KR102361511B1 - Colored photosensitive resin composition, color filter and image display device using the same - Google Patents

Abstract

The present invention comprises (A) a colorant, (B) a binder resin, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, (E) an antioxidant, and (F) a solvent; The colorant (A) includes a compound represented by the following formula (1), and at least one selected from a pigment and a dye, and the (E) antioxidant is selected from a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant A colored photosensitive resin composition, characterized in that it comprises at least one selected from a mixed antioxidant comprising at least one of A color filter manufactured using this and an image display device including the color filter are provided:
[Formula 1]

Description

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

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

A color filter is widely used in various display devices such as an imaging device and a liquid crystal display (LCD), and its application range is rapidly expanding. The color filter used in the image pickup device, liquid crystal display device, etc. is made of a coloring pattern of three colors of red, green, and blue, or yellow, magenta and cyan ( It consists of a coloring pattern of 3 colors of Cyan).

The colored pattern of each color filter is generally formed using a colored photosensitive resin composition including a colorant such as a pigment or dye, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent. The coloring pattern processing using the colored photosensitive resin composition is generally performed by a lithography process.

In recent years, various display devices including solid-state imaging devices such as digital cameras, and color filters for liquid crystal displays (LCDs) have been required to have high luminance and high coloration in order to improve fairness and quality. not being satisfied

For example, Korean Patent Publication No. 2013-0134494 discloses C.I Pigment Green 7 and C.I. Although a resin composition using Pigment Yellow 185 has been disclosed, it has a disadvantage that high brightness and high coloring properties are not simultaneously satisfied.

In the colored photosensitive resin composition, heat resistance is a very important property required because it is related to color change after a high-temperature process and the resulting luminance.

Republic of Korea Patent Publication No. 2009-0066076 discloses a colored photosensitive resin composition for a color filter comprising an acrylic binder resin, an acrylic carboxylate resin containing a double bond, a photopolymerizable monomer, a photoinitiator, a pigment, an antioxidant and a solvent. have. In the present invention, as the antioxidant, a mixture of a first antioxidant selected from the group consisting of a quinol-based compound, an amine-based compound, a phenol-based compound, and a mixture thereof and a second antioxidant including a phosphite-based compound is used as the antioxidant. It is described that the thermal stability can be improved by preventing oxidation of the resin composition.

However, as in the present invention, a color filter manufactured using the colored photosensitive resin composition containing only a pigment has a disadvantage in that the luminance is low. Therefore, a colored photosensitive resin composition including a dye to improve luminance is being studied. However, when the dye is included, an effective solution has not yet been found because it is difficult to obtain a desired luminance due to low heat resistance.

Republic of Korea Patent Publication No. 2013-0134494 Republic of Korea Patent Publication No. 2009-0066076

The present invention has been devised to solve the above problems of the prior art,

An object of the present invention is to provide a colored photosensitive resin composition having excellent heat resistance and exhibiting excellent luminance with little color change after a high-temperature process even if a dye is included.

Moreover, it aims at providing the coloring photosensitive resin composition which is excellent in a brightness|luminance and colorability, and has high sensitivity.

Another object of the present invention is to provide a color filter including the colored photosensitive resin composition and an image display device including the same.

The present invention is

(A) a colorant, (B) a binder resin, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, (E) an antioxidant, and (F) a solvent;

The colorant (A) includes a compound represented by the following formula (1), and at least one selected from pigments and dyes,

The (E) antioxidant is

A mixed antioxidant comprising at least one selected from a phenol-based antioxidant and a phosphorus-based antioxidant and a sulfur-based antioxidant, and

Provided is a colored photosensitive resin composition comprising at least one selected from polyfunctional antioxidants having at least one of a phenol group, a phosphorus atom, and a sulfur atom in one molecule:

[Formula 1]

In Formula 1, A ¹ to A ¹⁶ are each independently Cl, Br, or H, and 1 to 6 of A ¹ to A ¹⁶ are H, 0 to 5 are Cl, and 5 to 13 are Br.

Also, the present invention

It provides a color filter comprising a colored pattern made of the colored photosensitive resin composition.

Also, the present invention

It provides an image display device including the color filter.

The colored photosensitive resin composition of the present invention has excellent heat resistance and provides an effect of exhibiting excellent luminance with little color change after a high-temperature process even if a dye is included.

