KR20200024023A - Diketopyrrolopyrrole Derivatives and Dye Comprising the Same - Google Patents

Abstract

The present invention relates to a diketopyrrolopyrrole derivative in which a benzophenone group substituted with hydroxy is introduced and a dye comprising the same. The diketopyrrolopyrrole derivative of the present invention suppresses change of the absorption spectrum to have a short wavelength, has excellent contrast ratio when applied to a color filter, and has excellent light resistance.

Description

Diketopyrrolopyrrole Derivatives and Dye Comprising the Same}

The present invention relates to a diketopyrrolopyrrole derivative and a dye comprising the same, and more particularly to a diketopyrrolopyrrole derivative introduced with a benzophenone group substituted with hydroxy and a dye comprising the same.

Color filters are widely used in imaging devices, liquid crystal display devices, and the like, and their application ranges are rapidly expanding. The color filter is usually heated and dried (hereinafter preliminarily baked) after uniformly applying a colored photosensitive resin composition containing a colorant corresponding to each color of red, green and blue on a substrate on which a black matrix is patterned by spin coating. It is manufactured by exposing and developing the coating film formed), and performing heat-hardening (it may also be called post-baking) further for each color, and forming the pixel of each color as needed.

Recently, the market demand for high quality display with high color reproduction is increasing. Accordingly, the content of the coloring material of the colored photosensitive resin composition used for manufacturing the color filter is continuously increasing. In the case of the coloring photosensitive resin composition for producing a red pixel, C.I. which has diketopyrrolopyrrole as a chromophore as a colorant. Pigment Red 254 is widely used because of its excellent brightness and excellent light resistance.

However, C.I. Pigment Red 254, when used as a pigment, has the disadvantage of causing light reflection and light scattering on the particle surface, resulting in a decrease in contrast ratio (CR) (see Republic of Korea Patent No. 10-1737001). C.I. Pigment Red 254 may be dissolved in N-methyl-2-pyrrolidone (NMP) and dyeed, but when dyeed, absorption spectrum is shortened and light resistance is inferior to pigments.

Accordingly, shortening of the spectrum is suppressed, and development of a red dye having excellent contrast ratio and excellent light resistance when applied to a color filter is required.

Republic of Korea Patent No. 10-1737001

One object of the present invention is to provide a diketopyrrolopyrrole derivative which is suppressed from shortening the spectrum, excellent contrast ratio and excellent light resistance when applied to a color filter.

Another object of the present invention is to provide a dye comprising the diketopyrrolopyrrole derivative.

Still another object of the present invention is to provide a colored photosensitive resin composition comprising the diketopyrrolopyrrole derivative.

On the other hand, the present invention provides a diketopyrrolopyrrole derivative represented by the following formula (1).

[Formula 1]

In the above formula,

A ¹ and A ² are each independently hydrogen or hydroxy, provided that at least one of A ¹ and A ² is hydroxy,

R ¹ are each independently a haloalkyl group or a cyano alkyl group of _{C 1 -C 6, C 1 -C} 6,

R ² are each independently halo, or cyano group of the alkyl group of _{C 1 -C 6, C 1 -C} 6,

n is an integer from 1 to 4,

m is an integer of 0-3.

In one embodiment of the present invention, the diketopyrrolopyrrole derivative represented by Formula 1 is A ¹ is hydroxy, A ² is hydrogen,

R ¹ are each independently a haloalkyl group or a cyano alkyl group of _{C 1 -C 6, C 1 -C} 6,

R ² are each independently halo, or cyano group of the alkyl group of _{C 1 -C 6, C 1 -C} 6,

n is an integer from 1 to 4,

m may be a compound of zero.

In one embodiment of the present invention, the diketopyrrolopyrrole derivative may be one of the compounds of formula 2 to 4.

[Formula 2]

[Formula 3]

[Formula 4]

On the other hand, the present invention provides a dye comprising a diketopyrrolopyrrole derivative.

On the other hand, the present invention provides a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the colorant comprises the diketopyrrolopyrrole derivative. .

In one embodiment of the present invention, the diketopyrrolopyrrole derivative may be included in an amount of 0.01 to 50% by weight based on 100% by weight of the total color photosensitive resin composition.

On the other hand, this invention provides the color filter formed using the said coloring photosensitive resin composition.

On the other hand, the present invention provides an image display device characterized in that the color filter is provided.

The diketopyrrolopyrrole derivative according to the present invention has a structure in which a benzophenone group substituted with hydroxy is introduced, and the absorption spectrum is suppressed from being shortened, and when applied to a color filter, it is excellent in contrast ratio and excellent light resistance.

