KR20230126891A - A colored curable resin composition, a color filter and a display device using the same - Google Patents

Abstract

The present invention includes a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the colorant includes a compound represented by Formula 1 below, and the solvent includes propylene glycol monomethyl ether acetate as a first solvent , A second solvent with a boiling point of less than 150 ° C. and at least one of a third solvent with a boiling point of 150 ° C. or more, characterized in that the B value calculated by the following formula 1 is 140 to 155 ° C., colored curable resin composition, It relates to a color filter and an image display device including the same, which has excellent solvent resistance and UV hashing resistance, excellent storage stability, suppression of foreign matter generation, and suppression of VD stains or Pin stains even after subsequent processes such as prebaking. and has excellent reliability effect.

Description

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

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

Color filters are widely used in various display devices such as image pickup devices, liquid crystal displays (LCDs) and organic light emitting diodes (OLEDs), and their application range is rapidly expanding.

Color filters used in display devices consist of three color patterns of red, green, and blue, or three colors of yellow, magenta, and cyan. It is made up of colored patterns.

Each color pattern of the color filter is generally formed using a colored curable resin composition containing a colorant such as a pigment and/or dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. Color pattern processing using the colored curable resin composition is usually performed through a lithography process.

In recent years, market demand for high-quality displays with high color reproducibility has increased, and accordingly, the content of colorants included in colored curable resin compositions used in the manufacture of color filters has been continuously increased, with better coloring strength, contrast ratio and reliability. The use of colorants is being considered.

However, when the content of the colorant is increased, not only the manufacturing cost is improved, but also the reverse taper phenomenon occurs when forming a pattern with the colored curable resin composition, and the sensitivity is lowered, resulting in difficulties in forming steps using a half-tone mask. As a result, problems of fairness and reliability may arise.

In addition, when the colored curable resin composition is exposed to the external environment, there is a problem in that the storage stability is deteriorated due to a decrease in viscosity or foreign substances are generated. remained, resulting in VD stains or Pin stains during subsequent processes such as prebaking, resulting in a decrease in the reliability of the color filter.

Republic of Korea Patent Publication No. 10-2007-0092662 discloses a technique for preparing a coloring composition for a color filter by mixing two or more organic solvents having different boiling points and different conductivity, but the published patent addresses the above-mentioned problems. Can't offer an alternative.

Republic of Korea Patent Publication No. 10-2007-0092662

The present invention is to improve the above-mentioned conventional technical problems, and has excellent solvent resistance and reliability such as UV ashing, excellent storage stability, suppression of foreign matter generation, and even after subsequent processes such as prebaking, VD stains or Pin stains It is an object of the present invention to provide a colored curable resin composition with suppressed occurrence and excellent reliability.

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

However, the problem to be solved by the present application is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

In order to achieve the above object, the present invention includes a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the colorant includes a compound represented by Formula 1 below, and the solvent includes propylene glycol as a first solvent It includes monomethyl ether acetate, and includes at least one of a second solvent having a boiling point of less than 150 ° C. and a third solvent having a boiling point of 150 ° C. or more, and the B value calculated by the following formula 1 is 140 to 155 ° C. To provide a colored curable resin composition.

In addition, the present invention provides a color filter comprising the colored curable resin composition.

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

The colored curable resin composition of the present invention has excellent solvent resistance and UV ashing effects by including the compound represented by Formula 1 as a colorant.

In addition, the colored curable resin composition of the present invention contains propylene glycol monomethyl ether acetate as a first solvent as a solvent, and at least one of a second solvent having a boiling point of less than 150 ° C. and a third solvent having a boiling point of 150 ° C. or higher. And, by controlling the B value calculated by Equation 1 to be 140 to 155 ° C, the storage stability is excellent, the generation of foreign substances is suppressed, and the occurrence of VD stains or Pin stains is suppressed even after subsequent processes such as prebaking, resulting in excellent reliability. have an effect

The present invention includes a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant includes a compound represented by Formula 1, and the solvent includes propylene glycol monomethyl ether acetate as a first solvent, A colored curable resin composition comprising at least one of a second solvent having a boiling point of less than 150 ° C and a third solvent having a boiling point of 150 ° C or more and having a B value of 140 to 155 ° C calculated by Equation 1, using the same It relates to a prepared color filter and an image display device including the color filter, and the colored curable resin composition according to the present invention includes the compound represented by Formula 1 as a colorant, thereby obtaining excellent solvent resistance and UV ashing effects. And, by including at least one of the first solvent, the second solvent, and the third solvent as a solvent, and controlling the B value calculated by Equation 1 to be 140 to 155 ° C., the storage stability is excellent, and the foreign matter The present invention was completed by experimentally confirming that the generation of VD stains or Pin stains was suppressed even after subsequent processes such as prebaking, and thus the reliability was excellent.

The colored curable resin composition may be characterized in that it is for forming a red pixel.

Hereinafter, each component constituting the colored curable resin composition of the present invention will be described in detail. However, the present invention is not limited by these components.

<Colored Curable Resin Composition>

coloring agent

The colorant is characterized by including a compound represented by Formula 1 below, and may include additional pigments, dyes, and mixtures thereof as necessary within a range that does not impair the object of the present invention.

[Formula 1]

In Formula 1, L ¹ is a group represented by formula (ph1), A is a group represented by formula (ia), and B is a group represented by formula (ib).

(In formula (ph1), X ¹ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -NH ₂ , -CONH ₂ , -COOH, -CN, an alkoxy group having 1 to 10 carbon atoms, Represents an alkylthio group having 1 to 4 carbon atoms or a halogen atom, -CH ₂ - contained in the hydrocarbon group may be substituted with -O-, -CO- or -NH-, and -CH= contained in the hydrocarbon group is -N= may be substituted.

n represents an integer of 0 to 4;

When n is an integer greater than or equal to 2, several X ¹ may be the same or different. When n is an integer of 2 or greater and X ¹ is bonded to adjacent carbon atoms, X ¹ bonded to adjacent carbon atoms may bond to each other to form a ring.

* represents the number of bonds with A, and ** represents the number of bonds with B.)

The hydrocarbon group for X ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be a saturated or unsaturated hydrocarbon group, and may be a chain or alicyclic hydrocarbon group. In addition, the alicyclic hydrocarbon group may be a monocyclic or polycyclic hydrocarbon group. The number of carbon atoms in the hydrocarbon group is more preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4.

(In formulas (ia) and (ib), each of X ⁶ to X ⁹ independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the hydrocarbon group is -O It may be substituted with -, -CO- or -NH-, -CH= contained in the hydrocarbon group may be substituted with -N=, and -CH< contained in the hydrocarbon group may be replaced with -N< , An oxygen atom, a nitrogen atom or a carbonyl group may be inserted between the carbon atoms constituting the hydrocarbon group.

X ⁶ and X ⁷ may be bonded to each other to form a ring, and X ⁸ and X ⁹ may be bonded to each other to form a ring.

* indicates the number of bonds with L ¹ .)

Examples of the monovalent saturated hydrocarbon group for X ⁶ to X ⁹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group, Linear alkyl groups such as icosyl group; isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, sec-butyl group, tert-butyl group, 1,3-dimethylbutyl group, 2- Branched chain alkyl groups such as ethylbutyl group; saturated alicyclic hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group. The number of carbon atoms in the monovalent saturated hydrocarbon group is more preferably 1 to 10, still more preferably 1 to 6, still more preferably 1 to 4.

The hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group, a halogen atom such as a fluorine atom, or a hydroxy group.

In addition, L ¹ may be a group represented by formula (ph2).

(In formula (ph2), X ² to X ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -NH ₂ , -CONH ₂ , -COOH, -CN, an alkoxy group having 1 to 4 carbon atoms, and a carbon atom 1 represents an alkylthio group of ~4 or a halogen atom.

X ² and X ³ and X ⁴ and X ⁵ may combine with each other to form a ring.

* indicates the number of bonds with A, and ** indicates the number of bonds with B.)