In addition, the colored photosensitive resin composition of the present invention has excellent luminance and colorability, and provides excellent sensitivity.

In addition, since the image display device of the present invention is manufactured using the colored photosensitive resin composition as described above, it provides a high-resolution image.

1 is A-1 or A-2 represented by Formula 1; It is a graph showing the transmission spectrum when a colorant containing G58 or G7 is used.

the present invention

(A) a colorant, (B) a binder resin, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, (E) an antioxidant, and (F) a solvent;

The colorant (A) includes a compound represented by the following formula (1), and at least one selected from pigments and dyes,

The (E) antioxidant is

A mixed antioxidant comprising at least one selected from a phenol-based antioxidant and a phosphorus-based antioxidant and a sulfur-based antioxidant, and

It relates to a colored photosensitive resin composition comprising at least one selected from polyfunctional antioxidants having at least one of a phenol group, a phosphorus atom and a sulfur atom in one molecule:

[Formula 1]

In Formula 1, A ¹ to A ¹⁶ are each independently Cl, Br, or H, and 1 to 6 of A ¹ to A ¹⁶ are H, 0 to 5 are Cl, and 5 to 13 are Br.

Hereinafter, the coloring photosensitive resin composition of this invention is demonstrated in detail for each component.

(A) Colorant

The colorant contains at least one pigment (a1) and at least one dye (a2) as essential components.

Pigment (a1)

The colorant (A) contained in the colored photosensitive resin composition of the present invention comprises a compound represented by the following formula (1) as the pigment (a1). The compound represented by the following Chemical Formula 1 has a structure of ZnPc (Zinc Phthalocyanine). When the colorant (A) of the present invention includes a compound represented by the following formula (1), there is an advantage of high color reproduction.

[Formula 1]

In Formula 1, A ¹ to A ¹⁶ are each independently Cl, Br, or H, 1 to 6 of A ¹ to A ¹⁶ are H, 0 to 5 are Cl, and 5 to 13 are Br;

more preferably 1 to 6 are H, 0 to 5 are Cl, and 7 to 13 are Br;

More preferably, 2 to 5 may be H, 0 to 3 may be Cl, and 8 to 13 may be Br. In this case, it is preferable in that the effect of the present invention is further maximized.

C.I. Pigment Green 58 (G58) has the advantage of high luminance, but the content of pigment is increased in order to realize high colorability. There may be a problem that the sensitivity is lowered.

However, in the present invention, by using the pigment represented by Formula 1 as a colorant, it is possible to design a resist with high color reproduction even if the content of the pigment is small.

On the other hand, C.I. Pigment Green 7 (G7), when included in the resin composition, can exhibit high colorability even with a small amount of pigment, which is advantageous for use, but has a problem of low luminance. However, the compound of Formula 1 contained in the colored photosensitive resin composition of the present invention is a pigment of C.I. While showing a transmission spectrum and color coordinates similar to those of Pigment Green 7, it is included in the colored photosensitive resin composition and functions to exhibit excellent luminance. As can be seen in Figure 1, the compound of Formula 1 is C.I. Similar to Pigment Green 7, it has a transmission spectrum at a wavelength of 400 nm to 610 nm.

In the present specification, Tmax means the wavelength at the point where the transmittance of the pigment is maximum, and T50% means the wavelength at the point where the transmittance of the pigment is 50% or more of the maximum value.

In an embodiment of the present invention, the Tmax of the compound represented by Formula 1 may be 500 to 530 nm, and in this case, it is preferable in terms of excellent colorability.

In addition, in another embodiment of the present invention, T50% of the compound represented by Formula 1 may be 445 to 580 nm, and in this case, it is preferable in terms of excellent colorability.

The compound of Formula 1 is preferably contained in an amount of 0.05 to 30% by weight, more preferably in an amount of 0.05 to 25% by weight, and more preferably in an amount of 0.05 to 20% by weight, based on the total weight of the solid content in the colored photosensitive resin composition of the present invention. It is more preferable to be included. When the compound of Formula 1 is included within the above range, it is preferable to express high-brightness resist while having excellent colorability.

The colorant (A) according to the present invention is a component capable of expressing colors such as red, green, or blue so as to produce a pattern having a desired color, in addition to the compound of Formula 1, and a pigment commonly used in the art; It may further include one or more selected from dyes, and may be prepared in the form of a wheat base.