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

One embodiment of the present invention relates to a diketopyrrolopyrrole derivative represented by the following formula (1).

[Formula 1]

In the above formula,

A ¹ and A ² are each independently hydrogen or hydroxy, provided that at least one of A ¹ and A ² is hydroxy,

R ¹ are each independently a haloalkyl group or a cyano alkyl group of _{C 1 -C 6, C 1 -C} 6,

R ² are each independently halo, or cyano group of the alkyl group of _{C 1 -C 6, C 1 -C} 6,

n is an integer from 1 to 4,

m is an integer of 0-3.

As used herein, an alkyl group of C ₁ -C _{6 means} a straight or branched monovalent hydrocarbon having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, i-propyl, n-butyl , i-butyl, t-butyl, n-pentyl, n-hexyl, and the like.

As used herein, a C ₁ -C ₆ haloalkyl group refers to a straight or branched hydrocarbon of 1 to 6 carbon atoms substituted with one or more halogens selected from the group consisting of fluorine, chlorine, bromine and iodine, for example Trifluoromethyl, trichloromethyl, trifluoroethyl, and the like, but are not limited thereto.

In one embodiment of the present invention, the diketopyrrolopyrrole derivative represented by Formula 1 is A ¹ is hydroxy, A ² is hydrogen,

R ¹ are each independently a haloalkyl group or a cyano alkyl group of _{C 1 -C 6, C 1 -C} 6,

R ² are each independently halo, or cyano group of the alkyl group of _{C 1 -C 6, C 1 -C} 6,

n is an integer from 1 to 4,

m may be a compound of zero.

Representative compounds of the diketopyrrolopyrrole derivatives of the present invention may be one of the compounds of formulas (2) to (4).

[Formula 2]

[Formula 3]

[Formula 4]

The preparation method of the diketopyrrolopyrrole derivative of the present invention is shown in Scheme 1 below. The methods described in the following reaction schemes are merely representative of the methods used, and reaction reagents, reaction conditions, and the like may be changed as needed.

Scheme 1

As shown in Scheme 1, the diketopyrrolopyrrole derivative of the present invention is a compound of formula (5) and the compound of formula (6) in the presence of a catalyst Friedel-Crafts Acylation to obtain a compound of formula (7) The compound of formula 7 can then be prepared by reacting with dimethyl succinate in the presence of a base.

Catalysts used for the Friedel-Craft acylation reactions include Lewis acid catalysts such as FeCl ₃ , AlCl ₃ , SnCl ₄ , ZnCl ₂ , TiCl ₄ , SbCl ₅ , BF ₃ , BiCl ₃ , trifluoromethanesulfonic acid, graphite, etc. May be used, in particular AlCl ₃ may be used.

The Friedel-Craft acylation reaction can be carried out in a solvent or in the absence of a solvent. The solvent may be used without limitation as long as it is an inert solvent under reaction conditions. For example, 1,2-dichloroethane, methylene chloride, chlorobenzene, dichlorobenzene, nitrobenzene, and the like may be used. These solvent can be used individually or in mixture of 2 or more types.

The Friedel-Craft acylation reaction may be carried out at a reaction temperature of -78 to 200 ℃, preferably 0 to 100 ℃.

The base may be an alkali metal or alkaline earth metal alkoxide such as sodium methoxide, sodium t-butoxide, potassium t-butoxide, and the like.

The diketopyrrolopyrrole derivative according to the present invention is suppressed from shortening the absorption spectrum by the carbonyl group in the benzophenone group, and the light resistance is improved by the hydroxy group. Accordingly, the diketopyrrolopyrrole derivatives according to the present invention are useful as dyes, especially dyes used in color filters of display devices such as liquid crystal display devices. In addition, there is an advantage that the contrast ratio is excellent when applied as a dye in the color filter.

Accordingly, one embodiment of the present invention relates to a dye comprising the diketopyrrolopyrrole derivative according to the present invention.

Moreover, one Embodiment of this invention is a coloring photosensitive resin composition containing a coloring agent, alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, The coloring photosensitive resin in which the said coloring agent contains the diketopyrrolopyrrole derivative which concerns on this invention. It relates to a composition.

Hereinafter, the coloring photosensitive resin composition which concerns on one Embodiment of this invention is demonstrated in detail for each component.