The group represented by the formula (ia) and the group represented by the formula (ib) may each independently be any one of the groups represented by formulas (t1) to (t5).

(In the formulas (t1) to (t5), R ¹ to R ¹⁶ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and a carbon number 6 to which may have a substituent A 12-membered aromatic hydrocarbon group, a 3- to 10-membered heterocyclic group, -CN, -OH, or a halogen atom.

* indicates the number of bonds with L ¹ .)

Examples of the monovalent saturated hydrocarbon group for R ¹ to R ¹⁶ include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl; isopropyl; branched chain alkyl groups such as isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, tricyclodecyl group, etc. an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms. As for carbon number of the said monovalent saturated hydrocarbon group, it is more preferable that it is 1-6, and it is still more preferable that it is 1-4.

The hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group, a halogen atom such as a fluorine atom, or a hydroxy group.

Examples of the aromatic hydrocarbon group for R ¹ to R ¹⁶ include a phenyl group, a tolyl group, a xylyl group and a naphthyl group, and a phenyl group and a tolyl group are preferable. Moreover, as a substituent which the said aromatic hydrocarbon group may have, Halogen atoms, such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom; Alkoxy groups of 1-6 carbon atoms, such as a methoxy group and an ethoxy group; -OH; _-SO3H ; -SO ₃ ^- ; -SO ₂ NR ¹⁷ R ¹⁸ ; Alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl groups; Alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl groups; and the like.

R ¹⁷ is an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms which may have a halogen atom, -OH or -NH ₂ as a substituent, or an alicyclic group having 3 to 10 carbon atoms which may have a halogen atom, -OH or -NH ₂ as a substituent represents a hydrocarbon group.

R ¹⁸ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.

The heterocyclic group for R ¹ to R ¹⁶ may be a phenyl group which may have a substituent or a heterocyclic group having a benzene ring, preferably a phenyl group or benzoimidazoline group which may have a halogen atom.

The compound represented by Chemical Formula 1 may include a counterion if necessary. The counter ion may be a cation containing an alkaline earth metal, preferably at least one selected from the group consisting of a magnesium cation, a calcium cation, a strontium cation, and a barium cation, and more preferably a barium cation.

The compound represented by Formula 1 may be included in an amount of 10 to 70% by weight, preferably 20 to 60% by weight, based on the total weight of the colorant. When the compound represented by Formula 1 satisfies the above content range, high brightness and high color reproduction are possible and the content of the colorant in the colored curable resin composition can be reduced, which is preferable because reliability such as solvent resistance and UV ashing is excellent.

The colorant may further include at least one selected from the group consisting of red pigments, yellow pigments, purple pigments, and xanthene-based dyes.

The red pigment is C.I. Pigment Red 177, C.I. Pigment Red 179, C.I. Pigment Red 202, C.I. Pigment Red 242, C.I. Pigment Red 254 and C.I. It may include one or more selected from the group consisting of Pigment Red 291, preferably C.I. Pigment Red 177, C.I. Pigment Red 202, C.I. Pigment Red 254 and C.I. It may include one or more selected from the group consisting of Pigment Red 291.

The yellow pigment is C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 185 and C.I. It may include one or more selected from the group consisting of Pigment Yellow 231, preferably C.I. It may be Pigment Yellow 139.

The purple pigment is C.I. Pigment Violet 19, C.I. Pigment Violet 23 and C.I. It may include one or more selected from the group consisting of Pigment Violet 29, preferably C.I. It may be Pigment Violet 19.

The xanthene-based dye may include at least one selected from the group consisting of compounds represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;

R ₂₇ and R ₂₈ each independently represent a hydrogen atom, -COOH, -COO ^- , -SO ₃ ^- , -SO ₃ H, -SO ₃ Na, -COOCH ₃ or -COOCH ₂ CH ₃ .

As the additional pigment, organic pigments or inorganic pigments commonly used in the art may be used, and these may be used alone or in combination of two or more.

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 Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71;

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.

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 curable 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 the additional dye, one or more dyes may be added without limitation as long as they are soluble in organic solvents. 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. Dyes and their derivatives may 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 ; 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 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 , 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 ; 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 , 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 may be included in an amount of 1 to 15% by weight, preferably 1.5 to 10% by weight, based on the total weight of the colored curable resin composition. When the colorant satisfies the content range, it is preferable because the color concentration of the pixel is sufficient and the solvent resistance and UV ashing resistance are excellent.

binder resin

The binder resin is a component that imparts solubility to an alkali developing solution used in a developing process when forming a pattern, and the binder resin may contain an ethylenically unsaturated monomer having a carboxy group and be polymerized.

The ethylenically unsaturated monomer having the carboxyl group is not particularly limited, and examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid, and their anhydrides; and omega-carboxypolycaprolactone mono(meth)acrylate, and the like, mono(meth)acrylates of polymers having carboxy groups and hydroxyl groups at both ends, and the like, preferably acrylic acid and methacrylic acid. These can be used individually or in mixture of 2 or more types.

The binder resin according to the present invention may be polymerized by further including at least one other monomer copolymerizable with the above monomers. For example, styrene, vinyltoluene, methyl styrene, p-chlorostyrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p- Aromatic vinyl compounds, such as 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, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m -N-substituted maleimide compounds such as methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-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, 2-dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, etc. alicyclic (meth)acrylates; aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. The unsaturated oxetane compound of , etc. are mentioned. These can be used individually or in mixture of 2 or more types.

In this specification, (meth)acrylate means acrylate or methacrylate.

In addition, in order to secure the developability of the colored curable resin composition, the binder resin preferably has an acid value of 20 to 200 mgKOH/g, preferably 30 to 150 mgKOH/g. When the acid value of the binder resin satisfies the above range, the colored curable resin composition can secure a sufficient development rate, and it is preferable to improve adhesion to the substrate to prevent short-circuiting of the pattern.

The weight average molecular weight (Mw) of the binder resin of the present invention may be 3,000 to 30,000, preferably 5,000 to 25,000. In addition, the molecular weight distribution of the binder resin of the present invention, that is, the weight average molecular weight relative to the number average molecular weight (weight average molecular weight (Mw) / number average molecular weight (Mn)) may be 1.5 to 6.0, preferably 1.8 to 4.0, When the binder resin satisfies the ranges of the weight average molecular weight and molecular weight distribution, there is an advantage of excellent developability.

The amount of the binder resin may be included in an amount of 0.5 to 20% by weight, preferably 1 to 15% by weight, based on the total weight of the colored curable resin composition. When the binder resin is included within the above range, it is preferable because it has sufficient solubility in a developing solution to prevent residue generation and facilitate pattern formation.

photopolymerizable compound

The photopolymerizable compound included in the colored curable resin composition of the present invention is a compound that can be polymerized by active radicals, acids, etc. generated from a photopolymerization initiator described later by light irradiation, and is a compound that can be polymerized by the action of the photopolymerization initiator described below. , A monofunctional monomer, a bifunctional monomer, or a multifunctional monomer may be used, and preferably a bifunctional or more polyfunctional monomer 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, but are not limited thereto.

Specific examples of the bifunctional monomer include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate,

Neopentylglycoldi(meth)acrylate, triethylene glycoldi(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A or 3-methylpentanedioldi(meth)acrylate, etc., but limited thereto it is not going to be

Specific examples of the multifunctional monomer include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and pentaerythritol tri (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate acrylate or dipentaerythritol hexa(meth)acrylate, but is not limited thereto.

The photopolymerizable compound may be included in an amount of 1 to 10% by weight, preferably 2 to 5% by weight, based on the total weight of the colored curable resin composition of the present invention. When the photopolymerizable compound is included within the above range, sensitivity and developability are excellent.

photopolymerization initiator

The photopolymerization initiator is a compound that generates a radical or the like capable of initiating polymerization of the photopolymerizable compound described above by exposure to radiation such as visible light, ultraviolet light, deep ultraviolet light, electron beam, or X-ray.

