Colored photosensitive resin composition for solid-state imaging device, color filter, and solid-state imaging device

Abstract

The present invention provides: a colored photosensitive resin composition for a solid-state imaging device, the composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a silsesquioxane compound, a photopolymerization initiator, and a solvent, wherein the silsesquioxane compound is contained in an excess amount compared to the photopolymerizable compound; a color filter formed using same; and a solid-state imaging device comprising the color filter. The colored photosensitive resin composition for a solid-state imaging device according to the present invention can reduce film etching during plasma treatment and improve surface roughness defects.

Description

Colored photosensitive resin composition for solid-state imaging device, color filter and solid-state imaging device

[0001] The present invention relates to a colored photosensitive resin composition for a solid-state imaging device, a color filter, and a solid-state imaging device, and more particularly, to a colored photosensitive resin composition for a solid-state imaging device capable of reducing film abrasion and improving surface roughness defects during plasma treatment, a color filter formed using the same, and a solid-state imaging device equipped with the color filter.

[0002] A solid-state image sensor is a device that converts an image captured through optical energy into electrical information, and may include a color filter under the lens. For example, in the case of a CMOS image sensor (CIS), a color filter with a finer pitch and patterned at a higher resolution than the color filters corresponding to the pixels of a typical display device is used. The color filter of a CIS typically has a coloring pattern of the three primary colors of red (R), green (G), and blue (B), and is responsible for decomposing transmitted light into the three primary colors.

[0003] Recently, as the number of pixels in color filters used in solid-state image sensors has increased, the pixels in the solid-state image sensors have been miniaturized. This miniaturization of pixels has led to a demand for thinner film thicknesses while maintaining spectral characteristics. To form a color filter that satisfies these conditions, the concentration of pigments in the colored photosensitive resin composition must be increased. However, if the pigment content is excessively high, the content of photopolymerizable compounds, photopolymerization initiators, etc. may rapidly decrease. In such cases, the curing degree of the colored photosensitive resin composition is insufficient, which causes problems such as excessive film peeling during the plasma process after pattern formation and a rapid increase in surface roughness.

[0004] Korean Patent Publication No. 10-2009-0072754 discloses a composition for a color filter including a pigment and a binder resin, but it is difficult to secure plasma resistance for the composition for a color filter.

[0005] Therefore, there is a need for technological development of a colored photosensitive resin composition for a solid-state imaging device that can reduce film abrasion and improve surface roughness during plasma treatment.

[0006] One object of the present invention is to provide a colored photosensitive resin composition for a solid-state imaging device that can reduce film abrasion and improve surface roughness during plasma treatment.

[0007] Another object of the present invention is to provide a color filter formed using the colored photosensitive resin composition for a solid-state imaging device.

[0008] Another object of the present invention is to provide a solid-state imaging device having the color filter.

[0009] On the one hand, the present invention comprises a colorant, an alkali-soluble resin, a photopolymerizable compound, a silsesquioxane compound, a photopolymerization initiator and a solvent,

[0010] The above silsesquioxane compound provides a colored photosensitive resin composition for a solid-state imaging device, wherein the silsesquioxane compound is included in an amount of 50 wt% or more based on 100 wt% of the total amount of the photopolymerizable compound and the silsesquioxane compound.

[0011] In one embodiment of the present invention, the silsesquioxane compound may include a caged silsesquioxane compound.

[0012] In one embodiment of the present invention, the silsesquioxane compound may include a compound represented by the following chemical formula 1.

[0013] [Chemical Formula 1]

[0014]

[0015] In the above formula,

[0016] R1 to R8 are each independently a hydrogen atom, a substituted or unsubstituted C1~C30 alkyl group, a substituted or unsubstituted C2~C30 alkenyl group, a substituted or unsubstituted C2~C30 alkynyl group, a substituted or unsubstituted C1~C30 alkoxy group, a substituted or unsubstituted C3~C10 cycloalkyl group, a substituted or unsubstituted C1~C30 silyloxy group, or a substituted or unsubstituted aryl group.

