a compound represented by Formula 1, a photosensitive resin composition including the same, and a color filter prepared using the photosensitive resin composition.
[Formula 1]

(In Formula 1, each substituent is as defined in the specification.)

Description

Novel compound, photosensitive resin composition and color filter comprising same {NOVEL COMPOUND, PHOTOSENSITIVE RESIN COMPOSITION INCLUDING THE SAME AND COLOR FILTER}

The present disclosure relates to a novel compound, a photosensitive resin composition comprising the same, and a color filter manufactured using the same.

The liquid crystal display device, which is one of the display devices, has advantages such as light weight, thinness, low cost, low power consumption, and excellent bonding with an integrated circuit, and thus its use range is expanding for notebook computers, monitors, and TV images. The liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and an ITO pixel electrode are formed, an active circuit unit consisting of a liquid crystal layer, a thin film transistor, and a capacitor capacitor layer, and an upper substrate on which an ITO pixel electrode is formed. The color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate for shielding boundaries between pixels, and a plurality of colors for forming each pixel, typically red (R), green (G), and blue (B). ) Has a structure in which the pixel portions arranged in the predetermined order in the three primary colors are stacked one by one.

The pigment dispersion method, which is a method of implementing a color filter, coats a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix, exposes a pattern of a form to be formed, and then removes a non-exposed portion with a solvent. It is a method in which a colored thin film is formed by repeating a series of processes of thermosetting. The coloring photosensitive resin composition used for manufacturing the color filter by the pigment dispersion method generally consists of alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, an epoxy resin, a solvent, other additives, etc. The pigment dispersion method is actively applied to manufacture LCDs of mobile phones, notebook computers, monitors, TVs and the like. However, in recent years, in the photosensitive resin composition for color filters using the pigment dispersion method which has various advantages, not only the outstanding pattern characteristic but also the further improved performance are calculated | required. In particular, high luminance and high contrast ratios, along with high color reproduction, are urgently required.

An image sensor refers to a component of an image capturing device that generates an image from a mobile phone camera or a digital still camera (DSC). The image sensor is largely complementary to a solid-state charge coupled device (CCD) image sensor according to its manufacturing process and application method. It may be classified as a complementary metal oxide semiconductor (CMOS) image sensor. The color image pickup device used in the solid state image pickup device or the complementary metal oxide semiconductor includes a color filter including a filter segment of an additive mixed primary color of red, green, and blue on the light receiving device. It is common to install color filters separately and to separate the colors. Recently, the pattern size of the color filter mounted on the color image pickup device has a size of 2 μm or less, which is 1/100 to 1/200 times of the conventional color filter pattern for LCD. Accordingly, the increase in resolution and the reduction of residues are important factors that determine the performance of the device.

In the color filter made of the pigment-type photosensitive resin composition, there is a limit of the brightness and contrast ratio resulting from the pigment particle size. In addition, 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 these demands, there is an attempt to implement a color filter having improved brightness and contrast ratio by preparing a photosensitive resin composition suitable for dyes by introducing a dye that does not form particles instead of a pigment. However, in the case of dyes, the degradation of luminance due to the deterioration of durability, such as light and heat resistance compared to the pigment is concerned.

One embodiment is to provide a novel compound excellent in brightness and contrast ratio.

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

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

One embodiment provides a compound represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁴ are each independently a hydrogen atom or a substituent represented by the following general formula (2), provided that any one of R ¹ to R ⁴ is a substituent represented by the following general formula (2),

[Formula 2]

In Chemical Formula 2,

L ¹ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

R ¹³ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted acrylate group, a substituted or unsubstituted silane Group or a substituted or unsubstituted C10 to C20 fused ring group,

R ⁵ to R ⁸ are each independently a hydrogen atom or a hydroxy group, provided that any one of R ⁵ to R ⁸ is necessarily a hydroxy group,

R ⁹ to R ¹² are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

R ¹ may be represented by Formula 2

R ⁵ may be a hydroxyl group.

The substituted or unsubstituted acrylate group may be represented by the following formula (3).

