KR102661296B1 - 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, an antioxidant, and a solvent. The colorant includes a compound represented by the following formula (1), and the antioxidant includes a phenol-based antioxidant, a phosphorus-based antioxidant, and It relates to a colored curable resin composition, characterized in that it contains at least one member selected from the group selected from sulfur-based antioxidants, and a color filter and image display device containing the same, wherein high color reproduction is achieved even at a relatively low colorant weight concentration (PWC). At the same time, it has excellent brightness and UV ashing effects, and has excellent heat resistance and adhesion, improving reliability from the external environment.

Description

Colored curable resin composition, color filter and display device manufactured using the same {A COLORED CURABLE RESIN COMPOSITION, A COLOR FILTER AND A DISPLAY DEVICE 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 imaging devices, liquid crystal displays (LCDs), and organic light emitting diodes (OLEDs), and their application range is rapidly expanding.

The color filter used in the display device consists of three coloring patterns: Red, Green, and Blue, or three colors: Yellow, Magenta, and Cyan. It is made up of colored patterns.

The colored pattern of each of the color filters 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. Colored pattern processing using the colored curable resin composition is typically performed through a lithography process.

Recently, the market demand for high-quality displays with high color reproduction is growing, and accordingly, the content of colorants included in the colored curable resin composition used to manufacture color filters is continuously increasing, with better coloring power, contrast ratio, and reliability. The use of colorants is being considered.

As the content of the colorant increases, not only does the manufacturing cost improve, but a reverse taper phenomenon occurs when forming a pattern with the colored curable resin composition, and sensitivity decreases, making it difficult to form steps using a halftone mask, which increases fairness. , reliability problems may arise.

Additionally, when manufacturing a color filter using the colored curable resin composition, there was a problem such as the generation of polymer by-products during exposure and development.

In Republic of Korea Patent Publication No. 10-2009-0041338, C.I. Blue pigments such as Pigment Blue 15:6, C.I. A technology for producing a radiation-sensitive composition is disclosed by adding a purple pigment such as Pigment Violet 19 and any antioxidant selected from the group consisting of phenol-based, phosphorus-based, and sulfur-based, but the published patent does not provide an alternative to the above-mentioned problems. I can't do it.

Republic of Korea Patent Publication No. 10-2009-0041338

The present invention is intended to improve the conventional technical problems described above, and enables high color reproduction even at low colorant weight concentration (PWC: Pigment Weight Concentration), resulting in excellent brightness and sensitivity, excellent reliability against UV ashing, etc., and heat resistance and adhesion. The purpose is to provide a colored curable resin composition with improved reliability from the external environment due to its excellent properties, etc.

Another object of the present invention is to provide a color filter manufactured 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 problems mentioned above, 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, an antioxidant, and a solvent. The colorant includes a compound represented by the following formula (1), and the antioxidant is a phenol-based A colored curable resin composition is provided, characterized in that it contains at least one type selected from the group selected from antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

Additionally, the present invention provides a color filter containing the colored curable resin composition.

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

The colored curable resin composition of the present invention contains the compound represented by Chemical Formula 1 as a colorant, enabling high color reproduction even at a relatively low colorant concentration (PWC), resulting in excellent luminance and excellent reliability in UV ashing, etc.

In addition, the colored curable resin composition of the present invention includes an azo compound represented by Formula 1 as a colorant, and the antioxidant includes at least one type selected from the group selected from phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. By controlling this, the brightness is excellent even at a low colorant weight concentration (PWC: Pigment Weight Concentration), and the reliability from the external environment is improved due to excellent heat resistance and adhesion.

The present invention includes a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, an antioxidant, and a solvent. The colorant includes a compound represented by the following formula (1), and the antioxidant includes a phenol-based antioxidant, a phosphorus-based antioxidant, and It relates to a colored curable resin composition, characterized in that it contains at least one member selected from the group selected from sulfur-based antioxidants, a color filter and an image display device containing the same, a color filter manufactured using the same, and the color filter. The colored curable resin composition according to the present invention is capable of reproducing high colors even at a relatively low colorant concentration (PWC), has excellent luminance, has excellent reliability such as UV ashing, and has heat resistance. The present invention was completed by experimentally confirming that it has excellent adhesion and improved reliability from the external environment.

The colored curable resin composition may be used for forming red pixels.

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 to these components.

<Colored curable resin composition>

coloring agent

The colorant is characterized in that it contains a compound represented by the following formula (1), and may include additional pigments, dyes, and mixtures thereof as needed to the extent that they do not impair the purpose of the present invention.

[Formula 1]

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

( _In the formula ⁽ ph1) _, It represents an alkylthio group or a halogen atom having 1 to 4 carbon atoms, and -CH ₂ - contained in the hydrocarbon group may be substituted with -O-, -CO- or -NH-, and -CH= contained in the hydrocarbon group is It may be substituted with -N=.

n represents an integer from 0 to 4.

If n is an integer greater than or equal to 2, multiple X ^1s may be the same or different. When n is an integer of 2 or more and X ¹ is bonded to an adjacent carbon atom, X ¹ bonded to an adjacent carbon atom 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 Additionally, the alicyclic hydrocarbon group may be a monocyclic or polycyclic hydrocarbon group. The number of carbon atoms of the hydrocarbon group is more preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

( _In formula (ia) and formula (ib), X ^{6 to} , -CO- or -NH- may be substituted, -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, a sulfur atom, or a carbonyl group may be inserted between the carbon atoms constituting the hydrocarbon group.

X ⁶ and X ⁷ may combine with each other to form a ring, and X ⁸ and X ⁹ may combine with each other to form a ring.

* indicates the number of bonds with L ^1. )

The monovalent hydrocarbon group for X ^{6 to} Straight-chain alkyl groups such as sil groups; isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, sec-butyl group, tert-butyl group, 1,3-dimethylbutyl group, 2-ethyl Branched alkyl groups such as butyl groups; alicyclic hydrocarbon groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group. The number of carbon atoms of the monovalent saturated hydrocarbon group is more preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

When the monovalent hydrocarbon group is an alicyclic hydrocarbon group, the number of carbon atoms of the alicyclic hydrocarbon group is more preferably 3 to 12, more preferably 3 to 10, and most preferably 3 to 8.

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, a hydroxy group, -CN, -SO ₃ H, -SO ₃ ^-, etc. do.

Additionally, L ¹ may be a group represented by the formula (ph2).

( _In the formula (ph2 ₎ , X ^{2 to} It represents ~4 alkylthio groups or halogen atoms.

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

* represents the number of bonds with A, and ** represents 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 of the groups represented by the formulas (t1) to (t5).

(In formulas (t1) to (t5), R ¹ to R ¹⁶ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms that may have a substituent, or a carbon number of 6 to 10 that may have a substituent. It represents 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. )

Monovalent saturated hydrocarbon groups 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 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. Examples include alicyclic saturated hydrocarbon groups having 3 to 10 carbon atoms. The number of carbon atoms of the monovalent saturated hydrocarbon group is more preferably 1 to 6, and even 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.

Examples of the aromatic hydrocarbon group for R ¹ to R ¹⁶ include phenyl group, tolyl group, xylyl group, naphthyl group, etc., and phenyl group and tolyl group are preferred. In addition, substituents that the aromatic hydrocarbon group may have include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group; -OH; -SO ₃ H ; -SO ₃ ^- ; -SO ₂ NR ¹⁷ R ¹⁸ ; Alkylsulfonyl groups with 1 to 6 carbon atoms, such as methylsulfonyl group; Alkoxycarbonyl groups with 11 to 6 carbon atoms, such as methoxycarbonyl group and ethoxycarbonyl group; and the like.

