KR102512980B1 - A colored photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, a color filter and an image display device prepared using the same, wherein the colored photosensitive resin composition comprises a colorant comprising a compound represented by Formula 1.

Description

Colored photosensitive resin composition, color filter and image display device manufactured using the same

The present invention relates to a colored photosensitive resin composition, a color filter and an image display device manufactured using the same.

Recently, a liquid crystal display device has been spotlighted as a next-generation high-tech display device with low power consumption, good portability, technology-intensive, and high added value.

Among these liquid crystal display devices, the active matrix type liquid crystal display device equipped with a thin film transistor, which is a switching element capable of controlling the on/off of voltage for each pixel, has the highest resolution and ability to implement moving pictures. It is getting attention.

In general, a liquid crystal display device forms an array substrate and a color filter substrate through a process of manufacturing an array substrate for forming a thin film transistor and a pixel electrode and a process for manufacturing a color filter substrate for forming a color filter and a common electrode, respectively, and the two substrates It is completed through a liquid crystal cell process with a liquid crystal interposed therebetween.

The color filter includes pixels composed of each color of red (R), green (G), and blue (B), and the light passing through the liquid crystal cell expresses a desired color while passing through the color filter.

However, with the recent spread of liquid crystal display devices, their uses are also expanding to various monitors and TVs, and further improvement in color reproducibility is required. In order to meet this demand, provision of a color filter with a wide color reproduction range is required. In particular, in TV applications, expansion of the color reproduction range has been demanded compared to the prior art.

Further, in addition to the expansion of the color reproduction range, improvement of display quality by high luminance is also required.

Korean Patent Publication No. 2011-0065424 relates to a colored curable composition, a color filter and a method for manufacturing the same, and a solid-state imaging device, specifically (A) a structural unit having a carboxyl group bonded to a main chain through a linking group including an ester group Disclosed is a colored curable composition comprising a polymer comprising, (B) a photopolymerization initiator, (C) a polymerizable compound, (D) a pigment, and (E) a dispersant containing a phosphoric acid group.

However, when trying to expand the color reproduction range, there is a limit to increase in transmittance.

Republic of Korea Patent Publication No. 2011-0065424 (2011.06.15)

An object of the present invention is to provide a colored photosensitive resin composition capable of producing patterns with excellent luminance for high color reproduction.

In addition, an object of the present invention is to provide a colored photosensitive resin composition capable of suppressing a phenomenon in which a display defect occurs due to peeling of a pattern during a developing process due to deterioration in sensitivity or adhesion due to deterioration in coloring strength during manufacture of a color filter.

In addition, another object of the present invention is to provide a color filter and an image display device manufactured using the colored photosensitive resin composition.

The present invention provides a colored photosensitive resin composition comprising a colorant comprising; a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

A and B are each independently a halogen group; or a substituted or unsubstituted NR ³ R ⁴ ;

However, A and B are not halogen groups at the same time,

이고,R ¹ and R ² are each independently hydrogen; or

ego,

;이거나, 또는 R³ 및 R⁴는 서로 결합하여 N. O, 및 S에서 선택되는 1 이상의 헤테로 원자를 포함 또는 비포함할 수 있는 환을 형성할 수 있으며,R ³ and R ⁴ are each independently a substituted or unsubstituted C1 to C18 alkyl group, a C1 to C18 hydroxyalkyl group, a C1 to C18 haloalkyl group, or

; Or, R ³ and R ⁴ may combine with each other to form a ring that may or may not contain one or more heteroatoms selected from N. O, and S,

When R ³ and R ⁴ are bonded to each other to form a ring, a hydroxy group, a substituted or unsubstituted C1 to C18 alkyl group, a C1 to C18 hydroxyalkyl group, a C1 to C18 haloalkyl group or a C3 to C10 cycloalkyl group substituted,

R ⁵ are each independently hydrogen; C1 to C4 alkyl group; or a (meth)acrylic group;

a and b are independently of each other an integer from 1 to 5,

n is an integer from 0 to 4 independently of each other.

In addition, the present invention provides a color filter comprising a cured product of the colored photosensitive resin composition described above.

In addition, the present invention provides an image display device including the color filter described above.

The colored photosensitive resin composition according to the present invention has the advantage of being able to produce patterns with excellent luminance for high color reproduction.

In addition, the colored photosensitive resin composition according to the present invention has an advantage of suppressing a phenomenon in which a display defect occurs due to peeling of a pattern during a developing process due to a decrease in sensitivity or adhesion due to a decrease in coloring strength during manufacture of a color filter.

In addition, in the present invention, a color filter and an image display device prepared using the colored photosensitive resin composition have excellent color reproducibility and luminance.

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

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

In the present invention, when a part "includes" a certain component, it means that it may further include other components, not excluding other components unless otherwise stated.

