KR102762228B1 - A photosensitive resin composition, a color filter prepared using the composition, and a display device comprising thereof - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, comprising a photopolymerization initiator, wherein in a region (A) defined by a normalized emission spectrum of an exposure device for a wavelength of 350 to 390 nm; a region (P) defined by an absorption spectrum of a photopolymerization initiator; and a region (B) defined as an overlapping region of the region (A) and the region (P), an area ratio of the region (B) to the region (A) is 0.4 or more, a color filter manufactured using the same, and a display device including the same.

Description

Photosensitive resin composition, color filter prepared using the same, and display device including the same {A PHOTOSENSITIVE RESIN COMPOSITION, A COLOR FILTER PREPARED USING THE COMPOSITION, AND A DISPLAY DEVICE COMPRISING THEREOF}

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

Color filters are widely used in various display devices such as image sensors and liquid crystal displays (LCDs), and their application range is rapidly expanding. The color filter is composed of a coloring pattern of three colors: red, green, and blue, or a coloring pattern of three colors: yellow, magenta, and cyan.

The coloring pattern of each of the above color filters is generally formed using a coloring photosensitive resin composition including a coloring agent such as a pigment or dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the coloring photosensitive resin composition is typically performed using a lithography process.

Specifically, a photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photocurable pattern, and in this process, a photosensitive resin composition that can improve pattern characteristics and process yield and prevent pattern peeling is required.

Meanwhile, the photosensitive resin composition can form a photocurable pattern by a wide range of wavelengths. In particular, as the density of integrated circuits has been achieved through recent improvements and reductions in circuit technology and device structures, the wavelength of exposure devices has also become increasingly shorter, such as G-line (436 nm) and I-line (365 nm).

Korean Patent Publication No. 10-2016-0140652 also discloses a photopolymerization initiator for use in an exposure device that emits near-ultraviolet light in the I-line (365 nm) region. However, film loss before and after development still occurs, hole formation is difficult, and pattern peeling occurs, so there is a need for a photosensitive resin composition to solve these problems.

Republic of Korea Publication Patent No. 10-2016-0140652

The purpose of the present invention is to provide a photosensitive resin composition having improved hole characteristics.

In addition, an object of the present invention is to provide a photosensitive resin composition in which the film reduction rate before and after development is minimized.

In addition, an object of the present invention is to provide a photosensitive resin composition capable of preventing peeling of a formed pattern.

In addition, the present invention aims to provide a color filter manufactured using the photosensitive resin composition and a display device including the same.

The present invention relates to a photosensitive resin composition, which comprises a photopolymerization initiator, wherein, in a region (A) defined by a normalized emission spectrum of an exposure device for a wavelength of 350 to 390 nm; a region (P) defined by an absorption spectrum of a photopolymerization initiator; and a region (B) defined as an overlapping region of the region (A) and the region (P), an area ratio of the region (B) to the region (A) is 0.4 or more.

In the first aspect of the present invention, the normalized emission spectrum may be normalized by the maximum emission wavelength of the exposure device at a wavelength of 350 to 390 nm.

In the second aspect of the present invention, the concentration of the photopolymerization initiator used in measuring the absorption spectrum may be 10 ppm.

In the third aspect of the present invention, the photopolymerization initiator may have a maximum absorption wavelength at a wavelength of 340 to 380 nm.

The present invention, in its fourth aspect, may further include a colorant, an alkali-soluble resin, a photopolymerizable compound and a solvent.

In the fifth aspect of the present invention, the colorant may include a red pigment.

In the sixth aspect of the present invention, the red pigment may include C.I. Pigment Red 242.

The present invention, in its seventh aspect, may include, based on the total weight of the solid content of the photosensitive resin composition, 1 to 50 wt% of a colorant; 5 to 70 wt% of an alkali-soluble resin; 5 to 50 wt% of a photopolymerizable compound; 1 to 10 wt% of a photopolymerization initiator; and 60 to 90 wt% of a solvent based on the total weight of the photosensitive resin composition.

The present invention, in its eighth aspect, may further include at least one selected from the group consisting of a filler, another polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-coagulant, a dispersant, and an ink repellent.

In the ninth aspect of the present invention, the exposure device may be an LED exposure device.

In addition, the present invention relates to a color filter manufactured using the photosensitive resin composition.

In addition, the present invention relates to a display device including the color filter.

According to the photosensitive resin composition of the present invention, hole characteristics can be further improved compared to conventional photosensitive resin compositions.

In addition, according to the photosensitive resin composition of the present invention, the film reduction rate before and after development can be further minimized compared to conventional photosensitive resin compositions.

In addition, according to the photosensitive resin composition of the present invention, peeling of the formed pattern can be further prevented compared to conventional photosensitive resin compositions.

Figures 1 to 3 are diagrams showing spectra according to one embodiment of the present invention.

The present invention relates to a photosensitive resin composition including a photopolymerization initiator satisfying specific spectral characteristics, a color filter manufactured using the same, and a display device including the same.

More specifically, the present invention is characterized by including a photopolymerization initiator, wherein, in a region (A) defined by a normalized emission spectrum of an exposure device with respect to a wavelength of 350 to 390 nm; a region (P) defined by an absorption spectrum of a photopolymerization initiator; and a region (B) defined as an overlapping region of the region (A) and the region (P), an area ratio of the region (B) to the region (A) is 0.4 or more.

By using a photosensitive resin composition including a photopolymerization initiator satisfying the above spectral characteristics, the hole characteristics and the residual film rate can be improved, and peeling of the formed pattern can be prevented, thereby improving the resolution and light efficiency of a color filter or a display device.

The “solid content” described in the present invention means the remaining components excluding the solvent.

Hereinafter, the contents of the present invention are divided into <photosensitive resin composition> , <color filter>, and <display device> and explained.

<Photosensitive resin composition>

The photosensitive resin composition of the present invention may include a photopolymerization initiator in which, in a region (A) defined by a normalized emission spectrum of an exposure device with respect to a wavelength of 350 to 390 nm; a region (P) defined by an absorption spectrum of a photopolymerization initiator; and a region (B) defined as an overlapping region of the region (A) and the region (P), an area ratio of the region (B) to the region (A) is 0.4 or greater. In one embodiment, the photosensitive resin composition may further include a colorant, an alkali-soluble resin, a photopolymerizable compound, and a solvent.

The above exposure device is not particularly limited as long as it is capable of photocuring a photosensitive resin composition, but is preferably an LED (Light Emitting Diode) exposure device. In this case, there is an advantage in that it is possible to selectively irradiate light of a specific wavelength. In one embodiment, the exposure device may be an LED exposure device that emits a wavelength in the I-line (365 nm) region, and preferably, it may be an LED exposure device that selectively emits only a wavelength in the I-line (365 nm) region.

coloring agent

The above colorant may contain one or more pigments.

The above pigment may be an organic pigment or an inorganic pigment commonly used in the relevant field.

The pigment above can be any of various pigments used in printing ink, inkjet ink, etc., and specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, ferrilene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, pravanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, etc.

Examples of the above inorganic pigments include metal compounds such as metal oxides or metal complexes, and specifically, examples thereof include oxides or composite metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black.

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, pigments having the following color index (C.I.) numbers, but are not necessarily limited thereto.

C.I. Pigment Yellow 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.

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

Among the above-mentioned C.I. 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 Green 59, C.I. Pigment Violet 23, C.I. A pigment selected from the group consisting of Pigment Blue 15:3 and Pigment Blue 15:6 can be preferably used.

In one embodiment, the photosensitive resin composition of the present invention may include, in particular, C.I. Pigment Red 242. In this case, there is an advantage in that hole characteristics can be improved and peeling of the formed pattern can be prevented.

Specifically, there is a trade-off relationship between the sensitivity according to the absorbance of the pigment and the hole characteristic according to the pattern line width. Therefore, when the absorbance of the pigment at a specific wavelength is low, as the sensitivity of the photosensitive resin composition at the corresponding wavelength increases, the line width of the formed pattern also increases, which may deteriorate the hole characteristic. In addition, when the content of the photopolymerization initiator included in the photosensitive resin composition is reduced in order to improve the hole characteristic, the pattern is not sufficiently cured, resulting in the phenomenon of the pattern peeling off after development.

C.I. Pigment Red 177 and C.I. Pigment Red 254 exhibit relatively low absorbance for the wavelength in the I-line (365 nm) region. Therefore, the sensitivity of the photosensitive resin composition to the emission wavelength in the I-line (365 nm) region of the exposure equipment increases, resulting in difficulty in forming holes.