R ¹⁷ is an aliphatic saturated hydrocarbon group of 1 to 10 carbon atoms that may have a halogen atom, -OH or -NH ₂ as a substituent, or an alicyclic group of 3 to 10 carbon atoms that 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, and preferably a phenyl group or a benzoimidazoline group which may have a halogen atom.

The compound represented by Formula 1 may include a counter ion if necessary. The counter ion may be a cation containing an alkaline earth metal, and is preferably at least one selected from the group consisting of magnesium cation, calcium cation, strontium cation, and barium cation, and is more preferably 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, it is preferable because high brightness and high color reproduction are possible while the colorant content in the colored curable resin composition can be lowered, thereby improving the reliability of UV ashing, etc.

The colorant may further include one or more selected from the group consisting of red pigment, yellow pigment, purple pigment, and xanthene dye.

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. Pigment Red 291 may include one or more selected from the group consisting of C.I. Pigment Red 177, C.I. Pigment Red 202, C.I. Pigment Red 254 and C.I. It may include one or more types 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. Pigment Yellow 231 may contain at least one selected from the group consisting of 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 contain one or more types selected from the group consisting of Pigment Violet 29, preferably C.I. It could be Pigment Violet 19.

The xanthene dye may include at least one selected from the group consisting of compounds represented by the following formula (2).

[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 field may be used, and these may be used alone or in combination of two or more types.

The organic or inorganic pigments can be various types of pigments used in printing ink, inkjet ink, etc. Specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoin pigments, etc. Doline pigment, perylene pigment, perinone pigment, dioxazine pigment, anthraquinone pigment, dianthraquinonyl pigment, anthrapyrimidine pigment, anthanthrone pigment, indanthrone pigment, pravanthrone pigment, pyran Examples include pyranthrone pigments and diketopyrroropyrrole pigments.

Examples of the inorganic pigment include metal compounds such as metal oxides, complex metal oxides, and metal complex salts; Or carbon black, etc. may be mentioned. Specifically, the metals include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. In particular, the organic pigments and inorganic pigments include compounds classified as pigments in the color index (published by The Society of Dyers and Colourists), and more specifically, the color index (C.I.) numbers as follows: Pigments may be mentioned, but are 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, etc. can be mentioned.

The above pigments can be used individually or in combination of two or more.

Among the above pigments, organic pigments may, if necessary, undergo surface treatment using pigment derivatives into which acidic or basic groups are introduced, graft treatment on the surface of the pigment using polymer compounds, etc., atomization treatment using sulfuric acid refinement, etc., or removal of impurities. It can be treated by washing with organic solvents and water to remove them, or by removing ionic impurities using an ion exchange method.

When using a pigment as the colorant, it is preferable to use a pigment with a uniform average particle diameter. Methods for uniformizing the particle size of the pigment include a method of performing dispersion treatment by containing a surfactant as a pigment dispersant. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, and amphoteric surfactants, which can be used individually or in combination of two or more. The pigment dispersant may be included in the form of an additive to be described later, and an acrylic pigment dispersant is preferably used. A commercial product such as Disper byk-2001 may be used, 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 parts 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 based on the above criteria, it is preferable because a pigment with a uniform average particle diameter can be obtained.

As the additional dye, one or more types can be added without limitation as long as it has solubility in organic solvents. Preferably, it is desirable to use a dye that has solubility in organic solvents and can ensure reliability such as solubility in alkaline developers and heat resistance. The dye may be selected from acid dyes having an acidic group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamide series of acid dyes, and their derivatives. In addition, acidic dyes of azo and phthalocyanine series may be used. Dyes and their derivatives can also be selected. The dye may be a compound classified as a dye in the color index (published by The Society of Dyers and Colourists) or a known dye described in a dyeing note (color dyeing yarn).

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, 130;

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

Additionally, the C.I. As 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 , 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, etc.;

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 , 335, 340, etc. blue dyes;

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

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

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, 141, etc., yellow dyes;

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, etc.;

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 , 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, 293, etc.;

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;

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

Additionally, 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;

Orange colors such as C.I. 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;

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

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 above content range, it is preferable because the color density of the pixel is sufficient and UV ashing resistance is excellent.

binder resin

The binder resin is a component that provides solubility to an alkaline developer used in the development process when forming a pattern, and the binder resin may be polymerized by containing an ethylenically unsaturated monomer having a carboxyl group.

The ethylenically unsaturated monomer having the carboxyl group is not particularly limited, and 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 their anhydrides; Examples include polymer mono(meth)acrylates having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, and preferably acrylic acid and methacrylic acid. These can be used alone or in combination of two 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 monomer. For example, styrene, vinyltoluene, methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl 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. unsaturated oxetane compounds, etc. These can be used alone or in combination of two or more types.

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

Additionally, in order to ensure 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, it is preferable because the colored curable resin composition can secure a sufficient development speed and 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, If the binder resin satisfies the ranges of weight average molecular weight and molecular weight distribution, it has the advantage of excellent developability.

The content of the binder resin may be 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 the developer, prevents residues from occurring, and makes pattern formation easy.

photopolymerizable compound

The photopolymerizable compound included in the colored curable resin composition of the present invention is a compound that can be polymerized by light irradiation by active radicals, acids, etc. generated from a photopolymerization initiator described later, and is a compound that can be polymerized by the action of the photopolymerization initiator below. , monofunctional monomers, difunctional monomers, or polyfunctional monomers can be used, and preferably bifunctional or more polyfunctional monomers can be used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, or N-vinylpy. Lolidon, etc., but is not limited thereto.

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

Neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, or 3-methylpentanediol di(meth)acrylate, etc., but are limited to these. It doesn't work.

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 or dipentaerythritol hexa(meth)acrylate, etc., but are 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, there is an advantage of excellent sensitivity and developability.

photopolymerization initiator

The photopolymerization initiator is a compound that generates radicals that can initiate polymerization of the photopolymerizable compound described above upon exposure to radiation such as visible light, ultraviolet rays, deep ultraviolet rays, electron beams, or X-rays.

The photopolymerization initiator is not particularly limited as long as it is commonly 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, and commercially available products include Irgacure® OXE-01 and OXE-02 from BASF. OXE-03, etc. may be 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 it is capable of polymerizing the binder resin and the photopolymerizable compound without impairing the purpose of the present invention. there is.

The commonly used photopolymerization initiators include, for example, triazine-based compounds, acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and benzoin-based compounds.

The triazine-based compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethyl Toxy styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxy naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2 -(p-methoxy phenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl-4,6-bis(trichloromethyl)-s-triazine, 2- Pipenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichlorobetyl)-6-styryl-s-triazine, 2-(naphtho 1-yl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-trichloromethyl( Piperonyl)-6-triazine, 2,4-trichloromethyl(4'-methoxy styryl)-6-triazine, etc. can be mentioned.

Specific examples of the acetophenone 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. can be mentioned.

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, etc. are mentioned.

The thioxanthone-based compounds include thioxanthone, 2-chlorolthioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-diisopropyl ti. Oxanthone, 2-chlorothioxanthone, etc. can be mentioned.

Examples of the benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethyl ketal.