<Colored photosensitive resin composition>

One aspect of the present invention relates to a colored photosensitive resin composition comprising a colorant comprising; a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

A and B are each independently a halogen group; or a substituted or unsubstituted NR ³ R ⁴ ;

However, A and B are not halogen groups at the same time,

이고,R ¹ and R ² are each independently hydrogen; or

ego,

;이거나, 또는 R³ 및 R⁴는 서로 결합하여 N. O, 및 S에서 선택되는 1 이상의 헤테로 원자를 포함 또는 비포함할 수 있는 환을 형성할 수 있으며,R ³ and R ⁴ are each independently a substituted or unsubstituted C1 to C18 alkyl group, a C1 to C18 hydroxyalkyl group, a C1 to C18 haloalkyl group, or

; Or, R ³ and R ⁴ may combine with each other to form a ring that may or may not contain one or more heteroatoms selected from N. O, and S,

When R ³ and R ⁴ combine with each other to form a ring, a hydroxy group, a substituted or unsubstituted C1 to C18 alkyl group, a C1 to C18 hydroxyalkyl group, a C1 to C18 haloalkyl group or a C3 to C10 cycloalkyl group substituted,

R ⁵ are each independently hydrogen; C1 to C4 alkyl group; or a (meth)acrylic group;

a and b are independently of each other an integer from 1 to 5,

n is an integer from 0 to 4 independently of each other.

The colored photosensitive resin composition according to the present invention has excellent color reproducibility by including a specific colorant, and thus has an advantage of being able to produce a pattern having excellent luminance. In addition, there is an advantage in that it is possible to suppress a phenomenon in which a display defect occurs due to peeling of a pattern during a developing process due to deterioration in sensitivity or adhesion due to deterioration of coloring strength during manufacture of a color filter.

coloring agent

The colored photosensitive resin composition according to the present invention includes a colorant including a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

A and B are each independently a halogen group; or a substituted or unsubstituted NR ³ R ⁴ ;

However, A and B are not halogen groups at the same time,

이고,R ¹ and R ² are each independently hydrogen; or

ego,

;이거나, 또는 R³ 및 R⁴는 서로 결합하여 N. O, 및 S에서 선택되는 1 이상의 헤테로 원자를 포함 또는 비포함할 수 있는 환을 형성할 수 있으며,R ³ and R ⁴ are each independently a substituted or unsubstituted C1 to C18 alkyl group, a C1 to C18 hydroxyalkyl group, a C1 to C18 haloalkyl group, or

; Or, R ³ and R ⁴ may combine with each other to form a ring that may or may not contain one or more heteroatoms selected from N. O, and S,

When R ³ and R ⁴ combine with each other to form a ring, a hydroxy group, a substituted or unsubstituted C1 to C18 alkyl group, a C1 to C18 hydroxyalkyl group, a C1 to C18 haloalkyl group or a C3 to C10 cycloalkyl group substituted,

R ⁵ are each independently hydrogen; C1 to C4 alkyl group; or a (meth)acrylic group;

a and b are independently of each other an integer from 1 to 5,

n is an integer from 0 to 4 independently of each other.

In the present invention, "halogen group" refers to F, Cl, Br or I.

In the present invention, the “hetero atom” may be any one of O, N, and S as a heterogeneous element.

In the present invention, "substituted or unsubstituted" is a halogen group, a nitrile group, a nitro group, an amino group, a C1 to C20 alkyl group, a C3 to C20 cycloalkyl group, a C1 to C20 alkenyl group, a C6 to C20 aryl group , C3 to C20 heterocyclic group, C1 to C20 aralkyl group, C1 to 20 aralkenyl group, C3 to C20 alkylaryl group, C3 to C20 alkylamine group, C3 to C20 heteroarylamine group and C3 It means that it is substituted or unsubstituted with one or more of the arylamine groups of C20.

In the present invention, the "alkyl group" may be straight or branched chain, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1 -Ethyl-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2- Ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl- propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.

In the present invention, "hydroxyalkyl group" refers to an alkyl containing a hydroxyl group (hydroxy) in the aforementioned alkyl group.

In the present invention, "haloalkyl group" means an alkyl group substituted with one or more halogen groups in the above-mentioned alkyl group.

In the present invention, "cycloalkyl group" is cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

When the compound represented by Formula 1 is included, color reproducibility is excellent, and thus, there is an advantage in that a pattern having excellent luminance can be manufactured. In addition, there is an advantage in that it is possible to suppress a phenomenon in which a display defect occurs due to peeling of a pattern during a developing process due to deterioration in sensitivity or adhesion due to deterioration of coloring strength during manufacture of a color filter.