The photopolymerization initiator is not particularly limited as long as it is generally used in this field, but preferably includes an oxime-based compound.

Examples of the oxime-based compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one. Commercially available products include BASF's Irgacure® OXE-01 and OXE-02 OXE-03 etc. are mentioned.

In addition, the photopolymerization initiator may further include other photopolymerization initiators commonly used in this field in addition to the oxime-based compound, as long as the photopolymerization initiator can polymerize the binder resin and the photopolymerizable compound within a range that does not impair the object of the present invention. there is.

Examples of the commonly used photopolymerization initiator include triazine-based compounds, acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and benzoin-based compounds.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethine Toxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxy naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2 -(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl-4,6-bis(trichloromethyl)-s-triazine, 2- Pipenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloro butyl)-6-styryl-s-triazine, 2-(naphtho 1-yl)-4,6- Bis (trichloromethyl) -s-triazine, 2- (4-methoxy naphtho 1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4-trichloro methyl ( piperonyl)-6-triazine, 2,4-trichloromethyl(4'-methoxystyryl)-6-triazine, and the like.

Specific examples of the acetophenone-based compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and p-t-butyltrichloroacetophenone. , p-t-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane -1-one etc. are mentioned.

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

The thioxanthone-based compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone. Oxanthone, 2-chloro thioxanthone, etc. are mentioned.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethylketal.

The photopolymerization initiator may be included in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the total weight of the colored curable resin composition of the present invention. When the photopolymerization initiator is included within the above range, photopolymerization may sufficiently occur during exposure in the pattern forming process, and transmittance may not decrease due to remaining unreacted initiator after photopolymerization.

solvent

In one embodiment of the present invention, the solvent may include propylene glycol monomethyl ether acetate as the first solvent, and at least one of a second solvent having a boiling point of less than 150°C and a third solvent having a boiling point of 150°C or more. Preferably, the solvent includes propylene glycol monomethyl ether acetate as the first solvent, and may include both a second solvent having a boiling point of less than 150 °C and a third solvent having a boiling point of 150 °C or more.

Specific examples of the second solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, benzene, toluene, xylene, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, ethanol, propanol, butanol, γ-butyrolactone, methyl methacrylate, ethyl methacrylate, lauryl methacrylate, and the like, Preferably, propylene glycol monomethyl ether, 3-methoxymethyl butyl acetate and the like are used.

Specific examples of the third solvent include ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, ethylene glycol dibutyl ether, and methyl cellosolve acetate. , ethyl cellosolve acetate, methoxybutyl acetate, mesitylene, cyclohexanone, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, n-butyl methacrylate, dimethyl acrylamide, etc. and preferably propylene glycol diacetate and 4-hydroxy-4methyl-2-pentanone.

In another embodiment of the present invention, the mixed solvent including the first solvent, the second solvent, and the third solvent may have a B value calculated by the following formula 1 of 140 to 155 ° C, preferably 140 to 150 may be °C.

[Equation 1]

[In Equation 1 above,

m _k is the mole fraction of each solvent relative to the mixed solvent, p _k is the boiling point of each solvent,

l is an integer from 0 to 3.]

When the mixed solvent including the first solvent, the second solvent, and the third solvent satisfies the numerical range of the B value calculated by Equation 1, the storage stability is excellent, the generation of foreign substances is suppressed, and the subsequent It is preferable because the generation of VD stains or Pin stains is suppressed even after the process and has an effect of excellent reliability.

In addition, the mole fraction of the first solvent with respect to the mixed solvent may be 1 to 98 mol%, the mole fraction of the second solvent may be 0.5 to 70 mol%, and the mole fraction of the third solvent may be 1 to 50 mol%. Preferably, the mole fraction of the first solvent with respect to the mixed solvent may be 2 to 96 mol%, the mole fraction of the second solvent may be 1 to 55 mol%, and the mole fraction of the third solvent may be 1 to 30 mol%.

When the first solvent, the second solvent, and the third solvent satisfy the numerical range of the mole fraction, the boiling point of the mixed solvent satisfies the numerical range of the B value calculated by Equation 1, and the storage stability is excellent. , foreign matter generation is suppressed, VD stains do not occur in the VD process, and pin stains are suppressed during prebaking due to a low solvent residual amount even after the VD process, thereby providing a highly reliable colored curable resin composition.

In another embodiment of the present invention, the mixed solvent including the first solvent, the second solvent, and the third solvent may have an S value of 8.0 to 10 cal/cm ³ calculated by Equation 2 below, preferably 9.0 to 10 cal/cm ³ .

[Equation 2]

[In Equation 2 above,

a _k is the mole fraction of each solvent with respect to the mixed solvent, b _k is the solubility of each solvent,

l is an integer from 0 to 3.]

When the mixed solvent including the first solvent, the second solvent, and the third solvent satisfies the numerical range of the S value calculated by Equation 2, the storage stability is excellent, the generation of foreign substances is suppressed, and the subsequent It is preferable because the generation of VD stains or Pin stains is suppressed even after the process and has an effect of excellent reliability.

In addition, the mole fraction of the first solvent with respect to the mixed solvent may be 1 to 98 mol%, the mole fraction of the second solvent may be 0.5 to 70 mol%, and the mole fraction of the third solvent may be 1 to 50 mol%. Preferably, the mole fraction of the first solvent with respect to the mixed solvent may be 2 to 96 mol%, the mole fraction of the second solvent may be 1 to 55 mol%, and the mole fraction of the third solvent may be 1 to 30 mol%.

A phenomenon in which, when the first solvent, the second solvent, and the third solvent satisfy the numerical range of the mole fraction, the solubility parameter of the mixed solvent satisfies the numerical range of the S value calculated by Equation 2, and the lightness decreases can be suppressed, the dissolution time of the colored curable resin composition is shortened, storage stability is improved, the occurrence of foreign substances is suppressed, and the occurrence of VD stains or Pin stains can be suppressed even after subsequent processes such as prebaking.

The solvent may be included in an amount of 60 to 95% by weight, preferably 70 to 85% by weight, based on the total weight of the colored curable resin composition. When the solvent is included within the above content range, coating properties are improved when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), an inkjet, and the like, and storage It is preferable because it has excellent stability, suppresses generation of foreign substances, and suppresses generation of VD stains or Pin stains even after subsequent processes such as pre-baking to have excellent reliability.

additive

Additives may be selectively added as needed, and may include, for example, at least one selected from the group consisting of other polymer compounds, curing agents, surfactants, adhesion accelerators, ultraviolet absorbers, and anti-aggregation agents.

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 ether, polyfluoroalkyl acrylate, polyester and polyurethane, and the like. 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, and an oxetane compound.

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 the above epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co)polymer epoxides, isoprene ( co)polymer epoxides, glycidyl (meth)acrylate (co)polymers, and triglycidyl isocyanurate; and the like.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

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. Examples of commercially available products include Adekahadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Ricasiddo HH (manufactured by Nippon Ewha Co., Ltd.), and MH-700 (manufactured by Shinnippon Ewha Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant can be used to further improve the film formation of the colored curable resin composition, and silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric surfactants and the like can be preferably used.

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH-11PA, SH-21PA, and SH-8400 of Dow Corning Toray Silicon as commercial products, and TSF-4440, TSF-4300, and TSF-4445 of GE Toshiba Silicone. , TSF-4446, TSF-4460 and TSF-4452.

Examples of the fluorine-based surfactant include Megapiece F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink & Chemicals Kogyo Co., Ltd. as commercial products.

In addition, commercial products that can be used are KP (Shin-Etsu Chemical High School Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (Tochem Products), Megafac (MEGAFAC) (Dinippon Ink Kagaku High School Co., Ltd.), Flourad (Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) , EFKA (EFKA Chemicals), PB 821 (Ajinomoto Co., Ltd.) and Disperbyk-series (BYK-chemi).

The surfactants exemplified above may be used alone or in combination of two or more, respectively.