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 sufficiently occurs during exposure in the pattern formation process, and transmittance may not be reduced due to unreacted initiator remaining after photopolymerization.

solvent

In one embodiment of the present invention, the solvent is not particularly limited as long as the colored curable resin composition has appropriate viscosity and can easily dissolve the remaining components, and various organic solvents used in the field of colored curable resin compositions can be used. there is.

Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and thylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and ethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic esters, such as γ-butyrolactone, etc. are mentioned.

Among the above solvents, organic solvents having a boiling point of 100°C to 200°C are preferred in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, or , esters such as methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and ethyl 3-ethoxypropionate. , methyl 3-methoxypropionate, etc.

The above solvents can be used individually or in combination of two or more types.

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 contained within the above content range, the applicability is improved when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes called a die coater), or inkjet. It is desirable because it provides

antioxidant

In one embodiment of the present invention, the antioxidant may include one or more types selected from the group selected from phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

The phenolic antioxidant may include a phenolic antioxidant and a phenolic antioxidant having a protecting group that can be decomposed by heat, and may include one or more types of compounds represented by the following formulas 3 to 6.

[Formula 3]

(In Formula 3 above,

R ₁ to R ₅ are each independently the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, or a carbon number. Represents a monoalkylpropionate group of 4 to 20 carbon atoms or a dialkylpropionate group of 4 to 20 carbon atoms,

At least one of R ₁ to R ₅ is a tetrabutyl group,

Z is hydrogen, tetrabutyloxycarbonyl group, tetrabutyldimethylsilyl group, tetrabutyldiphenylsilyl group, tetrahydropyranyl group, triphenylmethyl group, benzyloxycarbonyl group, trimethylsilylethoxymethyl group, methoxyethoxymethyl group, It is a toxymethyl group or tetrahydropyranyl group.)

The alkyl group having 1 to 20 carbon atoms refers to a straight-chain or branched monovalent hydrocarbon containing 1 to 20 carbon atoms. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-peltyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group. It includes, but is not limited to, etc.

The cycloalkyl group having 3 to 10 carbon atoms refers to a simple or fused cyclic monovalent hydrocarbon containing 3 to 10 carbon atoms. For example, it includes, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

The mono(di)alkylpropionate group having 4 to 20 carbon atoms refers to a straight-chain or branched monovalent alkylpropionate having 4 to 20 carbon atoms. For example, (di)methylpropionate, (di)ethylpropionate, (di)n-propylpropionate, (di)isopropylpropionate, (di)n-butylpropionate, iso It includes but is not limited to butyl propionate.

Specific examples of the compound represented by Formula 3 include 2-t-butylphenol, 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 2-sec-butylphenol, 2,6- Di-sec-butylphenol, 2,4-di-sec-butylphenol, 2,6-di-t-butyl-4-ethylphenol, 2-isopropylphenol, 2,6-diisopropylphenol, 2, 4-diisopropylphenol, 2-t-octylphenol, 2,6-di-t-octylphenol, 2,4-di-t-octylphenol, 2-cyclopentylphenol, 2,6-dicyclopentylphenol , 2,4-dicyclopentylphenol, 2-t-butyl-p-cresol, 2,6-di-t-amylphenol, 2,4-di-t-amylphenol, 6-t-butyl-o -Cresol, 2,6-di-t-dodecylphenol, 2,4-di-t-dodecylphenol, 2-sec-butyl-p-cresol, 2,6-di-t-octylphenol, 2,4-di-t-octylphenol, 6-sec-butyl-o-cresol, 2-t-octyl-p-cresol, 2-t-dodecyl-p-cresol, 2-t-butyl -6-isopropylphenol, 6-t-octyl-o-cresol, 6-t-dodecyl-o-cresol and octadecyl-3-(3,5-di-t-butyl-4-hydroxy Phenyl) propionate, etc. are mentioned.

[Formula 4]

(In Formula 4 above,

R ₁ to R ₅ are each independently the same or different from each other, and are a direct bond, a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cyclo having 3 to 10 carbon atoms. Represents an alkyl group, a monoalkylpropionate group having 4 to 20 carbon atoms, or a dialkylpropionate group having 4 to 20 carbon atoms,

At least one of R ₁ to R ₅ forms a direct bond,

At least one of R ₁ to R ₅ is a tetrabutyl group,

Z is hydrogen, tetrabutyloxycarbonyl group, tetrabutyldimethylsilyl group, tetrabutyldiphenylsilyl group, tetrahydropyranyl group, triphenylmethyl group, benzyloxycarbonyl group, trimethylsilylethoxymethyl group, methoxyethoxymethyl group, It is a toxymethyl group or tetrahydropyranyl group,

X represents a substituted or unsubstituted divalent alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent arylalkylene group having 6 to 30 carbon atoms, an oxygen atom or a sulfur atom,

L is a single bond or an alkylpropionate having 4 to 20 carbon atoms.)

The alkyl (lene) group having 1 to 20 carbon atoms refers to a straight-chain or branched monovalent hydrocarbon containing 1 to 20 carbon atoms. For example, methyl (lene) group, ethyl (lene) group, n-propyl (lene) group, isopropyl (lene) group, n-butyl (lene) group, isobutyl (lene) group, n-peltyl ( Includes, but is not limited to, a ren) group, n-hexyl (lene) group, n-heptyl (lene) group, n-octyl (lene) group, n-nonyl (lene) group, etc.

The cycloalkyl group having 3 to 10 carbon atoms refers to a simple or fused cyclic monovalent hydrocarbon containing 3 to 10 carbon atoms. For example, it includes, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

The mono(di)alkylpropionate group having 4 to 20 carbon atoms refers to a straight-chain or branched monovalent alkylpropionate having 4 to 20 carbon atoms. For example, (di)methylpropionate, (di)ethylpropionate, (di)n-propylpropionate, (di)isopropylpropionate, (di)n-butylpropionate, iso It includes but is not limited to butyl propionate.

The arylalkylene group having 6 to 30 carbon atoms is composed of 6 to 30 carbon atoms, and at least one of the hydrogen atoms (H) contained in the arylene group is lower alkylene, such as methylene, ethylene, propylene, etc. It means substituted with a radical. For example, benzylene, phenylethylene, etc. are included, but are not limited thereto.

Specifically, specific examples of the compound represented by Formula 4 include 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t- butylphenol), 1,6-hexanediol-bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-t -butyl-5-methyl-4-hydroxyphenyl)propionate] and 4,4'-butyridenebis(6-tert-butyl-3-methylphenol), etc., preferably 4,4. It may be '-butyridenebis(6-tert-butyl-3-methylphenol).

[Formula 5]

(In Formula 5 above,

R ₁ to R ₅ are each independently the same or different from each other, and are a direct bond, a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cyclo having 3 to 10 carbon atoms. Represents an alkyl group, a monoalkylpropionate group having 4 to 20 carbon atoms, or a dialkylpropionate group having 4 to 20 carbon atoms,

At least one of R ₁ to R ₅ forms a direct bond,

At least one of R ₁ to R ₅ is a tetrabutyl group,

Z is hydrogen, tetrabutyloxycarbonyl group, tetrabutyldimethylsilyl group, tetrabutyldiphenylsilyl group, tetrahydropyranyl group, triphenylmethyl group, benzyloxycarbonyl group, trimethylsilylethoxymethyl group, methoxyethoxymethyl group, It is a toxymethyl group or tetrahydropyranyl group,

X shows a saturated hydrocarbon group of 3 feas from 1 to 10 carbon at least 1 to 10, an aromatic hydrocarbon machine, a nitrogen atom, or a phosphorus of 3 -family carbon at 6 to 12.