On the other hand, C.I. Pigment Red 242 exhibits higher absorbance than pigments such as C.I. Pigment Red 177 and C.I. Pigment Red 254 for the wavelength in the I-line (365 nm) region. Therefore, by appropriately controlling the content of a photopolymerization initiator exhibiting high absorbance for the wavelength in the I-line (365 nm) region, the hole characteristics can be improved while simultaneously preventing pattern peeling.

It is preferable that the above pigment use a pigment dispersion in which the particle size of the pigment is uniformly dispersed. Examples of methods for uniformly dispersing the particle size of the pigment include a method of carrying out dispersion treatment by containing a pigment dispersant, and according to the above method, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

The above pigment dispersant is added to deagglomerate and maintain stability of the pigment, and any of those commonly used in the field can be used without limitation.

Specific examples of the pigment dispersants mentioned above include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine, and each of these can be used alone or in combination of two or more.

In addition to the pigment dispersants described above, other resin-type pigment dispersants may be used as the pigment dispersants. Examples of the pigment dispersants of the other resin-type pigment dispersants include known resin-type pigment dispersants, particularly polycarboxylic acid esters represented by polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or amides formed by the reaction of polyesters having free carboxyl groups with poly(lower alkylene imine)s or salts thereof, and oily dispersants; Examples thereof include water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinyl pyrrolidone; polyesters; modified polyacrylates; adducts of ethylene oxide/propylene oxide and phosphate esters. Pigment dispersants of other resin types may also be used. As the pigment dispersant of the other resin type, known resin type pigment dispersants, in particular, polycarboxylic acid esters represented by polyurethane, polyacrylate, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or amides formed by the reaction of a polyester having a free carboxyl group with a poly(lower alkylene imine) or salts thereof, oily dispersants; water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinyl pyrrolidone; polyesters; Modified polyacrylates; adducts of ethylene oxide/propylene oxide and phosphate esters, etc.

As for the commercial products of the above-mentioned resin-type dispersant, as a cationic resin dispersant, for example, BYK Chemistry's product 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; BASF trade names: 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; Lubirzol trade names: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 /10; Kawaken Fine Chemicals trade names: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Examples thereof include Ajinomoto Co., Ltd.'s trade names: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Kyoeisha Chemical Co., Ltd.'s trade names: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc. The above-mentioned resin type pigment dispersants can be used singly or in combination of two or more, and can also be used in combination with an acrylic dispersant.

The pigment dispersant may be included in an amount of 5 to 60 wt%, preferably 15 to 50 wt%, based on the total weight of the solid content in the pigment dispersion. If the pigment dispersant exceeds 60 wt%, the viscosity may increase, and if it is included in an amount of less than 5 wt%, it may be difficult to atomize the pigment, and problems such as gelation after dispersion may occur.

In one embodiment of the present invention, the colorant may additionally include a dye generally used in the art.

The above dyes can be additionally used without limitation as long as they are soluble in organic solvents or can be dispersed. It is preferable to use dyes that have solubility in organic solvents and can secure reliability such as solubility in alkaline developers, heat resistance, and solvent resistance.

As the dyes mentioned above, those selected from acid dyes having acid groups such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof can be used. In addition, acid dyes of azo, xanthene, and phthalocyanine series and derivatives thereof can also be selected. Preferably, the dyes mentioned above are compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists), or known dyes described in dyeing notes (color dyeing).

Specific examples of the above dyes include C.I. solvent dyes,

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

Blue dyes such as C.I. Solvent Blue 5, 35, 36, 37, 44, 59, 67, 70;

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

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

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

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

Among the above C.I. solvent dyes, C.I. solvent red 8, 49, 89, 111, 122, 132, 146, 179; C.I. solvent blue 35, 36, 44, 45, 70; C.I. solvent violet 13, which have excellent solubility in organic solvents, are preferable, and C.I. solvent red 8, 122, 132 are more preferable.

Also, as a C.I. acid dye,

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, Red dyes such as 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;

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, Yellow dyes such as 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, 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, etc.

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 Blue dye for the back;

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

Examples include 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.

As the acid dyes, C.I. Acid Red 92; C.I. Acid Blue 80, 90; and C.I. Acid Violet 66, which have excellent solubility in organic solvents, are preferable.

Also, as a C.I. direct dye,

Red dyes such as 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;

Yellow dyes such as 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;

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, Blue dyes such as 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;

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;

Examples include 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.

Also, as a C.I. 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;

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

Orange dyes 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;

Blue dyes such as C.I. Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 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;

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

These dyes can be used alone or in combination of two or more.

The content of the colorant may be included in an amount of 1 to 50 wt%, preferably 10 to 45 wt%, based on the total weight of the solid content in the colored photosensitive resin composition. When the colorant is included within the above range, the color density of the pixel is sufficient when forming a thin film, and the omission of non-pixel portions is not reduced when developing, so that residue is unlikely to occur, which is preferable.

Alkali soluble resin

The above alkali-soluble resin has reactivity under the action of light or heat and alkali solubility, acts as a dispersion medium for the solid content included in the photosensitive resin composition, and, as long as it performs the function of a binding resin, any resin known in the art can be selected and used without any special restrictions.

Specifically, it is preferable that the alkali-soluble resin is a copolymer of an unsaturated carboxyl group-containing monomer and another monomer copolymerizable therewith.

Examples of the above unsaturated carboxyl group-containing monomer include unsaturated carboxylic acids having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids.

Examples of the above unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc.

Examples of the above unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc.

The above unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the above unsaturated polycarboxylic acid may be a mono(2-methacryloyloxyalkyl)ester thereof, and examples thereof include succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxyethyl), phthalic acid mono(2-acryloyloxyethyl), and phthalic acid mono(2-methacryloyloxyethyl). The above unsaturated polycarboxylic acid may be a mono(meth)acrylate of a dicarboxy polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like.

The above unsaturated carboxyl group-containing monomers can be used alone or in combination of two or more.

Other monomers copolymerizable with the above unsaturated carboxyl group-containing monomer include, for example, aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butylacrylate, n-butyl methacrylate, i-butylacrylate, i-butyl methacrylate, sec-butylacrylate, sec-butyl methacrylate, t-butylacrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutylacrylate, 2-Hydroxybutyl methacrylate, 3-Hydroxybutyl methacrylate, 3-Hydroxybutyl methacrylate, 4-Hydroxybutyl acrylate, 4-Hydroxybutyl methacrylate, Allyl acrylate, Allyl methacrylate, Benzyl acrylate, Benzyl methacrylate, Cyclohexylacrylate, Cyclohexyl methacrylate, Phenyl acrylate, Phenyl methacrylate, 2-Methoxyethyl acrylate, 2-Methoxyethyl methacrylate, 2-Phenoxyethyl acrylate, 2-Phenoxyethyl methacrylate, Methoxydiethylene glycol acrylate, Methoxydiethylene glycol methacrylate, Methoxytriethylene glycol acrylate, Methoxytriethylene glycol methacrylate, Methoxypropylene glycol acrylate, Unsaturated carboxylic acid esters such as methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; Unsaturated carboxylic acid aminoalkyl esters such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; cyanide vinyl compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imides such as maleimide, N-benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; And examples thereof include macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butylacrylate, poly-n-butyl methacrylate, and polysiloxane. These monomers may be used singly or in combination of two or more.

The content of the alkali-soluble resin may be included in an amount of 5 to 70 wt%, preferably 5 to 50 wt%, based on the total weight of the solid content in the photosensitive resin composition. When the alkali-soluble resin is included within the above range, the solubility in the developer is sufficient, so that the formation of a cured film is easy, and the film reduction of the pixel portion of the exposed portion is prevented during development, so that the omission property of the unexposed portion is improved, which is preferable.

The acid value of the alkali-soluble resin is preferably 30 to 150 mgKOH/g, and accordingly, the aging stability of the photosensitive resin composition can be improved. When the acid value of the alkali-soluble resin is less than 30 mgKOH/g, it is difficult for the photosensitive resin composition to secure a sufficient developing speed, and when it exceeds 150 mgKOH/g, the adhesion with the substrate is reduced, so that pattern short-circuiting easily occurs, and the aging stability of the photosensitive resin composition may deteriorate, causing the viscosity to increase.