The compound represented by Formula 1 and at least one selected from pigments and dyes are preferably 1:0.050 to 1:18.0, more preferably 1:0.1 to 1:9, still more preferably 1:0.2 to It is preferable to be included in a weight ratio of 1:4. When included in the above weight ratio, there are advantages of high coloration and high brightness, and it is preferable because of the advantages of improved process margin and excellent sensitivity.

The pigment (a1) includes an organic pigment and an inorganic pigment, which may be used alone or in combination of two or more. It may be more preferable to use an organic pigment in terms of excellent heat resistance and color development. The organic pigment may be a synthetic pigment or a natural pigment.

The organic pigment may be treated with rosin, if necessary; surface treatment using a pigment derivative into which an acidic group or a basic group is introduced; graft treatment to the surface of the pigment using a polymer compound or the like; fine-graining treatment by a sulfuric acid fine-graining method or the like; or washing treatment with an organic solvent or water to remove impurities; it may have been

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black Or a composite metal oxide etc. are mentioned. In particular, the organic and inorganic pigments may include compounds classified as pigments in the color index (published by Thesociety of Dyers and Colorists), and more specifically, the following color index (CI) pigments , but is not necessarily limited thereto.

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

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

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

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

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

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58

C.I Pigment Brown 28

C.I Pigment Black 1 and 7 etc.

Each of the pigments (a1) may be used alone or in combination of two or more.

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

dye (a2)

The dye may be used without limitation as long as it has solubility in organic solvents. Preferably, it is preferable to use a dye that has solubility in organic solvents and can secure reliability such as solubility in alkali developer, heat resistance, and solvent resistance.

As a specific example of the dye, C.I. As a solvent dye,

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

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

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

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

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

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

C.I. Among solvent dyes, C.I. Solventred 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Blue 35, 36, 44, 45, 70;

C.I. Solvent Violet 13 is preferred and dual C.I. Solvent Red 8, 122, and 132 are more preferable.

Also, C.I. As an acid dye,

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

CI 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;

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;

CI 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 blue dyes, such as;

Violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66;

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

C.I. Acid Red 92, which has excellent solubility in organic solvents among acid dyes; C.I. Acid Blue 80, 90; C.I. Acid Violet 66 is preferred.

Also as a C.I. direct dye,

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105,

106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218,

red dyes such as 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58,

yellow dyes such as 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

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;

CI 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 blue dyes;

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

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

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

CI 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;

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

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

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

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

As a dye in the present invention, Solvent Red 124 (Clariant's trade name: Savinyl Fire Red 3GLS) may be preferably used.

Each of the above dyes may be used alone or in combination of two or more.

The content of the dye in the colorant is preferably included in an amount of 0.5 to 80% by weight based on the total weight of the colorant based on the solid content, more preferably 0.5 to 60% by weight, and even more preferably 1 to 50% by weight.

If the content of the dye in the colorant is within the above range, it is possible to prevent a problem of a decrease in reliability in which the dye is eluted by an organic solvent after pattern formation, and it is preferable because of its excellent sensitivity.

The content of the (A) colorant is preferably 5 to 80% by weight, preferably 10 to 45% by weight based on the total weight of the solid content in the colored photosensitive resin composition. When the colorant is included in the above range, the color density of the pixel is sufficient even when a thin film is formed, and the omission property of the non-pixel portion does not decrease during development, so residues are hardly generated, which is preferable.

In the present invention, the solid content in the colored photosensitive resin composition means the total content of the remaining components excluding the solvent from the colored photosensitive resin composition.

(B) binder resin

The binder resin contained in the coloring photosensitive resin composition of this invention is a component which provides solubility with respect to the alkaline developing solution used in the image development process. In the present invention, the binder resin is not particularly limited, but is preferably a copolymer of a monomer having a carboxyl group and another monomer copolymerizable therewith.

The monomer having a carboxyl group is not particularly limited, and specific examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; Polymer mono(meth)acrylates having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate, etc. are mentioned, and acrylic acid and methacrylic acid are more preferable. These can be used by selecting one or more types.