L is a single bond or an alkylpropionate having 4 to 20 carbon atoms.)

The alkyl group having 1 to 20 carbon atoms refers to a straight-chain or branched monovalent hydrocarbon containing 1 to 20 carbon atoms. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-peltyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group. It includes, but is not limited to, etc.

The cycloalkyl group or cycloalkylene group having 3 to 10 carbon atoms refers to a simple or fused cyclic monovalent hydrocarbon consisting of 3 to 10 carbon atoms. For example, it includes, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

The mono(di)alkylpropionate group having 4 to 20 carbon atoms refers to a straight-chain or branched monovalent alkylpropionate having 4 to 20 carbon atoms. For example, (di)methylpropionate, (di)ethylpropionate, (di)n-propylpropionate, (di)isopropylpropionate, (di)n-butylpropionate, iso It includes but is not limited to butyl propionate.

Examples of the trivalent saturated hydrocarbon group having 1 to 10 carbon atoms include straight-chain alkyl groups such as methyl, ethyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; Branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodehyde. Examples include, but are not limited to, alicyclic saturated hydrocarbon groups having 3 to 10 carbon atoms, such as actual groups.

Examples of the trivalent aromatic hydrocarbon group having 6 to 12 carbon atoms include phenyl group, tolyl group, xylyl group, naphthyl group, etc., preferably phenyl group and tolyl group, but are not limited thereto.

Specific examples of the compound represented by Formula 5 include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-tris(4-hydroxybenzyl) ) benzene and 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene.

[Formula 6]

(In Formula 6 above,

R ₁ to R ₅ are each independently the same or different from each other, and are a direct bond, a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cyclo having 3 to 10 carbon atoms. Represents an alkyl group, a monoalkylpropionate group having 4 to 20 carbon atoms, or a dialkylpropionate group having 4 to 20 carbon atoms,

At least one of R ₁ to R ₅ forms a direct bond,

At least one of R ₁ to R ₅ is a tetrabutyl group,

Z is hydrogen, tetrabutyloxycarbonyl group, tetrabutyldimethylsilyl group, tetrabutyldiphenylsilyl group, tetrahydropyranyl group, triphenylmethyl group, benzyloxycarbonyl group, trimethylsilylethoxymethyl group, methoxyethoxymethyl group, It is a toxymethyl group or tetrahydropyranyl group,

X represents a substituted or unsubstituted tetravalent saturated hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted tetravalent aromatic hydrocarbon group having 6 to 12 carbon atoms, or a carbon atom,

L is a single bond or an alkylpropionate having 4 to 20 carbon atoms.)

The alkyl group having 1 to 20 carbon atoms refers to a straight-chain or branched monovalent hydrocarbon containing 1 to 20 carbon atoms. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-peltyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group. It includes, but is not limited to, etc.

The cycloalkyl group or cycloalkylene group having 3 to 10 carbon atoms refers to a simple or fused cyclic monovalent hydrocarbon consisting of 3 to 10 carbon atoms. For example, it includes, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

The mono(di)alkylpropionate group having 4 to 20 carbon atoms refers to a straight-chain or branched monovalent alkylpropionate having 4 to 20 carbon atoms. For example, (di)methylpropionate, (di)ethylpropionate, (di)n-propylpropionate, (di)isopropylpropionate, (di)n-butylpropionate, iso It includes but is not limited to butyl propionate.

Examples of the tetravalent saturated hydrocarbon group having 1 to 10 carbon atoms include straight-chain alkyl groups such as methyl, ethyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; Branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodehyde. Examples include, but are not limited to, alicyclic saturated hydrocarbon groups having 3 to 10 carbon atoms, such as actual groups.

Examples of the tetravalent aromatic hydrocarbon group having 6 to 12 carbon atoms include phenyl group, tolyl group, xylyl group, naphthyl group, etc., preferably phenyl group and tolyl group, but are not limited thereto.

Specific examples of the compound represented by the above formula (6) include pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], and tetrakis[methylene-3- (3,5'-di-t-butyl-4'-hydroxyphenylpropionate)] methane, etc., preferably pentaerythritol-tetrakis[3-(3,5-di-t -butyl-4-hydroxyphenyl)propionate].

The phosphorus-based antioxidant is 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] Phosphite compounds having a spiro ring skeleton such as undecane, diisodecylpentaerythritol diphosphite, and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite; 2,2'-methylenebis(4,6-di-t-butyl-1-phenyloxy)(2-ethylhexyloxy)phosphorus, 6-[3-(3-t-butyl4-hydroxy- 5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[ d,f][ 1,3,2]dioxaphosphepine, triphenylphosphite, diphenylisodecylphos Phyte, phenyl diisodecyl phosphite, 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl ditridecyl) phosphite, octadecyl phosphite, tris(nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-sphaphenanthrene-10-oxide, tris (2,4-di-t -Butylphenyl) phosphite, cyclic pentanetetraylbis(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis(2,6-di-t-butylphenyl) phosphite , 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, tris(2,4-di-t-butylphenyl)phosphite, trakis(2,4-di-t- Butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester, phosphonic acid, 2 ,2'-methylenebis(4,6-di-t-butyl-1-phenyloxy)(2-ethylhexyloxy)phosphorus, 3,9-bis(2,6-di-tert-butyl-4 -methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane and bis(2,4-di-tert-butylphenol)pentaerythritol diphosphite. It may include more than one type in the group.

The sulfur-based antioxidants include 2-mercaptobenzimidazole, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'. -Compounds having a thioether structure such as thiodipropionate and pentaerythrityl-tetrakis(3-laurylthiopropionate); 2-Mercaptobenzimidazole, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl-bis[3-(dodecylthio)propionate ], 2-mercaptobenzimidazole, and the like.

When it contains at least one member selected from the group consisting of the phenol-based antioxidant, the phosphorus-based antioxidant, and the sulfur-based antioxidant, the colored curable resin composition can be reproduced in high color and has excellent luminance and US ashing effects, while maintaining heat resistance. It is desirable because it has excellent adhesion and improves reliability from the external environment.

In addition, the antioxidant may further include an antioxidant containing a phenol group and a phosphite group in the molecule.

Specific examples of antioxidants containing a phenol group and a phosphite group in the molecule include calcium bis[monoethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate], 6-[3-(3) -t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosphepine, etc. , preferably 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f ] [1,3,2] It may be dioxaphosphepine.

When the antioxidant further contains an antioxidant containing a phenol group and a phosphite group in the molecule, high color reproduction of the colored curable resin composition is possible, resulting in excellent brightness and US ashing effects, as well as excellent heat resistance and adhesion. This is desirable because it can improve reliability from the external environment.

The antioxidant may be included in an amount of 0.05 to 0.5% by weight, preferably 0.1 to 0.4% by weight, based on the total weight of the colored curable resin composition. When the antioxidant is included within the above content range, the colored curable resin composition has excellent heat resistance and adhesion, which improves reliability from the external environment, and at the same time has the advantage of further improving luminance when manufacturing a color filter, which is preferable. do.

additive

Additives may be selectively added as needed, and may include, for example, one or more selected from the group consisting of other polymer compounds, curing agents, surfactants, adhesion promoters, ultraviolet absorbers, and aggregation inhibitors.

Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. I can hear it.

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

Specific examples of the epoxy compound in the curing agent include bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, noblock-type epoxy resin, other aromatic epoxy resins, and cycloaliphatic epoxy resin. , glycidyl ester-based resin, glycidylamine-based resin, or brominated derivatives of the above epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxide, isoprene ( Examples include co)polymer epoxide, glycidyl (meth)acrylate (co)polymer, and triglycidyl isocyanurate.

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 that can cause ring-opening polymerization of the epoxy group of an epoxy compound and the oxetane skeleton of an oxetane compound.

The curing auxiliary compounds include, for example, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, and acid generators. The above polyhydric carboxylic acid anhydride can be used as a commercially available epoxy resin curing agent. Examples of the commercially available products include Adeka Hadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Rika Siddo HH (manufactured by Nippon Ewha Co., Ltd.), and MH-700 (manufactured by Nippon Ewha Co., Ltd.). The curing agents exemplified above can be used alone or in a mixture of two or more types.

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, etc. can be preferably used.

The silicone-based surfactant is, for example, commercially available products such as DC3PA, DC7PA, SH-11PA, SH-21PA, and SH-8400 from Dow Corning Toray Silicone, and TSF-4440, TSF-4300, and TSF-4445 from GE Toshiba Silicone. , TSF-4446, TSF-4460, and TSF-4452.

Examples of the fluorine-based surfactant include commercially available products such as Megapeace F-470, F-471, F-475, F-482, F-489, and F-554 manufactured by Dainippon Ink Chemicals.

In addition, other commercially available products include KP (Shin-etsu Chemical Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (Tochem Products Co., Ltd.), and MegaFAC (MEGAFAC). (Dainipbon Ink Chemicals Co., Ltd.), Flourad (Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) , EFKA (EFKA Chemicals), PB 821 (Ajinomoto Co., Ltd.), and Disperbyk-series (BYK-chemi).

The surfactants exemplified above can be used individually or in combination of two or more types.

The type of the adhesion accelerator is not particularly limited, and specific examples of usable adhesion accelerators include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, and 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-isocyanate propyltrimethoxysilane, and 3-isocyanate propyltriethoxysilane.

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-chlorobenzothiriazole, alkoxybenzophenone, etc. .

The type of the anti-agglomeration agent is not particularly limited, but specific examples that can be used include sodium polyacrylate and the like.

The additives exemplified above can be used individually or in combination of two or more. The additive may typically be included in an amount of 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 manufacturing using the colored curable resin composition described above. The color filter according to one 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 it in a predetermined pattern.

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

The method of forming a pattern using the colored curable resin composition of the present invention may use methods known in the art, but typically include an application step; exposure step; and a removal step. The colored curable resin composition of the present invention can be applied to a substrate, photo-cured and developed to form a pattern, allowing it to be used as colored pixels (colored images).

Specifically, the colored curable resin composition is applied to a glass substrate on which nothing has been applied and a glass substrate on which SiNx (protective film) has been applied to a thickness of 500 to 1,500 Å using an appropriate method such as spin coating or slit coating, to a thickness of 2.0 to 1,500 Å. Apply with a thickness of 3.4 ㎛. After application, light is irradiated to form the pattern required for the color filter. After irradiating light, the applied layer is treated with an alkaline developer, so that the unirradiated portion of the applied layer is dissolved and the pattern required for the color filter is formed. By repeating this process according to the number of required R, G, and B colors, a color filter with a desired pattern can be obtained. In addition, in the above process, crack resistance, solvent resistance, etc. can be further improved by heating the image pattern obtained through development again or hardening it by irradiation with actinic rays, etc.

<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 not only for conventional liquid crystal displays (LCDs), but also for various display devices such as electroluminescent displays (EL), plasma displays (PDP), field emission displays (FED), and organic light emitting devices (OLED). It can be applied to.

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

A display device according to an embodiment of the present invention includes, in addition to the color filter described above, 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. Additional filters can be provided. In such cases, the emission light of the light source applied to the image display device is not particularly limited, but in terms of better color reproduction, a light source that emits blue light can be preferably used.

In addition to the color filter described above, the display device according to an embodiment of the present invention may further include a color filter including only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer. In such case, the color filter further includes a transparent pattern layer that does not contain quantum dot particles. In the case where only two color pattern layers are provided, a light source that emits light with a wavelength representing the remaining colors not included can be used. For example, when it includes only a red pattern layer and a green pattern layer, a light source that emits blue light can be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer emits blue light as it is and appears blue.

Hereinafter, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are merely examples and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and furthermore, it includes all changes within the scope and meaning equivalent to the record of the claims. In addition, in the following examples and comparative examples, “%” and “part” indicating content are based on mass unless otherwise specified.

<Example>

Synthesis Example: Synthesis of an azo compound represented by Formula 1

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

4.0 parts of water, 10 parts of acetic acid, 10 parts of methanol, and 25 parts of 98% sulfuric acid were added to 5.0 parts of 2,5-dichloro-4-nitroaniline and stirred. After ice cooling, an aqueous solution of 2.0 parts of sodium nitrite dissolved in 3.0 parts of water was added to the reaction solution and stirred for 2 hours to obtain a suspension containing diazonium salt. Meanwhile, 15 parts of methanol was added to 3.0 parts of barbituric acid (α), and then 100 parts of an ice-cooled 25% sodium hydroxide aqueous solution was added and stirred. A suspension containing the above-mentioned diazonium salt was added dropwise here. After the dropwise addition was completed, 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).

Next, 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 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).

Next, 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) and stirred. After the reaction mixture was ice-cooled, 0.6 parts of sodium nitrite was 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 diazonium salt. Meanwhile, 0.8 parts of methanol was added to 0.8 parts of barbituric acid (β), and then 15 parts of a 25% sodium hydroxide aqueous solution was added and stirred under ice cooling. Here, a suspension containing the diazonium salt described previously was added dropwise. After completion of the dropwise addition, the mixture was stirred again at room temperature for 1 hour to obtain a red suspension. After filtering and washing the suspension, the obtained solid was dried at 60°C under reduced pressure to obtain 1.7 parts (57% yield) 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)

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

(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) is mixed with 1.8 parts of 3-cyano-1-butyl-6-hydroxy-4-methyl-2-pyridone (α), and 0.8 parts of barbituric acid (β) is mixed with 3-cyano-1. 3.9 parts (yield 66%) of the compound represented by formula (A-3) was obtained in the same manner as in Synthesis Example 1 except that it was replaced with 1.4 parts of -butyl-6-hydroxy-4-methyl-2-pyridone (β). got it

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

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

Barbituric acid (α) 3.0 parts 3-methyl-1-phenyl-5-pyrazolone (α) 4.2 parts, barbituric acid (β) 0.8 parts 3-methyl-1-phenyl-5-pyrazolone (β) 0.5 parts 0.8 parts (53% yield) of the compound represented by formula (A-4) was obtained in the same manner as in Synthesis Example 1 except that it was replaced with a 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) is mixed with 4.9 parts of 3-methyl-1-(4-sulfophenyl)-2-pyrazolin-5-one (α), 0.8 parts of barbituric acid (β) is mixed with 3-methyl-1-( 1.2 parts (58% yield) of the compound represented by formula (A-5) was obtained in the same manner as in Synthesis Example 1, except that 0.7 parts of 4-sulfophenyl)-2-pyrazolin-5-one (β) was substituted.