In one embodiment of the present invention, the compound represented by Formula 1 may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ¹ and R ² are as defined in Formula 1,

Z is independently of each other carbon or nitrogen,

When Z is carbon, R ⁶ are each independently a hydroxy group or a substituted or unsubstituted hydroxyalkyl group;

When Z is nitrogen, R ⁶ is each independently a substituted or unsubstituted C1 to C18 alkyl group, C1 to C18 hydroxyalkyl group, C1 to C18 haloalkyl group or C3 to C10 cycloalkyl group,

c and d are each independently an integer of 1 to 5;

In another embodiment of the present invention, the compound represented by Formula 1 may be represented by Formula 3 below.

[Formula 3]

In Formula 3,

R ⁷ and R ⁸ are each independently hydrogen, a substituted or unsubstituted C1 to C4 alkyl group or a (meth)acrylic group,

m is independently an integer from 0 to 4;

m' is an integer of 1 to 3 independently of each other.

In another embodiment of the present invention, the compound represented by Formula 1 may be represented by Formula 4 below.

[Formula 4]

In Formula 4,

X' is a halogen group,

A' is a structure represented by the following formula 5 or formula 6 independently of each other,

X 'and A' bond independently of each other to the phenyl ring,

a' is 1 or 2, b' is 0 or 1, a'+b'=2,

[Formula 5]

[Formula 6]

In Formulas 5 to 6,

p and q are independently integers from 0 to 5, and p+q≥1,

R ⁹ is each independently a hydroxy group, a substituted or unsubstituted C1 to C18 alkyl group or a C1 to C18 hydroxyalkyl group,

R ¹⁰ is a substituted or unsubstituted C1 to C18 alkyl group, C1 to C18 hydroxyalkyl group, or C3 to C10 cycloalkyl group;

o is an integer from 1 to 4;

In another embodiment of the present invention, when a' is 2, the two A's are each bonded to the 4-position of the two phenyl rings, and the two A's may be identical to each other.

In another embodiment of the present invention, when a' is 1 and b' is 1, A' and X' may each bond to the 4-position of the two phenyl rings.

The colorant is a compound corresponding to the case where a' is 2, the two A' are each bonded to the 4-position of the two phenyl rings, and the two A' are the same, and the a' is 1 and b' is In the case of 1, A' and X' may include all compounds corresponding to the case of binding to the 4-position of the two phenyl rings, respectively, but are not limited thereto.

At this time, the a' is 2, the two A' are each bonded to the 4-position of the two phenyl rings, and the two A' are the same as the two phenyl ring substituents of the compound corresponding to each other and the a' 1 and b' is 1, when A' and X' are each bonded to the 4-position of two phenyl rings, any one phenyl ring substituent of the corresponding compound may be the same as each other.

In another embodiment of the present invention, the compound represented by Formula 1 may be represented by any one of the following structures.

In another embodiment of the present invention, the compound represented by Formula 1 may be included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the total solid content of the colored photosensitive resin composition.

In another embodiment of the present invention, the compound represented by Formula 1 may be included in an amount of 1 to 40 parts by weight, preferably 5 to 35 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition.

When the compound represented by Formula 1 is included within the above range, it is possible to manufacture a pattern having sufficient color concentration and excellent luminance when manufacturing a color filter, and also, when manufacturing a color filter, the sensitivity or adhesion is deteriorated due to poor coloring power. It is preferable because suppression of a phenomenon in which display defects occur due to peeling of the pattern during the developing process can be maximized.

In the present invention, the solid content of the colored photosensitive composition means the total of components from which the solvent has been removed.

In another embodiment of the present invention, the colorant may further include one or more selected from the group consisting of pigments and dyes. Specifically, the colorant may further include additional pigments and dyes in addition to the compound represented by Formula 1. More specifically, the colorant may include the compound represented by Formula 1 alone, or may include the compound represented by Formula 1 and one or more pigments.

As the organic or inorganic pigment, various pigments used in printing ink, inkjet ink, etc. may be used. Specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoin Doline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, pravanthrone pigments, pyrans A pyranthrone pigment, a diketopyrroropyrrole pigment, etc. are mentioned. Examples of the inorganic pigment include metal compounds such as metal oxides, composite metal oxides, and metal complex salts; Or carbon black etc. are mentioned. Specifically, examples of the metal include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. In particular, the organic and inorganic pigments include compounds classified as pigments in the color index (published by The Society of Dyers and Colourists), more specifically, the following color index (C.I.) numbers Although a pigment can be mentioned, it is not necessarily limited to these.

For example, C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264 and 269;

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 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;

C.I Pigment Brown 28;

C.I Pigment Black 1 and 7 and the like.

These pigments may be used alone or in combination of two or more.

The above exemplified C.I. Among the pigment pigments, C.I. Pigment Red 179, C.I. Pigment Red 208, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Pigment Red 269, C.I. Pigment Yellow 139, C.I. A pigment selected from Pigment Yellow 185 and C.I. Pigment Violet 23 can be preferably used.