[Formula 3]

In Chemical Formula 3,

R ¹⁴ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

The substituted or unsubstituted silane group may be represented by the following formula (4).

[Formula 4]

In Chemical Formula 4,

R ¹⁵ to R ¹⁷ are each independently a substituted or unsubstituted C1 to C10 alkyl group.

The substituted or unsubstituted C10 to C20 fused ring group may be an adamantyl (ADAMANTYL) group.

The compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 5.

[Formula 5]

In Chemical Formula 5,

L ¹ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

R ⁹ to R ¹² are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

R ¹⁸ is represented by any one of the following Formulas 5-1 to 5-7,

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

[Formula 5-7]

In Chemical Formulas 5-1 to 5-4 and 5-6,

R ¹⁹ is a halogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, * -C (= 0) OR ^x or * -OC (= 0) R ^x , wherein R ^x is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ^y and R ^z are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ²⁰ to R ²² are each independently a substituted or unsubstituted C1 to C8 alkyl group,

p1 is an integer of 0-5.

The compound represented by Chemical Formula 1 may be represented by any one selected from the group consisting of Chemical Formulas 1-1 to 1-7.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

Another embodiment provides a photosensitive resin composition comprising the compound.

The compound may be a dye.

The dye may be a green dye.

The photosensitive resin composition may further include a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

The photosensitive resin composition may further include a pigment.

The pigment may be included in 10 wt% to 20 wt% with respect to the total amount of the photosensitive resin composition.

The photosensitive resin composition is 1 wt% to 10 wt% of the compound, based on the total amount of the photosensitive resin composition; 1 wt% to 10 wt% of the binder resin; 5 wt% to 15 wt% of the photopolymerizable monomer; 0.1 wt% to 5 wt% of the photopolymerization initiator; And the balance of the solvent.

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

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

Other specific details of embodiments of the present invention are included in the following detailed description.

By using the compound according to the embodiment, it is possible to implement a color filter having excellent brightness and contrast ratio.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the present specification, "substituted" means that at least one hydrogen atom of the compound is a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, already Nogi group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof , C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group A C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, or a combination thereof.

Unless otherwise specified in the specification, "heterocycloalkyl group", "heterocycloalkenyl group", "heterocycloalkynyl group" and "heterocycloalkylene group" are each cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkyl. It means that at least one hetero atom of N, O, S or P is present in the ring compound of the len.

Unless otherwise specified herein, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible.

Unless otherwise stated herein, "combination" means mixed or copolymerized.

Unless otherwise defined in the chemical formulas herein, when a chemical bond is not drawn at the position where the chemical bond is to be drawn, it means that a hydrogen atom is bonded at the position.

Unless stated otherwise in the present specification, the term fused means a ring in which two or more rings share at least one or more carbon-carbon bonds with each other.

Also, unless stated otherwise in the present specification, "*" means a part connected with the same or different atoms or formulas.

Compound according to one embodiment is represented by the formula (1).

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁴ are each independently a hydrogen atom or a substituent represented by the following general formula (2), provided that any one of R ¹ to R ⁴ is a substituent represented by the following general formula (2),

[Formula 2]

In Chemical Formula 2,

L ¹ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

R ¹³ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted acrylate group, a substituted or unsubstituted silane Group or a substituted or unsubstituted C10 to C20 fused ring group,

R ⁵ to R ⁸ are each independently a hydrogen atom or a hydroxy group, provided that any one of R ⁵ to R ⁸ is necessarily a hydroxy group,

R ⁹ to R ¹² are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

The compound represented by Chemical Formula 1 has three resonance structures, as shown in the following scheme, but for the sake of convenience, the compound represented by Chemical Formula 1 may be represented by only one resonance structure. That is, the compound represented by Chemical Formula 1 may be represented by any one of the three resonance structures.

[scheme]

As the compound according to the embodiment is represented by Chemical Formula 1, in particular, since the functional group including the urethane linking group is present as a substituent of the benzene ring, the luminance is superior to other squarylium-based compounds having no structure represented by Chemical Formula 1 And contrast ratio.

