JP7766770B2 - Colored photosensitive resin composition, color filter, and image display device - Google Patents

Description

The present invention relates to a colored photosensitive resin composition, a color filter, and an image display device. More specifically, the present invention relates to a colored photosensitive resin composition that has excellent developability and adhesion, and can also improve pigment dispersibility, making it possible to form sophisticated patterns with high resolution; a color filter formed using the same; and an image display device equipped with the color filter.

A solid-state imaging device is a device that converts images captured using light energy into electrical information, and may include a color filter below the lens. For example, a CMOS Image Sensor (CIS) uses fine-pitch color filters that are patterned at a higher resolution than the color filters that correspond to the pixels of a typical display device. The color filters of a CIS typically have a colored pattern of the three primary colors: red (R), green (G), and blue (B), and are responsible for separating transmitted light into the three primary colors.

In recent years, as the pixel count of color filters used in this type of image sensor has increased, the pigment content in colored photosensitive resin compositions has increased. This has led to a decrease in the degree of cure of the colored photosensitive resin composition, making it difficult to maintain pattern characteristics and resulting in the generation of residue.

Therefore, there has been a demand for the development of a colored photosensitive resin composition that has high pigment dispersibility, enables fine patterning, and excellent patterning properties such as residue or film retention and linearity, as well as developability and adhesion.

Korean Patent Publication No. 10-2009-0072754 discloses a color filter composition containing a pigment and a binder resin, but it is not suitable for use in the color filters for the high-resolution solid-state imaging devices mentioned above.

One object of the present invention is to provide a colored photosensitive resin composition that has excellent developability and adhesion, as well as improved pigment dispersibility, and is capable of forming sophisticated patterns with high resolution.

Another object of the present invention is to provide a colored pattern formed using the colored photosensitive resin composition.

Another object of the present invention is to provide a color filter including the colored pattern.

A further object of the present invention is to provide an image display device equipped with the above-described color filter.

A further object of the present invention is to provide a solid-state imaging device equipped with the above-described color filter.

On the other hand, the present invention provides a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the alkali-soluble resin comprises a first repeating unit represented by the following chemical formula 1 and a second repeating unit represented by the following chemical formula 2:

In the above formula,
R ¹ to R ⁹ are each independently hydrogen, halogen, a C ₁ -C ₁₀ alkyl group, or a C ₁ -C ₁₀ alkoxy group;
R ¹⁰ is hydrogen or a methyl group;
R ¹¹ is hydrogen or a methyl group;
R ¹² is a C ₁ -C ₁₀ alkylene group;
R ¹³ is a C ₃ -C ₇ alkylene group;
n is an integer from 1 to 20.

In one embodiment of the present invention,
R ¹ to R ⁹ are hydrogen;
R ¹² is a C ₁ -C ₃ alkylene group;
R ¹³ is a C ₃ -C ₅ alkylene group;
n may be an integer from 1 to 5.

In one embodiment of the present invention, the first repeating unit represented by Chemical Formula 1 may be contained in a range of 10 to 80 mol % relative to 100 mol % of all repeating units constituting the alkali-soluble resin.

In one embodiment of the present invention, the second repeating unit represented by Chemical Formula 2 may be contained in a range of 10 to 70 mol % relative to 100 mol % of all repeating units constituting the alkali-soluble resin.

On the other hand, the present invention provides a colored pattern formed using the colored photosensitive resin composition.

On the other hand, the present invention provides a color filter including the colored pattern.

On the other hand, the present invention also provides an image display device characterized by being equipped with the above-mentioned color filter.

On the other hand, the present invention provides a solid-state imaging device characterized by being equipped with the above-mentioned color filter.

In one embodiment of the present invention, the solid-state imaging device may include a CMOS image sensor.

The colored photosensitive resin composition of the present invention contains an alkali-soluble resin that includes a first repeating unit containing a phenoxybenzyl group of a specific structure and a second repeating unit containing a caprolactone-modified hydroxyalkyl group. This allows for excellent developability with TMAH (tetramethyl ammonium hydroxide), leaving no residue when forming a colored pattern, excellent adhesion and linear pattern formation, and improved pigment dispersibility.

The present invention is described in more detail below.

One embodiment of the present invention relates to a colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), wherein the alkali-soluble resin (B) comprises a first repeating unit containing a phenoxybenzyl group of a specific structure and a second repeating unit containing a caprolactone-modified hydroxyalkyl group.

The colored photosensitive resin composition according to one embodiment of the present invention will be described in detail below, with each component being described in detail.

[Colorant (A)]
In one embodiment of the present invention, the colorant (A) may be an organic pigment, an inorganic pigment, or a dye that is commonly used in this field.

The organic pigment may be any of the various pigments used in printing inks, inkjet inks, etc., and specific examples include phthalocyanine water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, and diketopyrrolopyrrole pigments.

If necessary, the pigment may be subjected to a resin treatment, a surface treatment using a pigment derivative into which an acidic or basic group has been introduced, a grafting treatment onto the pigment surface using a polymer compound, a micronization treatment using a sulfuric acid micronization method, a washing treatment using an organic solvent or water to remove impurities, or a treatment to remove ionic impurities using an ion exchange method.