Among the pigments, organic pigments are surface treatment using a pigment derivative having an acidic group or basic group introduced as necessary, graft treatment of the pigment surface using a polymer compound, etc., atomization treatment by sulfuric acid refinement, or impurities. It can be treated by washing treatment with an organic solvent and water for removal, removal treatment by an ion exchange method of ionic impurities, and the like.

When using a pigment as the colorant, it is preferable to use a pigment having a uniform average particle diameter. As a method for uniformizing the particle size of the pigment, a method in which a surfactant is incorporated as a pigment dispersant and subjected to dispersion treatment, etc., can be cited. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

As said pigment dispersant, surfactant, such as cationic, anionic, nonionic, amphoteric, etc. are mentioned, for example, These can be used individually or in combination of 2 or more types, respectively. The pigment dispersant may be included in the form of an additive to be described later, preferably, an acrylic pigment dispersant may be used, and Disper byk-2001 may be used as a commercially available product, but is not limited thereto.

The pigment dispersant is used in an amount of 1 part by weight or less, preferably 0.05 to 0.5 part by weight, based on 1 part by weight of the colorant in the colored photosensitive resin composition. When the pigment dispersant is used within the above range on the basis of the above, it is preferable because a pigment having a uniform average particle diameter can be obtained.

As long as the dyes of the present invention have solubility in organic solvents, one or more of them may be added without limitation. Preferably, it is preferable to use a dye capable of securing reliability such as solubility in an alkaline developing solution, heat resistance, and solvent resistance while having solubility in organic solvents. As the dye, acid dyes having an acid group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof may be used. Acid dyes of the system and their derivatives can also be selected. The above dyes include compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists) and known dyes described in dyeing notes (color dyeing yarns).

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

C.I. yellow dyes such as Solvent Yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. red dyes such as Solvent Red 8, 45, 49, 122, 125, and 130;

C.I. orange dyes such as Solvent Orange 2, 7, 11, 15, 26, 45, 56, 62;

C.I. blue dyes such as Solvent Blue 35, 37, 45, 59, and 67;

C.I. and green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35.

Also C.I. as an acid dye

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 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, etc. ;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 217 ,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 , 382, 383, 394, 401, 412, 417, 418, 422, 426 and the like red dyes;

orange dyes such as C.I. 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;

violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19;

green dyes such as C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109; and the like.

Also as a C.I. direct dye

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 , 136, 138, yellow dyes such as 141;

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 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

orange dyes such as C.I. 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, 189 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, blue dyes such as 293;

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

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

Also, C.I. as modanto dye

yellow dyes such as C.I. 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, red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C.I. Orange 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 dyes;

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, blue dyes such as 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

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

green dyes such as C.I. Modanto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53; and the like.

The colorant is Pyridone-Azo dye, Quinophthalone dye, Xanthene dye, Dipyrromethane dye, Perylene dye, Anthraquinone dye, C.I. Pigman Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Red 177, C.I. Pigment Red 254, C.I. Pigment Red 269 and 3,6-bis(4-bromophenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (3,6-Bis(4-bromophenyl) ) -2,5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione) may further include a compound selected from the group consisting of, but is not limited thereto.

In another embodiment of the present invention, the colorant may be included in an amount of 3 to 60 parts by weight, preferably 5 to 55 parts by weight, based on 100 parts by weight of the total solid content in the colored photosensitive resin composition.

When the content of the colorant satisfies the above range based on the above criteria, the color concentration is sufficient when the color filter is manufactured, and the polymer to be described later included in the colored photosensitive resin composition may be included in a required amount, so that the mechanical strength is sufficient. There is an advantage of being able to form a pattern.

In another embodiment of the present invention, the colored photosensitive resin composition may further include one or more selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive.

alkali soluble resin

The alkali-soluble resin contained in the colored photosensitive resin composition of the present invention is a component that imparts solubility to an alkali developing solution used in the developing step. In the present invention, the alkali-soluble resin is not particularly limited, but is preferably a copolymer of a monomer having a carboxyl group and another monomer copolymerizable therewith.

The monomer having the carboxyl group is not particularly limited, and specific examples include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as omega-carboxypolycaprolactone mono(meth)acrylate. Acrylic acid and methacrylic acid are more preferred. These can be used by selecting one or more types.

The other copolymerizable monomer is not particularly limited as long as it is a monomer having a carbon-carbon unsaturated bond, and specific examples include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate unsaturated carboxylate compounds such as acrylate; unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-methyl-3-methacryloxyethyloxetane, etc. Unsaturated oxetane carboxylate compounds of , etc. are mentioned. These monomers can be used individually or in combination of 2 or more types, respectively.