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

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

The acid value of the binder resin is preferably 30 to 170 mgKOH/g based on solid content, and more preferably 50 to 150 mgKOH/g. When the acid value of the binder resin is less than 30 mgKOH/g, it is difficult for the colored photosensitive resin composition to secure a sufficient development speed. It is not preferable because there is a possibility that a problem occurs in compatibility with the colorant and the colorant in the colored photosensitive resin composition is precipitated, or the storage stability of the colored photosensitive resin composition is lowered and the viscosity is increased.

The (B) binder resin is preferably contained in an amount of 5 to 85% by weight, more preferably 10 to 70% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. (B) When the content of the binder resin is included in the above range, the solubility in the developer is sufficient, so that the development residue of the non-pixel portion on the substrate is difficult to occur, and the film reduction of the pixel portion of the exposed portion is prevented during development. Since the omission property of a pixel part tends to be favorable, it is preferable.

(C) photopolymerization monomer

In the present invention, the photopolymerizable monomer is a monomer that can be polymerized by active radicals, acids, etc. generated from the photopolymerization initiator by irradiation with light.

Specific examples of the photopolymerizable monomer include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and pentaerythriacrylic Late, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A di Acrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4- butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, KAYARAD DPHA (manufactured by Nippon Kayaku), and the like.

The photopolymerizable monomer is preferably included in an amount of 5 to 45 wt%, more preferably in an amount of 10 to 35 wt%, based on the total weight of the solid content in the colored photosensitive resin composition. When the content of the photopolymerizable monomer is included in the above range, it is preferable because the intensity or flatness of the pixel portion is improved.

(D) light curing initiator

The photopolymerization initiator may be used without particularly limiting its kind as long as it can polymerize the (B) binder resin and the photopolymerizable monomer (C). In particular, from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, etc., it is preferable to use at least one compound selected from the group consisting of triazine-based compounds, acetophenone-based compounds, biimidazole-based compounds and oxime compounds. desirable.

Specific examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -(4-Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2- yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine etc. are mentioned.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyl) oxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one; 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1 -one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. are mentioned.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4, 4'5,5'-tetraphenyl-1,2'-biimidazole or the imidazole compound in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group, etc. are mentioned.

Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole and 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole are preferably used do.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and compounds represented by the following Chemical Formulas 2 to 4, and the like.

[Formula 2]

[Formula 3]

[Formula 4]

Moreover, as long as the effect of this invention is not impaired, other photoinitiators etc. which are normally used in this field|area can also be used together further. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds, and these can be used either alone or in combination of two or more.

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

Examples of the benzophenone-based compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'- tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. etc.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. etc.

Others 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, OXE-01 (made by BASF), etc. are mentioned.

In addition, the (D) photoinitiator may be used in combination with a (D-1) photopolymerization initiator adjuvant. When a photoinitiator adjuvant is used together with a photoinitiator, since the coloring photosensitive resin composition containing these becomes more highly sensitive and improves productivity, it is preferable.

As the photopolymerization initiation adjuvant, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group may be preferably used.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylamino 2-ethylhexyl benzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone), 4,4'-bis(diethyl) Aromatic amine compounds, such as amino) benzophenone, are mentioned. As the amine compound, an aromatic amine compound is preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichloro and aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercapto) butyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. can be heard

The content of the (D) photopolymerization initiator is preferably contained in an amount of 0.1 to 40 wt%, more preferably 1 to 30 wt%, based on the total weight of the solid content in the colored photosensitive resin composition.

When the photopolymerization initiator is included in the above range, the colored photosensitive resin composition is highly sensitive and exposure time is shortened, so productivity is improved and high resolution can be maintained. Since negative surface smoothness becomes favorable, it is preferable.

In addition, when the (D-1) photopolymerization initiation aid is used, it is preferably contained in an amount of 0.1 to 50% by weight, more preferably 1 to 40% by weight, based on the total weight of the solid content in the colored photosensitive resin composition.

When the photopolymerization initiation adjuvant is included in the above range, the sensitivity of the colored photosensitive resin composition is further increased, and the productivity of a color filter formed using the composition is improved, so it is preferable.

(E) antioxidants

The antioxidant serves to improve thermal stability by preventing oxidation of the colored resin composition during the preparation of the colored resin composition.