The type of adhesion promoter is not particularly limited, and specific examples of usable adhesion promoters 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-methacryloxy Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. are mentioned.

The type of the ultraviolet absorber is not particularly limited, but specific examples that can be used include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyriazole, alkoxybenzophenone, and the like. .

The type of the aggregation inhibitor is not particularly limited, but specific examples that can be used include sodium polyacrylate and the like.

The additives exemplified above may be used alone or in combination of two or more, respectively. The additive may be included in an amount of usually 0.01 to 5% by weight, preferably 0.05 to 2% by weight, based on the total weight of the colored curable resin composition.

<Color filter>

Another aspect of the present invention relates to a color filter formed by being manufactured using the colored curable resin composition described above. A color filter according to an embodiment of the present invention is characterized by including a colored pattern formed by applying the above-described colored curable resin composition on a substrate and exposing and developing in a predetermined pattern.

Hereinafter, the pattern formation method using the colored curable resin composition of the present invention will be described in detail.

A method for forming a pattern using the colored curable resin composition of the present invention may use a method known in the art, but typically includes an application step; exposure step; and a removal step. By applying the colored curable resin composition of the present invention on a substrate, photocuring and developing to form a pattern, it can be used as a colored pixel (colored image).

Specifically, the colored curable resin composition is applied on a glass substrate to which nothing is coated and a glass substrate to which SiNx (protective film) is applied to a thickness of 500 to 1,500 Å using an appropriate method such as spin coating or slit coating, It is applied in a thickness of 3.4 μm. After application, light is irradiated to form a pattern required for the color filter. After light is irradiated, when the coating layer is treated with an alkaline developer, the unirradiated portion of the coating layer is dissolved and a pattern required for the color filter is formed. 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 addition, 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 irradiation with actinic rays or the like.

<Display device>

One embodiment of the present invention relates to a display device including the color filter described above.

The color filter of the present invention is used in various display devices such as not only a normal liquid crystal display (LCD) but also an electroluminescence display (EL), a plasma display (PDP), a field emission display (FED), and an organic light emitting diode (OLED). can be applied to

The display device of the present invention includes configurations known in the art, except for having the color filter described above.

A display device according to an embodiment of the present invention includes, in addition to the above-described color filter, 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. A filter may be additionally provided. In such a case, the emission light of the light source applied to the image display device is not particularly limited, but a light source emitting blue light may be preferably used in terms of better color reproducibility.

A display device according to an exemplary embodiment of the present invention may further include a color filter including only pattern layers of two colors among a red pattern layer, a green pattern layer, and a blue pattern layer, in addition to the color filter described above. In such a case, the color filter further includes a transparent pattern layer that does not contain quantum dot particles. In the case of having only two color pattern layers, a light source emitting light of a wavelength representing the colors other than those not included may be used. For example, in the case of including only a red pattern layer and a green pattern layer, a light source emitting blue light may 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 transmits blue light as it is, showing a blue color.

Hereinafter, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are only examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention has been indicated in the claims, and furthermore contains all changes within the meaning and range equivalent to the written claims. Incidentally, in the following examples and comparative examples, "%" and "parts" indicating content are based on mass unless otherwise specified.

<Example>

Synthesis Example: Synthesis of Azo Compound Represented by Formula 1

Synthesis Example 1: Synthesis of colorant (A-1)

5.0 parts of 2,5-dichloro-4-nitroaniline were added with 4.0 parts of water, 10 parts of acetic acid, 10 parts of methanol, and 25 parts of 98% sulfuric acid, followed by stirring. After ice-cooling, an aqueous solution obtained by dissolving 2.0 parts of sodium nitrite in 3.0 parts of water was added to the reaction solution and stirred for 2 hours to obtain a suspension containing a diazonium salt. On the other hand, after adding 15 parts of methanol to 3.0 parts of barbituric acid (α), 100 parts of 25% sodium hydroxide aqueous solution was added under ice cooling and stirred. The suspension containing the said diazonium salt was dripped here. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour to obtain an orange suspension. The orange solid obtained by filtration was dried at 60°C under reduced pressure to obtain a compound represented by formula (1).

Subsequently, 97 parts of water, 4.1 parts of sodium bicarbonate, and 3.8 parts of sodium sulfide hydrate were added to 8.4 parts of the compound represented by Formula (1), and the mixture was stirred at 85°C for 2 hours. After cooling the reaction solution to room temperature, the reaction solution was neutralized to pH 6 with 35% hydrochloric acid and precipitated to obtain a solid. The obtained solid was washed with water and filtered, and the obtained red solid was dried at 60° C. under reduced pressure to obtain 6.3 parts of the compound represented by Formula (2).

Subsequently, 20 parts of water, 6.7 parts of acetic acid, and 33 parts of 98% sulfuric acid were added to 2.1 parts of the compound represented by Formula (2), followed by stirring. After cooling the reaction mixture on ice, 0.6 parts of sodium nitrite were dissolved in 3.3 parts of water. The aqueous solution was added to the reaction solution and stirred for 2 hours to obtain a suspension containing a diazonium salt. On the other hand, after adding 0.8 parts of methanol to 0.8 parts of barbituric acid (β), 15 parts of 25% sodium hydroxide aqueous solution were added under ice-cooling and stirred. Here, the suspension containing the diazonium salt described above was added dropwise. After completion of the dropwise addition, a red suspension was obtained by further stirring at room temperature for 1 hour. After filtering and washing the suspension solution, the obtained solid was dried at 60° C. under reduced pressure to obtain 1.7 parts (yield: 57%) of an azo compound represented by Formula (A-1).

(Mass Spectrometry) Ionization Mode=ESI: m/z=453.0 [MH] ^-

Synthesis Example 2: Synthesis of colorant (A-2)

Replacement of 3.0 parts of barbituric acid (α) with 5.1 parts of 1,3-dicyclohexyl barbituric acid (α) and 0.8 parts of barbituric acid (β) with 0.7 parts of 1,3-dicyclohexylbarbituric acid (β) Other than that, 0.4 part (yield: 15%) of the compound represented by formula (A-2) was obtained in the same manner as in Synthesis Example 1.

(mass spectrometry) ionization mode=ESI: m/z = 783 . 4 [ M + H ] ⁺

Synthesis Example 3: Synthesis of colorant (A-3)

3.0 parts of barbituric acid (α) 3-cyano-1-butyl-6-hydroxy-4-methyl-2-pyridone (α) 1.8 parts, 0.8 parts of barbituric acid (β) 3-cyano-1 -Butyl-6-hydroxy-4-methyl-2-pyridone (β) 3.9 parts (yield: 66%) of the compound represented by Formula (A-3) was prepared in the same manner as in Synthesis Example 1 except for replacing with 1.4 parts. got it

(mass spectrometry) ionization mode=ESI: m/z = 609 . 2 [ M - H ] ^-

Synthesis Example 4: Synthesis of colorant (A-4)

3.0 parts of barbituric acid (α) to 4.2 parts of 3-methyl-1-phenyl-5-pyrazolone (α), 0.8 part of barbituric acid (β) 0.5 part of 3-methyl-1-phenyl-5-pyrazolone (β) 0.8 part (yield: 53%) of the compound represented by formula (A-4) was obtained in the same manner as in Synthesis Example 1 except for replacing with part.

(mass spectrometry) ionization mode=ESI: m/z = 547 . 2 [ M + H ] ⁺

Synthesis Example 5: Synthesis of colorant (A-5)

3.0 parts of barbituric acid (α) 3-methyl-1-(4-sulfophenyl)-2-pyrazolin-5-one (α) 4.9 parts, 0.8 parts of barbituric acid (β) 3-methyl-1-( 1.2 parts of the compound represented by Formula (A-5) (yield: 58%) was obtained in the same manner as in Synthesis Example 1 except for replacing with 0.7 parts of 4-sulfophenyl)-2-pyrazolin-5-one (β).