Photopolymerizable compound

The above photopolymerizable compound is a compound that can be polymerized by light and heat. Any polymerizable compound known in the art can be selected and used without any particular limitation as long as it can be polymerized by light and heat. Specifically, a monofunctional monomer, a difunctional monomer, or other polyfunctional monomers can be used.

The type of the above monofunctional monomer is not particularly limited, and examples thereof include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc.

The type of the above bifunctional monomer is not particularly limited, and examples thereof 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, and 3-methylpentanediol di(meth)acrylate.

The type of the above-mentioned multifunctional monomer is not particularly limited, and examples thereof include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

The content of the photopolymerizable compound may be included in an amount of 5 to 50 wt%, preferably 10 to 40 wt%, based on the total weight of the solid content in the photosensitive resin composition. When the photopolymerizable compound is included within the above range, it is preferable in terms of the strength or smoothness of the pixel portion.

Photopolymerization initiator

The photopolymerization initiator may have an area ratio of the region (B) to the region (A) of 0.4 or more, preferably 0.5 to 0.7, in a region (A) defined by a normalized emission spectrum of an exposure device for a wavelength of 350 to 390 nm; a region (P) defined by an absorption spectrum of the photopolymerization initiator; and a region (B) defined as an overlapping region of the region (A) and the region (P).

When the photopolymerization initiator satisfies the above spectral characteristics, the hole characteristics can be improved, the reduction of the film before and after development can be minimized, and the peeling of the formed pattern can be prevented.

Specifically, conventional mercury exposure devices emit light in the range of 315 nm to 335 nm in addition to the I-line (365 nm), thereby inducing sufficient photoactivity of conventional photopolymerization initiators, thereby obtaining sufficient surface sensitivity and easily minimizing the film reduction rate before and after development. On the other hand, in the case of exposure devices that emit only the I-line (365 nm), such as an LED exposure device, there is a problem that the surface sensitivity may be poor because sufficient photoactivity is not induced due to the absence of short-wavelength light in conventional mercury exposure devices.

The present invention, in order to overcome such problems, uses a specific photopolymerization initiator satisfying the above spectral characteristics to exhibit high photoactivity in the I-line (365 nm) region, thereby improving hole characteristics and minimizing film reduction before and after development.

The normalization of the above exposure device emission spectrum is not particularly limited as long as it is for obtaining consistent results through repeated experiments. In one embodiment, it may be normalized to the maximum emission wavelength of the exposure device in the I-line region (350 to 390 nm), for example, the emission spectrum of the exposure device in the I-line region (350 to 390 nm) may be divided by the spectral value of the maximum emission wavelength of the I-line region, and the spectral value of the maximum emission wavelength may be normalized to 1.

In order to enable a person skilled in the art to clearly understand and easily reproduce the contents of the invention, with reference to FIGS. 1 to 3, the meanings of areas (A), (P), and (B), and with reference to Tables 1 and 2 of the reference examples described below, the method for calculating the areas of areas (A), (P), and (B) will be explained as examples as follows.

FIGS. 1 to 3 are diagrams showing spectra according to embodiments of the present invention. Specifically, FIG. 1 is a diagram showing a region (A) defined by a normalized emission spectrum of an LED exposure device for a wavelength of 350 to 390 nm, FIG. 2 is a diagram showing a region (P) defined by an absorption spectrum for 10 ppm of DFI-020 (manufactured by Daitochemics Co., Ltd.), which is an embodiment of a photopolymerization initiator satisfying the above-described spectral characteristics for a wavelength of 350 to 390 nm, and FIG. 3 is a diagram showing a region (B) defined as an overlapping region of the regions (A) and (P).

Referring to FIG. 1, an area (A) defined by a normalized emission spectrum of an exposure device for a wavelength of 350 to 390 nm may mean an area surrounded by a normalized emission spectrum curve of an exposure device, a straight line (λ=350 nm and 390 nm) having wavelengths (λ) of 350 nm and 390 nm, and a wavelength (λ) axis (i.e., x-axis) when the wavelength (λ) is the x-axis (nm) and the value of the normalized emission spectrum is the y-axis.

Referring to FIG. 2, a region (P) defined by an absorption spectrum of a photopolymerization initiator for a wavelength of 350 to 390 nm may mean a region surrounded by an absorption spectrum curve of the photopolymerization initiator, a straight line (λ=350 nm and 390 nm) having wavelengths (λ) of 350 nm and 390 nm, and a wavelength (λ) axis (i.e., x-axis) when the wavelength (λ) is the x-axis (nm) and the absorbance is the y-axis.

Referring to FIG. 3, region (B) defined as an overlapping region of region (A) and region (P) for wavelengths of 350 to 390 nm may mean a region where region (A) and region (P) overlap when wavelength (Wavelength; λ) is on the x-axis (nm) and the value or absorbance of a normalized emission spectrum is on the y-axis (i.e., when the spectra of FIGS. 1 and 2 are overlapped).

Referring to Tables 1 and 2 of the reference examples, first, the emission spectrum for light in the I-line (365 nm) region of the exposure device is measured, and the measured emission spectrum is divided into 1 nm intervals to calculate the spectrum integration ratio for each wavelength. For example, as disclosed in Table 1, the integration ratio of the exposure device emission spectrum for a wavelength of 350 nm may be 0.0358, and the integration ratio of the exposure device emission spectrum for each wavelength up to 390 nm may be calculated at 1 nm intervals.

Thereafter, the normalized emission spectrum of the exposure device can be obtained by dividing the emission spectrum integration ratio of each wavelength by 0.7763 (367 nm), which is the maximum value of the emission spectrum integration ratio of the exposure device. For example, as disclosed in Table 1, the values of the normalized emission spectra for wavelengths of 350 nm and 367 nm can be 0.0461 and 1.0000, respectively.

Thereafter, the area of the region (A) may be calculated by adding up the values of the normalized emission spectra at wavelengths of 350 to 390 nm. For example, as disclosed in Table 2, the area of the region (A) may be 8.7225.

Meanwhile, separately from calculating the area of the above-described region (A), the region (P) is defined by measuring the absorption spectrum for 10 ppm of DFI-020. In addition, the measured absorption spectrum is divided into 1 nm intervals, and the average absorbance for each wavelength is calculated. For example, as disclosed in Table 1, the average absorbance of the DFI-020 absorption spectrum for a wavelength of 350 nm may be 0.5700, and the average absorbance of the DFI-020 absorption spectrum for each wavelength up to 390 nm may be calculated at 1 nm intervals.

Thereafter, the value of the normalized emission spectrum of the exposure device corresponding to the region (B), which is the overlapping region of the region (A) and the region (P), or the average absorbance of the photopolymerization initiator is extracted. For example, as disclosed in Table 2, the extraction value for a wavelength of 350 nm may be 0.0461, and the extraction value for each wavelength up to 390 nm may be extracted at 1 nm intervals.

Thereafter, the area of the region (B) may be calculated by adding up the extracted values at wavelengths of 350 to 390 nm. For example, as disclosed in Table 2, the area of the region (B) of DFI-020 may be 5.8959.

Hereinafter, since the ratio of the area of the region (B) to the area of the region (A) is 0.68, DFI-020 can be defined as a photopolymerization initiator having an area ratio of the region (B) to the region (A) of 0.4 or more.

Meanwhile, as mentioned above, the method for calculating the area of the above-described areas (A), (P) and (B) is exemplary and is not limited thereto.

The concentration of the photopolymerization initiator sample for measuring the absorption spectrum of the above photopolymerization initiator is not particularly limited and may be appropriately selected in accordance with the normalization method of the emission spectrum of the exposure device. In one embodiment, the concentration of the photopolymerization initiator used for measuring the absorption spectrum of the photopolymerization initiator may be 1 to 50 ppm, and preferably 10 ppm.

In one embodiment, it is preferable that the photopolymerization initiator has a maximum absorption wavelength at a wavelength of 340 to 380 nm. Commercially available products include "DFI-020" from Daitochemics, "PBG-345" from Trolly, "OXE-03" from BASF, and "NCI-831" from ADEKA. The photopolymerization initiators may be used alone or in combination of two or more.

The content of the photopolymerization initiator may be 1 to 10 wt%, preferably 1 to 7 wt%, based on the total weight of the solid content in the photosensitive resin composition. In this case, the photosensitive resin composition is highly sensitive, so that the exposure time is shortened, which improves productivity and maintains high resolution, which is preferable. In addition, the strength of the pixel portion formed using the photosensitive resin composition and the smoothness on the surface of the pixel portion can be improved.