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

The pigments used in the present invention may be organic or inorganic pigments commonly used in this field, and these may be used alone or in combination of two or more types.

In particular, the pigment may be a compound classified as a pigment in the Colour Index (published by The Society of Dyers and Colourists). More specifically, pigments with the following Colour Index (C.I.) numbers may be used, but are not necessarily limited to these.

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, 185, and 242
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, 264, and 277
C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, and 38
C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, and 76
C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58, 59, 62, and 63
C.I. Pigment Brown 28
C.I. Pigment Black 1 and 7, etc. Among the C.I. pigment pigments exemplified above, preferably, a pigment selected from C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15:6, C.I. Pigment Green 7, C.I. Pigment Green 36, and C.I. Pigment Green 58 may be used.

It is preferable to use a pigment dispersion in which the pigment is uniformly dispersed. One example of a method for uniformly dispersing the pigment is to add a pigment dispersant and perform a dispersion treatment. This method makes it possible to obtain a pigment dispersion in which the pigment is uniformly dispersed in the solution.

Examples of the pigment dispersant include cationic, anionic, nonionic, cationic, polyester, and polyamine surfactants, which may be used alone or in combination of two or more.

Specific examples of the surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. Other product names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products Co., Ltd.), MEGAFAC (manufactured by Dainippon Ink and Chemicals, Inc.), Flourad (manufactured by Sumitomo 3M Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Zeneca Corporation), EFKA (manufactured by EFKA Chemicals), and PB. 821 (manufactured by Ajinomoto Co., Inc.) and others.

The pigment dispersant is typically used in an amount of 1 part by weight or less per 1 part by weight of pigment, and preferably in the range of 0.05 to 0.5 parts by weight. Using the pigment dispersant in the above-mentioned amounts is preferable because it allows for the production of dispersed pigments with uniform particle sizes.

The dye may be any dye that is soluble in organic solvents without any particular limitations. Preferably, a dye that is soluble in organic solvents and can ensure reliability, such as solubility in alkaline developers, heat resistance, and solvent resistance, may be used.

The dye may be selected from acid dyes having an acidic group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof. Other dyes that can be selected include azo, xanthene, and phthalocyanine acid dyes and their derivatives.

Preferably, the dye is a compound classified as a dye in the Color Index (published by The Society of Dyersand Colourists) or a known dye listed in Dyeing Notes (Shikisensha).

Specific examples of the dyes include C.I. solvent dyes,
Yellow dyes such as C.I. Solvent Yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162;
Red dyes such as C.I. Solvent Red 8, 45, 49, 122, 125, and 130;
Orange dyes such as C.I. Solvent Orange 2, 7, 11, 15, 26, and 56;
Blue dyes such as C.I. Solvent Blue 35, 37, 59, and 67;
Examples of green dyes include C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35.

Also, as a C.I. acid dye,
C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, Yellow dyes such as 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;
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, 2 Red dyes such as 11, 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;
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;
Blue dyes such as 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;
Violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, and 19;
Examples of green dyes include C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109.

In addition, as a C.I. direct dye,
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, and 141;
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;
Orange dyes such as C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, and 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, 17 Blue dyes such as 1, 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;
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, and 104;
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 are also included.

Also, as a C.I. mordant dye,
Yellow dyes such as C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65;
Red dyes such as C.I. Mordant 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. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, and 48;
Blue dyes such as C.I. Mordant 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. Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, and 58;
Examples of green dyes include C.I. Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53.

One or more of the above pigments or dyes may be used in combination.

The colorant (A) may be contained in an amount of 10 to 70% by weight, preferably 10 to 60% by weight, based on 100% by weight of the total solids content of the colored photosensitive resin composition. When the content of the colorant (A) is within this range, there are advantages in that the pixel color density is sufficient when a thin film is formed, and there is no decrease in the loss of non-pixel areas during development, and no residue is generated.

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

[Alkali-soluble resin (B)]
In one embodiment of the present invention, the alkali-soluble resin (B) generally has reactivity due to the action of light or heat and alkali-solubility, and acts as a dispersion medium for the coloring material.

The alkali-soluble resin (B) contains a first repeating unit represented by the following chemical formula 1 and a second repeating unit represented by the following chemical formula 2:

In the above formula,
R ¹ to R ⁹ are each independently hydrogen, halogen, a C ₁ -C ₁₀ alkyl group, or a C ₁ -C ₁₀ alkoxy group;
R ¹⁰ is hydrogen or a methyl group;
R ¹¹ is hydrogen or a methyl group;
R ¹² is a C ₁ -C ₁₀ alkylene group;
R ¹³ is a C ₃ -C ₇ alkylene group;
n is an integer from 1 to 20.

As used herein, a C ₁ -C ₁₀ alkyl group means a straight or branched chain hydrocarbon group containing from 1 to 10 carbon atoms, including, but not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, and the like.

As used herein, a C ₁ -C ₁₀ alkoxy group refers to a linear or branched alkoxy group containing 1 to 10 carbon atoms, including, but not limited to, methoxy, ethoxy, n-propanoxy, butoxy, pentoxy, etc.