In Formula 1, R ¹ may be represented by Formula 2, and R ⁵ may be a hydroxy group. By the presence of the functional group and the hydroxyl group including the urethane linking group in this position, there is an advantageous effect excellent in brightness and contrast ratio.

The substituted or unsubstituted acrylate group may be represented by the following formula (3).

[Formula 3]

In Chemical Formula 3,

R ¹⁴ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

The substituted or unsubstituted silane group may be represented by the following formula (4).

[Formula 4]

In Chemical Formula 4,

R ¹⁵ to R ¹⁷ are each independently a substituted or unsubstituted C1 to C10 alkyl group.

The substituted or unsubstituted C10 to C20 fused ring group may be an adamantyl (ADAMANTYL) group.

For example, the compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 5.

[Formula 5]

In Chemical Formula 5,

L ¹ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

R ⁹ to R ¹² are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

R ¹⁸ is represented by any one of the following Formulas 5-1 to 5-7,

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

[Formula 5-7]

In Chemical Formulas 5-1 to 5-4 and 5-6,

R ¹⁹ is a halogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, * -C (= 0) OR ^x or * -OC (= 0) R ^x , wherein R ^x is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ^y and R ^z are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ²⁰ to R ²² are each independently a substituted or unsubstituted C1 to C8 alkyl group,

p1 is an integer of 0-5.

For example, the compound represented by Chemical Formula 1 may be represented by any one selected from the group consisting of Chemical Formulas 1-1 to 1-7.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

The compound according to one embodiment may be used alone as a green dye, or may be used in combination with a color dye.

Examples of the dye include triaryl methane dyes, anthraquinone dyes, benzylidene dyes, cyanine dyes, phthalocyanine dyes, azapopyrine dyes, indigo dyes, and xanthene dyes.

The compounds according to one embodiment can also be used in admixture with pigments.

As the pigment, a red pigment, a green pigment, a blue pigment, a yellow pigment, a black pigment, or the like can be used.

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 89; and the like. Examples of the green pigment include C.I. Green pigment 36, C.I. Green pigment 7, C.I. Green pigment 58; and the like. Examples of the blue pigment 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. Copper phthalocyanine pigments such as blue pigment 16 and the like. Examples of the yellow pigment include C.I. Isoindolin pigments such as yellow pigment 139 and the like, C.I. Quinophthalone pigments such as yellow pigment 138 and the like, C.I. Nickel complex pigments such as yellow pigment 150 and the like. Examples of the black pigment include aniline black, perylene black, titanium black, carbon black and the like. The pigments may be used alone or by mixing two or more thereof, but are not limited to these examples.

The pigment may be included in the photosensitive resin composition in the form of a dispersion. Such a pigment dispersion may be composed of the pigment and a solvent, a dispersant, a dispersion resin and the like.

As the solvent, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and the like can be used, and among these, propylene glycol methyl ether acetate can be used. Can be.

The dispersant helps to uniformly disperse the pigment in the dispersion, and can be used for both nonionic, anionic or cationic dispersants. Specifically, polyalkylene glycol or ester thereof, polyoxy alkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkyl amide alkylene oxide addition Water, alkyl amine, etc. can be used, These can be used individually or in mixture of 2 or more types.

The dispersion resin may use an acrylic resin including a carboxyl group, which may not only improve the stability of the pigment dispersion but also improve the pattern of the pixel.

When using a mixture of the compound and the pigment dispersion according to one embodiment may be used by mixing in a weight ratio of 1: 9 to 9: 1, specifically, 1: 1 to 1: 5. When mixed in the weight ratio range, it may have a high brightness and contrast ratio while maintaining color characteristics.

According to another embodiment, a photosensitive resin composition including the compound represented by Chemical Formula 1 is provided.

The photosensitive resin composition may include (A) a colorant (compound represented by Formula 1), (B) binder resin, (C) photopolymerizable monomer, (D) photopolymerization initiator, and (E) solvent.

Each component is demonstrated concretely below.

(A) colorant

The colorant may include a compound represented by Chemical Formula 1, and the compound represented by Chemical Formula 1 has been described above.

The colorant may further include a pigment in addition to that represented by Chemical Formula 1, and the pigment has been described above.