(mass spectrometry) ionization mode=ESI: m/z = 705 . 0 [ M - H ] ⁺

Synthesis Example 6: Synthesis of colorant (A-6)

Represented by Formula (A-6) in the same manner as in Synthesis Example 1 except that 0.8 parts of barbituric acid (β) was replaced with 1.2 parts of 3-cyano-1-butyl-6-hydroxy-4-methyl 2-pyridone. 1.9 parts of the compound to be obtained (yield 56%).

(mass spectrometry) ionization mode=ESI: m/z = 533 . 0 [ M + H ] ⁺

Synthesis Example 7: Synthesis of colorant (A-7)

1.5 parts of the compound represented by Formula (A-7) in the same manner as in Synthesis Example 1 except that 0.8 parts of barbituric acid (β) was replaced with 1.0 parts of 3-methyl-1-phenyl-5-pyrazolone (yield 54%) got

(mass spectrometry) ionization mode=ESI: m/z = 499 . 1 [ M - H ] ^-

Synthesis Example 8: Synthesis of colorant (A-8)

Represented by Formula (A-8) in the same manner as in Synthesis Example 1 except that 0.8 part of barbituric acid (β) was replaced with 0.5 part of 3-methyl-1-(4-sulfophenyl)-2-pyrazolin-5-one. 1.2 parts of the compound to be obtained (yield 37%).

(mass spectrometry) ionization mode=ESI: m/z = 579 . 0 [ M - H ] ^-

Synthesis Example 9: Synthesis of colorant (A-9)

A compound represented by formula (A-9) in the same manner as in Synthesis Example 2, except that 0.7 part of 1,3-dicyclohexylbarbituric acid (β) was replaced with 0.2 part of 3-methyl-1-phenyl-5-pyrazolone. 0.3 part (yield 31%) was obtained.

(mass spectrometry) ionization mode=ESI: m/z = 664 . 0 [ M ] ^-

Synthesis Example 10: Synthesis of Colorant (A-10)

The same method as in Synthesis Example 4 except that 4.2 parts of 3-methyl-1-phenyl-5-pyrazolone (α) was replaced with 18 parts of 3-methyl-1-(4-sulfophenyl)-2-pyrazolin-5-one. As a result, 35 parts (yield: 73%) of the compound represented by formula (A-10) was obtained.

(mass spectrometry) ionization mode=ESI: m/z = 625 . 1 [ M - H ] ^-

Synthesis Example 11: Synthesis of Colorant (A-11)

15 parts of chloroform and 0.4 part of N,N-dimethylformamide were added to 1.5 parts of the azo compound represented by Formula (A-10), stirred, and 0.6 part of thionyl chloride was added dropwise while maintaining the temperature at 20°C or lower. After completion of the dropwise addition, the temperature was raised to 50°C, reacted at the same temperature for 3 hours, and then cooled to 20°C. After cooling, a mixture of 0.5 parts of 2-methylcyclohexylamine and 1.9 parts of triethylamine was added dropwise while maintaining the reaction solution at 20° C. or less under stirring. Then, it was reacted for 5 hours at the same temperature. Subsequently, after removing the solvent from the obtained reaction mixture with an evaporator, a small amount of methanol was added and vigorously stirred. This mixture was added dropwise to 45 parts of 20% sodium chloride aqueous solution while stirring to precipitate crystals. The precipitated crystals were washed with water and dried at 60° C. under reduced pressure to obtain 1.2 parts of the compound represented by Formula (A-11) (74% yield).

(mass spectrometry) ionization mode=ESI: m/z = 720 . 2 [ M - H ] -

Synthesis Example 12: Synthesis of Colorant (A-12)

0.8 part of the compound represented by formula (A-12) (58% yield) was obtained in the same manner as in Synthesis Example 11 except that 0.5 part of 2-methylcyclohexylamine was replaced with 2.1 part of 3,5-di-tert-butylaniline. .

(mass spectrometry) ionization mode=ESI: m/z = 813 . 2 [M]-

Synthesis Example 13: Synthesis of Colorant (A-13)

1.2 parts of the compound represented by Formula (A-13) (yield: 74%) was obtained in the same manner as in Synthesis Example 11 except that 0.5 parts of 2-methylcyclohexylamine was replaced with 1.3 parts of aniline.

(mass spectrometry) ionization mode=ESI: m/z = 701 . 1 [M]-

Synthesis Example 14: Synthesis of Colorant (A-14)

Except for replacing 0.5 parts of 2-methylcyclohexylamine with 1.8 parts of 1-adamantanamine, 0.9 parts of the compound represented by formula (A-14) was obtained in the same manner as in Synthesis Example 11 (59% yield).

(mass spectrometry) ionization mode=ESI: m/z = 759 . 2 [ M ]

Synthesis Example 15: Synthesis of Colorant (A-15)

Except for replacing 0.5 parts of 2-methylcyclohexylamine with 1.2 parts of 1,3-dimethylbutylamine, 0.9 parts of the compound represented by Formula (A-15) (yield: 62%) was obtained in the same manner as in Synthesis Example 11.

(mass spectrometry) ionization mode=ESI: m/z = 709 . 2 [M]-

Synthesis Example 16: Synthesis of Colorant (A-16)

To 0.5 part of the azo compound represented by Formula (A-10), 60 parts of water and 60 parts of N,N-dimethylformamide were added and stirred, and 1.2 parts of barium acetate were added. The temperature was raised to 60°C, reacted at the same temperature for 2 hours, and then cooled to 20°C. After cooling, the reaction solution was filtered, washed with methanol, and then dried at 60°C under reduced pressure to obtain 0.4 part (yield: 76%) of the compound represented by the formula (A-16).

Synthesis Example 17: Synthesis of Colorant (A-17)

1.5 parts of the azo compound represented by the formula (A-10) to 12 parts of the azo compound represented by the formula (A-5), 0.4 parts of N,N-dimethylformamide to 0.3 parts, 0.6 parts to 9.4 parts of thionyl chloride, 2-methyl 0.4 part of the compound represented by the formula (A-17) (yield: 28%) was obtained in the same manner as in Synthesis Example 11, except that 0.5 part of cyclohexylamine was changed to 2.3 parts and 1.9 parts of triethylamine was changed to 5.3 parts.

(mass spectrometry) ionization mode=ESI: m/z = 895 . 2 [ M - H ] -

Synthesis Example 18: Synthesis of Colorant (A-18)

3.2 parts of the compound represented by formula (A-18) in the same manner as in Synthesis Example 7, except that 5.0 parts of 2,5-dichloro-4-nitroaniline was replaced with 3.0 parts of 2-methyl-4-nitroaniline (yield: 65%) got

(mass spectrometry) ionization mode=ESI: m/z = 445 . 2 [ M - H ] -

Synthesis Example 19: Synthesis of Colorant (A-19)

4.0 parts of the compound represented by formula (A-19) in the same manner as in Synthesis Example 10, except that 5.0 parts of 2,5-dichloro-4-nitroaniline was replaced with 6.0 parts of 2-methyl-4-nitroaniline (yield: 90%) got

(mass spectrometry) ionization mode=ESI: m/z = 571 . 2 [ M - H ] -

Synthesis Example 20: Synthesis of Colorant (A-20)

0.3 parts of the compound represented by the formula (A-20) in the same manner as in Synthesis Example 11, except that 1.5 parts of the azo compound represented by the formula (A-10) was replaced with 1.5 parts of the azo compound represented by the formula (A-19) Yield 20%) was obtained.

(mass spectrometry) ionization mode=ESI: m/z = 666 . 3 [ M - H ] -

Synthesis Example 21: Synthesis of Colorant (A-21)

1.3 parts of the compound represented by formula (A-21) in the same manner as in Synthesis Example 4, except that 5.0 parts of 2,5-dichloro-4-nitroaniline was replaced with 3.0 parts of 2-chloro-4-nitroaniline (yield: 40%) got

(mass spectrometry) ionization mode=ESI: m/z = 513 . 3 [ M + H ]

Synthesis Example 22: Synthesis of Colorant (A-22)

0.3 part of the compound represented by Formula (A-22) in the same manner as in Synthesis Example 4, except that 5.0 parts of 2,5-dichloro-4-nitroaniline was replaced with 3 parts of 2,6-dichloro-4-nitroaniline (yield: 21 %) was obtained.