In some embodiments, a photopolymerization initiator other than the above photopolymerization initiator may be additionally used in combination.

It is preferable to use at least one compound selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, thioxanthone compounds, and carbazole compounds.

Specific examples of the above acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc.

Examples of the above benzophenone compounds include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

Specific examples of the above triazine compounds 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, Examples thereof include 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.

Specific examples of the above biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)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 imidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted by a carboalkoxy group. Among these, 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.

Examples of the above thioxanthone compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

Examples of the carbazole compounds include 3-(2-methyl-2-dimethylamino propionyl) carbazole, 3-(2-methyl-2-morpholino propionyl)-9-methylcarbazole, 3-(2-methyl-hydroxy propionyl)-9-methyl carbazole, 3-(1-hydroxy cyclohexanoyl)-9-butylcarbazole, etc.

In addition, the photopolymerization initiator may further include a photopolymerization initiation assistant in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention can further improve the sensitivity by containing the photopolymerization initiation assistant, thereby improving the productivity.

The photopolymerization initiation assistant may preferably be one or more compounds selected from the group consisting of, for example, amine compounds, carboxylic acid compounds, and polyfunctional thiol compounds.

As the above amine compound, it is preferable to use an aromatic amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and the like can be used.

The above carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples thereof include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

The above-mentioned multifunctional thiol compounds include Tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, Trimethylolpropane tris-3-mercaptopropionate, Pentaerythritol tetrakis-3-mercaptopropionate, and Dipentaerythritol hexa-3-mercaptopropionate.

When the photopolymerization initiation auxiliary agent is further included, the content of the photopolymerization initiation auxiliary agent may be included in an amount of 0.1 to 40 wt%, preferably 1 to 30 wt%, based on the total weight of the solid content of the alkali-soluble resin and the photopolymerizable compound. When the photopolymerization initiation auxiliary agent is included within the above range, the sensitivity of the colored photosensitive resin composition may be further increased, and the productivity of the color filter formed using the colored photosensitive resin composition may be improved.

solvent

The above solvent may be any organic solvent known in this field without any particular limitation.

Specific examples of the above solvents include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; methyl ethyl ketone, acetone, methyl amyl ketone, and methyl isobutyl ketone; Examples thereof include ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.

In terms of applicability and drying property, the solvent may preferably be an organic solvent having a boiling point of 100°C to 200°C, more preferably an alkylene glycol alkyl ether acetate, a ketone, an ester such as ethyl 3-ethoxypropionate or methyl 3-methoxypropionate, and even more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. may be used.

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

The content of the above solvent may be comprised in an amount of 60 to 90 wt%, preferably 75 to 90 wt%, based on the total weight of the photosensitive resin composition. When the above solvent is comprised within the above content range, it is preferable because it provides an effect of improving the coatability when applied using a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes also called a die coater), or an inkjet.

Additives

The photosensitive resin composition according to the present invention may further contain additives as needed, and the types of the additives may be determined according to the needs of the user and are not specifically limited in the present invention, but examples thereof include fillers, other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-coagulants, dispersants, ink repellents, etc. The additives exemplified above may be used alone or in a mixture of two or more.

Specifically, the filler may be glass, silica, alumina, etc., but is not limited thereto.

Specific examples of the other polymer compounds include, but are not limited to, curable resins such as epoxy resins and maleimide resins; thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The above curing agent is used to increase deep curing and mechanical strength, and specifically, epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, etc. can be used, but are not limited thereto. Specifically, the epoxy compound can be bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, novolak-type epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester-based resins, glycidyl amine-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 (co)polymer epoxides, glycidyl (meth)acrylate (co)polymers, triglycidyl isocyanurate, etc., but are not limited thereto. The above oxetane compound may specifically be, but is not limited to, carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexane dicarboxylic acid bisoxetane, etc.

The above curing agent can use 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. Specific examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators. The carboxylic anhydrides can be those commercially available as epoxy resin curing agents. Examples of the commercially available epoxy resin curing agents include (Adekahadona EH-700) (manufactured by Adeka Kogyo Co., Ltd.), (Rikashiddo HH) (manufactured by Shin Nippon Eika Co., Ltd.), and (MH-700) (manufactured by Shin Nippon Eika Co., Ltd.).

The curing agents and curing auxiliary compounds exemplified above may be used alone or in combination of two or more.

As the above surfactant, a commercially available surfactant can be used, and examples thereof include silicone-based surfactants, fluorine-based surfactants, and mixtures thereof. Examples of the silicone-based surfactant include surfactants having a siloxane bond. Commercially available products include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone 29SHPA, Toray Silicone SH30PA, polyether modified silicone oil SH8400 (manufactured by Toray Silicone Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.).

Examples of the above fluorinated surfactants include surfactants having a fluorocarbon chain. Specifically, Prolinate (trade name) FC430, Prolinate FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack (trade name) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, Megapack F183, Megapack F251, Megapack F410, Megapack F430, Megapack F444, Megapack F477, Megapack F551, Megapack F553, Megapack F554, Megapack F556, Megapack F557, Megapack F558, Megapack F559, Megapack F562, Megapack F563, Megapack F565, Megapack F570, Megapack R30, Megapack R40, Megapack R41, Megapack Examples include R43, Megapack R94 (manufactured by DIC, Japan), F-Top (trade name) EF301, F-Top EF303, F-Top EF351, F-Top EF352 (manufactured by Shin-Akitaka Sei Co., Ltd.), Surflon (trade name) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemicals Kenkyusho Co., Ltd.), BM-1000, BM-1100 (trade name: manufactured by BMChemie).

The adhesion accelerator may be specifically selected from the group consisting of 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-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane, or a mixture thereof. there is.

The above antioxidant may include, for example, at least one selected from the group consisting of a phosphorus-based antioxidant, a sulfur-based antioxidant, and a phenol-based antioxidant, in which case it is possible to suppress a color change phenomenon that may occur at a high temperature during a process or a yellowing phenomenon that may be caused by a light source after display manufacturing. The above antioxidant may include at least one selected from the group consisting of a phenol-based compound, a phosphorus-based compound, and a sulfur-based compound, and these may be used as a combination of a phenol-phosphorus compound, a phenol-sulfur compound, a phosphorus-sulfur compound, or a phenol-phosphorus-sulfur compound.

The above ultraviolet absorbent may specifically be, but is not limited to, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzothiazole, alkoxybenzophenone, etc.

The above-mentioned anti-coagulant may specifically include, but is not limited to, sodium polyacrylate.

The above dispersant is added to maintain the dispersion stability of the pigment, and any of those commonly used in the field can be used without limitation.

The above ink-repellent agent has a fluorine atom in its molecule. As a result, the ink-repellent agent has a property of migrating to the upper surface (upper surface migration property) and ink repellency in the process of forming a cured film using a photosensitive resin composition containing the ink-repellent agent. By using the ink-repellent agent, the upper layer including the upper surface of the obtained cured film becomes a layer in which the ink-repellent agent is densely present (hereinafter, sometimes referred to as an "ink-repellent layer"), and ink repellency is imparted to the upper surface of the cured film. Furthermore, from the viewpoint of improving the fixation of the ink-repellent agent to the ink-repellent layer, the ink-repellent agent is preferably a compound having an ethylenic double bond. Since the ink-repellent agent has an ethylenic double bond, a radical acts on the ethylenic double bond of the ink-repellent agent that has migrated to the upper surface, and crosslinking by (co)polymerization becomes possible between the ink-repellent agent or between the ink-repellent agent and another component having an ethylenic double bond contained in the photosensitive resin composition for forming a partition wall.

The type of the ink repellent is not particularly limited, and examples thereof include a partial hydrolysis condensation product of a hydrolyzable silane compound. The hydrolyzable silane compound may be used alone, or two or more types may be used in combination. An ink repellent composed of a partial hydrolysis condensation product of a hydrolyzable silane compound and further containing a fluorine atom may be used, and an ink repellent composed of a compound having a main chain of a hydrocarbon chain and a side chain containing a fluorine atom may also be used.

The above additives can be appropriately added and used by those skilled in the art within a range that does not impede the effects of the present invention. For example, the above additives can be used in an amount of 0.05 to 10 wt%, preferably 0.1 to 10 wt%, and more preferably 0.1 to 5 wt%, based on the total weight of the photosensitive resin composition, but the present invention is not limited thereto.

The photosensitive resin composition of the present invention can be manufactured by a conventional method known in the art, and is not particularly limited in the present invention. For example, it can be manufactured by the following method.