As used herein, a C ₁ -C ₁₀ alkylene group refers to a straight or branched chain divalent hydrocarbon group containing from 1 to 10 carbon atoms, including, but not limited to, methylene, ethylene, propylene, butylene, and pentylene.

As used herein, a C3 _{- C7} alkylene group refers to a linear or branched divalent hydrocarbon group containing from 3 to 7 carbon atoms, including, but not limited to, propylene, butylene, pentylene, hexylene, and the like.

In one embodiment of the present invention, R ¹ to R ⁹ are hydrogen, R ¹² is a C ₁ -C ₃ alkylene group, R ¹³ is a C ₃ -C ₅ alkylene group, and n can be an integer from 1 to 5.

The first repeating unit represented by Chemical Formula 1 may be introduced using a compound represented by Chemical Formula 3 below.

In the above formula,
R ¹ to R ¹⁰ are as defined in Formula 1 above.

When the alkali-soluble resin (B) contains the first repeating unit represented by Chemical Formula 1, it is possible to improve high-resolution characteristics, fine patterning characteristics, and the like. For example, in the first repeating unit, two benzene ring units may be rotatably bonded by an ether bond. Due to the characteristics of this bond structure, the unexposed areas of the substrate can be cleanly removed by a developer. Therefore, a clean, linear colored pattern can be obtained in the unexposed areas between fine-pitch exposed areas without generating residue.

The second repeating unit represented by chemical formula 2 may be introduced using a compound represented by chemical formula 4 below.

In the above formula,
R ¹¹ to R ¹³ and n are as defined in Formula 2 above.

By including the second repeating unit represented by Chemical Formula 2 in the alkali-soluble resin (B), adhesion and developability can be improved, and linearity of the pattern can be ensured.

In one embodiment of the present invention, the alkali-soluble resin (B) may further contain a third repeating unit derived from a carboxylic acid monomer.

The carboxylic acid monomer may include an unsaturated monocarboxylic acid or an unsaturated dicarboxylic acid. For example, the carboxylic acid monomer may include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. These may be used alone or in combination of two or more.

In one embodiment of the present invention, the third repeating unit may be derived from the carboxylic acid monomer and a reactive monomer that can bond to or copolymerize with the carboxylic acid monomer.

The reactive monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, or vinyltoluene; an unsaturated carboxylate compound such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, or benzyl methacrylate; an unsaturated aminoalkyl carboxylate compound such as aminoethyl acrylate; an unsaturated glycidyl carboxylate compound such as glycidyl (meth)acrylate; or a vinyl compound such as vinyl acetate or vinyl propionate. vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; and unsaturated oxetane carboxylate compounds such as 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, and 3-methyl-3-methacryloxyethyloxetane. These may be used alone or in combination of two or more.

In one embodiment of the present invention, when an unsaturated glycidyl carboxylate compound such as glycidyl (meth)acrylate is used as the reactive monomer capable of bonding with the carboxylic acid monomer, the third repeating unit may be derived from the carboxylic acid monomer and the unsaturated glycidyl carboxylate compound, or may be derived from the carboxylic acid monomer, the unsaturated glycidyl carboxylate compound, and an acid anhydride capable of bonding with the unsaturated glycidyl carboxylate compound.

As used herein, acid anhydride includes succinic anhydride, methylsuccinic anhydride, (2-dodecen-1-yl)succinic anhydride, phenylsuccinic anhydride, phthalic anhydride, maleic anhydride, citraconic anhydride, and glutaric anhydride. Examples of the anhydride include, but are not limited to, 3,3-dimethylglutaric anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, and carbic anhydride. In terms of ease of reactivity, it is preferable to use maleic anhydride, phthalic anhydride, trimellitic anhydride, succinic anhydride, hexahydrophthalic anhydride, and/or carbic anhydride as the acid anhydride, with trimellitic anhydride, succinic anhydride, and/or hexahydrophthalic anhydride being particularly preferred.

In one embodiment of the present invention, the third repeating unit may include repeating units derived from (meth)acrylic acid and glycidyl (meth)acrylate, or may include repeating units derived from (meth)acrylic acid, glycidyl (meth)acrylate, and succinic anhydride. For example, the third repeating unit may include units derived from each of (meth)acrylic acid and glycidyl (meth)acrylate, or may include a structure in which glycidyl (meth)acrylate is bonded to a unit derived from (meth)acrylic acid, or may include a structure in which glycidyl (meth)acrylate and succinic anhydride are sequentially bonded to a unit derived from (meth)acrylic acid.

The third repeating unit can improve the developability of the alkali-soluble resin and improve the adhesion of the composition or colored pattern to the substrate.

The alkali-soluble resin (B) may be a block copolymer in which the first to third repeating units are each repeated at a regular interval, or a random copolymer in which these repeating units are repeated at random.

In one embodiment of the present invention, the first repeating unit may be contained in a range of 10 to 80 mol %, preferably 20 to 40 mol %, relative to 100 mol % of all repeating units constituting the alkali-soluble resin.

In one embodiment of the present invention, the second repeating unit may be contained in a range of 10 to 70 mol %, preferably 20 to 40 mol %, relative to 100 mol % of all repeating units constituting the alkali-soluble resin.