Colorant (A)

In one embodiment of the invention, the colorant (A) may comprise a dye (a1) and, if necessary, a pigment (a2).

dyes( a1 )

The dye (a1) includes a diketopyrrolopyrrole derivative represented by the following formula (1).

[Formula 1]

In the above formula,

A ¹ and A ² are each independently hydrogen or hydroxy, provided that at least one of A ¹ and A ² is hydroxy,

R ¹ are each independently a haloalkyl group or a cyano alkyl group of _{C 1 -C 6, C 1 -C} 6,

R ² are each independently halo, or cyano group of the alkyl group of _{C 1 -C 6, C 1 -C} 6,

n is an integer from 1 to 4,

m is an integer of 0-3.

The diketopyrrolopyrrole derivative represented by Formula 1 may be included in an amount of 0.01 to 50% by weight based on 100% by weight of the total color photosensitive resin composition. If the diketopyrrolopyrrole derivative represented by the formula (1) is included in an amount of less than 0.01% by weight may not be obtained the color of the desired concentration, if it is included in an amount of more than 50% by weight precipitation may occur.

In one embodiment of the present invention, the dye (a1) may further comprise another dye in addition to the diketopyrrolopyrrole derivative represented by the formula (1).

The dye can be used without limitation so long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility in solvents, solvent resistance and stability over time.

The dye may be selected from acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof, and azo, xanthene, and phthalocyanines. Acidic dyes of the systems and derivatives thereof can also be selected. Preferably, the dye may be a compound classified as a dye in the color index (Published by The Society of Dyers and Colourists), or a known dye described in a dye note (color dyed yarn).

Specific examples of the dye include C.I. As solvent dyes,

C.I. Red dyes such as solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;

C.I. Blue dyes such as solvent blue 5, 35, 36, 37, 44, 45, 59, 67, 70 and the like;

C.I. Violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49 and the like;

C.I. Yellow dyes such as solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 56

C.I. Green dyes, such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. are mentioned.

C.I. exemplified above. C.I. excellent solubility in organic solvents in solvent dyes. Solvent yellow 14, 16, 21, 56, 79, 93, 151; C.I. Solvent red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent orange 41, 45, 62; C.I. Solvent blue 35, 36, 44, 45, 70; C.I. Solvent violet 13 is preferred, and C.I. Solvent yellow 21, 79; C.I. Solvent red 8, 122, 132; C.I. Solvent orange 45, 62 is more preferable.

In addition, C.I. As an acid dye,

C.I. Acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, Red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426;

C.I. Acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, Yellow dyes such as 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251

C.I. Orange dyes such as acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173

C.I. Acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, Blue dyes such as 335 and 340;

C.I. Violet dyes such as acid violet 6B, 7, 9, 17, 19, 66, etc.

C.I. And green dyes such as acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109.

The solubility in organic solvents in the C.I.acid dyes exemplified above is excellent in C.I. Acid yellow 42; C.I. Acid red 92; C.I. Acid blue 80, 90; C.I. Acid violet 66; C.I. Acid green 27 is preferred.

See also C.I. As a direct dye,

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, Red dyes such as 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250;

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, Yellow dyes such as 136, 138, and 141;

C.I. Orange dyes such as direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, Blue dyes such as 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293 and the like;

C.I. Violet dyes such as direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and the like;

C.I. Green dyes, such as direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. are mentioned.

See also C.I. As a modanto dye,

C.I. Yellow dyes such as modanto yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 Red dyes such as, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95 and the like;

C.I. Orange dyes such as Modanto Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc. ;

C.I. Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 Blue dyes such as, 44, 48, 49, 53, 61, 74, 77, 83, 84 and the like;

C.I. Violet dyes such as modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58;

C.I. Green dyes, such as modanto green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. are mentioned.

The said dye can be used individually or in combination of 2 or more types, respectively.

Pigments a2 )

The pigment (a2) may be used an organic pigment or an inorganic pigment generally used in the art.

As the organic pigment or the inorganic pigment, various pigments used in printing ink, inkjet ink, etc. may be used, and specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, and isoindolinone pigments. , Isoindolin pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinoneyl pigments, anthrapyrimidine pigments, ananthronerone pigments, indanthrone pigments, pravantron Pigments, pyranthrone pigments, diketopyrrolopyrrole pigments and the like.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specific examples include oxides or composite metals of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. Oxide, carbon black, and the like.