The antioxidant is a phenol-based antioxidant, a mixed antioxidant comprising at least one selected from a phosphorus antioxidant and a sulfur-based antioxidant, and a polyfunctional oxidation having at least one of a phenol group, a phosphorus atom and a sulfur atom in one molecule It is characterized in that it contains one or more selected from inhibitors.

When the antioxidant as described above is included, other antioxidants may also be included and used.

When the antioxidant as described above is used, heat resistance, adhesion, transmittance and luminance are high, and development sensitivity is good even at a low exposure dose.

A well-known compound can be used as a phenolic antioxidant. Specifically, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethoxy]-2,4,8 having a spirocyclic skeleton such as , 10-tetraoxaspiro [5.5] undecane, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] phenolic compounds; 1,3,5,-trimethyl-2,4,6,-tris(3'5'-di-t-butyl-4-hydroxybenzyl)benzene, triethyleneglycol-bis[3-(3-t- Butyl-5-methyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-t-butyl-3-methylphenol), tris- (3,5-di-t-butyl- 4-Hydroxybenzyl)-isocyanurate, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate, 1,6-hexanediol -bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl- 4-hydroxyphenyl) propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2, 4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,4-bis[(octylthio)methyl]-O-cresol, 1,6-hexanediol-bis- [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propio Nate, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), 1,1,3 -tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-tris(4-hydroxybenzyl)benzene, tetrakis[methylene-3-(3,5'- di-t-butyl-4'-hydroxyphenylpropionate)]methane, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy] -1,1-Dimethylethoxy]-2,4,8,10-tetraoxasaspiro[5.5]undecane, 1,3,5,-trimethyl-2,4,6,-tris(3'5' -di-t-butyl-4-hydroxybenzyl)benzene, pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], triethylene glycol -bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6-t-butyl-3-methylphenol), tris-( 3,5-di-t-Butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-iso Cyanurate, 1,6-Hexanediol-bis[3-(3,5-di -t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris(3,5-di -t-butyl-4-hydroxybenzyl)benzene, 2,4-bis[(octylthio)methyl]-O-cresol, AO-60 (manufactured by Adeka), AO-80 (manufactured by Adeka), etc. .

A well-known compound can be used as a phosphorus antioxidant. Specifically, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane , a phosphite compound having a spiro ring skeleton such as diisodecylpentaerythritol diphosphite and bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite; 2,2'-methylenebis(4,6-di-t-butyl-1-phenyloxy)(2-ethylhexyloxy)phosphorus, 6-[3-(3-t-butyl-4-hydroxy -5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosphepine, triphenylphosphite, diphenylisodecyl Phosphite, phenyldiisodecylphosphite, 4,4'-butylidene-bis(3-methyl-6-t-butylphenylditridecyl)phosphite, octadecylphosphite, 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-phosphaphenanthrene-10-oxide, tris(2,4-di -t-butylphenyl)phosphite, cyclic neopentanetetraylbis(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, tetrakis(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, 6-[3-(3-t-butyl-4-hydroxy-5) -methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphospepine, HP-10 (manufactured by Adeka), etc. .

As the sulfur-based antioxidant, a known compound can be used. Specifically, 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl-bis[3-(dodecylthio)propionate], 2- Mercaptobenzimidazole, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, compounds having a thioether structure such as pentaerythrityl-tetrakis(3-laurylthiopropionate); 2-Mercaptobenzimidazole, 2,2-bis({[<231> 3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl-bis[3-(dodecylthio) propionate] and 2-mercaptobenzimidazole.

In the mixed antioxidant, the mixing ratio of the phenol-based antioxidant and at least one selected from the phosphorus antioxidant and the sulfur-based antioxidant is preferably 1: 0.2 to 0.7, more preferably 1: 0.4 to 0.6, by weight. It is still more preferably 1:0.5.

When the mixing ratio satisfies the above range, heat resistance of the colored photosensitive resin composition may be enhanced and excellent luminance may be exhibited.

However, when the mixing ratio of at least one selected from the phosphorus-based antioxidant and the sulfur-based antioxidant is larger, problems of lowering luminance and sensitivity may occur.

A polyfunctional antioxidant having at least one of a phenol group, a phosphorus atom and a sulfur atom in one molecule may be used, and a representative example thereof may be Sumilizer GP (manufactured by Sumitomo).