According to the present invention, the molecular weight distribution of the alkali-soluble resin, that is, the weight average molecular weight relative to the number average molecular weight (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 1.5 to 6.0, more preferably 1.8 to 4.0 is good in terms of developability.

The acid value of the alkali-soluble resin is preferably 30 to 170 mgKOH / g based on solid content, and more preferably 50 to 150 mgKOH / g. If the acid value of the alkali-soluble resin is less than 30 mgKOH / g, it is difficult to secure a sufficient development rate for the colored photosensitive resin composition, and if the acid value exceeds 170 mgKOH / g, adhesion to the substrate is reduced, resulting in a short circuit of the pattern. It is easy to do, and compatibility problems with the colorant occur, and the colorant in the colored photosensitive resin composition is precipitated, or the storage stability of the colored photosensitive resin composition is lowered and the viscosity is increased, which is not preferable.

The alkali-soluble resin is preferably included in an amount of 5 to 85 parts by weight, more preferably 10 to 70 parts by weight, based on 100 parts by weight of the total solid content in the colored photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, the solubility in the developing solution is sufficient so that it is difficult to generate development residues on the substrate of the non-pixel portion, and film reduction of the pixel portion of the exposed portion is prevented during development to prevent non-pixel This is preferable because the omission of parts tends to be good.

photopolymerization compound

The photopolymerizable compound included in the colored photosensitive resin composition of the present invention is a compound that can be polymerized by active radicals, acids, etc. generated from a photopolymerization initiator to be described later by light irradiation, especially if it is a compound that can be polymerized by the action of a photopolymerization initiator. Not limited. Preferably, a monofunctional monomer, a bifunctional monomer, or a trifunctional or more multifunctional monomer may be used, and one or more types of monomers selected therefrom may be used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N-vinyl group. Rolidone and the like, commercially available products include Aronix M-101 (Doagosei), KAYARAD TC-110S (Nippon Kayaku) or Biscott 158 (Osaka Yuki Kagaku High School), but are limited thereto It is not.

Specific examples of the bifunctional monomer include 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. Rate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, propylene glycol dimethacrylate, urethane (meth)acrylate and the like, and commercially available products include Aronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nippon Kayaku), Biscott 260 (Osaka Yuki Gagaku High School), AH-600, AT- 600 or UA-306H (Kyoeisha Chemical Co.) and the like, but are not limited thereto.

Specific examples of the trifunctional or higher functional photopolymerizable compound include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propoxylated trimethylolpropane tri(meth)acrylate. , pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaeryth lithol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc., commercially available products include Aronix M-309, TO-1382 (Toagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku), etc., but are not limited thereto.

Among the photopolymerizable compounds exemplified above, it is more preferable to use a trifunctional or more functional monomer, and (meth)acrylates and urethane (meth)acrylates have excellent polymerizability and can improve strength. desirable.

The photopolymerizable compound may be included in 5 to 45 parts by weight, more preferably 10 to 37 parts by weight, based on 100 parts by weight of the total solid content in the colored photosensitive resin composition. When the photopolymerizable compound is contained within the above range, it is preferable because the strength and smoothness of the pixel portion become good.

light polymerization initiator

The photopolymerization initiator preferably contains an acetophenone-based compound. Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1-[4 -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane- 1-one oligomers and the like, preferably 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one and the like.

The acetophenone-based compounds may be used alone or in combination of two or more. The photopolymerization initiator may be used in combination with other types of photopolymerization initiators in addition to the acetophenone-based compound. Other types of photopolymerization initiators include active radical generators, sensitizers and acid generators that generate active radicals by irradiation with light. Examples of the active radical generating agent include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds.

Specific examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Specific examples of the benzophenone-based compound include o-benzoylmethylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra (t-butylper Oxycarbonyl) benzophenone, 2,4,6-trimethyl benzophenone, etc. are mentioned.

Specific examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4 -Propoxythioxanthone etc. are mentioned.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) - 6-(4-methoxynaphthyl)-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-(3,4dimethoxyphenyl)ethenyl]-1,3,5- A triazine etc. are mentioned. Specifically, as the sensitizer, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2' -biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like. . As the acid generator, specifically, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate , 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenylsulfonium p-toluenesulfonate Onium salts, such as phenyliodonium hexafluoroantimonate, or nitrobenzyl tosylate, benzoin tosylate, etc. are mentioned.

Among the above compounds, there are also compounds that simultaneously generate active radicals and acids. For example, triazine-based compounds are also used as acid generators.

The photopolymerization initiator may be included in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on solid content, based on 100 parts by weight of the total of the alkali-soluble resin and the photopolymerizable compound. When the content of the photopolymerization initiator is included within the above range based on the above standards, the colored photosensitive resin composition is highly sensitive and the exposure time is shortened, thereby improving productivity and maintaining high resolution.