The compound represented by Chemical Formula 1 may be included in an amount of 1 wt% to 10 wt%, such as 2 wt% to 8 wt%, based on the total amount of the photosensitive resin composition, and the pigment may be 10 wt% to the total amount of the photosensitive resin composition. It may be included in 20% by weight. When the compound and the pigment represented by Formula 1 are each used within the above range, high luminance and contrast ratio may be expressed at a desired color coordinate.

(B) binder resin

The binder resin is a copolymer of the first ethylenically unsaturated monomer and the second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin including one or more acrylic repeating units.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxyl groups, and specific examples thereof may include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5 wt% to 50 wt%, such as 10 wt% to 40 wt%, based on the total amount of the binder resin.

The second ethylenically unsaturated monomer is an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethyl ether, etc .; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate and a vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; Vinyl cyanide compounds such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These etc. can be mentioned, These can be used individually or in mixture of 2 or more.

Specific examples of the binder resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer And methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc. are mentioned, It is not limited to these, These can also be used individually or in combination of 2 or more types.

The weight average molecular weight of the binder resin may be 3,000 g / mol to 150,000 g / mol, such as 5,000 g / mol to 50,000 g / mol, such as 20,000 g / mol to 30,000 g / mol. When the weight average molecular weight of binder resin is the said range, it is excellent in adhesiveness with a board | substrate, physical and chemical properties are good, and viscosity is appropriate.

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

The binder resin may be included in an amount of 1 wt% to 10 wt%, such as 1 wt% to 5 wt%, based on the total amount of the photosensitive resin composition. In the case where the binder resin is included in the above range, the developability and the crosslinkability of the color filter may be improved to obtain excellent surface smoothness.

(C) Photopolymerizable  Monomer

As the photopolymerizable monomer, a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, the photopolymerizable monomer may form a pattern having excellent heat resistance, light resistance, and chemical resistance by causing sufficient polymerization during exposure in the pattern forming process.

Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate and neopentyl glycol Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether Le (meth) acrylate, trimethylol propane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate, and the like.

Examples of commercially available products of the photopolymerizable monomer are as follows. Examples of the monofunctional ester of (meth) acrylic acid include Aronix M-101 ^® , M-111 ^® , M-114 ^®, and the like manufactured by Toagosei Kagaku Kogyo Co., Ltd .; Nihon Kayaku Co., Ltd. KAYARAD TC-110S ^® , TC-120S ^®, etc .; The V-158 ^® and V-2311 ^{® of} Osaka Yuki Chemical Co., Ltd. are mentioned. Examples of the difunctional ester of the (meth) acrylic acid include, but are not limited to, Aronix M-210 ^® , M-240 ^® , M-6200 ^®, etc. manufactured by Toagosei Chemical Industries, Ltd .; Nihon Kayaku Co., Ltd. KAYARAD HDDA ^® , HX-220 ^® , R-604 ^®, etc .; And V-260 ^® , V-312 ^® and V-335 HP ^{® from} Osaka Yuki Kagaku Kogyo Co., Ltd. Examples of the trifunctional ester of (meth) acrylic acid include Aronix M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , M-450 ^{® from} Toagosei Kagaku Kogyo Co., Ltd. -7100 ^® , M-8030 ^® , M-8060 ^®, etc .; Nihon Kayaku Co., Ltd., KAYARAD TMPTA ^® , DPCA-20 ^® , East-30 ^® , East-60 ^® , East-120 ^®, etc .; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. The above products can be used alone or in combination of two or more.

The photopolymerizable monomer may be used by treating with an acid anhydride in order to impart better developability.

The photopolymerizable monomer may be included in an amount of 5 wt% to 15 wt%, such as 5 wt% to 10 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included in the above range, it is excellent in pattern characteristics and developability when manufacturing a color filter.

(D) Photopolymerization Initiator

The photopolymerization initiator may be an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, or the like.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4 '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone etc. are mentioned.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal and the like.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s-triazine and 2- (3 ', 4'- Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-biphenyl 4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4-tri chloromethyl (Piperonyl) -6-triazine, 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine, etc. are mentioned.