In one embodiment of the present invention, the third repeating unit may be contained in a range of 10 to 70 mol %, preferably 20 to 50 mol %, relative to 100 mol % of all repeating units constituting the alkali-soluble resin.

When the first repeating unit and the second repeating unit are each contained within the above mole percent ranges, the composition exhibits excellent developability and adhesion, and also improves pigment dispersibility, making it possible to form sophisticated patterns with high resolution.

Furthermore, when the third repeating unit is contained within the above-mentioned mole percent range, developability and adhesion may be improved.

The alkali-soluble resin may have an acid value in the range of 20 to 100 (mg KOH/g). Here, the acid value is measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of polymer, and can usually be determined by titration with an aqueous potassium hydroxide solution.

The weight-average molecular weight (hereinafter simply referred to as "weight-average molecular weight") of the alkali-soluble resin, measured by gel permeation chromatography (GPC; using tetrahydrofuran as an elution solvent), in terms of polystyrene, is preferably in the range of 5,000 to 20,000.

The double bond equivalent (DBE) of the alkali-soluble resin may be in the range of 300 to 800 g/mol.

Within the above acid value, weight average molecular weight, and double bond equivalent ranges, excellent developability and pattern characteristics can be achieved, and pigment dispersibility can be improved.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the alkali-soluble resin is preferably 1.0 to 6.0, and more preferably 1.5 to 6.0.

A molecular weight distribution of 1.0 to 6.0 is preferred as it provides excellent reliability.

The alkali-soluble resin (B) may be contained in an amount of 5 to 80% by weight, preferably 10 to 70% by weight, and more preferably 10 to 40% by weight, based on 100% by weight of the total solids content in the colored photosensitive resin composition. If the alkali-soluble resin content is less than 5% by weight, the sensitivity of the unexposed areas to dissolution in the developer may decrease, resulting in the generation of residue. If the content exceeds 80% by weight, the degree of photocuring may decrease, causing the exposed areas to dissolve in the developer.

[Photopolymerizable compound (C)]
In one embodiment of the present invention, the photopolymerizable compound (C) is a compound that can be polymerized by the action of a photopolymerization initiator (D) described later, and examples thereof include a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, and a trifunctional or higher polyfunctional photopolymerizable compound.

Specific examples of the monofunctional photopolymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.

Specific examples of the bifunctional photopolymerizable compound 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.

Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, and propoxylated dipentaerythritol hexa(meth)acrylate.

The photopolymerizable compounds exemplified above may be used alone or in combination of two or more.

The photopolymerizable compound may be contained in an amount of 0.5 to 70% by weight, preferably 5 to 50% by weight, based on 100% by weight of the total solids content of the colored photosensitive resin composition of the present invention. When the photopolymerizable compound is contained in this range, there is no reduction in photosensitivity, the film has sufficient strength, the pattern does not disappear during development, the pattern is well constructed even in fine pattern areas, and the smoothness of the resist tends to be good, which is preferable.

[Photopolymerization initiator (D)]
In one embodiment of the present invention, the photopolymerization initiator (D) may be any compound capable of polymerizing the photopolymerizable compound (C) without any particular limitation. In particular, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, cost, etc., it is preferable to use, as the photopolymerization initiator (D), one or more compounds selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, oxime-based compounds, and thioxanthone-based compounds. In particular, acetophenone-based compounds are preferable in terms of pattern characteristics.

Specific examples of the acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl 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, and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one.

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

Specific examples of the 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, and 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran)-2-yl]-1,3,5-triazine. Examples of suitable amines include 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, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine. Commercially available products include TAZ-PP (manufactured by New Japan Chemical Co., Ltd.).

Specific examples of the 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, and biimidazole compounds in which the phenyl groups at the 4,4',5,5' positions are substituted with carboalkoxy groups. 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.

Specific examples of the oxime compounds include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), and the like. Commercially available products include CGI-124 (manufactured by Ciba-Geigy), CGI-224 (manufactured by Ciba-Geigy), Irgacure OXE-01 (manufactured by BASF), Irgacure OXE-02 (manufactured by BASF), N-1919 (manufactured by Adeka Corporation), and NCI-831 (manufactured by Adeka Corporation).

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

The photopolymerization initiator (D) may be used in combination with a photopolymerization initiation aid (d1) to improve the sensitivity of the colored photosensitive resin composition of the present invention. By including the photopolymerization initiation aid (d1), the colored photosensitive resin composition according to one embodiment of the present invention can further enhance sensitivity and improve productivity.

The photopolymerization initiation aid (d1) may preferably be, for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and organic sulfur compounds having a thiol group.

Specific examples of the amine compound that can be used include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, and aromatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), and 4,4'-bis(diethylamino)benzophenone, with aromatic amine compounds being particularly preferred.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples 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, 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, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate).

The photopolymerization initiator (D) may be contained in an amount of 0.01 to 20% by weight, preferably 0.1 to 15% by weight, based on 100% by weight of the total solids content of the colored photosensitive resin composition of the present invention. Within this range, the colored photosensitive resin composition becomes highly sensitive and exposure time is shortened, thereby improving productivity and maintaining high resolution. Furthermore, the strength of pixel portions formed using the composition and the smoothness of the surface of the pixel portions may be improved.