The photopolymerization initiator may be used in combination with a photopolymerization initiation aid. The photopolymerization initiation aid may be used to accelerate the polymerization of a photopolymerizable monomer whose polymerization is initiated by the photopolymerization initiator.

Examples of the photopolymerization initiation aid include amine-based compounds and alkoxyanthracene-based compounds. Specific examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate , 4-dimethylaminobenzoic acid, 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name, Michler's ketone), 4,4'-bis(diethylamino) ) benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, 4,4'-di(N,N'-dimethylamino)-benzophenone, etc., among which 4,4'-di (N,N'-dimethylamino)-benzophenone is preferred.

Specific examples of the alkoxyanthracene-based compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. can be heard The photopolymerization initiation aids may be used alone or in combination of two or more. In addition, the photopolymerization initiation aid may be a commercially available product, such as EAB-F (manufactured by Hodogaya Gagaku Kogyo Co., Ltd.).

Specific examples of preferred combinations of the photopolymerization initiator and the photopolymerization initiation aid include diethoxyacetophenone and 4,4'-bis(diethylamino)benzophenone; 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one and 4,4'-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-phenylpropan-1-one and 4,4'-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one and 4,4'-bis(diethylamino)benzophenone; 1-hydroxycyclohexylphenyl ketone and 4,4'-bis(diethylamino)benzophenone; oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one and 4,4'-bis(diethylamino)benzophenone; combinations of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and 4,4'-bis(diethylamino)benzophenone; Combination of -methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one and 4,4'-bis(diethylamino)benzophenone, 2-benzyl-2-dimethylamino-1 A combination of -(4-morpholinophenyl)butan-1-one and 4,4'-di(N,N'-dimethylamino)-benzophenone; and the like.

When the photopolymerization initiator and the photopolymerization initiation auxiliary are used together, the amount of the photopolymerization initiation auxiliary is preferably 0.01 to 5 moles based on 1 mole of the photopolymerization initiator. When the photopolymerization initiation auxiliary is included within the above content range, the sensitivity of the colored photosensitive resin composition is further increased, and the productivity of a color filter formed using the composition is improved, so it is preferable.

solvent

As long as the solvent is effective in dissolving other components included in the colored photosensitive resin composition, solvents used in conventional colored photosensitive resin compositions may be used without particular limitation, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, and esters. or amides are preferred.

The solvent is specifically ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, methyl ethyl ketone , acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3- Cyclic esters, such as esters, such as methoxy methyl propionate, and (gamma)-butyrolactone, etc. are mentioned.

The solvent is preferably an organic solvent having a boiling point of 100 ℃ to 200 ℃ in terms of coating and drying properties, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalak tate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like can be used.

Each of the above-exemplified solvents may be used alone or in combination of two or more, and may be included in an amount of 60 to 90 parts by weight, preferably 70 to 88 parts by weight, based on 100 parts by weight of the colored photosensitive resin composition of the present invention.

When the solvent satisfies the above range, it provides an effect of improving coating properties when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), inkjet, or the like. do.

additive

The additives may be selectively added as needed, and include, for example, other polymer compounds, curing agents, surfactants, adhesion accelerators, antioxidants, ultraviolet absorbers, and aggregation inhibitors.

Specific examples of the other polymer compounds 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, and polyurethanes. can be heard

The curing agent is used for deep curing and increasing mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like.

Specific examples of the epoxy compound in the curing agent include bisphenol A-based epoxy resins, hydrogenated bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, noblock type epoxy resins, other aromatic epoxy resins, and alicyclic epoxy resins. , glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic 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 bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.

The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound together with the curing agent. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. The polyhydric carboxylic acid anhydrides may be commercially available as epoxy resin curing agents. Specific examples of the epoxy resin curing agent include a trade name (Adeka Hadona EH-700) (manufactured by Adeka Industrial Co., Ltd.), a trade name (Rikashiddo HH) (manufactured by Shinnippon Ewha Co., Ltd.), a trade name (MH-700) (new manufactured by Nippon Ewha Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve the film formation of the 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 from Dow Corning Toray Silicon as commercial products, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, and TSF-4460 from GE Toshiba Silicone. , TSF-4452, etc. Examples of the fluorine-based surfactant include Megapiece F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink and Chemicals Co., Ltd. as commercial products. The surfactants exemplified above may be used alone or in combination of two or more.

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-mercaptopropyltrimethyne Toxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned. Adhesion promoters exemplified above may be used alone or in combination of two or more.

The adhesion promoter may be included in a weight fraction of 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the total solid content of 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-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyriazole, alkoxybenzophenone, and the like.

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

The additives may be added in an appropriate amount and used within a range that does not impair the object of the present invention. For example, the additive may be included in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the colored photosensitive resin composition, but is not limited thereto.