(mass spectrometry) ionization mode=ESI: m/z = 545 . 3 [ M - H ] -

Synthesis Example 23: Synthesis of Colorant (A-23)

2.4 parts of the compound represented by Formula (A-23) (yield: 73%) was obtained in the same manner as in Synthesis Example 4, except that 5.0 parts of 2,5-dichloro-4-nitroaniline was replaced with 2.0 parts of 4-nitroaniline.

(mass spectrometry) ionization mode=ESI: m/z = 479 . 5 [ M + H ]+

Synthesis Example 24: Synthesis of Colorant (A-24)

0.3 part of the compound represented by Formula (A-24) in the same manner as in Synthesis Example 4, except that 5.0 parts of 2,5-dichloro-4-nitroaniline was replaced with 1.0 part of 2,5-dimethoxy-4-nitroaniline (yield) 15%) was obtained.

(mass spectrometry) ionization mode=ESI: m/z = 537 . 2 [ M - H ] -

Preparation Example: Preparation of Azo Compound Dispersion and Colorant Dispersion

Preparation Example 1: Azo compound dispersion (a1-1)

4.5 parts of the compound represented by formula (A-1) obtained in Synthesis Example 1, 0.5 parts of binder (k), 5.7 parts of dispersing agent (BYKLPN-6919 manufactured by BYK) (converted to solid content), dispersion resin (30 parts of methacrylic acid and benzyl A copolymer of 70 parts of methacrylate, an acid value of 80 mgKOH/g, a weight average molecular weight in terms of polystyrene of 11,000) (solid content) of 9.9 parts, propylene glycol monomethyl ether acetate 74.3 parts and diacetone alcohol 5.0 parts were mixed, and 0.2 mm zirconia beads 300 Part was added, mixed and dispersed to obtain an azo compound dispersion (a1-1).

Preparation Example 2: Azo compound dispersion (a1-2)>

An azo compound dispersion (a1-2) was obtained in the same manner as in Preparation Example 1 except that the compound represented by Formula (A-1) was replaced with the compound represented by Formula (A-2) obtained in Synthesis Example 2.

Preparation Example 3: Azo compound dispersion (a1-3)>

An azo compound dispersion (a1-3) was obtained in the same manner as in Preparation Example 1 except that the compound represented by formula (A-1) was replaced with the compound represented by formula (A-4) obtained in Synthesis Example 4.

Preparation Example 4: Azo compound dispersion (a1-4)>

An azo compound dispersion (a1-4) was obtained in the same manner as in Preparation Example 1 except that the compound represented by formula (A-1) was replaced with the compound represented by formula (A-15) obtained in Synthesis Example 15.

Preparation Example 5: Azo compound dispersion (a1-5)>

An azo compound dispersion (a1-5) was obtained in the same manner as in Production Example 1, except that the compound represented by formula (A-1) was replaced with the compound represented by formula (A-21) obtained in Synthesis Example 21.

Preparation Example 6: Azo compound dispersion (a1-6)>

An azo compound dispersion (a1-6) was obtained in the same manner as in Preparation Example 1 except that the compound represented by formula (A-1) was replaced with the compound represented by formula (A-24) obtained in Synthesis Example 24.

Preparation Example 7: Yellow colorant dispersion (a2)

C.I. A yellow colorant dispersion (a2) was obtained in the same manner as in Preparation Example 1 except for replacing with Pigment Yellow 139.

Preparation Example 8: Red colorant dispersion (a3)

C.I. A red colorant dispersion (a3) was obtained in the same manner as in Preparation Example 1 except for replacing with Pigment Red 254.

Preparation Example 9: Red colorant dispersion (a4)

C.I. A red colorant dispersion (a4) was obtained in the same manner as in Preparation Example 1 except for replacing with Pigment Red 291.

Preparation Example 10: Red colorant dispersion (a5)

C.I. A red colorant dispersion (a5) was obtained in the same manner as in Preparation Example 1 except for replacing with Pigment Red 177.

Preparation Example 11: Red colorant dispersion (a6)

C.I. A red colorant dispersion (a6) was obtained in the same manner as in Preparation Example 1 except for replacing with Pigment Red 202.

Preparation Example 12: Purple colorant dispersion (a7)

C.I. A purple colorant dispersion (a7) was obtained in the same manner as in Preparation Example 1 except for replacing with Pigment Violet 19.

Examples 1 to 14 and Comparative Examples 1 to 8: Preparation of colored curable resin composition

Colored curable resin compositions were prepared according to the compositions and contents of Tables 1 to 3 below.

Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 (A) a1-1 24 24 24 24 24 24 24 a5 23 23 23 23 23 23 23 a7 4 4 4 4 4 4 4 (B) 7 7 7 7 7 7 7 (C) 4 4 4 4 4 4 4 (D) One One One One One One One (E-1) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (E-2) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (F) F-1 31.8 34.4 33.2 33.2 29.5 24.7 28.7 F-2 4.9 4.9 9.7 4.9 F-3 2.3 2.3 2.3 F-4 3.5 3.1 F-5 3.5

Example
8 Example
9 Example 10 Example 11 Example 12 Example 13 Example 14 (A) a1-1 24 24 a1-2 24 a1-3 24 a1-4 24 a1-5 24 a1-6 24 a5 23 23 23 23 23 23 23 a7 4 4 4 4 4 4 4 (B) 7 7 7 7 7 7 7 (C) 4 4 4 4 4 4 4 (D) One One One One One One One (E-1) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (E-2) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (F) F-1 28.7 30.9 29.5 29.5 29.5 29.5 29.5 F-2 4.9 4.9 4.9 4.9 4.9 4.9 F-3 2.3 2.3 2.3 2.3 2.3 2.3 F-4 3.5 F-5 3.1

comparative example
One comparative example
2 comparative example
3 comparative example
4 comparative example
5 comparative example
6 comparative example
7 comparative example
8 (A) a1-1 24 24 24 24 24 - - - a2 13 a3 11 11 a5 23 23 23 23 23 33 26 33 a7 4 4 4 4 4 6 5 6 (B) 7 7 7 7 7 One 6 One (C) 4 4 4 4 4 3 3 3 (D) One One One One One One One One (E-1) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (E-2) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (F) F-1 22.3 9.3 20.4 27.6 12.3 40.8 35 25 F-2 10.4 17.6 9.1 5.9 8.5 19.7 F-3 6.5 18.5 2.2 F-4 9.8 9.8 F-5 4 3.9

(A) colorant

(a1-1 to a1-6): Azo compound dispersions according to Preparation Examples 1 to 6

(a2): Yellow colorant dispersion according to Preparation Example 13

(a3): Red colorant dispersion according to Preparation Example 14

(a5): Red colorant dispersion according to Preparation Example 16

(a7): Purple colorant dispersion according to Preparation Example 18

(B) binder resin: methyl methacrylate 10 parts by weight, cyclohexyl methacrylate 30 parts by weight, glycidyl methacrylate 56 parts by weight, n-dodecanethiol 5 parts by weight copolymer binder resin

(C) Photopolymerizable compound: A9550 (Shin Nakamura Co.)

(D) Photopolymerization initiator: OXE-02 (Basf Company)

(E-1) Additive 1: Silicone surfactant (SH-8400)

(E-2) Additive 2: adhesion promoter (3-methacryloxypropyltrimethoxysilane)

(F) Solvent

(F-1): Propylene glycol monomethyl ether acetate

(F-2): propylene glycol monomethyl ether

(F-3): propylene glycol diacetate

(F-4): 4-hydroxy-4methyl-2-pentanone

(F-5): 3-methoxymethylbutylacetate

Experimental example

1. Manufacture of color filters

The colored curable resin composition according to Examples and Comparative Examples 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 in). 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.