When the photopolymerization initiation aid (d1) is further used, it is preferable to use it in the same content range as the photopolymerization initiator (D). Using it in this content range can further improve the sensitivity of the colored photosensitive resin composition and can also improve the productivity of color filters formed using the composition.

[Solvent (E)]
In one embodiment of the present invention, the solvent may be any solvent used in a typical colored photosensitive resin composition, without any particular limitation, as long as it is effective in dissolving other components contained in the colored photosensitive resin composition of the present invention.

Specific examples of the solvent (E) 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; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, alkylene glycol alkyl ether acetates such as 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, and cyclic esters such as γ-butyrolactone.

Of the above solvents, it is more preferable to use organic solvents with a boiling point of 100°C to 200°C in terms of application and drying properties. Examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.

The above-listed solvents may be used alone or in combination of two or more.

The solvent may be contained in an amount ranging from 20 to 95% by weight, preferably from 25 to 85% by weight, based on 100% by weight of the total colored photosensitive resin composition of the present invention. When the solvent is contained in this range, it has the effect of improving coatability when applied using a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes called a die coater), or inkjet.

[Additive (F)]
The colored photosensitive resin composition of the present invention may be used in combination with additives (F) such as other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, and anti-aggregation agents, if necessary.

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

The curing agent is used to achieve deep curing and increase mechanical strength. Specific examples of curing agents include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

Specific examples of epoxy compounds in the curing agent include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolac epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of such epoxy resins; aliphatic, alicyclic, or aromatic epoxy compounds other than epoxy resins and their brominated derivatives; epoxidized butadiene (co)polymers; epoxidized isoprene (co)polymers; glycidyl (meth)acrylate (co)polymers; and triglycidyl isocyanurate.

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

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

The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of an epoxy compound or the oxetane skeleton of an oxetane compound. Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators.

The polycarboxylic acid anhydrides may be commercially available as epoxy resin curing agents. Specific examples of epoxy resin curing agents include ADEKA HARDNER EH-700 (manufactured by ADEKA Kogyo Co., Ltd.), RIKACID HH (manufactured by New Japan Chemical Co., Ltd.), and MH-700 (manufactured by New Japan Chemical Co., Ltd.).

The surfactant may be used to further improve the film-forming properties of the colored photosensitive resin composition, and a fluorine-based surfactant, a silicone-based surfactant, or the like may be preferably used.
Commercially available examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Dow Corning Toray Silicones, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, and TSF-4452 manufactured by GE Toshiba Silicones. Commercially available examples of the fluorine-based surfactant include Megafac F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink and Chemicals, Inc. The surfactants exemplified above may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

The adhesion promoters exemplified above may be used alone or in combination of two or more.

Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate.

Specific examples of the anti-agglomerating agent include, but are not limited to, sodium polyacrylate.

The colored photosensitive resin composition according to one embodiment of the present invention can be produced, for example, by the following method.

First, the pigment of the colorant (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle size of the pigment is approximately 0.2 μm or less. At this time, if necessary, a pigment dispersant, part or all of the alkali-soluble resin (B), or a dye may be mixed with the solvent (E) and dissolved or dispersed. The remaining alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and the additive (F), as well as the solvent (E) if necessary, are added to the mixed dispersion to achieve a predetermined concentration, thereby producing the colored photosensitive resin composition of the present invention.

The colored photosensitive resin composition according to the present invention may be used to form a colored pattern. Furthermore, as described below, the colored pattern may be used, for example, in a color filter, specifically, a color filter included in an image display device or a solid-state imaging device.

Accordingly, one embodiment of the present invention relates to a colored pattern and a color filter formed using the above-described colored photosensitive resin composition. The color filter according to one embodiment of the present invention may be manufactured by applying the above-described colored photosensitive resin composition to a substrate, exposing it to light in a predetermined pattern, and developing it to form a colored pattern.

For example, the above-described colored photosensitive resin composition may be applied to a substrate and dried to form a preliminary colored film.

When the color filter is applied to an image display device, the substrate may be a glass substrate with no coating, or a glass substrate coated with SiNx (protective film) to a thickness of 500 to 1,500 Å.

When the color filter is applied to a solid-state imaging device, the substrate may include a photoelectric conversion element substrate (e.g., a silicon substrate for a CCD or CMOS) used in the solid-state imaging device. The substrate may include a black matrix or black stripes to isolate each pixel.

The application process may include, for example, a coating or printing process such as roll coating, spin coating, slit coating, inkjet printing, etc.

The pre-colored film may then be exposed and developed to form a colored pattern corresponding to each pixel.

The exposure step may include laser exposure using a mask that selectively exposes the pixel regions. The non-exposed regions may then be selectively removed with a developer to form the colored pattern.

The developer may contain, for example, an inorganic or organic alkaline compound. Examples of inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and ammonia. Examples of organic alkaline compounds include tetramethylammonium hydroxide (TMAH), 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. These compounds may be used alone or in combination of two or more.

After the development step, a post-baking step may be performed, for example, at 150 to 230°C.