First, the pigment among the above colorants is mixed with a solvent and dispersed using a bead mill or the like until the average particle size of the pigment becomes 30 to 300 nm. At this time, if necessary, a pigment dispersant, a part or all of the alkali-soluble resin, or a dye can be mixed with the solvent to dissolve or disperse it. The remainder of the alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a photoacid generator, an epoxy compound, a scatterer, and additives, and if necessary, a solvent, are further added to the mixed dispersion to a predetermined concentration, thereby producing a colored photosensitive resin composition according to the present invention.

<Color Filter>

The present invention provides a color filter manufactured using the photosensitive resin composition.

In one embodiment, the color filter is characterized by including a pattern formed by applying the photosensitive resin composition described above on a substrate and exposing and developing it in a predetermined pattern.

Hereinafter, a method for forming a pattern using the photosensitive resin composition of the present invention will be described in detail.

The method for forming a pattern using the photosensitive resin composition of the present invention can use a method known in the art, but typically includes a coating step; an exposure step; and a removal step. By applying the photosensitive resin composition of the present invention onto a substrate and performing photocuring and development to form a pattern, it can be used as a pixel (colored image).

First, the photosensitive resin composition is applied onto a substrate and then heated and dried to remove volatile components such as solvents, thereby forming a smooth film.

The coating method may be, for example, spin coating, flexible coating, roll coating, slit-and-spin coating, or slit coating. After coating, the coating is heated and dried (prebaked), or after reduced pressure drying, heated to volatilize volatile components such as solvents. Here, the heating temperature is usually 70 to 150°C, preferably 80 to 130°C. The coating film thickness after heating and drying is usually about 2.0 to 3.5 μm.

The film thus obtained is irradiated with ultraviolet rays through a mask to form the desired pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel rays are irradiated uniformly over the entire exposure area and accurate alignment of the mask and substrate is achieved.

It is preferable to use I-ray (365 nm) as the above ultraviolet ray, and the area irradiated with ultraviolet ray forms radicals by the above-described photopolymerization initiator, which reacts with the polymerizable compound and photocuring occurs.

By contacting the photocured film with a developer to dissolve the unexposed portion, a pattern required for the color filter is formed. By repeating this process according to the required number of red (R), green (G), and blue (B), a color filter having a desired pattern can be obtained.

The pattern shape obtained in this way can be made hard through a post-curing process, and the heating temperature is usually 150 to 250°C, preferably 180 to 230°C. The heating time is usually 5 to 30 minutes, preferably 15 to 20 minutes.

<Display Device>

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

The display device of the present invention may include a display device developed in the past or later, and in one or more embodiments, may include a liquid crystal display (LCD), an electroluminescent (EL) display, a plasma display panel (PDP), a field emission display (FED), an organic light emitting diode (OLED) display, etc.

The above display device may include a configuration commonly known in the art, except that it includes the color filter described above.

According to one embodiment of the present invention, a display device may additionally include a color filter including a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles, in addition to the color filter described above. In such a case, the light emitted by a light source applied to the display device is not particularly limited, but in terms of better color reproducibility, a light source emitting blue light is preferably used.

According to one embodiment of the present invention, a display device may additionally include, in addition to the color filter described above, 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 a case, the color filter further includes a transparent pattern layer that does not contain quantum dot particles. In the case of including only two color pattern layers, a light source that emits light of a wavelength representing the remaining colors that are not included can be used. For example, in the case of including only a red pattern layer and a green pattern layer, a light source that emits blue light can be used. In such a case, red quantum dot particles emit red light, green quantum dot particles emit green light, and the transparent pattern layer directly transmits the blue light to represent 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 illustrative, 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 modifications within the meaning and scope equivalent to the claims. In addition, "%" and "part" indicating the content in the following examples and comparative examples are based on mass unless specifically stated.

<Reference example: Wavelength-specific spectrum analysis of exposure device and photopolymerization initiator>

The emission spectrum and its normalized emission spectrum for wavelengths of 350 to 390 nm of an LED exposure device emitting light in the I-line (365 nm) region; and the absorption spectrum of a 10 ppm photopolymerization initiator relative to the total weight of propylene glycol monomethyl ether acetate (PGMEA) were measured by wavelength, and are shown in Table 1 below.

In addition, the values of the normalized emission spectrum of the exposure device or the values of the absorption spectrum of the photopolymerization initiator corresponding to the region (B) defined as the overlapping region of the region (A) defined by the normalized emission spectrum of the exposure device for wavelengths of 350 to 390 nm and the region (P) defined by the absorption spectrum of the photopolymerization initiator are shown in Table 2 below.

Additionally, for each photopolymerization initiator, the area ratio of area (B) to area (A) is shown in Table 2 below.

The emission spectrum of the above exposure device was normalized to 1 by setting the spectral value at the maximum emission wavelength of 367 nm.

wavelength
(nm) Exposure device
radiation
spectrum Exposure device
Normalization
radiation
spectrum Absorption spectrum of photopolymerization initiator DFI-
020 PBG-
345 OXE-
03 NCI-
831 OXE-
01 PBG-
327 OXE-
02 NCI-
730 DFI-
306 350 0.0358 0.0461 0.5700 0.2820 0.2300 0.2300 0.1770 0.1690 0.2354 0.2790 0.2390 351 0.0345 0.0444 0.5640 0.2908 0.2330 0.2270 0.1670 0.1550 0.2120 0.2700 0.2220 352 0.0334 0.0430 0.5560 0.2986 0.2310 0.2290 0.1580 0.1430 0.1955 0.2620 0.2050 353 0.0329 0.0424 0.5470 0.3063 0.2370 0.2310 0.1510 0.1380 0.1842 0.2530 0.1900 354 0.0356 0.0459 0.5370 0.3140 0.2390 0.2320 0.1410 0.1310 0.1689 0.2440 0.1750 355 0.0464 0.0598 0.5250 0.3233 0.2430 0.2330 0.1350 0.1220 0.1571 0.2340 0.1600 356 0.0470 0.0606 0.5150 0.3309 0.2410 0.2370 0.1230 0.1150 0.1415 0.2240 0.1470 357 0.0508 0.0655 0.5030 0.3380 0.2390 0.2400 0.1160 0.1090 0.1255 0.2150 0.1340 358 0.0496 0.0639 0.4890 0.3450 0.2370 0.2430 0.1090 0.0990 0.1102 0.2060 0.1220 359 0.0512 0.0660 0.4780 0.3511 0.2360 0.2450 0.1020 0.0940 0.0950 0.1970 0.1120 360 0.0566 0.0729 0.4670 0.3566 0.2330 0.2470 0.0940 0.0850 0.0806 0.1880 0.1020 361 0.0671 0.0864 0.4500 0.3598 0.2280 0.2480 0.0870 0.0780 0.0724 0.1780 0.0930 362 0.0908 0.1169 0.4340 0.3627 0.2270 0.2480 0.0810 0.0730 0.0605 0.1690 0.0850 363 0.1409 0.1816 0.4190 0.3642 0.2270 0.2500 0.0760 0.0660 0.0516 0.1600 0.0780 364 0.2705 0.3485 0.4010 0.3634 0.2250 0.2530 0.0720 0.0630 0.0429 0.1510 0.0700 365 0.5313 0.6845 0.3870 0.3605 0.2240 0.2530 0.0650 0.0560 0.0329 0.1420 0.0640 366 0.6988 0.9002 0.3710 0.3545 0.2210 0.2530 0.0590 0.0520 0.0293 0.1340 0.0600 367 0.7763 1.0000 0.3530 0.3482 0.2210 0.2550 0.0550 0.0490 0.0223 0.1260 0.0560 368 0.6565 0.8458 0.3350 0.3415 0.2160 0.2550 0.0500 0.0440 0.0186 0.1190 0.0520 369 0.5315 0.6847 0.3170 0.3332 0.2140 0.2530 0.0460 0.0400 0.0160 0.1120 0.0480 370 0.4240 0.5462 0.3000 0.3216 0.2120 0.2530 0.0440 0.0360 0.0130 0.1050 0.0450 371 0.3282 0.4228 0.2810 0.3093 0.2070 0.2510 0.0400 0.0340 0.0107 0.0980 0.0410 372 0.2520 0.3247 0.2640 0.2953 0.2010 0.2470 0.0350 0.0320 0.0088 0.0910 0.0380 373 0.1937 0.2495 0.2460 0.2809 0.1940 0.2440 0.0320 0.0280 0.0070 0.0840 0.0350 374 0.1526 0.1966 0.2280 0.2649 0.1850 0.2430 0.0300 0.0270 0.0049 0.0780 0.0330 375 0.1274 0.1641 0.2110 0.2486 0.1740 0.2380 0.0280 0.0260 0.0041 0.0720 0.0300 376 0.1115 0.1436 0.1940 0.2325 0.1600 0.2340 0.0260 0.0240 0.0037 0.0660 0.0280 377 0.0968 0.1247 0.1770 0.2146 0.1470 0.2320 0.0230 0.0200 0.0026 0.0610 0.0260 378 0.0860 0.1108 0.1610 0.1983 0.1320 0.2260 0.0200 0.0180 0.0011 0.0550 0.0250 379 0.0824 0.1062 0.1490 0.1809 0.1160 0.2210 0.0190 0.0160 0.0011 0.0500 0.0230 380 0.0836 0.1077 0.1360 0.1647 0.1010 0.2160 0.0170 0.0150 0.0003 0.0460 0.0220 381 0.0743 0.0957 0.1240 0.1506 0.0870 0.2110 0.0160 0.0140 -0.0002 0.0420 0.0200 382 0.0685 0.0883 0.1130 0.1373 0.0740 0.2040 0.0150 0.0120 -0.0002 0.0380 0.0190 383 0.0672 0.0866 0.1040 0.1241 0.0640 0.1970 0.0140 0.0110 -0.0009 0.0350 0.0180 384 0.0610 0.0786 0.0950 0.1119 0.0540 0.1900 0.0120 0.0110 -0.0010 0.0310 0.0160 385 0.0570 0.0735 0.0860 0.0997 0.0450 0.1850 0.0120 0.0100 0.0001 0.0280 0.0160 386 0.0565 0.0727 0.0770 0.0889 0.0380 0.1770 0.0100 0.0100 -0.0003 0.0250 0.0150 387 0.0561 0.0722 0.0710 0.0788 0.0300 0.1700 0.0080 0.0090 -0.0009 0.0230 0.0140 388 0.0530 0.0683 0.0640 0.0706 0.0240 0.1640 0.0070 0.0080 -0.0012 0.0200 0.0140 389 0.0511 0.0659 0.0590 0.0624 0.0200 0.1560 0.0060 0.0080 -0.0013 0.0180 0.0130 390 0.0504 0.0649 0.0550 0.0553 0.0170 0.1480 0.0050 0.0070 -0.0010 0.0160 0.0120