Examples of the oxime compounds include O-acyl oxime compounds, 2- (O-benzoyl oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyl oxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. Can be used Specific examples of the O-acyl oxime compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane- 1-one, 1- (4-phenylsulfanylphenyl) -butane-1,2-dione-2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O-acetate, 1- (4-phenylsulfanylphenyl) -butane-1-one oxime- O-acetate can be used.

In addition to the compound, the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, or the like.

The photopolymerization initiator may be included in an amount of 0.1 wt% to 5 wt%, such as 0.5 wt% to 3 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included in the above range, the photopolymerization occurs sufficiently during exposure in the pattern forming process for manufacturing the color filter, so that the sensitivity is excellent and the transmittance is improved.

(E) solvent

The solvent is not particularly limited, and specific examples thereof include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl 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-n-butylkenone, methyl-n-amyl ketone and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate and butyl hydroxyacetate; Acetate alkoxyalkyl esters, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate and methyl 2-hydroxy-3-methylbutanoate; Or ketone acid esters such as ethyl pyruvate, and N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid Ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like, and these may be used alone or in combination of two or more thereof.

Considering miscibility and reactivity in the solvent, glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycols such as diethylene glycol monomethyl ether; Propylene glycol alkylether acetates such as propylene glycol monomethylether acetate and propylene glycol propylether acetate can be used.

The solvent may be included as a balance with respect to the total amount of the photosensitive resin composition, for example, may be included in 60% by weight to 80% by weight. When a solvent is contained in the said range, the applicability | paintability of the photosensitive resin composition is excellent, and the flatness excellent in the film | membrane of 3 micrometers or more in thickness can be maintained.

(F) other additives

The photosensitive resin composition may be used to prevent stains or spots upon application, to improve leveling performance, and to prevent generation of residues due to undeveloped malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; Additives, such as a radical polymerization initiator, may be further included.

In addition, the photosensitive resin composition may further include an additive such as an epoxy compound in order to improve adhesiveness with a substrate.

As an example of the said epoxy compound, a phenol novolak epoxy compound, a tetramethyl biphenyl epoxy compound, a bisphenol-A epoxy compound, an alicyclic epoxy compound, or a combination thereof is mentioned.

The content of the additive can be easily adjusted according to the desired physical properties.

Another embodiment provides a color filter manufactured using the photosensitive resin composition described above. The manufacturing method of the color filter is as follows.

On a glass substrate on which nothing is applied, or on a glass substrate on which a protective film of SiN _x is applied in a thickness of 500 kPa to 1500 kPa, the photosensitive resin composition for color filters described above may be applied using a suitable method such as spin coating or slit coating. And 1 micrometer-3 micrometers in thickness, respectively. After application, light is irradiated to form a pattern required for the color filter. After irradiating the light, the coating layer is treated with an alkaline developer, so that the unilluminated portion of the coating layer is dissolved and a pattern necessary for the color filter is formed. By repeating this process in accordance with the required number of R, G, and B colors, a color filter having a desired pattern can be obtained.

Further, in the above process, crack resistance, solvent resistance, and the like can be further improved by heating the image pattern obtained by development again or curing by active ray irradiation or the like.

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

( Single molecule  Compound preparation)

(Intermediate Synthesis Example  1: synthesis of intermediate A-1)

LC / MS: 333.56 m / z

3-aminophenol (10 mol) and 1-bromo-2-ethylhexane (20 mmol) were added to ethanol and refluxed for 24 hours. The solvent was removed under reduced pressure, ethyl acetate was added and the mixture was washed twice with water to extract an organic layer. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by Intermediate A-1.

(Intermediate Synthesis Example  2: synthesis of intermediate A-2)

LC / MS: 745.15 m / z

Formed by refluxing Intermediate A-1 (60 mmol), 3,4-dihydroxy-3-cyclobutyne-1,2-dione (30 mmol) in toluene (200 mL) and butanol (200 mL) The water is removed with a Dean-stark distillation unit. After stirring for 12 hours, the green reaction was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by Intermediate A-2.