2. Calculation of colorant concentration

The colorant concentration (weight concentration of the colorant based on the total solid weight of the composition) of the colored curable resin composition according to the Examples and Comparative Examples prepared above was calculated. The colorant concentration of the colored curable resin composition of Comparative Example 1 was set as the standard (100%), and the colorant concentration of the colored curable resin composition according to the remaining Examples and Comparative Examples was calculated as a relative value (%) in comparison with this. The lower the numerical value, the better the physical properties. The results are shown in Tables 10 to 12 below.

3. Solvent resistance evaluation

After cutting the color filter prepared above into 3x3cm, it was immersed in 14.6 ml of NMP (N-Methyl-2-pyrrolidone) solution at 80°C/40 minutes. After that, the absorbance of the immersion liquid was measured using a UV-Vis spectrometer to evaluate solvent resistance according to the following evaluation criteria, and the results are shown in Tables 10 to 12 below.

< Solvent Resistance Evaluation Criteria >

○: Absorbance 2 or less

△: Absorbance greater than 2 and less than or equal to 4

×: absorbance greater than 4

4. Evaluation of UV ashing resistance

UV of 2000 mW/cm ³ was irradiated on the color filter prepared above using an ultraviolet ozone cleaning device (UV-312, manufactured by technovision.inc), and the color difference β ^* before and after UV irradiation was calculated using Equation 1 below After that, UV ashing resistance was evaluated according to the following evaluation criteria, and the results are shown in Tables 10 to 12 below.

[Equation 1]

ΔEab ^* =[(ΔL ^* ) ² +(Δa ^* ) ² +(Δb ^* ) ² ] ^1/2

< UV ashing resistance evaluation criteria >

○: △Eab ^* = less than 5

×: ΔEab ^* = 5 or more

5. Boiling Point Calculation of Mixed Solvents Included in Colored Curable Resin Composition

The boiling point of the mixed solvent included in the colored curable resin composition according to the Examples and Comparative Examples was measured and calculated with reference to Equation 1 and Table 2 below. Measurement and calculation results are shown in Tables 4 to 6 below.

[Equation 1]

(In Equation 1 above,

m _k is the mole fraction of each solvent relative to the mixed solvent, p _k is the boiling point of each solvent,

l is an integer from 0 to 3.)

Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 m ₁ (mol%) 81.6 94.8 89.3 91.3 76.5 60.5 72.8 p ₁ (℃) 147 147 147 147 147 147 147 m ₂ (mol%) 18.4 5.2 10.7 8.7 18.6 34.8 18.2 p ₂ (℃) 119 191 166 172 119 119 119 m ₃ (mol%) 4.9 4.7 9.0 p ₃ (℃) 191 191 166 B(℃) 141.8 149.3 149.0 149.2 143.9 139.3 143.6

Example
8 Example
9 Example
10 Example
11 Example
12 Example
13 Example
14 m ₁ (mol%) 74.2 84.0 76.5 76.5 76.5 76.5 76.5 p ₁ (℃) 147 147 147 147 147 147 147 m ₂ (mol%) 18.6 5.2 18.6 18.6 18.6 18.6 18.6 p ₂ (℃) 119 191 119 119 119 119 119 m ₃ (mol%) 7.2 10.8 4.9 4.9 4.9 4.9 4.9 p ₃ (℃) 172 166 191 191 191 191 191 B(℃) 143.6 151.3 143.9 143.9 143.9 143.9 143.9

comparative example
One comparative example
2 comparative example
3 comparative example
4 comparative example
5 comparative example
6 comparative example
7 comparative example
8 m ₁ (mol %) 54.2 20.1 55.3 67.4 34 91.3 76.5 46.4 p ₁ (℃) 147 147 147 147 147 147 147 147 m ₂ (mol%) 37 55.8 14.5 32.6 23.9 8.7 18.6 53.6 p ₂ (℃) 119 119 191 119 119 172 119 119 m ₃ (mol%) 8.8 24.1 30.2 42.1 4.9 p ₃ (℃) 172 166 166 191 191 B(℃) 152.2 136 159.1 137.9 158.9 149.2 143.9 132.0

6. Measurement of solubility parameters of mixed solvents included in colored curable resin composition

Solubility parameters of the mixed solvents included in the colored curable resin compositions according to Examples and Comparative Examples were measured and calculated with reference to Equation 2 and Table 3 below. Measurement and calculation results are shown in Tables 7 to 9 below.

[Equation 2]

(In Equation 2 above,

a _k is the mole fraction of each solvent with respect to the mixed solvent, b _k is the solubility of each solvent,

l is an integer from 0 to 3.)

Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 a ₁ (mol %) 81.6 94.8 89.3 91.3 76.5 60.5 72.8 b ₁ (cal/cm ³ ) 8.7 8.7 8.7 8.7 8.7 8.7 8.7 _a2 (mol%) 18.4 5.2 10.7 8.7 18.6 34.8 18.2 b ₂ (cal/cm ³ ) 12.1 9.6 14.8 8.7 12.1 12.1 12.1 a ₃ (mol%) 4.9 4.7 9.0 b ₃ (cal/cm ³ ) 9.6 9.6 14.8 S(cal/cm ³ ) 9.3 8.7 9.4 8.7 9.4 9.9 9.9

Example
8 Example
9 Example
10 Example
11 Example
12 Example
13 Example
14 a ₁ (mol %) 74.2 84.0 76.5 76.5 76.5 76.5 76.5 b ₁ (cal/cm ³ ) 8.7 8.7 8.7 8.7 8.7 8.7 8.7 _a2 (mol%) 18.6 5.2 18.6 18.6 18.6 18.6 18.6 b ₂ (cal/cm ³ ) 12.1 9.6 12.1 12.1 12.1 12.1 12.1 a ₃ (mol%) 7.2 10.8 4.9 4.9 4.9 4.9 4.9 b ₃ (cal/cm ³ ) 8.7 14.8 9.6 9.6 9.6 9.6 9.6 S(cal/cm ³ ) 9.3 9.4 9.4 9.4 9.4 9.4 9.4

comparative example
One comparative example
2 comparative example
3 comparative example
4 comparative example
5 comparative example
6 comparative example
7 comparative example
8 a ₁ (mol%) 54.2 20.1 55.3 67.4 34 91.3 76.5 46.4 b ₁ (cal/cm ³ ) 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7 _a2 (mol%) 37 55.8 14.5 32.6 23.9 8.7 18.6 53.6 b ₂ (cal/cm ³ ) 12.1 12.1 9.6 12.1 12.1 8.7 12.1 12.1 a ₃ (mol%) 8.8 24.1 30.2 42.1 4.9 b ₃ (cal/cm ³ ) 8.7 14.8 14.8 9.6 9.6 S(cal/cm ³ ) 10.9 12.1 10.7 9.8 9.9 8.7 9.4 10.5

7. Assessment of storage stability

The viscosity of the colored curable resin composition was measured using a viscometer. After storing this colored curable composition at 40° C. for 7 days, the viscosity was measured and the thickening rate was calculated according to the following formula. The evaluation results are shown in Tables 10 to 12 below.

Thickening rate = (viscosity after 7 days storage) / (viscosity immediately after preparation) * 100

○: More than 97% and 103% or less

△: more than 95% and less than or equal to 97%, more than 103% and less than or equal to 105%

×: 95% or less, greater than 105%

8. Foreign body evaluation

The colored photosensitive resin compositions prepared in Examples and Comparative Examples were stored at 5° C. for 1 month, respectively, and then observed under a reflection type optical microscope (observation magnification: 2,500 times) to evaluate foreign matter over time according to the following criteria. The evaluation results are shown in Tables 10 to 12 below.

○: less than 3 foreign substances

△: 3 to 10 foreign bodies

×: 11 or more foreign substances

9. VD stain evaluation

The red photosensitive resin composition was applied to a 2-inch glass substrate ("EAGLE XG", manufactured by Corning) by spin coating to have the same thickness, and then a vacuum drying process was performed, and the stain was observed with the naked eye. . The evaluation results are shown in Tables 10 to 12 below.