[0017] In one embodiment of the present invention, the substituents of the C1 to C30 alkyl group, the C2 to C30 alkenyl group, the C2 to C30 alkynyl group, the C1 to C30 alkoxy group, the C3 to C10 cycloalkyl group, the C1 to C30 silyloxy group and the aryl group may each independently be a hydroxy group, an epoxy group, a thiol group, a (meth)acryloxy group, a trivinylsilyl group or a diphenylvinylsilyl group.

[0018] In one embodiment of the present invention, R1 to R8 can each independently be a hydrogen atom or a group represented by any one of the following chemical formulas 1-1 to 1-16.

[0019] [Chemical Formula 1-1]

[0020]

[0021] [Chemical Formula 1-2]

[0022]

[0023] [Chemical Formula 1-3]

[0024]

[0025] [Chemical Formula 1-4]

[0026]

[0027] [Chemical Formula 1-5]

[0028]

[0029] [Chemical Formula 1-6]

[0030]

[0031] [Chemical Formula 1-7]

[0032]

[0033] [Chemical Formula 1-8]

[0034]

[0035] [Chemical Formula 1-9]

[0036]

[0037] [Chemical Formula 1-10]

[0038]

[0039] [Chemical Formula 1-11]

[0040]

[0041] [Chemical Formula 1-12]

[0042]

[0043] [Chemical Formula 1-13]

[0044]

[0045] [Chemical Formula 1-14]

[0046]

[0047] [Chemical Formula 1-15]

[0048]

[0049] [Chemical Formula 1-16]

[0050]

[0051] In the above formula,

[0052] R a is a hydrogen or methyl group.

[0053] In one embodiment of the present invention, the photopolymerizable compound may include a polyfunctional photopolymerizable compound having five or more functional groups.

[0054] On the other hand, the present invention provides a color filter formed using the colored photosensitive resin composition for the solid-state imaging device.

[0055] On the other hand, the present invention provides a solid-state imaging device including the color filter.

[0056] A solid-state imaging device according to one embodiment of the present invention may include a CMOS image sensor.

[0057] The colored photosensitive resin composition for a solid-state imaging device according to the present invention can reduce film peeling during plasma treatment and improve surface roughness by including a silsesquioxane compound in an excessive amount compared to a photopolymerizable compound.

[0058] Hereinafter, the present invention will be described in more detail.

[0059]

[0060] One embodiment of the present invention relates to a colored photosensitive resin composition for a solid-state imaging device, which comprises a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a silsesquioxane compound (D), a photopolymerization initiator (E), and a solvent (F), wherein the silsesquioxane compound (D) is contained in an amount of 50 wt% or more based on 100 wt% of the total amount of the photopolymerizable compound (C) and the silsesquioxane compound (D).

[0061]

[0062] Hereinafter, a colored photosensitive resin composition for a solid-state imaging device according to one embodiment of the present invention will be described in detail for each component.

[0063]

[0064] Colorant (A)

[0065] In one embodiment of the present invention, the colorant (A) comprises a pigment (a1) and / or a dye (a2).

[0066]

[0067] pigment (a1)

[0068] The above pigment may be an organic pigment or an inorganic pigment commonly used in the relevant field.

[0069] The above organic pigment may 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, ferrinon pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, pravanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, etc.

[0070] Examples of the above inorganic pigments include metal compounds such as metal oxides or metal complexes, and specific examples include oxides or composite metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony; carbon black, and the like.

[0071] In particular, the organic pigments and inorganic pigments include compounds classified as pigments in the color index (published by The Society of Dyers and Colorists), and more specifically, pigments having the following color index (CI) numbers, but are not necessarily limited thereto.

[0072] CI Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, and 185

[0073] CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71

[0074] CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255, and 264

[0075] CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, and 38

[0076] CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64, and 76

[0077] CI Pigment Green 7, 10, 15, 25, 36, 47, and 58

[0078] CI Pigment Brown 28

[0079] CI Pigment Black 1 and 7, etc.

[0080] Among the CI pigment pigments exemplified above, a pigment selected from CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Orange 38, CI Pigment Red 122, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 208, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Violet 23, CI Pigment Blue 15:3, Pigment Blue 15:6, CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58 can be preferably used.

[0081] These can be used individually or in combination of two or more.