wavelength
(nm) Exposure device
Normalization
radiation
spectrum The value of the normalized emission spectrum of the exposure device corresponding to the area (B) defined as the overlapping area or the absorption spectrum of the photopolymerization initiator DFI-020 PBG-345 OXE-03 NCI-831 OXE-01 PBG-327 OXE-02 NCI-730 DFI-306 350 0.0461 0.0461 0.0461 0.0461 0.0461 0.0461 0.0461 0.0461 0.0461 0.0461 351 0.0444 0.0444 0.0444 0.0444 0.0444 0.0444 0.0444 0.0444 0.0444 0.0444 352 0.0430 0.0430 0.0430 0.0430 0.0430 0.0430 0.0430 0.0430 0.0430 0.0430 353 0.0424 0.0424 0.0424 0.0424 0.0424 0.0424 0.0424 0.0424 0.0424 0.0424 354 0.0459 0.0459 0.0459 0.0459 0.0459 0.0459 0.0459 0.0459 0.0459 0.0459 355 0.0598 0.0598 0.0598 0.0598 0.0598 0.0598 0.0598 0.0598 0.0598 0.0598 356 0.0606 0.0606 0.0606 0.0606 0.0606 0.0606 0.0606 0.0606 0.0606 0.0606 357 0.0655 0.0655 0.0655 0.0655 0.0655 0.0655 0.0655 0.0655 0.0655 0.0655 358 0.0639 0.0639 0.0639 0.0639 0.0639 0.0639 0.0639 0.0639 0.0639 0.0639 359 0.0660 0.0660 0.0660 0.0660 0.0660 0.0660 0.0660 0.0660 0.0660 0.0660 360 0.0729 0.0729 0.0729 0.0729 0.0729 0.0729 0.0729 0.0729 0.0729 0.0729 361 0.0864 0.0864 0.0864 0.0864 0.0864 0.0864 0.0780 0.0724 0.0864 0.0864 362 0.1169 0.1169 0.1169 0.1169 0.1169 0.0810 0.0730 0.0605 0.1169 0.0850 363 0.1816 0.1816 0.1816 0.1816 0.1816 0.0760 0.0660 0.0516 0.1600 0.0780 364 0.3485 0.3485 0.3485 0.2250 0.2530 0.0720 0.0630 0.0429 0.1510 0.0700 365 0.6845 0.3870 0.3605 0.2240 0.2530 0.0650 0.0560 0.0329 0.1420 0.0640 366 0.9002 0.3710 0.3545 0.2210 0.2530 0.0590 0.0520 0.0293 0.1340 0.0600 367 1.0000 0.3530 0.3482 0.2210 0.2550 0.0550 0.0490 0.0223 0.1260 0.0560 368 0.8458 0.3350 0.3415 0.2160 0.2550 0.0500 0.0440 0.0186 0.1190 0.0520 369 0.6847 0.3170 0.3332 0.2140 0.2530 0.0460 0.0400 0.0160 0.1120 0.0480 370 0.5462 0.3000 0.3216 0.2120 0.2530 0.0440 0.0360 0.0130 0.1050 0.0450 371 0.4228 0.2810 0.3093 0.2070 0.2510 0.0400 0.0340 0.0107 0.0980 0.0410 372 0.3247 0.2640 0.2953 0.2010 0.2470 0.0350 0.0320 0.0088 0.0910 0.0380 373 0.2495 0.2460 0.2495 0.1940 0.2440 0.0320 0.0280 0.0070 0.0840 0.0350 374 0.1966 0.1966 0.1966 0.1850 0.1966 0.0300 0.0270 0.0049 0.0780 0.0330 375 0.1641 0.1641 0.1641 0.1641 0.1641 0.0280 0.0260 0.0041 0.0720 0.0300 376 0.1436 0.1436 0.1436 0.1436 0.1436 0.0260 0.0240 0.0037 0.0660 0.0280 377 0.1247 0.1247 0.1247 0.1247 0.1247 0.0230 0.0200 0.0026 0.0610 0.0260 378 0.1108 0.1108 0.1108 0.1108 0.1108 0.0200 0.0180 0.0011 0.0550 0.0250 379 0.1062 0.1062 0.1062 0.1062 0.1062 0.0190 0.0160 0.0011 0.0500 0.0230 380 0.1077 0.1077 0.1077 0.1010 0.1077 0.0170 0.0150 0.0003 0.0460 0.0220 381 0.0957 0.0957 0.0957 0.0870 0.0957 0.0160 0.0140 -0.0002 0.0420 0.0200 382 0.0883 0.0883 0.0883 0.0740 0.0883 0.0150 0.0120 -0.0002 0.0380 0.0190 383 0.0866 0.0866 0.0866 0.0640 0.0866 0.0140 0.0110 -0.0009 0.0350 0.0180 384 0.0786 0.0786 0.0786 0.0540 0.0786 0.0120 0.0110 -0.0010 0.0310 0.0160 385 0.0735 0.0735 0.0735 0.0450 0.0735 0.0120 0.0100 0.0001 0.0280 0.0160 386 0.0727 0.0727 0.0727 0.0380 0.0727 0.0100 0.0100 -0.0003 0.0250 0.0150 387 0.0722 0.0710 0.0722 0.0300 0.0722 0.0080 0.0090 -0.0009 0.0230 0.0140 388 0.0683 0.0640 0.0683 0.0240 0.0683 0.0070 0.0080 -0.0012 0.0200 0.0140 389 0.0659 0.0590 0.0624 0.0200 0.0659 0.0060 0.0080 -0.0013 0.0180 0.0130 390 0.0649 0.0550 0.0553 0.0170 0.0649 0.0050 0.0070 -0.0010 0.0160 0.0120 area 8.7225
(Area (A)) 5.8959
(Area (B)) 5.9645
(Area (B)) 4.5188
(Area (B)) 5.2327
(Area (B)) 1.6199
(Area (B)) 1.5074
(Area (B)) 1.0072
(Area (B)) 2.8398
(Area (B)) 1.7129
(Area (B)) (B)/(A) 0.68 0.68 0.52 0.60 0.19 0.17 0.12 0.33 0.20

Referring to Tables 1 and 2 above, photopolymerization initiators having an area ratio of area (B) to area (A) of 0.4 or more are DFI-020, PBG-345, OXE-03, and NCI-831, and the remaining photopolymerization initiators have an area ratio of less than 0.4.