(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) were replaced with 1.2 parts of 3-cyano-1-butyl-6-hydroxy-4-methyl2-pyridone. 1.9 parts (yield 56%) of the compound was obtained.

(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) was prepared 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 it

(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 parts of barbituric acid (β) were replaced with 0.5 parts of 3-methyl-1-(4-sulfophenyl)-2-pyrazolin-5-one. 1.2 parts (yield 37%) of the compound was obtained.

(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) was prepared in the same manner as in Synthesis Example 2, except that 0.7 parts of 1,3-dicyclohexylbarbituric acid (β) was replaced with 0.2 parts of 3-methyl-1-phenyl-5-pyrazolone. 0.3 copies (yield 31%) were obtained.

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

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

Same method as Synthesis Example 4 except that 4.2 parts of 3-methyl-1-phenyl-5-pyrazolone (α) were replaced with 18 parts of 3-methyl-1-(4-sulfophenyl)-2-pyrazolin-5-one 35 parts (73% yield) of the compound represented by formula (A-10) were 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 parts of N, N-dimethylformamide were added to 1.5 parts of the azo compound represented by formula (A-10), stirred, and 0.6 parts of thionyl chloride were added dropwise while maintaining the temperature below 20°C. After the dropwise addition was completed, 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 to the reaction solution while maintaining the temperature below 20°C while stirring. Afterwards, it was reacted at the same temperature for 5 hours. After removing the solvent from the reaction mixture obtained using an evaporator, a small amount of methanol was added and stirred vigorously. 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 (yield 74%) of the compound represented by formula (A-11).

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

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

0.8 parts (58% yield) of the compound represented by formula (A-12) 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 (74% yield) of the compound represented by formula (A-13) 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)

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

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

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

0.9 parts of the compound represented by formula (A-15) (yield 62%) was obtained in the same manner as in Synthesis Example 11, except that 0.5 parts of 2-methylcyclohexylamine was replaced with 1.2 parts of 1,3-dimethylbutylamine.

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

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

60 parts of water and 60 parts of N, N-dimethylformamide were added to 0.5 part of the azo compound represented by formula (A-10), 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 dried at 60°C under reduced pressure to obtain 0.4 parts (76% yield) of the compound represented by formula (A-16).

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

1.5 parts of the azo compound represented by the formula (A-10) is replaced by 12 parts of the azo compound represented by the formula (A-5), 0.4 parts of N, N-dimethylformamide is converted into 0.3 parts, 0.6 parts of thionyl chloride is converted into 9.4 parts, and 2-methyl 0.4 parts (yield 28%) of the compound represented by formula (A-17) was obtained in the same manner as in Synthesis Example 11, except that 0.5 parts of cyclohexylamine were changed to 2.3 parts and 1.9 parts of triethylamine were 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) was obtained in the same manner as in Synthesis Example 7 except that 5.0 parts of 2,5-dichloro-4-nitroaniline were replaced with 3.0 parts of 2-methyl-4-nitroaniline (yield 65%). got it

(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) was prepared in the same manner as in Synthesis Example 10 except that 5.0 parts of 2,5-dichloro-4-nitroaniline were replaced with 6.0 parts of 2-methyl-4-nitroaniline (yield 90%). got it

(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) was prepared 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) was obtained in the same manner as in Synthesis Example 4, except that 5.0 parts of 2,5-dichloro-4-nitroaniline were replaced with 3.0 parts of 2-chloro-4-nitroaniline (yield 40%). got it

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

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

0.3 parts of the compound represented by formula (A-22) was obtained in the same manner as in Synthesis Example 4 except that 5.0 parts of 2,5-dichloro-4-nitroaniline were 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 (73% yield) of the compound represented by formula (A-23) 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 parts (yield) of the compound represented by formula (A-24) was obtained in the same manner as in Synthesis Example 4 except that 5.0 parts of 2,5-dichloro-4-nitroaniline were replaced with 1.0 parts of 2,5-dimethoxy-4-nitroaniline. 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 the formula (A-1) obtained in Synthesis Example 1, 0.5 parts of the compound represented by the formula (a), 5.7 parts of the dispersant (BYKLPN-6919 manufactured by BYK) (converted to solid content), and Resin B-2 ( 9.9 parts (in terms of solid content), 74.3 parts of propylene glycol monomethyl ether acetate, and 5.0 parts of diacetone alcohol were mixed, 300 parts of 0.2 mm zirconia beads were added, shaken, and zirconia beads were removed through filtration to obtain a dispersion (a1-1). .

Preparation Examples 2 to 6: Azo compound dispersion (a1-2 to 6)

Dispersions (a1-2) to (a1-6) were obtained in the same manner as in Dispersion Preparation Example 1, except that the compound shown in formula (A-1) in Dispersion Preparation Example 1 was changed to the compound below.

Azo compound dispersion liquid (a1-2): Compound dispersion liquid represented by formula (A-2) obtained in Synthesis Example 2,

Azo compound dispersion liquid (a1-3): Compound dispersion liquid represented by formula (A-4) obtained in Synthesis Example 4,

Azo compound dispersion (a1-4): Compound dispersion represented by formula (A-10) obtained in Synthesis Example 10,

Azo compound dispersion liquid (a1-5): Compound dispersion liquid represented by formula (A-17) obtained in Synthesis Example 17,

Azo compound dispersion (a1-6): A dispersion of the compound represented by formula (A-20) obtained in Synthesis Example 20 was prepared.

Preparation Example 7: Red colorant dispersion (a2)

C.I. as a colorant. Red colorant dispersion (a2) was prepared in the same manner as Preparation Example 1 except that Pigment Red 202 was used.

Preparation Example 8: Purple colorant dispersion (a3)

C.I. as a colorant. Red colorant dispersion (a3) was prepared in the same manner as Preparation Example 1, except that Pigment Violet 19 was used.

Preparation Example 9: Red colorant dispersion (a5)

C.I. as a colorant. Red colorant dispersion (a5) was prepared in the same manner as Preparation Example 1 except that Pigment Red 254 was used.

Preparation Example 10: Red colorant dispersion (a6)

C.I. as a colorant. Red colorant dispersion (a6) was prepared in the same manner as Preparation Example 1 except that Pigment Red 177 was used.

Examples 1 to 18 and Comparative Examples 1 to 5: Preparation of colored curable resin composition

A colored curable resin composition was prepared according to the composition and content in Tables 1 to 3 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example
9 Example 10 (A) a1-1 7.1 45.7 33.8 33.8 33.8 33.8 33.8 33.8 33.8 33.8 a1-2 a1-3 a1-4 a1-5 a1-6 a2 31.5 a3 2.5 a4 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 a5 4.1 a6 36.6 (B) 5.2 2.4 2.4 11.3 11.3 11.3 11.3 11.3 11.3 11.3 (C) 2.4 2.7 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 (D) D-1 0.1 0.1 0.1 D-2 0.1 0.3 0.1 D-3 0.1 D-4 0.1 0.1 0.1 D-5 0.1 0.1 0.1 (E) One One One One One One One One One One (F-1) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (F-2) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (G) 43.2 13.8 48 48 48 48 48 47.8 47.9 47.8