[0082] It is preferable to use a pigment dispersion liquid in which the particle size of the pigment is uniformly dispersed. An example of a method for uniformly dispersing the particle size of the pigment includes a method of dispersing the pigment by incorporating a pigment dispersant (a3), and according to this method, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.

[0083]

[0084] pigment dispersant (a3)

[0085] The above pigment dispersant (a3) ​​is added to deagglomerate and maintain stability of the pigment. Specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and other surfactants, and these may be used singly or in combination of two or more.

[0086] In addition, it is preferable to include an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). Commercially available products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and the acrylate-based dispersants may be used singly or in combination of two or more.

[0087] The pigment dispersant (a3) ​​may be a pigment dispersant of a resin type other than the above-described acrylate-based dispersant. Examples of the pigment dispersant of the other resin type 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-containing polycarboxylic acids and their modified products, or amides formed by the reaction of polyesters having free carboxyl groups with poly(lower alkylene imine)s or their salts, and the like. 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.

[0088] Commercially available products of the above resin-type dispersant include cationic resin dispersants, for example, BYK (Big) 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; Lubrizol trade names: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Kawaken Fine Chemicals trade names: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Examples include Ajinomoto Co., Ltd.'s product names: AJISPUR PB-821, AJISPUR PB-822, and AJISPUR PB-823; and Kyoeisha Chemical Co., Ltd.'s product names: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, and FLORENE DOPA-44.

[0089] In addition to the above-mentioned acrylic dispersant, other resin-type pigment dispersants may be used singly or in combination of two or more, and may also be used in combination with the acrylic dispersant.

[0090] The content of the pigment dispersant (a3) ​​is 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the pigment (a1). If the content of the pigment dispersant (a3) ​​exceeds 60 parts by weight, the viscosity may increase, and if it is less than 5 parts by weight, it may be difficult to atomize the pigment, or problems such as gelation after dispersion may occur.

[0091]

[0092] dye (a2)

[0093] The above dye (a2) can be used without limitation as long as it is soluble in an organic solvent. Preferably, it is preferable to use a dye that is soluble in an organic solvent and can ensure reliability in terms of solubility in an alkaline developer, heat resistance, solvent resistance, etc.

[0094] As the dyes mentioned above, those selected from acid dyes having acidic groups such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamide-based acid dyes, and derivatives thereof can be used. In addition, azo-based, xanthene-based, phthalocyanine-based acid dyes and their derivatives can also be selected.

[0095] Preferably, the dye is a compound classified as a dye in the Color Index (published by The Society of Dyers and Colourists) or a known dye listed in the dyeing notes (color dyes).

[0096] Specific examples of the above dyes include CI solvent dyes,

[0097] Yellow dyes such as CI Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;

[0098] Red dyes such as CI Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;

[0099] Orange dyes such as CI Solvent Orange 2, 7, 11, 15, 26, 41, 45, 56, 62;

[0100] Blue dyes such as CI Solvent Blue 5, 35, 36, 37, 44, 59, 67, 70;

[0101] Violet dyes such as CI Solvent Violet 8, 9, 13, 14, 36, 37, 47, 49;

[0102] Examples include green dyes such as CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35.

[0103] Among them, CI solvent dyes having excellent solubility in organic solvents, CI solvent yellow 14, 16, 21, 56, 79, 93, 151; CI solvent red 8, 49, 89, 111, 122, 132, 146, 179; CI solvent orange 41, 45, 62; CI solvent blue 35, 36, 44, 70; and CI solvent violet 13 are preferable, and among them, CI solvent yellow 21, 79; CI solvent red 8, 122, 132; and CI solvent orange 45, 62 are more preferable.

[0104] Also, as a CI acid dye,

[0105] CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, Yellow dyes such as 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

[0106] CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, Red dyes such as 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;

[0107] Orange dyes such as CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

[0108] Blue dyes such as CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;

[0109] Violet dyes such as CI Acid Violet 6B, 7, 9, 17, 19, 66;

[0110] Examples include green dyes such as CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109.

[0111] Among them, CI Acid Yellow 42; CI Acid Red 52, 92; CI Acid Blue 80, 90; CI Acid Violet 66; and CI Acid Green 27, which have excellent solubility in organic solvents among acid dyes, are preferable.