In particular, the organic pigments and inorganic pigments include compounds that are specifically classified as pigments in the Color Index (Published by The Society of Dyers and Colourists), and more specifically, the following color index (CI) numbers Although a pigment is mentioned, It is not necessarily limited to these.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185;

C.I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;

C.I. Pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C.I. Pigment blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64, and 76;

C.I. Pigment green 7, 10, 15, 25, 36, 47, 58, 59, 62 and 63;

CI Pigment Brown 28;

C.I Pigment Black 1 and 7 etc.

These pigments can be used individually or in combination of 2 or more types, respectively.

C.I. exemplified above. Among pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. Pigments selected from Pigment Green 58 may be preferably used.

It is preferable to use the said pigment as a pigment dispersion liquid in which the particle diameter of a pigment was disperse | distributed uniformly. Examples of the method for uniformly dispersing the particle diameter of the pigment include a method of containing a pigment dispersant and dispersing the same, and according to the above method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

Pigment dispersants ( a3 )

The pigment dispersant (a3) is added to maintain the deagglomeration and stability of the pigment, specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, etc. These can be used individually or in combination of 2 or more types, respectively.

It is also preferable to include an acrylate dispersant (hereinafter also referred to as an acrylic dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Commercially available products of the acrylate dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and the like. The acrylate dispersants may be used alone or in combination of two or more kinds. Can be.

The pigment dispersant may be a pigment dispersant of a resin type other than the acrylic dispersant described above. Such other resin type pigment dispersants include (partially) known pigment type dispersants, in particular polycarboxylic acid esters, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids represented by polyurethanes, polyacrylates. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free ) Oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with a poly (lower alkyleneimine); Water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, phosphate esters, and the like. As a commercial item of the above-mentioned resin type dispersing agent, it is a cationic resin dispersing agent, for example, brand names of BYK (BIC) company: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK- 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF brand name: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Kawaken Fine Chemical's trade names: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Trade names of Ajinomoto Co., Ltd .: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; The brand names of Kyoeisha Chemical Co., Ltd .: FLORENE DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44, etc. are mentioned. In addition to the acrylic dispersant described above, pigment dispersants of other resin types may be used alone or in combination of two or more thereof, or may be used in combination with an acrylic dispersant.

The content of the pigment dispersant (a3) is 5 to 60 parts by weight, preferably 15 to 50 parts by weight based on 100 parts by weight of solids of the pigment (a2). When the content of the pigment dispersant (a3) exceeds 60 parts by weight, the viscosity may be increased. When the amount of the pigment dispersant (a3) is less than 5 parts by weight, atomization of the pigment may be difficult or may cause problems such as gelation after dispersion.

Solid content in the present invention means the remaining components except the solvent.

Alkali-soluble resin (B)

In one embodiment of the present invention, the alkali-soluble resin (B) is copolymerized by using an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to have solubility in an alkaline developer used in the development step of forming a pattern. It can manufacture.

Specific examples of the ethylenically unsaturated monomer having the carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; Anhydrides of dicarboxylic acids; Mono (meth) acrylates of the polymer which has a carboxyl group and a hydroxyl group in both terminal, such as (omega) -carboxypolycaprolactone mono (meth) acrylate, etc. are mentioned, Acrylic acid and methacrylic acid are preferable.

A hydroxyl group can be given to the said alkali-soluble resin in order to ensure further developability. As a method for imparting the hydroxyl group, a method of copolymerizing and preparing an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group, and adding a compound having a glycidyl group to a copolymer of an ethylenically unsaturated monomer having a carboxyl group And a method of producing by reacting a compound having a glycidyl group with a copolymer of an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group.

Specific examples of the ethylenically unsaturated monomer having the hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy- 3-phenoxypropyl (meth) acrylate, N-hydroxyethyl acrylamide, etc., Among these, 2-hydroxyethyl (meth) acrylate is preferable, The ethylenically unsaturated monomer which has the said hydroxyl group is 2 or more types Can be used in combination.

Specific examples of the compound having a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, Ethylglycidyl ether, glycidyl isopropyl ether, t-butylglycidyl ether, benzylglycidyl ether, glycidyl 4-t-butylbenzoate, glycidyl stearate, allyl glycidyl ether, Glycidyl ester of methacrylic acid, etc., Preferably, butyl glycidyl ether, allyl glycidyl ether, and methacrylic acid glycidyl ester are mentioned, The compound which has the said glycidyl group can be used in combination of 2 or more type. Can be.

The unsaturated monomers copolymerizable in the preparation of the alkali-soluble resin are exemplified below, but are not necessarily limited thereto.