Example
11 Example
12 Example
13 Example
14 Example
15 Example
16 Example
17 Example
18 (A) a1-1 33.8 7.1 7.1 a1-2 33.8 a1-3 33.8 a1-4 33.8 a1-5 33.8 a1-6 33.8 a2 a3 a4 2.1 2.1 2.1 2.1 2.1 2.1 a5 4.1 4.1 a6 36.6 36.6 (B) 11.3 11.3 11.3 11.3 11.3 11.3 5.2 5.2 (C) 3.4 3.4 3.4 3.4 3.4 3.4 2.4 2.4 (D) D-1 0.03 0.4 D-2 0.3 0.3 0.3 0.3 0.3 0.3 D-3 D-4 0.1 0.1 0.1 0.1 0.1 0.1 D-5 (E) One One One One One One One One (F-1) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (F-2) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (G) 47.7 47.7 47.7 47.7 47.7 47.7 43.27 42.9

Comparative example
One Comparative example
2 Comparative example
3 Comparative example
4 Comparative example
5 (A) a1-1 7.1 33.8 a1-2 a1-3 a1-4 a1-5 a1-6 a2 a3 a4 2.1 a5 13 13 13 4.1 a6 35 35 35 36.6 (B) 4.3 4.3 4.3 5 11.3 (C) 2.2 2.2 2.2 2 3.4 (D) D-1 0.01 0.1 D-2 D-3 D-4 D-5 (E) One One One One One (F-1) 0.2 0.2 0.2 0.2 0.2 (F-2) 0.1 0.1 0.1 0.1 0.1 (G) 44.2 44.19 44.1 43.9 48.1

(A) Colorant a1-1 to a1-6: Azo compound dispersion according to Preparation Examples 1 to 6

a2: C.I. Pigment Red 202 Dispersion

a3: C.I. Pigment Violet 19 Dispersion

a4: xanthylium salt, 3-dipropylamino, 6-diethylamino, 9-(2-sulfophenyl)-, intramolecular salt

a5: C.I. Pigment Red 254 Dispersion

a6: C.I. Pigment Red 177 Dispersion

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

(C) Photopolymerizable compound: A9550 (Shin Nakamura)

(D) Antioxidants

Antioxidant D-1: 4,4'-butyridenebis(6-tert-butyl-3-methylphenol)

Antioxidant D-2: Pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-tert-butyloxycarbonylphenyl)propionate

Antioxidant D-3: 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl-bis[3-(dodecylthio)propionate]

Antioxidant D-4: Bis(2,4-di-tert-butylphenol)pentaerythritol diphosphite

Antioxidant D-5: 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f ][1,3,2]dioxaphosphepine

(E) Photopolymerization initiator: OXE-02 (Basf)

(F) Additives

Additive (F-1): Silicone-based surfactant (SH-8400, manufactured by Toray Dow Corning Co., Ltd.)

Additive (F-2): Megapax F554 (made by Dainihon Ink Chemicals Co., Ltd.)

(G) Solvent: propylene glycol monomethyl ether acetate

Experiment example

1. Manufacturing of color filters

The colored curable resin composition according to the above examples and comparative examples was applied on a glass substrate (#1737, manufactured by Corning) by spin coating, then placed on a heating plate and maintained at a temperature of 100°C for 3 minutes to form a thin film. Next, a test photomask having a pattern that changes in a stepwise manner in the range of transmittance from 1 to 100% was placed on the thin film, the distance from the test photomask was set to 1000㎛, and an ultra-high pressure mercury lamp (USH-250D, Ushio Denki (USH-250D) was placed on the thin film. It was irradiated with light at an exposure dose of 40 mJ/cm ² (365 nm) under an atmospheric atmosphere using a product manufactured by Note). The ultraviolet irradiated thin film was developed in a KOH aqueous developing solution of pH 12.5 using a spray developer for 70 seconds. 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 ㎛.

2. Luminance evaluation

The color filter manufactured above was set in a spectroscopic colorimeter (CM-3700d, manufactured by Konica Minolta Sensing Co., Ltd.), and the transmitted chromaticity was measured on the X, Y, and Z coordinate axes at 2° of the C light source. The Y value of was adopted as the luminance. The luminance of the color filter manufactured using the colored curable resin composition of Comparative Example 1 was set as a standard (100%), and compared to this, the luminance of the color filter according to the remaining examples and comparative examples was calculated as a relative value (%). , the results are shown in Tables 4 to 6 below.

3. Colorant concentration calculation

The colorant concentration (weight concentration of the colorant relative to 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 a standard (100%), and compared with this, the colorant concentration of the colored curable resin composition according to the remaining examples and comparative examples was calculated as a relative value (%), and this relative The lower the value, the better the physical properties. The results are shown in Tables 4 to 6 below.

4. UV ashing resistance evaluation

The color filter manufactured above was irradiated with UV of 2000 mW/cm ³ using an ultraviolet ozone cleaning device (UV-312, manufactured by technovision.inc.), and the color difference before and after UV irradiation, △Eab ^*, was calculated using Equation 1 below. After calculation, UV ashing resistance was evaluated according to the following evaluation criteria, and the results are shown in Tables 4 to 6 below.

[Equation 1]

△Eab ^* =(△L ^* ) ² +(△a ^* ) ² +(△b ^* ) ² ] ^1/2

< UV ashing resistance evaluation criteria >

○: △Eab ^* = less than 5

×: △Eab ^* = 5 or more

5. Heat resistance evaluation

Heat resistance was measured by heating in an oven at 230°C for 3 hours using a colorimeter, and the ΔE*ab value was measured and evaluated according to the following criteria.

The evaluation criteria are as follows, and the results are shown in Tables 4 to 6 below.

<Evaluation criteria>

○: 0 ≤ △E*ab ≤ 1

△: 1 ≤ △E*ab ≤3

×: △E*ab>3

6. Adhesion evaluation

The fabricated substrate was cut into 100 matrix structures within an area of 10Х10mm, tape was attached on top, and the number of matrices that came off was measured while strongly releasing vertically.

The evaluation criteria are as follows, and the results are shown in Tables 4 to 6 below.

<Adhesion evaluation criteria>

○ (Excellent): Less than 5

△ (Good): 5 or more but less than 15

× (defective): 15 or more

Experiment result

Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 Example
8 Example
9 Example
10 Luminance 100.7% 101.8% 105.9% 105.9% 105.7% 106.0% 105.9% 106.5% 106.4% 106.8% heat resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Colorant concentration (PWC) 92% 81% 65% 65% 65% 65% 65% 65% 65% 65% UV ashing resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Adhesion Δ ○ Δ ○ ○ ○ ○ ○ ○ ○

Example
11 Example
12 Example
13 Example
14 Example
15 Example
16 Example
17 Example
18 Luminance 107.1% 107.0% 107.1% 107.1% 106.8% 107.0% 105.0% 106.7% heat resistance ○ ○ ○ ○ ○ ○ Δ ○ Colorant concentration (PWC) 65% 71% 63% 70% 72% 71% 65% 65% UV ashing resistance ○ ○ ○ ○ ○ ○ 92% 92% Adhesion ○ ○ ○ ○ ○ ○ ○ Δ

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Luminance 100.0% 100.0% 100.3% 100.5% 105.8% heat resistance Х Х Х Δ Δ Colorant concentration (PWC) 100% 100% 100% 92% 65% UV ashing resistance Х Х Х ○ ○ Adhesion Х Х Х Δ ○

Referring to Tables 4 to 6 above,

In the case of Examples 1 to 18, which contain an azo compound dispersion represented by Formula 1 and at least one type selected from the group selected from phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants, and contain an appropriate amount of antioxidants, they are compared. It was confirmed that the luminance was superior to the example, high color reproduction was possible even at low colorant concentration (PWC), and UV ashing resistance, heat resistance, and adhesion were good.