[0112] Also, as a CI direct dye,

[0113] Yellow dyes such as CI 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;

[0114] Red dyes such as CI 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;

[0115] Orange dyes such as CI Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

[0116] CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, Blue dyes such as 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;

[0117] Violet dyes such as CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

[0118] Examples include green dyes such as CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, and 82.

[0119] Also, as a CI modanto dye,

[0120] Yellow dyes such as CI Modanto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

[0121] Red dyes such as CI Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

[0122] Orange dyes such as CI Modanto Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

[0123] Blue dyes such as CI Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

[0124] Violet dyes such as CI Modanto Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

[0125] Examples include green dyes such as CI Modanto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53.

[0126] In the present invention, the dyes (a2) may be used singly or in combination of two or more.

[0127]

[0128] The above-mentioned colorant (A) may be included in an amount of 5 to 65 wt%, preferably 15 to 60 wt%, based on 100 wt% of the total solid content of the colored photosensitive resin composition for a solid-state imaging device. When the content of the colorant (A) is 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 during development, so there is an advantage in that no residue is generated.

[0129] In the present invention, the solid content of the colored photosensitive resin composition means the total of components excluding the solvent.

[0130]

[0131] Alkali-soluble resin (B)

[0132] In one embodiment of the present invention, the alkali-soluble resin (B) has reactivity and alkali solubility due to the action of light or heat, acts as a dispersion medium for solid components including a colorant, and performs the function of a binding resin, so long as it is a resin known in the art, it can be selected and used without any particular limitation.

[0133] The above alkali-soluble resin (B) may be a copolymer of an unsaturated carboxyl group-containing monomer and another monomer copolymerizable therewith.

[0134] Specific examples of the above unsaturated carboxyl group-containing monomers include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids; and mono(meth)acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono(meth)acrylate. Among these, acrylic acid and methacrylic acid are preferable.

[0135] Other monomers copolymerizable with the above unsaturated carboxyl group-containing monomer include hydroxyalkyl (meth)acrylate compounds such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate;

[0136] Aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, 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, and p-vinylbenzyl glycidyl ether;

[0137] N-substituted maleimide compounds such as N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide;

[0138] Alkyl (meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, sec-butyl (meth)acrylate, and t-butyl (meth)acrylate;

[0139] Alicyclic (meth)acrylate compounds such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, 2-dicyclopentanyloxyethyl (meth)acrylate, and isobornyl (meth)acrylate;

[0140] Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate;

[0141] Unsaturated oxetane compounds such as 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, and 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane;

[0142] Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl propionate;

[0143] Examples include cyanide vinyl compounds such as (meth)acrylonitrile and α-chloroacrylonitrile. These can be used singly or in combination of two or more.

[0144] In particular, it is preferable that the alkali-soluble resin (B) includes at least one of the repeating units represented by the following chemical formulas 2 to 4, in that it reduces film peeling during plasma treatment and improves poor surface roughness.

[0145] [Chemical Formula 2]

[0146]

[0147] [Chemical Formula 3]

[0148]

[0149] [Chemical Formula 4]

[0150]

[0151] In the above formula,

[0152] R 9 Inland R 18 are each independently hydrogen or a C1~C6 alkyl group,

[0153] R 19 and R 21 are each independently hydrogen or methyl group,

[0154] R 20 is an alkyl group of C1~C20.

[0155] The C1 to C6 alkyl group used in this specification means a straight-chain or branched monovalent hydrocarbon having 1 to 6 carbon atoms, and includes, but is not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, etc.

[0156] As used herein, the C1~C20 alkyl group means a straight-chain or branched hydrocarbon composed of 1 to 20 carbon atoms, and includes, but is not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, 2-ethylheptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, stearyl, nonadecyl, eicosanyl, etc.

[0157] The repeating unit represented by the above chemical formula 2 can be introduced by, for example, styrene, vinyltoluene, etc., the repeating unit represented by the above chemical formula 3 can be introduced by, for example, benzyl(meth)acrylate, and the repeating unit represented by the above chemical formula 4 can be introduced by, for example, an alkyl(meth)acrylate compound such as methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, etc.