Specific examples of the polymerization monomer having a copolymerizable unsaturated bond include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, and o-vinylbenzyl. Aromatic vinyl compounds such as methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, 2- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; And

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. Unsaturated oxetane compounds and the like.

The monomers exemplified above may be used alone or in combination of two or more thereof.

It is preferable that the said alkali-soluble resin has an acid value of 30-150 mgKOH / g. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, the development speed of the coloring photosensitive resin composition is slow, and when it exceeds 150 mgKOH / g, the adhesion to the substrate is reduced, the pattern short-circuit is likely to occur and compatibility with the dye A problem arises and dye in a colored photosensitive resin composition precipitates or storage stability falls, and a viscosity rises easily.

Photopolymerizable  Compound (C)

In one embodiment of the present invention, the photopolymerizable compound (C) is a compound which can be polymerized by the action of the photopolymerization initiator (D), and is a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, or a trifunctional or higher polyfunctional photopolymerizable compound. A compound etc. are mentioned, It is not limited to this.

The monofunctional photopolymerizable compound is, for example, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N- Vinylpyrrolidone, and the like, and commercially available products include Aronix M-101 (Doagosei), KAYARAD TC-110S (Nipbon Kayaku), or Biscot 158 (Osaka Yuki Kagaku High School).

The bifunctional photopolymerizable compound is, for example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like, and the like, and commercially available products include Aronix M-210, M-1100, and M-1200 ( Toagosei), KAYARAD HDDA (Nippon Kayaku), Biscotti 260 (Osaka Yuki Kagaku High School), AH-600, AT-600 or UA-306H (Kyoeisha Kagakusa).

Examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylolpropane tri (meth) acryl. Rate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxyl Graded dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are commercially available products such as Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku).

The photopolymerizable compound may be included in an amount of 3 to 35 wt% based on 100 wt% of the colored photosensitive resin composition of the present invention. When the photopolymerizable compound is included in the above range, optical properties and mechanical properties may be satisfied at the same time.

Photopolymerization Initiator (D)

In one embodiment of the present invention, the photopolymerization initiator (D) can be used without particular limitation as long as it can polymerize the photopolymerizable compound (C). In particular, the photopolymerization initiator (D) is an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound and the like from the viewpoint of polymerization characteristics, start efficiency, absorption wavelength, availability, and price. It is preferable to use at least one compound selected from the group consisting of thioxanthone compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1 -One, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

As said benzophenone type compound, for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4 And a biimidazole compound in which a phenyl group at a 4,4 ', 5,5' position is substituted by a carboalkoxy group, or the like. have. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole are preferred Used.

Specific examples of the oxime-based compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and OXE01 and OXE02 manufactured by BASF Corporation are typical examples of commercial products.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. There is this.

Moreover, the said photoinitiator (D) can be used together with a photoinitiation start adjuvant (d1) in order to improve the sensitivity of the coloring photosensitive resin composition of this invention. Since the coloring photosensitive resin composition which concerns on one Embodiment of this invention contains a photoinitiation adjuvant (d1), a sensitivity becomes further high and productivity can be improved.

As the photopolymerization initiation assistant (d1), for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group can be preferably used.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyl diethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethyl. Aminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (di Aromatic amine compounds, such as ethylamino) benzophenone, can be used, It is preferable to use an aromatic amine compound especially.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

Specific examples of the organic sulfur compound having the thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto Butyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) and the like Can be.

The photopolymerization initiator (D) may be included in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C) based on the solid content. When the said photoinitiator (D) is contained in the said range, since the coloring photosensitive resin composition becomes high sensitivity and an exposure time is shortened, since productivity is improved and high resolution can be maintained, it is preferable. In addition, the intensity of the pixel portion formed using the composition under the above-described conditions and smoothness on the surface of the pixel portion can be improved.

In addition, when using the said photoinitiator (d1) further, the said photoinitiator (d1) is 0.1-40 weight part with respect to 100 weight part of total amounts of alkali-soluble resin (B) and a photopolymerizable compound (C), Preferably Preferably 1 to 30 parts by weight. When the amount of the photopolymerization initiation assistant (d1) is in the above range, the sensitivity of the colored photosensitive resin composition may be higher, and productivity of the color filter formed using the composition may be improved.

Solvent (E)

In one embodiment of the present invention, the solvent may be used without particular limitation as long as it is effective in dissolving the other components included in the colored photosensitive resin composition of the present invention, and especially in the ether. And aromatic hydrocarbons, ketones, alcohols, esters or amides are preferred.

Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, and methoxy pentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters, such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; And cyclic esters such as γ-butyrolactone.

Among the solvents, it is more preferable to use an organic solvent having a boiling point of 100 ° C. to 200 ° C. in terms of applicability and dryness, and examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and 3 Ethyl ethoxy propionate, methyl 3-methoxypropionate, and the like.

The solvents exemplified above may be used alone or in combination of two or more thereof, and may be included in an amount of 30 to 95% by weight, preferably 40 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. When the solvent is in the range of 30 to 95% by weight, applicability becomes good when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. Provide effect.

In addition, the colored photosensitive resin composition may further include an additive as necessary.

Additive (F)

The colored photosensitive resin composition of this invention can use together additives, such as another high molecular compound, a hardening | curing agent, surfactant, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, as needed.

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be mentioned.

The curing agent is used to increase the core hardening and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds and the like.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, other aromatic epoxy resin, alicyclic epoxy Resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, aliphatic, cycloaliphatic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, isoprene (Co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, etc. are mentioned.

Specific examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane and the like.

The hardeners illustrated above can be used individually or in mixture of 2 or more types.

The said hardening | curing agent can use together the hardening | curing auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent. Examples of the curing aid compound include polyhydric carboxylic acids, polyhydric carboxylic anhydrides, and acid generators. As said polyhydric carboxylic acid anhydride, what is marketed can be used as an epoxy resin hardening | curing agent. As a specific example of the said epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) (New Nippon Ewha Co., Ltd.) etc. are mentioned.

The surfactant may be used to further improve the film formability of the colored photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant may be preferably used.

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. of Dow Corning Toray Silicone Co., Ltd. And TSF-4452. Examples of the fluorine-based surfactant include Megapieces F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink & Chemicals Co., Ltd. as commercially available products. Surfactant illustrated above can be used individually or in combination of 2 types or more, respectively.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimeth Oxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoter exemplified above can be used individually or in combination of 2 or more types, respectively. The adhesion promoter may be included in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on 100% by weight of the total solids in the colored photosensitive resin composition.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol and the like.

Specific examples of the ultraviolet absorber include 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like.

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The colored photosensitive resin composition according to the present invention may be widely used to form a color filter, a black matrix, a black column spacer, a color sensor (CS), a color image sensor (CIS), and the like.

Therefore, one Embodiment of this invention relates to the color filter formed using the coloring photosensitive resin composition mentioned above. The color filter according to one embodiment of the present invention can be produced by applying the above-described colored photosensitive resin composition on a substrate and exposing and developing in a predetermined pattern to form a colored layer.

Hereinafter, the pattern formation method using the coloring photosensitive resin composition of this invention is demonstrated in detail.

The method of forming a pattern using the colored photosensitive resin composition of the present invention may be a method known in the art, but is usually a coating step; An exposure step; And a removing step. The coloring photosensitive resin composition of this invention is apply | coated on a base material, and it can be used as a coloring pixel (color image) by photocuring and developing and forming a pattern.

Specifically, using a suitable method such as spin coating, slit coating, or the like on a glass substrate on which the colored photosensitive resin composition is not coated, or a glass substrate on which a SiNx (protective film) is coated at a thickness of 500 to 1,500 kPa, Apply to a thickness of 3.4 μm. After application, light is irradiated to form a pattern necessary for the color filter. After irradiating the light, the coating layer is treated with an alkali developer to dissolve the unilluminated portion of the coating layer to form a pattern necessary for the color filter. By repeating this process according to the required number of R, G and B colors, a color filter having a desired pattern can be obtained. 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.

One embodiment of the present invention relates to an image display device provided with the above-described color filter.

The color filter of the present invention displays not only a conventional liquid crystal display (LCD) but also various image displays such as an electroluminescent display (EL), a plasma display (PDP), a field emission display (FED), and an organic light emitting diode (OLED). Applicable to the device.

The image display apparatus of the present invention includes a configuration known in the art, except that the above-described color filter is provided.

An image display apparatus according to an embodiment of the present invention includes a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles in addition to the color filter described above. A color filter may be further provided. In such a case, the emission light of the light source applied to the image display device is not particularly limited, but in view of better color reproducibility, preferably a light source emitting blue light can be used.