On the other hand, in the case of Comparative Examples 1 to 3 that do not contain the azo compound dispersion represented by Formula 1, sufficient brightness cannot be achieved with the colorant, and the colorant concentration (PWC) is also high, so the effects of UV ashing resistance and adhesion are reduced. It was confirmed that reliability was low.

In addition, in the case of Comparative Example 2, in which the compound represented by Formula 1 was added outside the numerical range intended in the present invention but the antioxidant intended in the present invention was not added, it was confirmed that heat resistance and adhesion were poor, and the present invention In the case of Comparative Examples 4 and 5 in which the intended antioxidant was not added, it was confirmed that heat resistance was poor.

Claims (9)

Contains a colorant, binder resin, photopolymerizable compound, photopolymerization initiator, antioxidant and solvent,
The colorant includes a compound represented by the following formula (1),
The antioxidant is characterized in that it contains one or more types selected from the group selected from phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
Colored curable resin composition:
[Formula 1]

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

( _In the formula ⁽ ph1 ₎ , , represents an alkylthio group having 1 to 4 carbon atoms or a halogen atom, and -CH ₂ - contained in the hydrocarbon group may be substituted with -O-, -CO- or -NH-, and -CH= contained in the hydrocarbon group. may be replaced with -N=.
n represents an integer from 0 to 4. If n is an integer greater than or equal to 2, multiple X ^1s may be the same or different. When n is an integer of 2 or more and X ¹ is bonded to an adjacent carbon atom, X ¹ bonded to an adjacent carbon atom 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 formula (ia) and formula (ib), X ^{6 to} , -CO- or -NH- may be substituted, -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, a sulfur atom, or a carbonyl group may be inserted between the carbon atoms constituting the hydrocarbon group.
X ⁶ and X ⁷ may combine with each other to form a ring, and X ⁸ and X ⁹ may combine with each other to form a ring.
* indicates the number of bonds with L ^1. )
In claim 1,
A colored curable resin composition wherein L ¹ is a group represented by the formula (ph2):

( _In the formula (ph2 ₎ , X ^{2 to} It represents ~4 alkylthio groups or halogen atoms.
X ² and X ³ and X ⁴ and X ⁵ may combine with each other to form a ring.
* represents the number of bonds with A, and ** represents the number of bonds with B.)
In claim 1,
The phenol-based antioxidant is characterized in that it contains one or more types of compounds represented by the following formulas 3 to 6,
Colored curable resin composition:
[Formula 3]

(In Formula 3 above,
R ₁ to R ₅ are each independently the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, or a carbon number. Represents a monoalkylpropionate group of 4 to 20 carbon atoms or a dialkylpropionate group of 4 to 20 carbon atoms,
At least one of R ₁ to R ₅ is a tetrabutyl group,
Z is hydrogen, tetrabutyloxycarbonyl group, tetrabutyldimethylsilyl group, tetrabutyldiphenylsilyl group, tetrahydropyranyl group, triphenylmethyl group, benzyloxycarbonyl group, trimethylsilylethoxymethyl group, methoxyethoxymethyl group, It is a toxymethyl group or tetrahydropyranyl group.)
[Formula 4]

(In Formula 4 above,
R ₁ to R ₅ are each independently the same or different from each other, and are a direct bond, a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cyclo having 3 to 10 carbon atoms. Represents an alkyl group, a monoalkylpropionate group having 4 to 20 carbon atoms, or a dialkylpropionate group having 4 to 20 carbon atoms,
At least one of R ₁ to R ₅ forms a direct bond,
At least one of R ₁ to R ₅ is a tetrabutyl group,
Z is hydrogen, tetrabutyloxycarbonyl group, tetrabutyldimethylsilyl group, tetrabutyldiphenylsilyl group, tetrahydropyranyl group, triphenylmethyl group, benzyloxycarbonyl group, trimethylsilylethoxymethyl group, methoxyethoxymethyl group, It is a toxymethyl group or tetrahydropyranyl group,
X represents a substituted or unsubstituted divalent alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent arylalkylene group having 6 to 30 carbon atoms, an oxygen atom or a sulfur atom,
L is a single bond or an alkylpropionate having 4 to 20 carbon atoms.)
[Formula 5]

(In Formula 5 above,
R ₁ to R ₅ are each independently the same or different from each other, and are a direct bond, a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cyclo having 3 to 10 carbon atoms. Represents an alkyl group, a monoalkylpropionate group having 4 to 20 carbon atoms, or a dialkylpropionate group having 4 to 20 carbon atoms,
At least one of R ₁ to R ₅ forms a direct bond,
At least one of R ₁ to R ₅ is a tetrabutyl group,
Z is hydrogen, tetrabutyloxycarbonyl group, tetrabutyldimethylsilyl group, tetrabutyldiphenylsilyl group, tetrahydropyranyl group, triphenylmethyl group, benzyloxycarbonyl group, trimethylsilylethoxymethyl group, methoxyethoxymethyl group, It is a toxymethyl group or tetrahydropyranyl group,
X shows a saturated hydrocarbon group of 3 feas from 1 to 10 carbon at least 1 to 10, an aromatic hydrocarbon machine, a nitrogen atom, or a phosphorus of 3 -family carbon at 6 to 12.
L is a single bond or an alkylpropionate having 4 to 20 carbon atoms.)
[Formula 6]

(In Formula 6 above,
R ₁ to R ₅ are each independently the same or different from each other, and are a direct bond, a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cyclo having 3 to 10 carbon atoms. Represents an alkyl group, a monoalkylpropionate group having 4 to 20 carbon atoms, or a dialkylpropionate group having 4 to 20 carbon atoms,
At least one of R ₁ to R ₅ forms a direct bond,
At least one of R ₁ to R ₅ is a tetrabutyl group,
Z is hydrogen, tetrabutyloxycarbonyl group, tetrabutyldimethylsilyl group, tetrabutyldiphenylsilyl group, tetrahydropyranyl group, triphenylmethyl group, benzyloxycarbonyl group, trimethylsilylethoxymethyl group, methoxyethoxymethyl group, It is a toxymethyl group or tetrahydropyranyl group,
X represents a substituted or unsubstituted tetravalent saturated hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted tetravalent aromatic hydrocarbon group having 6 to 12 carbon atoms, or a carbon atom,
L is a single bond or an alkylpropionate having 4 to 20 carbon atoms.)
In claim 1,
The antioxidant is,
Further comprising an antioxidant containing a phenol group and a phosphite group in the molecule,
Colored curable resin composition.
In claim 1,
With respect to the total weight of the colored curable resin composition,
Containing 0.05 to 0.5% by weight of antioxidant,
Colored curable resin composition.
In claim 5,
With respect to the total weight of the colored curable resin composition,
1 to 15% by weight of colorant,
0.5 to 20% by weight of binder resin,
1 to 10% by weight of photopolymerizable compound,
0.1 to 10% by weight of a photopolymerization initiator and
Containing 60 to 95% by weight of solvent,
Colored curable resin composition.
In claim 1,
The colored curable resin composition is for forming red pixels.
A color filter comprising a colored pattern made from the colored curable resin composition according to any one of claims 1 to 7.
An image display device comprising the color filter of claim 8.