[0158] The method for producing the above copolymer is not particularly limited, and any conventionally known polymerization method may be used. Among the known polymerization methods, solution polymerization is preferred. Furthermore, the polymerization temperature and time vary depending on the type and ratio of the introduced monomers, the molecular weight, and the acid value of the desired alkali-soluble resin. However, for example, polymerization can be performed at 60 to 130°C for 1 to 10 hours.

[0159] When using a solvent during the above polymerization, a solvent used in a typical radical polymerization reaction can be used, and specifically, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide, etc. can be used. These solvents can be used alone or in combination of two or more.

[0160] As a polymerization initiator used in the above polymerization, a commonly used polymerization initiator can be added and is not particularly limited. Specifically, organic peroxides such as diisopropylbenzene hydroperoxide, di-t-butylperoxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate, and t-butylperoxy-2-ethylhexanoate; nitrogen compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl 2,2'-azobis(2-methylpropionate) can be mentioned. These can be used alone or in combination of two or more.

[0161] During the above polymerization, a chain transfer agent may be used to control the molecular weight or molecular weight distribution of the copolymer. Examples of the chain transfer agent include mercapto compounds such as n-dodecanethiol, mercaptoacetic acid, and methyl mercaptoacetate; α-methylstyrene dimer, and the like.

[0162] The acid value of the alkali-soluble resin (B) is 50 to 150 mgKOH / g, preferably 60 to 140 mgKOH / g, and more preferably 80 to 130 mgKOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the polymer, and can be typically obtained by titration using an aqueous potassium hydroxide solution. Within the above acid value range, the alkali-soluble resin has improved solubility in a developer, so that the unexposed area is easily dissolved and highly sensitive, and the pattern of the exposed area remains during development, thereby improving the film residue rate.

[0163] In addition, an alkali-soluble resin having a polystyrene-converted weight average molecular weight (hereinafter simply referred to as “weight average molecular weight”) measured by gel permeation chromatography (GPC; using tetrahydrofuran as a dissolution solvent) of 5,000 to 50,000, preferably 8,000 to 40,000, and more preferably 10,000 to 30,000 is preferable. When the weight average molecular weight of the alkali-soluble resin (B) is within the above range, the film hardness is improved, an excellent film residue rate is exhibited, and good solubility in a developer of an unexposed area and improved resolution can be exhibited.

[0164] The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the alkali-soluble resin (B) is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. A molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.5 to 6.0 is preferable because the developability is excellent.

[0165]

[0166] The alkali-soluble resin (B) may be included in an amount of 10 to 80 wt%, preferably 10 to 70 wt%, based on 100 wt% of the total solid content of the colored photosensitive resin composition for a solid-state imaging device. When the alkali-soluble resin (B) is included in the above range, the solubility in a developer is sufficient, facilitating pattern formation, and preventing film reduction in the pixel portion of the exposed portion during development, thereby improving the omission property of the non-pixel portion, which is preferable.

[0167]

[0168] Photopolymerizable compound (C)

[0169] In one embodiment of the present invention, the photopolymerizable compound (C) is a compound that can be polymerized by the action of the following photopolymerization initiator (E), and a monofunctional monomer, a difunctional monomer, or other polyfunctional monomer can be used, and preferably a polyfunctional monomer having two or more functions can be used.

[0170] Specific examples of the above monofunctional monomer include, but are not limited to, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, or N-vinylpyrrolidone.

[0171] Specific examples of the above bifunctional monomers include, but are not limited to, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, or 3-methylpentanediol di(meth)acrylate.

[0172] Specific examples of the above other multifunctional monomers include, but are not limited to, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, or dipentaerythritol hexa(meth)acrylate.

[0173] In particular, when the photopolymerizable compound includes a multifunctional photopolymerizable compound having 5 or more functionalities, for example, 5 to 10 functionalities, the degree of curing increases, thereby improving plasma resistance.

[0174]

[0175] The above photopolymerizable compound (C) may be included in an amount of 0.1 to 25 wt% based on 100 wt% of the total solid content of the colored photosensitive resin composition for a solid-state imaging device. When the above photopolymerizable compound (C) is included in the above range, the intensity and smoothness of the pixel portion may be improved.