In addition, the (E) antioxidant may be included in an amount of 0.1 to 20 wt%, more preferably 1 to 10 wt%, based on the total weight of the solid content in the colored photosensitive resin composition. When included within the above range, the advantage of improving the heat resistance of the colored photosensitive resin composition is provided.

In addition, the (E) antioxidant may be included in an amount of 5 to 75 parts by weight based on 100 parts by weight of the (D) initiator. When it is included in the above range, heat resistance can be strengthened and excellent luminance can be obtained.

(F) Solvent

The solvent is not particularly limited as long as it is effective for dispersing or dissolving other components included in the colored photosensitive resin composition. In particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides are preferable.

The solvent is specifically ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether, 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 (gamma)-butyrolactone, etc. are mentioned.

Among the solvents exemplified above, in consideration of applicability and dryness, organic solvents having a boiling point of 100°C to 200°C are preferable, and more preferably, alkylene glycol alkyl ether acetates, ketones, 3-ethoxy Esters, such as ethyl propionate and 3-methoxy methyl propionate, are mentioned, More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy ethyl propionate, 3- Methyl methoxypropionate, etc. are mentioned. These can be used individually or in mixture of 2 or more types, respectively.

The (F) solvent may be included in an amount of 10 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition. When the solvent content is within the above range, the coating property tends to be good when applied with an application device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), inkjet, etc. It is preferable because

(G) Additives

It is also possible to add additives such as other high molecular compounds, curing agents, surfactants, adhesion promoters, aggregation inhibitors, and pigment dispersants to the colored photosensitive resin composition of the present invention in parallel as needed.

Specific examples of the other polymer compound include a curable resin such as an epoxy resin and maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. can be heard

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

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins , glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene ( A co)polymer epoxidized product, a glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc. are mentioned.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylenebisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane. The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. The curing auxiliary compound includes, for example, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, and acid generators. As the polyhydric carboxylic acid anhydrides, commercially available epoxy resin curing agents may be used. Specific examples of the epoxy resin curing agent include a trade name (Adekahadona EH-700) (manufactured by Adeka Industries, Ltd.), a trade name (Rikasiddo HH) (manufactured by Shin Nippon Ewha Co., Ltd.), a trade name (MH-700) (Shin Nippon Ewha Co., Ltd.) manufactured by Nippon Ewha Co., Ltd.) and the like. The curing agents exemplified above may be used alone or in combination of two or more.

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

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Dow Corning Toray Silicone Co. , TSF-4452, and the like. The fluorine-based surfactants include, for example, Megapiece F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink Chemical Co., Ltd. as a commercially available product. Each of the surfactants exemplified above may be used alone or in combination of two or more.

The surfactant may be included in an amount of usually 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the total weight of the solid content in the colored photosensitive resin composition.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-( 3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrime Toxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be included in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the solid content in the colored photosensitive resin composition.

Specific examples of the anti-aggregation agent include sodium polyacrylate.

The pigment dispersant is added to deagglomerate and maintain stability of the pigment, and those generally used in the art may be used without limitation. Preferably, an acrylate-based dispersant (hereinafter also referred to as “acrylic dispersant”) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA) may be used. Commercially available products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, and DISPER BYK LPN-6919. The acrylic dispersants exemplified above may be used alone or in combination of two or more.

As the pigment dispersant, a pigment dispersant of a resin type other than the above-mentioned acrylic dispersant may be used.

The pigment dispersants of the other resin types are, in particular, polyurethanes, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, polycarboxylic acids ammonium salts of, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modifications, or polyesters with free carboxyl groups and poly(lower) oleaginous dispersants such as amides or salts thereof formed by the reaction of alkyleneimines); water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; modified polyacrylates; adducts of ethylene oxide/propylene oxide and phosphate esters; and the like.

As a commercially available product of the above-mentioned resin type pigment dispersant, as a cationic resin dispersant, for example, BYK-Chemie's brand names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164 , DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; Trade names from BASF: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names from Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Trade names of Kawaken Fine Chemicals: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade names of Ajinomoto Corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemical Corporation: FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, fluorene DOPA-44, etc. are mentioned.

The pigment dispersant is preferably included in an amount of 5 to 60 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1) used. When the content of the pigment dispersant is included in less than 5 parts by weight, it is difficult to atomize the pigment or it may cause problems such as gelation after dispersion, and if it exceeds 60 parts by weight, the viscosity may increase, which is not preferable.