The image display apparatus according to the exemplary embodiment of the present invention may further include a color filter including only a pattern layer of two colors among the red pattern layer, the green pattern layer, and the blue pattern layer in addition to the color filter described above. In such a case, the color filter further includes a transparent pattern layer containing no quantum dot particles. When only the pattern layer of 2 colors is provided, the light source which emits the light of the wavelength which shows the remaining color which is not included can be used. For example, when only the red pattern layer and the green pattern layer are included, a light source that emits blue light can be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer shows blue light through the blue light as it is.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. These examples and experimental examples are only for illustrating the present invention, it is apparent to those skilled in the art that the scope of the present invention is not limited thereto.

Production Example  1: Preparation of Compound of Formula 2

Put 100 mL of methylene chloride as solvent in the reactor, dissolve the aluminum chloride (4.67g. 3.5mol) and then 4-tertbutylanisole (164g, 1.0mol) and 4-cyanobenzoyl chloride while cooling to 0 ℃. (248g, 1.5mol) was added, mixed and raised to room temperature, and then reacted for 10 hours to obtain 247g (yield: 84%) of an intermediate compound.

247 g of the intermediate compound, 218.6 g of dimethyl succinate and 286.0 g of sodium t-butoxide were charged to the reactor, heated to 100 ° C. within 60 minutes under stirring and nitrogen flow, and then maintained at 99-100 ° C. for 3 hours. And heated to 120 ° C. within 30 minutes and then held at 120 ° C. for 30 minutes. The reaction was cooled to 50 ° C. to yield 324 g of compound of formula 2 (yield 90%).

¹ H NMR (300 MHz, CDCl ₃ ) δ 1.34 (18H, m), 6.75 (2H, d), 7.30 (2H, d), 7.40 (4H, d), 7.56 (2H, d), 7.65 (4H, d)

Production Example  2: Preparation of Compound of Formula 3

280 g (yield 84%) of the compound of Formula 3 was obtained in the same manner as in Preparation Example 1, except that 4-cyanoanisole was used instead of 4-tertbutylanisole.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.01 (2H, d), 7.40 (4H, d), 7.53 (2H, d), 7.65 (4H, d), 7.78 (2H, d)

Production Example  3: Preparation of Compound of Formula 4

312 g (yield 91%) of the compound of Formula 4 was obtained by the same method as Preparation Example 1, except that 4-trifluoromethylanisole was used instead of 4-tertbutylanisole.

¹ H NMR (300 MHz, CDCl ₃ ) δ 6.75 (2H, d), 7.40 (4H, d), 7.47 (2H, d), 7.65 (4H, d), 7.72 (2H, d)

Comparative Production Example  1: Preparation of Compound of Formula a

[Formula a]

Except using 4-tertbutylbenzene instead of 4-tertbutylanisole, 287 g of a compound of formula a was obtained in the same manner as in Preparation Example 1 (yield: 85%).

¹ H NMR (300 MHz, CDCl ₃ ) δ 1.34 (18H, m), 7.28 (2H, d), 7.50 (2H, d), 7.47 (2H, d), 7.65 (4H, d), 7.72 (2H, d)

Production Example  4: Preparation of Pigment Dispersion

As a pigment, C.I. Pigment Red 254 40 parts by weight, 24 parts by weight of BYK2001 (Dispervic: BYK Co., Ltd., 45.1% by weight of solid content) as a dispersant (about 10.8 parts by weight in terms of solid content) and 136 parts by weight of propylene glycol methyl ether acetate as a solvent The mixed liquid containing part was mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion.

Synthesis Example  1: Synthesis of Alkali Soluble Resin

120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 13.0 parts by weight of acrylic acid, benzyl meta to a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot and a nitrogen introduction tube. 10 parts by weight of acrylate, 57.0 parts by weight of styrene, 20 parts by weight of methyl methacrylate and 3 parts by weight of n-dodecylmercaptan were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 110 ° C. and reacted for 6 hours. The solid acid value of the alkali-soluble resin thus synthesized was 100.2 mgKOH / g, and the weight average molecular weight (Mw) measured by GPC was about 15,110.

Example  1 to 3 and Comparative example  1 to 2: Preparation of colored photosensitive resin composition

Each component was mixed with the composition of Table 1 to prepare a colored photosensitive resin composition (unit: wt%).