( Synthesis Example  1: synthesis of formula 1-1)

Intermediate A-2 (10 mol) and phenylisocyanate (10 mol) are added to dichloromethane and catalytic amount of Bu ₂ Sn dilaurate is added. After stirring at 40 ° C. for 24 hours, the solvent was removed under reduced pressure and purified by column chromatography to obtain a compound represented by Chemical Formula 1-1.

Maldi-tof MS: 863.62 m / z

( Synthesis Example  2: synthesis of formula 1-2)

Except for using cyclohexyl isocyanate instead of phenyl isocyanate it was synthesized in the same manner as in Synthesis Example 1 to obtain a compound represented by the formula 1-2.

Maldi-tof MS: 869.66 m / z

( Synthesis Example  3: synthesis of formula 1-3)

Synthesis was carried out in the same manner as in Synthesis Example 1, except that isopropyl isocyanate was used instead of phenyl isocyanate to obtain a compound represented by Chemical Formula 1-3.

Maldi-tof MS: 829.63 m / z

( Synthesis Example  4: synthesis of formula 1-4)

Except for using 3- (Triethoxysilyl) propyl Isocyanate instead of Phenyl isocyanate was synthesized in the same manner as in Synthesis Example 1 to obtain a compound represented by the formula (1-4).

Maldi-tof MS: 991.70 m / z

( Synthesis Example  5: synthesis of formula 1-5)

Synthesis was carried out in the same manner as in Synthesis Example 1 except for using Methacryloyloxyethyl isocyanate instead of phenyl isocyanate to obtain a compound represented by Chemical Formula 1-5.

Maldi-tof MS: 899.64 m / z

( Synthesis Example  6: synthesis of formula 1-6)

Except for using Benzyl isocyanate instead of phenyl isocyanate it was synthesized in the same manner as in Synthesis Example 1 to obtain a compound represented by the formula (1-6).

Maldi-tof MS: 877.63 m / z

( Synthesis Example  7: synthesis of formula 1-7)

Except for using 1-Adamantyl Isocyanate instead of phenyl isocyanate synthesized in the same manner as in Synthesis Example 1 to obtain a compound represented by the formula (1-7).

Maldi-tof MS: 921.70 m / z

( Comparative Synthesis Example  1: synthesis of a compound represented by formula (C-1)

Into a 100 mL 3-neck flask, 398 mg of squariaic acid, N- (3-dibutylamino) phenylacetamide and 2.23 g of 3- (diethylamino) phenol were added, 40 mL of n-butanol and 20 mL of toluene were added, Heated to reflux for 5 hours. The DeanStark trap set was used to remove the water generated during the reaction and to promote the reaction. After the completion of the reaction, the mixture was cooled, extracted with methylene chloride, and then subjected to column chromatography to obtain a compound represented by Chemical Formula C-1 in 60% yield.

[Formula C-1]

Maldi-tof MS: 505.29 m / z

( Comparative Synthesis Example  2: synthesis of a compound represented by formula (C-2)

To 10.9 parts of 3-aminophenol, 19 parts by weight of triethoxysilane and 5 parts by weight of acetic acid were refluxed for 8 hours in 200 parts by weight of tetrahydrofuran. After the reaction was completed, tetrahydrofuran was distilled off to obtain a compound. 2.9 parts by weight of the obtained compound, 0.6 parts by weight of 3,4-dihydroxy-3-cyclobutene-1,2-dione, 90 parts by weight of 1-butanol and 60 parts by weight of toluene were mixed. The resulting mixture was stirred for 3 hours at 125 DEG C while removing the produced water using a Dean-Stark tube. After completion of the reaction, the solvent was distilled off, 15 parts by weight of acetic acid was added, and then 18% saline was added dropwise. The precipitated solid was filtered off. The solid taken by filtration was washed with hexane. The obtained solid was dried under reduced pressure and 3.4 weight part of compounds represented by following General formula (C-2) were obtained.

[Formula C-2]

LC-MS: 679.3 m / z

(Photosensitive resin composition production)

The specification of the component used for manufacture of the photosensitive resin composition is as follows.