In order to evaluate the performance of photopolymerization initiators satisfying the above spectral characteristics and those that do not, the following experiments were conducted.

<Manufacturing Example: Manufacturing of Pigment Dispersion>

Manufacturing Example 1: Pigment Dispersion M1

Pigment dispersion M1 was prepared by mixing and dispersing 14.0 parts by weight of C.I Pigment Red 254 as a pigment, 8.0 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone and 65.0 parts by weight of propylene glycol monomethyl ether acetate as solvents using a bead mill for 12 hours.

Manufacturing Example 2: Pigment Dispersion M2

Pigment dispersion M2 was prepared by mixing and dispersing 14.0 parts by weight of C.I Pigment Red 242 as a pigment, 8.0 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone and 65.0 parts by weight of propylene glycol monomethyl ether acetate as solvents using a bead mill for 12 hours.

Manufacturing Example 3: Pigment Dispersion M3

Pigment dispersion M3 was prepared by mixing and dispersing 14.0 parts by weight of C.I Pigment Red 177 as a pigment, 8.0 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone and 65.0 parts by weight of propylene glycol monomethyl ether acetate as solvents using a bead mill for 12 hours.

Manufacturing Example 4: Pigment Dispersion M4

Pigment dispersion M4 was prepared by mixing and dispersing 14.0 parts by weight of C.I Pigment Green 58 as a pigment, 8.0 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone and 65.0 parts by weight of propylene glycol monomethyl ether acetate as solvents using a bead mill for 12 hours.

Manufacturing Example 5: Pigment Dispersion M5

Pigment dispersion M5 was prepared by mixing and dispersing 14.0 parts by weight of C.I pigment green 63 as a pigment, 8.0 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone and 65.0 parts by weight of propylene glycol monomethyl ether acetate as solvents using a bead mill for 12 hours.

Manufacturing Example 6: Pigment Dispersion M6

Pigment dispersion M6 was prepared by mixing and dispersing 14.0 parts by weight of C.I Pigment Yellow 138 as a pigment, 8.0 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone and 65.0 parts by weight of propylene glycol monomethyl ether acetate as solvents using a bead mill for 12 hours.

Manufacturing Example 7: Pigment Dispersion M7

Pigment dispersion M7 was prepared by mixing and dispersing 14.0 parts by weight of C.I pigment blue 15:6 as a pigment, 8.0 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone and 65.0 parts by weight of propylene glycol monomethyl ether acetate as solvents using a bead mill for 12 hours.

Manufacturing Example 8: Pigment Dispersion M8

Pigment dispersion M8 was prepared by mixing and dispersing 11.0 parts by weight of C.I pigment blue 15:6 as a pigment, 3.0 parts by weight of C.I pigment violet 23, 8.0 parts by weight of LPN-6919 (manufactured by BYK) as a pigment dispersant, 13 parts by weight of 4-hydroxy-4-methyl-2-pentanone, and 65.0 parts by weight of propylene glycol monomethyl ether acetate as a solvent using a bead mill for 12 hours.

<Synthesis Example: Synthesis of Alkali-soluble Resin>

100 parts by weight of propylene glycol monomethyl ether acetate, 100 parts by weight of propylene glycol monomethyl ether, 5 parts by weight of AIBN, 15 parts by weight of vinyltoluene, 20.0 parts by weight of 2-phenylthioethyl acrylate, 3 parts by weight of methacrylate, and 30 parts by weight of methacrylic acid were placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen inlet tube, and the mixture was replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80°C while stirring, and the mixture was reacted for 6 hours.

After that, 15 parts by weight of glycidyl methacrylate was added to the generated reactant, the temperature was raised to 110°C, and the reaction was performed for 4 hours.

The solid acid value of the alkali-soluble resin thus synthesized was 71.9 mgKOH/g, and the weight average molecular weight (Mw) measured by GPC was approximately 12,160.

<Examples and Comparative Examples: Preparation of Photosensitive Resin Composition>

Photosensitive resin compositions according to Examples 1 to 15, Comparative Examples 1 to 13, and Reference Examples 1 to 3 were each manufactured according to the compositions in Tables 3 to 5 below.

unit:
weight% pigment dispersion profit Photopolymerizable compound Photopolymerization initiator solvent M1 M2 M3 M4 M5 M6 M7 M8 PI1 PI2 PI3 PI4 PI5 Example 1 19.90 　 23.10 　 　 　 　 　 1.60 4.50 0.30 　 　 　 　 50.60 Example 2 　 19.60 23.30 　 　 　 　 　 1.60 4.40 0.30 　 　 　 　 50.80 Example 3 16.30 　 21.60 　 　 3.20 　 　 1.60 4.50 0.30 　 　 　 　 52.50 Example 4 　 　 　 23.00 　 20.10 　 　 1.60 4.50 0.40 　 　 　 　 50.40 Example 5 　 　 　 　 20.10 22.30 　 　 1.60 4.50 0.40 　 　 　 　 51.10 Example 6 　 　 　 33.00 5.60 5.10 　 　 1.60 4.50 0.40 　 　 　 　 49.80 Example 7 　 　 　 　 　 　 22.90 　 1.60 4.30 0.60 　 　 　 　 70.60 Example 8 　 　 　 　 　 　 18.90 3.40 1.60 4.30 0.60 　 　 　 　 71.20 Example 9 　 19.60 23.30 　 　 　 　 　 1.60 4.30 　 0.30 　 　 　 50.90 Example 10 　 19.60 23.30 　 　 　 　 　 1.60 4.30 　 　 0.30 　 　 50.90 Example 11 　 19.60 23.30 　 　 　 　 　 1.60 4.30 0.10 0.10 　 　 　 51.00 Example 12 　 19.60 23.30 　 　 　 　 　 1.60 4.30 0.20 　 　 　 　 51.00 Example 13 　 19.60 23.30 　 　 　 　 　 1.60 4.30 0.19 　 　 0.20 　 50.81 Example 14 　 19.60 23.30 　 　 　 　 　 1.60 4.30 0.18 　 　 　 0.20 50.82 Example 15 　 19.60 23.30 　 　 　 　 　 1.60 4.30 0.80 　 　 　 　 50.40

unit:
weight% pigment dispersion profit Photopolymerizable compound Photopolymerization initiator solvent M1 M2 M3 M4 M5 M6 M7 M8 PI1 PI2 PI3 PI4 PI5 Comparative Example 1 19.90 　 23.10 　 　 　 　 　 1.60 4.50 　 　 　 0.30 　 50.60 Comparative Example 2 　 19.60 23.30 　 　 　 　 　 1.60 4.40 　 　 　 0.20 　 50.90 Comparative Example 3 16.30 　 21.60 　 　 3.20 　 　 1.60 4.50 　 　 　 0.30 　 52.50 Comparative Example 4 　 　 　 23.00 　 20.10 　 　 1.60 4.50 　 　 　 0.40 　 50.40 Comparative Example 5 　 　 　 　 20.10 22.30 　 　 1.60 4.50 　 　 　 0.40 　 51.10 Comparative Example 6 　 　 　 33.00 5.60 5.10 　 　 1.60 4.50 　 　 　 0.40 　 49.80 Comparative Example 7 　 　 　 　 　 　 22.90 　 1.60 4.30 　 　 　 0.60 　 70.60 Comparative Example 8 　 　 　 　 　 　 18.90 3.40 1.60 4.30 　 　 　 0.60 　 71.20 Comparative Example 9 19.90 　 23.10 　 　 　 　 　 1.60 4.30 　 　 　 　 0.30 50.80 Comparative Example 10 　 　 　 33.00 5.60 5.10 　 　 1.60 4.30 　 　 　 　 0.40 50.00 Comparative Example 11 　 　 　 　 　 　 18.90 3.40 1.60 4.30 　 　 　 　 0.60 71.20 Comparative Example 12 19.90 　 23.10 　 　 　 　 　 1.60 4.30 　 　 　 1.20 　 49.90 Comparative Example 13 19.90 　 23.10 　 　 　 　 　 1.60 4.30 　 　 　 　 1.20 49.90

unit:
weight% pigment dispersion profit Photopolymerizable compound Photopolymerization initiator solvent M1 M2 M3 M4 M5 M6 M7 M8 PI1 PI2 PI3 PI4 PI5 Reference Example 1 19.90 　 23.10 　 　 　 　 　 1.60 4.30 0.10 　 　 　 　 51.00 Reference Example 2 19.90 　 23.10 　 　 　 　 　 1.60 4.30 　 0.10 　 　 　 51.00 Reference Example 3 19.90 　 23.10 　 　 　 　 　 1.60 4.30 　 　 0.10 　 　 51.00