Example Comparative example One 2 3 One 2 coloring agent Compound of formula (2) 30 - - - - Compound of formula 3 - 30 - - - Compound of formula 4 - - 30 - - Pigment Red 254 - - - 30 - Compound of formula 5 - - - - 30 Alkali-soluble resins ^{1 )} 10 10 10 10 10 Photopolymerizable compound ^{2 )} 7.0 7.0 7.0 7.0 7.0 Photopolymerization initiator ^{3 )} 0.5 0.5 0.5 0.5 0.5 Solvent ^{4 )} 52.5 52.5 52.5 52.5 52.5

1) Alkali-soluble resin of Synthesis Example 1

2) KAYARAD DPHA

3) OXE-01 (BASF)

4) Propylene Glycol Monomethyl Ether Acetate

Experimental Example  One:

Solubility, maximum absorption wavelength, and light resistance were measured using the colored photosensitive resin compositions prepared in Examples and Comparative Examples as follows. The measurement results are shown in Table 2 below.

(1) solubility

Whether or not a colorant precipitated during the production of the colored photosensitive resin composition was evaluated according to the following evaluation criteria.

<Evaluation Criteria>

(Circle): Precipitation of a coloring agent does not generate | occur | produce.

×: precipitation of colorant occurs

(2) Maximum absorption wavelength

After dissolving each dye in propylene glycol monomethyl ether acetate, it was left for 30 minutes at 25 ℃ and the maximum absorption wavelength was measured using a UV-2550 (SHIMADZU) equipment.

(4) Light resistance

The colored photosensitive resin composition was applied onto a glass substrate ("EAGLE XG", manufactured by Corning Incorporated, Inc.), each having a length and width of 2 inches by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C for 3 minutes to form a thin film. Thereafter, the entire surface was exposed to an exposure condition of 50 mJ / cm 2 using an exposure machine (Ushio, HB-50110AA), and post-baking was performed at 230 ° C. for 30 minutes under an oven condition to complete the thin film specimen preparation.

For light resistance measurement, the thin film specimen was exposed to xenon lamp (0.68W intensity) at 60 ° C. for 2 hours, and then color coordinates were measured using MCPD 3000 equipment. As a standard, light resistance was evaluated in terms of del (E *) value.

Example Comparative example One 2 3 One 2 Solubility ○ ○ ○ × ○ Absorption wavelength 477 485 488 - 467 Light resistance 1.85 1.77 1.86 - 11.5

As shown in Table 2, the diketopyrrolopyrrole derivatives included in the colored photosensitive resin compositions of Examples 1 to 3 according to the present invention are excellent in solubility, short-wavelength absorption spectrum is suppressed as well as excellent light resistance It was confirmed. On the other hand, the diketopyrrolopyrrole derivatives contained in the colored photosensitive resin composition of Comparative Example 2 was confirmed that the absorption spectrum is shortened wavelength, the light resistance is inferior.

Having described the specific part of the present invention in detail, it is apparent to those skilled in the art that this specific technology is only a preferred embodiment, which is not limited to the scope of the present invention. Do. Those skilled in the art to which the present invention pertains will be able to perform various applications and modifications within the scope of the present invention based on the above contents.

Therefore, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

Claims (8)

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

In the above formula,
A ¹ and A ² are each independently hydrogen or hydroxy, provided that at least one of A ¹ and A ² is hydroxy,
R ¹ are each independently a haloalkyl group or a cyano alkyl group of _{C 1 -C 6, C 1 -C} 6,
R ² are each independently halo, or cyano group of the alkyl group of _{C 1 -C 6, C 1 -C} 6,
n is an integer from 1 to 4,
m is an integer of 0-3. The compound of claim 1, wherein A ¹ is hydroxy, A ² is hydrogen,
R ¹ are each independently a haloalkyl group or a cyano alkyl group of _{C 1 -C 6, C 1 -C} 6,
R ² are each independently halo, or cyano group of the alkyl group of _{C 1 -C 6, C 1 -C} 6,
n is an integer from 1 to 4,
m is a diketopyrrolopyrrole derivative. The diketopyrrolopyrrole derivative according to claim 1, wherein the diketopyrrolopyrrole derivative is one of the compounds of the following Chemical Formulas 2-4:
[Formula 2]

[Formula 3]

[Formula 4]

A dye comprising the diketopyrrolopyrrole derivative according to any one of claims 1 to 3. A coloring photosensitive resin composition comprising a coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the coloring agent comprises a coloring photosensitive resin comprising the diketopyrrolopyrrole derivative according to any one of claims 1 to 3. Composition. The colored photosensitive resin composition of claim 5, wherein the diketopyrrolopyrrole derivative is included in an amount of 0.01 to 50% by weight based on 100% by weight of the total photosensitive resin composition. The color filter formed using the coloring photosensitive resin composition of any one of Claims 5-6. An image display apparatus comprising a color filter according to claim 7.