(A) dye

(A-1) A compound prepared in Synthesis Example 1 (denoted by Chemical Formula 1-1)

(A-2) A compound prepared in Synthesis Example 2 (indicated by Chemical Formula 1-2)

(A-3) A compound prepared in Synthesis Example 3 (expressed as Chemical Formula 1-3)

(A-4) A compound prepared in Synthesis Example 4 (expressed by Chemical Formula 1-4)

(A-5) A compound prepared in Synthesis Example 5 (expressed by Chemical Formula 1-5)

(A-6) A compound prepared in Synthesis Example 6 (expressed by Chemical Formula 1-6)

(A-7) A compound prepared in Synthesis Example 7 (indicated by Chemical Formula 1-7)

(A-8) Compound prepared in Comparative Synthesis Example 1 (expressed as Chemical Formula C-1)

(A-9) Compound prepared in Comparative Synthesis Example 2 (expressed as Chemical Formula C-2)

(A ') Pigment Dispersion

(A'-1) C.I. Green Pigment 58

(A'-2) C.I. Green Pigment 36

(A'-3) C.I. Yellow Pigment 138

(B) binder resin

Methacrylic acid / benzyl methacrylate copolymer having a weight average molecular weight of 22,000 g / mol (mixed weight ratio 15wt% / 85wt%)

(C) Photopolymerizable  Monomer

Dipentaerythritol hexaacrylate

(D) Photopolymerization Initiator

(D-1) 1,2-octanedione

(D-2) 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one

(E) solvent

(E-1) cyclohexanone

(E-2) Propylene Glycol Methyl Ether Acetate

Example  1 to Example  7 and Comparative example  1 to Comparative example  4

Each component was mixed with the composition of Tables 1 to 3 to prepare a photosensitive resin composition. Specifically, after dissolving the photopolymerization initiator in a solvent, the mixture is stirred at room temperature for 2 hours, then added with a dye (or pigment dispersion) and stirred for 30 minutes, and then the binder resin and the photopolymerizable monomer are added thereto for room temperature for 2 hours. Stirred at. The solution was filtered three times to remove impurities to prepare a photosensitive resin composition.

(Unit: weight%) Example One 2 3 4 5 6 7 (A) dye A-1 5 - - - - - - A-2 - 5 - - - - - A-3 - - 5 - - - - A-4 - - - 5 - - - A-5 - - - - 5 - - A-6 - - - - - 5 - A-7 - - - - - - 5 A-8 - - - - - - - A-9 - - - - - - - (A ') pigment dispersion A'-1 - - - - - - - A'-2 - - - - - - - A'-3 15 15 15 15 15 15 15 (B) binder resin 3.5 3.5 3.5 3.5 3.5 3.5 3.5 (C) photopolymerizable monomer 8 8 8 8 8 8 8 (D) photoinitiator D-1 One One One One One One One D-2 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (E) solvent E-1 37 37 37 37 37 37 37 E-2 30 30 30 30 30 30 30 Total 100 100 100 100 100 100 100

(Unit: weight%) Comparative example One 2 3 4 (A) dye A-1 - - - - A-2 - - - - A-3 - - - - A-4 - - - - A-5 - - - - A-6 - - - - A-7 - - - - A-8 - - 5 - A-9 - - - 5 (A ') pigment dispersion A'-1 20 - - - A'-2 - 20 - - A'-3 15 15 15 15 (B) binder resin 2.5 2.5 3.5 3.5 (C) photopolymerizable monomer 5 5 8 8 (D) photoinitiator D-1 One One One One D-2 0.5 0.5 0.5 0.5 (E) solvent E-1 40 40 37 37 E-2 16 16 30 30 Total 100 100 100 100

(evaluation)

Luminance and Contrast Ratio Evaluation

The photosensitive resin composition prepared in Examples 1 to 7 and Comparative Examples 1 to 4 was coated on a glass substrate having a thickness of 1 mm degreased and washed, and then, on a hot plate at 90 ° C., Drying for minutes gave a coating. Subsequently, the coating film was exposed to light using a high pressure mercury lamp having a dominant wavelength of 365 nm, and then dried in a hot air circulation drying furnace at 200 ° C. for 5 minutes. The pixel layer was measured by using a spectrophotometer (MCPD3000, Otsuka electronic Co., Ltd.), color coordinates, brightness and contrast ratio, and the results are shown in Table 3 below.