The colored photosensitive resin composition according to the present invention has excellent color reproducibility by including a specific colorant, and thus has an advantage of being able to produce a pattern having excellent luminance. In addition, there is an advantage in that it is possible to suppress a phenomenon in which a display defect occurs due to peeling of a pattern during a developing process due to deterioration in sensitivity or adhesion due to deterioration of coloring strength during manufacture of a color filter.

In addition, the colored photosensitive resin composition according to the present invention can be usefully used for photocurable inks, photosensitive printing plates, various photoresists, color filter photoresists for LCDs, photoresists for resin black matrices, or transparent photoresists.

<Color filter>

Another aspect of the present invention relates to a color filter comprising a cured product of the colored photosensitive resin composition described above. Specifically, another aspect of the present invention relates to a color filter formed using the colored photosensitive resin composition described above. A color filter according to an embodiment of the present invention is characterized in that it includes a colored pattern layer formed by applying the above-described colored photosensitive resin composition on a substrate and exposing and developing in a predetermined pattern.

<Image display device>

The present invention provides an image display device including the color filter described above.

The color filter of the present invention can be applied to various image display devices such as an electroluminescence display, a plasma display, a field emission display, and a solid-state imaging device, as well as a typical liquid crystal display.

The image display device may include other components that may be included in a conventional image display device, such as a light emitting device such as a light source, a light guide plate, and an image display unit including a color filter according to the present invention, but the present invention is not limited thereto. don't

A color filter and an image display device prepared using the colored photosensitive resin composition according to the present invention have excellent pattern angles, and excellent residue characteristics, residual film rate, chemical stone resistance, and mechanical properties.

Hereinafter, examples will be described in detail in order to specifically describe the present specification. However, the embodiments according to the present specification may be modified in many different forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments herein are provided to more completely explain the present specification to those skilled in the art. In addition, "%" and "parts" indicating content below are based on weight unless otherwise specified.

Example and comparative example : Preparation of colored photosensitive resin composition

Colored photosensitive resin compositions according to Examples and Comparative Examples were prepared with compositions and configurations according to Table 1 below.

Example comparative example One 2 3 4 One 2 Colorant (A) A-1 6.06 - - - - - A-2 - 6.06 - 5.06 - - A-3 - - 6.06 - - - A-4 - - - - 6.06 - A-5 - - - - - 6.06 A-6 One Alkali-soluble resin (B) 5.17 5.17 5.17 5.17 5.17 5.17 Photopolymerizable Compound (C) 7.02 7.02 7.02 7.02 7.02 7.02 Photopolymerization initiator (D1) One One One One One One Photopolymerization initiation aid (D2) 0.55 0.55 0.55 0.55 0.55 0.55 Solvent (E) 80 80 80 80 80 80 Additive (F) 0.2 0.2 0.2 0.2 0.2 0.2 Colorant (A): Formulas (A-1) to (A-5) and commercially available pigments (A-6) (Colorant (A-6): CI Pigment red 177)
Alkali-soluble resin (B): methacrylic acid:benzyl methacrylate = 31:69 (molar ratio), weight average molecular weight = 30,000, acid value = 105 mgKOH / g, a copolymer of methacrylic acid and benzyl methacrylate
Photopolymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., acid value: 10 mgKOH/g. Polystyrene equivalent weight average molecular weight: 20,0000)
Photopolymerization initiator (D1): 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemical)
Photopolymerization initiation aid (D2): 4,4'-di(N,N'-dimethylamino)-benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.)
Solvent (E): Propylene glycol monomethyl ether acetate
Additive (F): Acrylic pigment dispersant (Disper byk-2001, manufactured by BYK)

<A-1>

<A-2>

<A-3>

<A-4>

<A-5>

<Manufacture of color filter>

The prepared colored photosensitive resin composition was applied on a glass substrate (#1737, manufactured by Corning) 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. Subsequently, a test photomask having a pattern that varies stepwise in a transmittance range of 1 to 100% is placed on the thin film, the distance between the test photomask and the test photomask is set to 1000 μm, and an ultra-high pressure mercury lamp (USH-250D, Ushio Denki ( Note) was irradiated with light at an exposure amount (365 nm) of 40 mJ/cm 2 in an air atmosphere using (manufactured by).

The thin film irradiated with ultraviolet rays was developed for 70 seconds using a spray developer in a developing solution of KOH aqueous solution having a pH of 12.5. The glass substrate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230° C. for 20 minutes to prepare a color filter. The pattern shape (thin film) thickness of the manufactured color filter was 2.0 to 2.5 μm.

< Experimental example >

Luminance, sensitivity, development speed, pencil hardness, reliability (chemical resistance), residue test, etc. of the color filters prepared according to Examples and Comparative Examples were performed in the following manner, and the results are shown in Table 2 below.