One embodiment of the present invention relates to an image display device equipped with the above-mentioned color filter.

The color filter of the present invention can be applied to various image display devices, including not only conventional liquid crystal display devices (LCDs), but also electroluminescent display devices (EL), plasma display devices (PDPs), field emission displays (FEDs), and organic light emitting diode (OLED) devices.

The image display device of the present invention includes a configuration known in the art, except for the inclusion of the color filters described above.

An image display device according to one embodiment of the present invention may further include, in addition to the color filters described above, 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 such cases, the light emitted by the light source used in the image display device is not particularly limited, but from the perspective of better color reproducibility, a light source that emits blue light may preferably be used.

An image display device according to one embodiment of the present invention may further include, in addition to the color filters described above, a color filter including only pattern layers of two hues from among a red pattern layer, a green pattern layer, and a blue pattern layer. In such cases, the color filter further includes a transparent pattern layer that does not contain quantum dot particles. When only pattern layers of two hues are included, a light source that emits light of a wavelength that represents the remaining hues may be used. For example, when only red and green pattern layers are included, a light source that emits blue light may be used. In such cases, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer allows blue light to pass through, resulting in a blue color.

One embodiment of the present invention relates to a solid-state imaging device equipped with the above-mentioned color filter.

The solid-state imaging element may include, for example, a CMOS Image Sensor (CIS).

The solid-state imaging element may include a support including a semiconductor element or a photoelectric conversion element and a microlens, and the color filter may be disposed between the support and the microlens.

The present invention will be explained in more detail below with reference to examples, comparative examples, and experimental examples. Note that these examples, comparative examples, and experimental examples are provided solely for the purpose of illustrating the present invention, and it will be obvious to those skilled in the art that the scope of the present invention is not limited to these examples.

Synthesis Example 1: Synthesis of alkali-soluble resin (b1-1)
A flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube was prepared. 25.43 g (0.1 mol) of (3-phenoxyphenyl)methyl acrylate, 188.8 g (0.4 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)], 36.03 g (0.5 mol) of acrylic acid, 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added through the monomer dropping funnel and stirred to prepare a mixture. 6 g of n-dodecanethiol and 24 g of PGMEA were added to a chain transfer agent dropping tank and stirred to prepare a mixture. Next, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed from air to nitrogen. The temperature of the flask was then raised to 90 ° C. while stirring. Next, the dropping of the monomer and chain transfer agent was started from each dropping funnel. The dropping was carried out for 2 hours while maintaining the temperature at 90°C. After 1 hour, the temperature was raised to 110°C and maintained for 3 hours, yielding an alkali-soluble resin (b1-1) having an acid value of 50 mgKOH/g of solids. At this time, the weight average molecular weight measured by GPC in terms of polystyrene was 10,000, and the molecular weight distribution (Mw/Mn) was 1.85. The GPC measurement conditions were as follows:

<GPC measurement conditions>
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection)
Column temperature: 40°C
Mobile phase solvent: tetrahydrofuran Flow rate: 1.0 ml/min Injection volume: 50 μl
Detector: RI
Measurement sample concentration: 0.6% by mass (solvent = tetrahydrofuran)
Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio of the weight average molecular weight to the number average molecular weight of the alkali-soluble resin obtained above was taken as the molecular weight distribution (Mw/Mn).

Synthesis Example 2: Synthesis of alkali-soluble resin (b1-2)
Alkali-soluble resin (b1-2) was obtained by synthesis in the same manner as in Synthesis Example 1, except that 50.86 g (0.2 mol) of (3-phenoxyphenyl)methyl acrylate, 188.8 g (0.4 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)], and 28.82 g (0.4 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 40 mgKOH/g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw/Mn) of 1.85.

Synthesis Example 3: Synthesis of alkali-soluble resin (b1-3)
Alkali-soluble resin (b1-3) was obtained by performing synthesis in the same manner as in Synthesis Example 1, except that 76.28 g (0.3 mol) of (3-phenoxyphenyl)methyl acrylate, 188.8 g (0.4 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)], and 21.62 g (0.3 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 30 mgKOH/g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw/Mn) of 1.85.

Synthesis Example 4: Synthesis of alkali-soluble resin (b1-4)
Alkali-soluble resin (b1-4) was obtained by performing synthesis in the same manner as in Synthesis Example 1, except that 101.71 g (0.4 mol) of (3-phenoxyphenyl)methyl acrylate, 188.8 g (0.4 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)], and 14.41 g (0.2 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 20 mgKOH/g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw/Mn) of 1.85.

Synthesis Example 5: Synthesis of alkali-soluble resin (b1-5)
Alkali-soluble resin (b1-5) was obtained by performing synthesis in the same manner as in Synthesis Example 1, except that 101.71 g (0.4 mol) of (3-phenoxyphenyl)methyl acrylate, 141.6 g (0.3 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)], and 21.62 g (0.3 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 30 mgKOH/g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw/Mn) of 1.85.