Luminance Contrast Ratio Example 1 65.5 14300 Example 2 65.3 14500 Example 3 65.7 14200 Example 4 65.4 14700 Example 5 65.1 14400 Example 6 65.6 14300 Example 7 65.3 14500 Comparative Example 1 63.8 12500 Comparative Example 2 62.1 12200 Comparative Example 3 62.7 12700 Comparative Example 4 62. 5 12400

From Table 3, Examples 1 to 7 including the compound according to the embodiment, compared with the case of Comparative Examples 1 to 4 not containing the compound, it was confirmed that the brightness and contrast ratio is excellent Can be.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (17)

Compound represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R ¹ is a substituent represented by the following formula (2), R ² to R ⁴ is a hydrogen atom,
[Formula 2]

In Chemical Formula 2,
L ¹ is a single bond or a C1 to C10 alkylene group,
R ¹³ is a C1 to C20 alkyl group, a C3 to C20 cycloalkyl group, a C6 to C20 aryl group, an acrylate group, a silane group or a C10 to C20 adamantyl (ADAMANTYL) group,
R ⁵ is a hydroxy group, R ⁶ to R ⁸ are a hydrogen atom,
R ⁹ to R ¹² are each independently a C1 to C20 alkyl group.
delete delete The method of claim 1,
The acrylate group is a compound represented by the following formula (3):
[Formula 3]

In Chemical Formula 3,
R ¹⁴ is a hydrogen atom or a C1 to C10 alkyl group.
The method of claim 1,
The silane group is a compound represented by the following formula (4):
[Formula 4]

In Chemical Formula 4,
R ¹⁵ to R ¹⁷ are each independently a C1 to C10 alkyl group.
delete The method of claim 1,
Compound represented by Formula 1 is a compound represented by the following formula (5):
[Formula 5]

In Chemical Formula 5,
L ¹ is a single bond or a C1 to C10 alkylene group,
R ⁹ to R ¹² are each independently a C1 to C20 alkyl group,
R ¹⁸ is represented by any one of the following Formulas 5-1 to 5-7,
[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

[Formula 5-7]

In Chemical Formulas 5-1 to 5-4 and 5-6,
R ¹⁹ is hydrogen,
R ²⁰ to R ²² are each independently a C1 to C8 alkyl group,
p1 is an integer of 0-5.

The method of claim 1,
Compound represented by Formula 1 is a compound represented by any one selected from the group consisting of Formula 1-1 to Formula 1-7.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

The photosensitive resin composition containing the compound of any one of Claims 1, 4, 5, 7, and 8.
The method of claim 9,
The compound is a photosensitive resin composition.
The method of claim 10,
The dye is a photosensitive resin composition is a green dye.
The method of claim 9,
The photosensitive resin composition further comprises a binder resin, a photopolymerizable monomer, a photopolymerization initiator and a solvent.
The method of claim 12,
The photosensitive resin composition further comprises a pigment.
The method of claim 13,
The pigment is a photosensitive resin composition containing 10 to 20% by weight based on the total amount of the photosensitive resin composition.
The method of claim 12,
The said photosensitive resin composition is with respect to the photosensitive resin composition total amount,
1 wt% to 10 wt% of the compound;
1 wt% to 10 wt% of the binder resin;
5 wt% to 15 wt% of the photopolymerizable monomer;
0.1 wt% to 5 wt% of the photopolymerization initiator; And
Residual solvent amount
Photosensitive resin composition comprising a.
The method of claim 12,
The photosensitive resin composition may further include a silane coupling agent, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof, including malonic acid, 3-amino-1,2-propanediol, a vinyl group, or a (meth) acryloxy group. Photosensitive resin composition containing.
The color filter manufactured using the photosensitive resin composition of Claim 9.