M1: Pigment dispersion M1 of manufacturing example 1

M2: Pigment dispersion M2 of manufacturing example 2

M3: Pigment dispersion M3 of manufacturing example 3

M4: Pigment dispersion M4 of manufacturing example 4

M5: Pigment dispersion M5 of manufacturing example 5

M6: Pigment dispersion M6 of manufacturing example 6

M7: Pigment dispersion M7 of manufacturing example 7

M8: Pigment dispersion M8 of manufacturing example 8

Resin: Alkali-soluble resin of synthetic example

Photopolymerizable compound: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

PI1: PBG-345 (manufactured by Tronly)

PI2: NCI-831 (manufactured by ADEKA)

PI3: OXE-03 (manufactured by BASF)

PI4: OXE-02 (manufactured by BASF)

PI5: PBG-327 (manufactured by Tronly)

Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

<Experimental example>

(1) Manufacturing of color filters

Color filters were manufactured using the photosensitive resin compositions according to Examples 1 to 15, Comparative Examples 1 to 13, and Reference Examples 1 to 3.

Specifically, a photosensitive resin composition was applied onto a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100° C. for 3 minutes to form a color layer thin film. Next, a test photomask having a hole pattern of 30 x 30 μm and a line/space pattern of 1 to 100 μm was placed, and ultraviolet rays were irradiated at a distance of 250 μm from the test photomask. At this time, an ultraviolet light source was used as a 60 mW LED exposure device containing only I-line (365 nm), irradiating a light amount of 50 mJ/cm2, and no special optical filter was used. The color layer thin film irradiated with ultraviolet rays was developed by immersing it in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes. The glass substrate on which the developed color layer thin film was formed was washed with distilled water, dried under a nitrogen gas atmosphere, and heat-cured in a heating oven at 230° C. for 30 minutes, thereby manufacturing a color filter.

(2) Hole characteristic evaluation

In each of the color filters manufactured using the photosensitive resin compositions according to Examples 1 to 15, Comparative Examples 1 to 13, and Reference Examples 1 to 3, a coating film having holes was obtained. Thereafter, the hole size was measured using an optical microscope, and the evaluation results are shown in Tables 6 to 8 below.

<Hole Characteristic Evaluation Criteria>

○: Formation of holes of 10㎛ or larger

X: Hole formation of 10㎛ or less or no hole formation

(3) Evaluation of residual rate

The film remaining ratio before and after development of the photosensitive resin compositions according to Examples 1 to 15, Comparative Examples 1 to 13, and Reference Examples 1 to 3 was evaluated, and the evaluation results are shown in Tables 6 to 8 below.

Residual film ratio = {film thickness after development and 230℃ heat curing after exposure / film thickness after exposure} x 100

<Residual rate evaluation criteria>

◎: Residual rate of 85% or more

○: Residual rate 80% or more but less than 85%

△: Residual rate 75% or more but less than 80%

X: Residual rate less than 75%

(4) Adhesion evaluation

Patterns formed using the photosensitive resin compositions according to Examples 1 to 15, Comparative Examples 1 to 13, and Reference Examples 1 to 3 were observed through an optical microscope, and the adhesion was evaluated according to the degree of pattern tearing, and the evaluation results are shown in Tables 6 to 8 below.

<Adhesion Evaluation Criteria>

◎ : No pattern tearing

○: 1 pattern tear occurred

△: 2 to 4 pattern tearings occur

X: 5 or more pattern tears

　 Hole characteristics Residual rate Adhesion Example 1 O O O Example 2 ◎ O O Example 3 O O O Example 4 O ◎ ◎ Example 5 O ◎ ◎ Example 6 O ◎ ◎ Example 7 O ◎ ◎ Example 8 O ◎ ◎ Example 9 ◎ O O Example 10 ◎ O O Example 11 ◎ O O Example 12 ◎ O O Example 13 ◎ O O Example 14 ◎ O O Example 15 ◎ ◎ ◎

　 Hole characteristics Residual rate Adhesion Comparative Example 1 O X X Comparative Example 2 O X X Comparative Example 3 O X X Comparative Example 4 O X X Comparative Example 5 O X X Comparative Example 6 O X X Comparative Example 7 O X X Comparative Example 8 O X X Comparative Example 9 O X X Comparative Example 10 O X X Comparative Example 11 O X X Comparative Example 12 X X O Comparative Example 13 X X O

　 Hole characteristics Residual rate Adhesion Reference Example 1 O △ O Reference Example 2 O △ O Reference Example 3 O △ O

Referring to Tables 6 to 8 above, it can be seen that the photosensitive resin compositions according to Examples 1 to 15, which include a photopolymerization initiator in which the area ratio of the region (B) to the region (A) is 0.4 or more, in a region (A) defined by a normalized emission spectrum of an exposure device at a wavelength of 350 to 390 nm; a region (P) defined by an absorption spectrum of a photopolymerization initiator; and a region (B) defined as an overlapping region of the region (A) and the region (P), not only have excellent hole characteristics compared to the photosensitive resin compositions according to Comparative Examples 1 to 13 which do not include the photopolymerization initiator, but also have improved film retention and adhesion.

In addition, referring to Examples 1 and 3 including C.I Pigment Red 254, and Example 15 including C.I Pigment Red 242, etc., it can be seen that including C.I Pigment Red 242 as the red pigment is more advantageous in terms of not only hole characteristics but also improvement of film residue rate and adhesion. Specifically, it can be seen that the photosensitive resin composition of Example 15 including C.I Pigment Red 242 can add a larger amount of photopolymerization initiator compared to the photosensitive resin compositions of Examples 1 and 3 including C.I Pigment Red 254, thereby further improving film residue rate and adhesion while maintaining hole characteristics.

In addition, it can be seen that when the photopolymerization initiator of the present invention is included in an amount of 1 wt% or more based on the total weight of the solid content in the photosensitive resin composition, the hole characteristics, residual film ratio, and adhesion can be further improved.

Claims (12)

For wavelengths between 350 and 390 nm,
Area (A) defined by the normalized emission spectrum of the exposure device;
A region (P) defined by the absorption spectrum of the photopolymerization initiator; and
In the area (B) defined as the overlapping area of the above areas (A) and (P),
Contains a photopolymerization initiator having an area ratio of area (B) to area (A) of 0.4 or more,
Contains a combination of CI Pigment Red 242 and CI Pigment Red 177 as colorants.
A photosensitive resin composition characterized in that it is used for forming a hole pattern.
A photosensitive resin composition according to claim 1, wherein the normalized emission spectrum is normalized by the maximum emission wavelength of the exposure device at a wavelength of 350 to 390 nm.
A photosensitive resin composition according to claim 1, wherein the concentration of the photopolymerization initiator used in the measurement of the absorption spectrum is 10 ppm.
A photosensitive resin composition according to claim 1, wherein the photopolymerization initiator has a maximum absorption wavelength at a wavelength of 340 to 380 nm.
A photosensitive resin composition according to claim 1, further comprising an alkali-soluble resin, a photopolymerizable compound and a solvent.
delete delete In claim 5,
With respect to the total weight of solid content in the above photosensitive resin composition,
1 to 50 wt% of colorant;
5 to 70 wt% of alkali-soluble resin;
5 to 50 wt% of a photopolymerizable compound;
1 to 10 wt% of a photopolymerization initiator; and
With respect to the total weight of the above photosensitive resin composition,
A photosensitive resin composition comprising 60 to 90 wt% of a solvent.
A photosensitive resin composition according to claim 5, further comprising at least one selected from the group consisting of a filler, another polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-coagulant, a dispersant, and an ink repellent.
A photosensitive resin composition according to claim 1, wherein the exposure device is an LED exposure device.
A color filter manufactured by the photosensitive resin composition of any one of claims 1 to 5 and 8 to 10.
A display device comprising a color filter of claim 11.