○: 5 or less VD stains

△: more than 5 and not more than 10 VD stains

X: >10 VD blobs

10. Pin Blot Assessment

After applying the red photosensitive resin composition to the same thickness on a 2-inch square glass substrate ("EAGLE XG" manufactured by Corning) by spin coating on the top of the glass substrate, vacuum drying it, and then placing it on a heating plate at 100 ° C. After maintaining at the temperature for 3 minutes, the stain was observed, and the color change value of the flat plate part and the pin part was evaluated. The evaluation results are shown in Tables 10 to 12 below.

○: △Rx 1/1,000 or less

△: △Rx more than 1/1,000 and less than 2/1,000

X: △Rx greater than 2/1,000

Experiment result

Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 colorant concentration 100% 100% 100% 100% 100% 100% 100% solvent resistance ○ ○ ○ ○ ○ ○ ○ UV ashing resistant ○ ○ ○ ○ ○ ○ ○ S 9.3 8.7 9.4 8.7 9.4 9.9 9.9 B 141.8 149.3 149 149.2 143.9 139.3 143.6 storage stability ○ ○ ○ ○ ○ ○ ○ foreign body evaluation ○ ○ ○ ○ ○ ○ ○ VD stain ○ ○ ○ ○ ○ ○ ○ Pin stain ○ ○ ○ ○ ○ ○ ○

Example
8 Example
9 Example
10 Example
11 Example
12 Example
13 Example
14 colorant concentration 100% 100% 104% 100% 102% 101% 100% solvent resistance ○ ○ ○ ○ ○ ○ ○ UV ashing resistant ○ ○ ○ ○ ○ ○ ○ S 9.3 9.4 9.4 9.4 9.4 9.4 9.4 B 143.6 151.3 143.9 143.9 143.9 143.9 143.9 storage stability ○ ○ ○ ○ ○ ○ ○ foreign body evaluation ○ ○ ○ ○ ○ ○ ○ VD stain ○ ○ ○ ○ ○ ○ ○ Pin stain ○ ○ ○ ○ ○ ○ ○

comparative example
One comparative example
2 comparative example
3
comparative example
4 comparative example
5 comparative example
6 comparative example
7 comparative example
8 color material concentration 100% 100% 100% 100% 100% 142% 117% 142% solvent resistance ○ ○ ○ ○ ○ Х Х Х UV ashing resistant ○ ○ ○ ○ ○ Х Х Х S 10.9 12.1 10.7 9.8 9.9 8.7 9.4 10.5 B 152.2 136 159.1 137.9 158.9 149.2 143.9 132.0 storage stability △ Х △ ○ ○ ○ ○ △ foreign body evaluation △ Х △ ○ ○ ○ ○ △ VD stain ○ Х ○ Х ○ ○ ○ Х Pin stain ○ ○ Х ○ Х ○ ○ ○

Referring to the experimental results of Tables 10 to 12 above,

Examples 1 to 14, which include the compound represented by Formula 1 intended in the present invention and the mixed solvent satisfies Formula 1 or Formula 2, have solvent resistance and UV ashing resistance. It was confirmed that the storage stability was excellent, the occurrence of foreign matter was suppressed, and the occurrence of VD stains and Pin stains that could occur in the manufacturing process of the colored curable resin composition were suppressed.

Comparative Examples 6 to 8, which do not contain the compound represented by Formula 1, have poor solvent resistance and UV ashing resistance, and Comparative Examples 1 to 5 and 8, in which mixed solvents do not satisfy Formula 1 or Formula 2, have poor storage stability. Foreign matter was generated, and it was confirmed that the occurrence of VD stains or Pin stains was not suppressed.

Claims (11)

A colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,
The colorant includes a compound represented by Formula 1 below,
The solvent includes propylene glycol monomethyl ether acetate as a first solvent,
At least one of a second solvent having a boiling point of less than 150 ° C. and a third solvent having a boiling point of 150 ° C. or more,
Characterized in that the B value calculated by Equation 1 is 140 to 155 ° C,
A colored curable resin composition.
[Formula 1]

(In Formula 1, L ¹ is a group represented by formula (ph1), A is a group represented by formula (ia), and B is a group represented by formula (ib).)

(In formula (ph1), X ¹ is a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -NH ₂ , -CONH ₂ , -COOH, -CN, or an alkoxy group having 1 to 10 carbon atoms) , represents an alkylthio group or halogen atom having 1 to 4 carbon atoms, -CH ₂ - contained in the hydrocarbon group may be substituted with -O-, -CO- or -NH-, and -CH contained in the hydrocarbon group = may be substituted with -N=.
n represents an integer of 0 to 4; When n is an integer greater than or equal to 2, several X ¹ may be the same or different. When n is an integer of 2 or greater and X ¹ is bonded to adjacent carbon atoms, X ¹ bonded to adjacent carbon atoms may bond to each other to form a ring.
* represents the number of bonds with A, and ** represents the number of bonds with B.)

(In formulas (ia) and (ib), X ⁶ to X ⁹ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the hydrocarbon group is -O It may be substituted with -, -CO- or -NH-, -CH= contained in the hydrocarbon group may be substituted with -N=, and -CH< contained in the hydrocarbon group may be replaced with -N< , An oxygen atom, a nitrogen atom or a carbonyl group may be inserted between the carbon atoms constituting the hydrocarbon group.
X ⁶ and X ⁷ may be bonded to each other to form a ring, and X ⁸ and X ⁹ may be bonded to each other to form a ring.
* indicates the number of bonds with L ¹ .)
[Equation 1]

(In Equation 1 above,
m _k is the mole fraction of each solvent relative to the mixed solvent, p _k is the boiling point of each solvent,
l is an integer from 0 to 3.)
The method of claim 1,
Said L ¹ is a group represented by formula (ph2), colored curable resin composition.

(In formula (ph2), X ² to X ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -NH ₂ , -CONH ₂ , -COOH, -CN, an alkoxy group having 1 to 4 carbon atoms, and a carbon atom 1 represents an alkylthio group of ~4 or a halogen atom.
X ² and X ³ and X ⁴ and X ⁵ may combine with each other to form a ring.
* indicates the number of bonds with A, and ** indicates the number of bonds with B.)
The method of claim 1,
The solvent is
A colored curable resin composition comprising the second solvent and the third solvent.
The method of claim 1,
The second solvent includes at least one selected from the group consisting of propylene glycol monomethyl ether and 3-methoxymethyl butyl acetate,
Characterized in that the third solvent includes at least one selected from the group consisting of propylene glycol diacetate and 4-hydroxy-4 methyl-2-pentanone.
A colored curable resin composition.
The method of claim 1,
The mole fraction of the first solvent is 1 to 98 mol%,
The mole fraction of the second solvent is 0.5 to 70 mol%,
Characterized in that the mole fraction of the third solvent is 1 to 50 mol%,
A colored curable resin composition.
The method of claim 1,
Characterized in that the S value calculated by Equation 2 is 8.0 to 10 cal / cm ³ ,
A colored curable resin composition.
[Equation 2]

(In Equation 2 above,
a _k is the mole fraction of each solvent with respect to the mixed solvent, b _k is the solubility of each solvent,
l is an integer from 0 to 3.)
The method of claim 1,
With respect to the total weight of the colored curable resin composition,
Colored curable resin composition containing 60 to 95% by weight of a solvent.
The method of claim 1,
With respect to the total weight of the colored curable resin composition,
1 to 15% by weight of a colorant;
0.5 to 20% by weight of a binder resin;
1 to 10% by weight of a photopolymerizable compound and
Containing 0.1 to 10% by weight of a photopolymerization initiator,
A colored curable resin composition.
The method of claim 1,
The colored curable resin composition is for forming a red pixel, colored curable resin composition.
A color filter comprising a colored pattern made of the colored curable resin composition according to any one of claims 1 to 9.
An image display device comprising the color filter of claim 10.