Luminance measurement method

It was measured using a microscopic spectrometer OSP-SP2000. Luminance was shown in Table 2 below.

The evaluation criteria of luminance (Y) are as follows.

<Evaluation Criteria>

◎: Y≥29.5, ○: 29.5>Y≥29, △: 28≤Y<29, X: Y<28

(When Rx=0.560)

Sensitivity and development speed

During the manufacturing process of the color filter, the development speed (seconds) was measured by measuring the time at which peeling of the non-exposed thin film portion appeared during development. In addition, during the manufacturing process of the color filter, sensitivity, which is the minimum exposure amount (mJ/cm 2 ) required to form a thin film without tearing of the pattern after development, was measured and shown in Table 2 below.

pencil hardness

The hardness of the coating film (heat cured film) was measured according to the test method of JIS-K-5400. When a load of 9.8 N was applied to the heat-cured film using a pencil hardness tester, the highest hardness at which no flaws were formed in the coating film was determined as hardness. The pencil used as a control was &quot;Mitsubishi Hiuni&quot;.

<Evaluation Criteria>

◎: 6H or more

○: 4H to 5H

Δ: 2H to 3H

×: 1H or less

Reliability - chemical resistance

After immersing the substrate manufactured by the above experimental method in NMP (N-Methyl-2-pyrrolidone) solution for 30 min, the color change (ΔE ^* ab) was measured. At this time, the color characteristics before and after NMP immersion were confirmed using a microscopic spectrophotometer (Model No. OSP-SP2000, Olympus).

The CIE color coordinate values before and after evaluation were respectively measured, calculated using Equation 1 below, and evaluated according to the following evaluation criteria.

[Equation 1]

ΔE ^* ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^{1 /2}

In Equation 1, ΔE ^* ab represents a color change, ΔL ^* represents a lightness difference, Δa ^* represents a color difference between red and green, and Δb ^* represents a color difference between yellow and blue.

<Evaluation Criteria>

○: △E ^* ab = less than 2.0

△: △E ^* ab = 2.0 or more and less than 3.0

×: ΔE ^* ab = 3.0 or more

residue Test

Using an ultra-depth 3D shape measuring microscope (VK-9500, Keyence), the surrounding area of the coating film of the pattern formed by the above method was observed to confirm the presence or absence of development residues on the substrate.

<Evaluation Criteria>

○: No development residue on the substrate

×: occurrence of development residues on the substrate

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 luminance ○ ◎ ○ ○ △ × Sensitivity (mJ/cm ² ) 20 20 20 20 30 30 Development speed (seconds) 18 19 18 18 22 25 pencil hardness ◎ ◎ ○ ○ ○ △ reliability ○ ○ ○ ○ △ △ residue ○ ○ ○ ○ × ×

As can be seen from Table 2, when comparing Examples and Comparative Examples from the viewpoint of the same color coordinates, it can be seen that the luminance value of Example is superior to that of Comparative Example, and the coloring power is also excellent in high color reproduction, resulting in liquid crystal It can be seen that the possibility of occurrence of display defects is low because it is advantageous for pattern formation in the display device.

Claims (12)

A colored photosensitive resin composition comprising a colorant comprising at least one of the compounds represented by Formula 2 and Formula 3 below:
[Formula 2]

(In Formula 2,
R ¹ and R ² independently of each other are hydrogen, or

ego;
Z is carbon;
R ⁶ are each independently a hydroxyl group or a substituted or unsubstituted hydroxyalkyl group;
c and d are independently of each other an integer from 1 to 5;
n is independently an integer from 0 to 4.)
[Formula 3]

(In Formula 3,
R ⁷ and R ⁸ are each independently hydrogen, a substituted or unsubstituted C1 to C4 alkyl group or a (meth)acrylic group;
m is independently an integer from 0 to 4;
m' is an integer from 1 to 3 independently of each other.)
delete delete delete According to claim 1,
A colored photosensitive resin composition in which the compound represented by Formula 1 is represented by any one of the following structures.

According to claim 1,
The coloring agent is a colored photosensitive resin composition further comprising at least one selected from the group consisting of pigments and dyes. According to claim 1,
The colored photosensitive resin composition in which the compound represented by Formula 1 is contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. According to claim 7,
The colored photosensitive resin composition in which the compound represented by Formula 1 is contained in an amount of 1 to 40 parts by weight based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. According to claim 1,
The coloring agent is a colored photosensitive resin composition that is included in 3 to 60 parts by weight based on 100 parts by weight of the total solid content of the colored photosensitive resin composition. According to claim 1,
A colored photosensitive resin composition further comprising at least one selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive. A color filter comprising a cured product of the colored photosensitive resin composition according to any one of claims 1 and 5 to 10. An image display device comprising the color filter according to claim 11 .