Also, the present invention

It provides a color filter made of the colored photosensitive resin composition and an image display device including the same.

The image display apparatus of the present invention includes a color filter of the present invention comprising a substrate and a color layer. The image display device includes a configuration known to those skilled in the art except for having the color filter.

The manufacturing method of the photosensitive resin composition of the present invention will be described by way of example.

First, the pigment (a1) among the colorants (A) is mixed with the solvent (F) and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, if necessary, part or all of the (B) binder resin may be mixed with part or all of the (F) solvent to be dissolved or dispersed.

To the mixture, (B) binder resin, (C) photopolymerizable monomer, (D) photoinitiator, (E) antioxidant and (F) solvent were further added to a predetermined concentration to obtain a colored photosensitive resin composition according to the present invention can be manufactured.

Hereinafter, the present invention will be described in more detail based on Examples, but the embodiments of the present invention disclosed below are illustrative, and the scope of the present invention is not limited to these embodiments.

In addition, in the following examples and comparative examples, "%" and "part" indicating the content are by weight unless otherwise specified.

Example 1-5 and comparative example 1-4: Preparation of colored photosensitive resin composition

A colored photosensitive resin composition was prepared by mixing the components shown in Table 1 in the corresponding composition ratio.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 coloring agent A-1 3.94 3.94 3.94 3.94 3.94 3.94 3.94 3.94 3.94 A-2 0.82 0.82 0.82 0.82 0.82 0.82 0.82 0.82 0.82 binder
Suzy B 3.56 3.56 3.56 3.56 3.56 3.56 3.56 3.56 3.56 photopolymerizable monomer C 3.56 3.56 3.56 3.56 3.56 3.56 3.56 3.56 3.56 light curing
initiator D 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Oxidation
inhibitor E-1 0.205 0.41 0.41 E-2 0.205 0.27 E-3 0.27 0.41 E-4 0.14 0.41 E-5 0.41 E-6 0.14 0.41 solvent F-1 70 70 70 70 70 70 70 70 70 F-2 15 15 15 15 15 15 15 15 15 additive G-1 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 G-2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 G-3 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01

(Unit: Weight % )

Pigment (A-1): C.I. Pigment Green 59

Dye (A-2): Solvent yellow 21 (manufactured by Ohyoung Industrial Co., Ltd.)

(B) Binder resin: methacrylic acid and benzyl methacrylate copolymer having a molar ratio of methacrylic acid units and benzyl methacrylate units of 31:69, a weight average molecular weight of 30,000, and an acid value of 105

Photopolymerizable monomer (C): KAYARAD DPHA (manufactured by Nippon Kayaku)

Photoinitiator (D): OXE-01 (manufactured by BASF)

Antioxidant (E)

E-1: Multifunctional antioxidant Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.)

E-2: Phenolic antioxidant AO-60 (manufactured by Adeka)

E-3: Phenolic antioxidant AO-80 (manufactured by Adeka)

E-4: sulfur-based antioxidant AO-412S (manufactured by Adeka)

E-5: sulfur-based antioxidant AO-503 (manufactured by Adeka)

E-6: Phosphorus antioxidant HP-10 (manufactured by Adeka)

Solvent (F)

F-1: propylene glycol monomethyl ether acetate

F-2: ethyl 3-ethoxypropionate

Additive (G)

G-1: Silicone-based surfactant (SH-8400)

G-2: pigment dispersant

G-3: adhesion promoter (3-methacryloxypropyltrimethoxysilane)

test example 1: Luminance and heat resistance evaluation

Color filters were prepared using the colored photosensitive resin compositions prepared in Examples 1 and 5 and Comparative Examples 1 to 4. Specifically, each of the colored photosensitive resin compositions was coated on a glass substrate by spin coating, placed on a heating plate, and maintained at a temperature of 100° C. for 3 minutes to form a thin film. Then, a test photomask having a pattern for changing the transmittance in a range of 1 to 100% stepwise and a line/space pattern of 1 μm to 50 μm is placed on the thin film, and the distance from the test photomask is set to 100 μm. UV light was irradiated. At this time, the ultraviolet light source was irradiated with an illuminance of 100 mJ/cm 2 using a 1KW high-pressure mercury lamp containing all of the g, h, and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet light was developed by immersing it in a developing solution of a KOH aqueous solution having a pH of 10.5 for 2 minutes. The glass plate coated with this thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220° C. for 1 hour to prepare a color filter. The film thickness of the color filter prepared above was 2.0㎛.