Synthesis Example 6: Synthesis of alkali-soluble resin (b1-6)
Alkali-soluble resin (b1-6) was obtained by performing synthesis in the same manner as in Synthesis Example 1, except that 101.71 g (0.4 mol) of (3-phenoxyphenyl)methyl acrylate, 94.40 g (0.2 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)], and 28.82 g (0.4 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 40 mgKOH/g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw/Mn) of 1.85.

Synthesis Example 7: Synthesis of alkali-soluble resin (b1-7)
Alkali-soluble resin (b1-7) was obtained by performing synthesis in the same manner as in Synthesis Example 1, except that 101.71 g (0.4 mol) of (3-phenoxyphenyl)methyl acrylate, 47.20 g (0.1 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)], and 36.03 g (0.5 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 50 mgKOH/g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw/Mn) of 1.85.

Comparative Synthesis Example 1: Synthesis of alkali-soluble resin (b2-1)
Except for using 101.71 g (0.4 mol) of (3-phenoxyphenyl)methyl acrylate and 43.24 g (0.6 mol) of acrylic acid, synthesis was carried out in the same manner as in Synthesis Example 1. The alkali-soluble resin thus synthesized had an acid value of 60 mgKOH/g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw/Mn) of 1.85.

Comparative Synthesis Example 2: Synthesis of alkali-soluble resin (b2-2)
Except for using 127.14 g (0.5 mol) of (3-phenoxyphenyl)methyl acrylate and 36.03 g (0.5 mol) of acrylic acid, synthesis was carried out in the same manner as in Synthesis Example 1. The alkali-soluble resin thus synthesized had an acid value of 50 mgKOH/g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw/Mn) of 1.85.

Comparative Synthesis Example 3: Synthesis of alkali-soluble resin (b2-3)
Except for using 152.57 g (0.6 mol) of (3-phenoxyphenyl)methyl acrylate and 28.82 g (0.4 mol) of acrylic acid, synthesis was carried out in the same manner as in Synthesis Example 1. The alkali-soluble resin thus synthesized had an acid value of 40 mgKOH/g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw/Mn) of 1.85.

Comparative Synthesis Example 4: Synthesis of alkali-soluble resin (b2-4)
Except for using 188.8 g (0.4 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)] and 43.24 g (0.6 mol) of acrylic acid, synthesis was carried out in the same manner as in Synthesis Example 1. The alkali-soluble resin thus synthesized had an acid value of 60 mgKOH/g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw/Mn) of 1.85.

Comparative Synthesis Example 5: Synthesis of alkali-soluble resin (b2-5)
Synthesis was carried out in the same manner as in Synthesis Example 1, except that 236 g (0.5 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)] and 36.03 g (0.5 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 50 mgKOH/g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw/Mn) of 1.85.

Comparative Synthesis Example 6: Synthesis of alkali-soluble resin (b2-6)
Synthesis was carried out in the same manner as in Synthesis Example 1, except that 283.2 g (0.6 mol) of α-[2-(methacryloyloxy)ethyl]-ω-hydroxytri[oxy(1-oxohexane-1,6-diyl)] and 28.82 g (0.4 mol) of acrylic acid were used. The alkali-soluble resin thus synthesized had an acid value of 40 mgKOH/g, a weight-average molecular weight of 10,000, and a molecular weight distribution (Mw/Mn) of 1.85.

[Examples 1 to 7 and Comparative Examples 1 to 6: Production of Colored Photosensitive Resin Compositions]
Each component was mixed according to the composition shown in Tables 1 and 2 below to prepare a colored photosensitive resin composition (unit: weight %).

Colorant: C.I. Pigment Blue 15:6 dispersion (pigment content 12.02% by weight, solid content 19.4% by weight)
b1-1: Alkali-soluble resin of Synthesis Example 1 (solid content: 36.5% by weight)
b1-2: Alkali-soluble resin of Synthesis Example 2 (solid content: 36.5% by weight)
b1-3: Alkali-soluble resin of Synthesis Example 3 (solid content: 36.5% by weight)
b1-4: Alkali-soluble resin of Synthesis Example 4 (solid content: 36.5% by weight)
b1-5: Alkali-soluble resin of Synthesis Example 5 (solid content: 36.5% by weight)
b1-6: Alkali-soluble resin of Synthesis Example 6 (solid content: 36.5% by weight)
b1-7: Alkali-soluble resin of Synthesis Example 7 (solid content: 36.5% by weight)
b2-1: Alkali-soluble resin of Comparative Synthesis Example 1 (solid content: 36.5% by weight)
b2-2: Alkali-soluble resin of Comparative Synthesis Example 2 (solid content: 36.5% by weight)
b2-3: Alkali-soluble resin of Comparative Synthesis Example 3 (solid content: 36.5% by weight)
b2-4: Alkali-soluble resin of Comparative Synthesis Example 4 (solid content: 36.5% by weight)
b2-5: Alkali-soluble resin of Comparative Synthesis Example 5 (solid content: 36.5% by weight)
b2-6: Alkali-soluble resin of Comparative Synthesis Example 6 (solid content: 36.5% by weight)
Photopolymerizable compound: dipentaerythritol hexaacrylate (DPHA, manufactured by Sigma-Aldrich)
Photopolymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (IRGACURE 369, manufactured by Ciba Specialty Chemicals)
Additive: Leveling agent SH-8400 (manufactured by Dow Corning Korea Co., Ltd.)
Solvent: Propylene glycol monomethyl ether acetate Experimental Example 1:
Colored patterns were formed using the colored photosensitive resin compositions prepared in the Examples and Comparative Examples as described below, and the adhesion, linearity and residue of the colored patterns were measured by the methods described below, and the results are shown in Table 3 below.