The luminance and heat resistance of the color filter prepared above were evaluated in the following manner, and the results are shown in Table 2 below.

<Luminance (Y)>

The luminance and color coordinates of the formed colored layer were measured using a microscopic spectrometer OSP-SP2000.

○: more than 17.8, △: 17.6~17.8, X: less than 17.6

<Heat resistance>

After heating the prepared color filter in a heating oven at 230° C. for 2 hours, the color change (ΔEab) before and after heating was measured, and the change in luminance (ΔY) before and after the heat resistance evaluation was confirmed.

△Eab

○: less than 3, △: 3-4, X: more than 4

ΔY

○: less than 0.3, △: 0.3 to 0.5, X: more than 0.5

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Luminance (Y) ○ ○ ○ ○ ○ △ △ △ △ heat resistance E*ab ○ △ ○ ○ ○ ○ ○ ○ ○ Y ○ ○ ○ ○ ○ △ △ △ △

(Based on Rx=0.262, Ry=0.640)

As shown in Table 2 above, polyfunctional antioxidants having at least one of a phenol group, a phosphorus atom and a sulfur atom in one molecule (Examples 1 to 3) and mixed antioxidants (Examples 4 and 5) of the present invention The colored photosensitive resin composition has excellent heat resistance compared to Comparative Examples 1 to 4 in which phenolic antioxidants, phosphorus antioxidants and sulfur antioxidants are used alone, so it can be confirmed that the luminance change is small even after additional heating and high luminance can be confirmed. there was.

As the specific part of the present invention has been described in detail above, for those of ordinary skill in the art to which the present invention pertains, it is clear that these specific techniques are only preferred embodiments, and the scope of the present invention is not limited thereto. do. Those of ordinary skill in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above contents.

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

Claims (7)

(A) a colorant, (B) a binder resin, (C) a photopolymerizable monomer, (D) a photoinitiator, (E) an antioxidant, and (F) a solvent;
The colorant (A) includes a compound represented by the following formula (1) and a dye,
the dye comprises CI solvent yellow 21;
The (E) antioxidant is
A mixed antioxidant comprising at least one selected from a phenol-based antioxidant and a phosphorus-based antioxidant and a sulfur-based antioxidant, and
A colored photosensitive resin composition comprising at least one selected from polyfunctional antioxidants having at least one of a phenol group, a phosphorus atom and a sulfur atom in one molecule:
[Formula 1]

In Formula 1, A ¹ to A ¹⁶ are each independently Cl, Br, or H, and 1 to 6 of A ¹ to A ¹⁶ are H, 0 to 5 are Cl, and 5 to 13 are Br. The method according to claim 1,
The color photosensitive resin composition, characterized in that the compound represented by Formula 1 and the dye are included in a weight ratio of 1: 0.050 to 1: 18.0. The method according to claim 1,
The colored photosensitive resin composition is based on the total weight of the solids contained in the composition,
(A) 5 to 80% by weight of a colorant, (B) 5 to 85% by weight of a binder resin, (C) 5 to 45% by weight of a photopolymerizable monomer, (D) 0.1 to 40% by weight of a photopolymerization initiator, and (E) an antioxidant 0.1 to 20% by weight,
With respect to the total weight of the colored photosensitive resin composition,
(F) A colored photosensitive resin composition comprising 10 to 90% by weight of a solvent. The method according to claim 1,
In the mixed antioxidant, a mixing ratio of at least one selected from a phenol-based antioxidant and a phosphorus-based antioxidant and a sulfur-based antioxidant is 1: 0.2 to 0.7 by weight. The colored photosensitive resin composition. The method according to claim 1,
Colored photosensitive resin composition, characterized in that it further comprises one or more additives selected from the group consisting of other high molecular compounds, curing agents, surfactants, adhesion promoters, aggregation inhibitors, and pigment dispersants. A color filter comprising a colored pattern made of the colored photosensitive resin composition of any one of claims 1 to 5. An image display device comprising the color filter of claim 6.

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