<Formation of Colored Pattern>
The colored photosensitive resin compositions of the Examples and Comparative Examples were spin-coated onto the surface of a 4-inch silicon wafer, and then the substrate was dried in an oven at 100°C for 90 seconds to volatilize the liquid components and form a thin film. After cooling to room temperature, the formed thin film was exposed using a pattern mask and an i-line stepper (manufactured by CANON). The silicon wafer substrate with the exposed coating film formed thereon was developed with a 0.2 wt% tetramethylammonium hydroxide (TMAH) aqueous solution, washed with water, and heated at 220°C for 180 seconds to form a colored pattern. The resulting pattern had a thickness of 1 μm.

(1) Measurement of Adhesion The obtained colored pattern was analyzed with an optical microscope VHX-7000 (manufactured by KEYENCE Corporation) to measure the minimum pattern size that could be formed without pattern loss.

(2) Evaluation of Pattern Characteristics The obtained colored patterns were analyzed with an optical microscope VHX-7000 (manufactured by KEYENCE Corporation), and the pattern characteristics (straightness and residue) were evaluated as follows.

<Evaluation criteria for straight-line stability>
5: All four side walls of the pattern are straight; 4: All four side walls of the pattern are substantially straight, but include some protrusions; 3: Some of the side walls of the four pattern are substantially uneven; 2: All four side walls of the pattern are substantially uneven; 1: No uniform pattern shape is formed.

<Residue evaluation criteria>
5: No residue observed between colored patterns 4: Residue distribution observed between colored patterns over more than 0% but less than 10% of the total area 3: Residue distribution observed between colored patterns over 10% or more but less than 20% of the total area 2: Residue distribution observed between colored patterns over 20% or more but less than 30% of the total area 1: Residue distribution observed between colored patterns over 30% or more of the total area

Experimental Example 2:
The pigment dispersibility of the colored photosensitive resin composition was measured by the following method, and the results are shown in Table 3 below.

(1) Pigment dispersibility (stability over time)
The viscosity of each of the colored photosensitive resin compositions of the Examples and Comparative Examples immediately after production and after standing at 40°C for 7 days was measured at 25°C using a Brookfield viscometer (Brookfield Viscometer DV-I+, manufactured by BROOKFIELD), and the difference from the initial viscosity was compared.

<Evaluation criteria>
◎: Viscosity difference 1% or less ○: Viscosity difference more than 1% and 2% or less △: Viscosity difference more than 2% and 5% or less ×: Viscosity difference more than 5%

As shown in Table 3 above, the colored photosensitive resin compositions of Examples 1 to 7, which contain a first repeating unit containing a phenoxybenzyl group of a specific structure and a second repeating unit containing a caprolactone-modified hydroxyalkyl group as an alkali-soluble resin, were confirmed to have excellent pigment dispersibility, excellent adhesion and linearity when forming colored patterns, and to leave almost no residue.

In contrast, the colored photosensitive resin compositions of Comparative Examples 1 to 6, which use alkali-soluble resins that do not contain any of the repeating units with the specific structures described above, were found to have poor pigment dispersibility, poor pattern adhesion and linearity, and to produce residue.

Although specific aspects of the present invention have been described in detail above, it will be clear to those skilled in the art to which this invention pertains that these specific descriptions are merely preferred embodiments and are not intended to limit the scope of the present invention. Those skilled in the art to which this invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above content.

Accordingly, the true scope of the present invention is defined by the claims and their equivalents.

Claims (8)

A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The alkali-soluble resin comprises a first repeating unit represented by the following chemical formula 1 and a second repeating unit represented by the following chemical formula 2:

In the above formula,
R ¹ to R ⁹ are hydrogen ;
R ¹⁰ is hydrogen or a methyl group;
R ¹¹ is hydrogen or a methyl group;
R ¹² is a C ₁ -C ₃ alkylene group;
R ¹³ is a C ₃ -C ₅ alkylene group;
n is an integer from 1 to 5 . The colored photosensitive resin composition according to claim 1, wherein the first repeating unit represented by Chemical Formula 1 is contained in an amount ranging from 10 to 80 mol % relative to 100 mol % of all repeating units constituting the alkali-soluble resin. The colored photosensitive resin composition according to claim 1, wherein the second repeating unit represented by chemical formula 2 is contained in an amount ranging from 10 to 70 mol % relative to 100 mol % of all repeating units constituting the alkali-soluble resin. A colored pattern formed using the colored photosensitive resin composition according to any one of claims 1 to 3 . A color filter comprising the colored pattern according to claim 4 . An image display device comprising the color filter according to claim 5 . A solid-state imaging device comprising the color filter according to claim 5 . 8. The solid-state imaging device of claim 7 , comprising a CMOS Image Sensor (CIS).