[0176]

[0177] Silsesquioxane compound (D)

[0178] In one embodiment of the present invention, the silsesquioxane compound (D) undergoes surface oxidation during plasma treatment to generate SiO2, thereby causing surface vitrification. This enhances resistance to film abrasion during plasma treatment and improves surface roughness.

[0179] Preferably, the silsesquioxane compound may include a caged silsesquioxane compound in terms of resistance to film abrasion and improvement of surface roughness during plasma treatment.

[0180] In particular, the silsesquioxane compound may include a compound represented by the following chemical formula 1.

[0181] [Chemical Formula 1]

[0182]

[0183] In the above formula,

[0184] R1 to R8 are each independently a hydrogen atom, a substituted or unsubstituted C1~C30 alkyl group, a substituted or unsubstituted C2~C30 alkenyl group, a substituted or unsubstituted C2~C30 alkynyl group, a substituted or unsubstituted C1~C30 alkoxy group, a substituted or unsubstituted C3~C10 cycloalkyl group, a substituted or unsubstituted C1~C30 silyloxy group, or a substituted or unsubstituted aryl group.

[0185] As used herein, the C1~C30 alkyl group means a straight-chain or branched hydrocarbon composed of 1 to 30 carbon atoms, and includes, but is not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, 2-ethylheptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, stearyl, nonadecyl, eicosanyl, behenyl, etc.

[0186] The C2~C30 alkenyl group used herein means a straight-chain or branched unsaturated hydrocarbon composed of 2 to 30 carbon atoms with one or more carbon-carbon double bonds, and includes, but is not limited to, ethyleneyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, etc.

[0187] The C2~C30 alkynyl group used in this specification means a straight-chain or branched unsaturated hydrocarbon composed of 2 to 30 carbon atoms with one or more carbon-carbon triple bonds, and includes, but is not limited to, acetylenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, and decynyl.

[0188] The C1~C30 alkoxy group used in this specification means a straight-chain or branched alkoxy group composed of 1 to 30 carbon atoms, and includes, but is not limited to, methoxy, ethoxy, n-propanoxy, butoxy, pentoxy, hexyloxy, etc.

[0189] As used herein, the C3~C10 cycloalkyl group means a simple or fused cyclic hydrocarbon composed of 3 to 10 carbon atoms, and includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0190] The C1~C30 silyloxy group used in this specification has the chemical formula -O-SiR b (R c )(R d ) of the flag (at this time R b , R c and R d are each independently hydrogen, a C1~C30 alkyl group, a C2~C30 alkenyl group, a C2~C30 alkynyl group, a C1~C30 alkoxy group, a hydroxy group or an aryl group, and R b , R c and R d (not all of them are hydrogen).

[0191] The aryl group used herein includes both an aromatic group and a heteroaromatic group and their partially reduced derivatives. The aromatic group is a simple or fused ring having 5 to 15 members, and the heteroaromatic group refers to an aromatic group containing at least one oxygen, sulfur, or nitrogen. Representative examples of aryl groups include, but are not limited to, phenyl, naphthyl, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, oxazolyl, thiazolyl, and tetrahydronaphthyl.

[0192] In one embodiment of the present invention, the substituents of the C1 to C30 alkyl group, the C2 to C30 alkenyl group, the C2 to C30 alkynyl group, the C1 to C30 alkoxy group, the C3 to C10 cycloalkyl group, the C1 to C30 silyloxy group and the aryl group may each independently be a hydroxy group, an epoxy group, a thiol group, a (meth)acryloxy group, a trivinylsilyl group or a diphenylvinylsilyl group.

[0193] Specifically, R1 to R8 can each independently be a hydrogen atom or a group represented by any one of the following chemical formulas 1-1 to 1-16.

[0194] [Chemical Formula 1-1]

[0195]

[0196] [Chemical Formula 1-2]

[0197]

[0198] [Chemical Formula 1-3]

[0199]

[0200] [Chemical Formula 1-4]

[0201]

[0202] [Chemical Formula 1-5]

[0203]

[0204] [Chemical Formula 1-6]

[0205]

[0206] [Chemical Formula 1-7]

[0207]

[0208] [Chemical Formula 1-8]

[0209]

[0210] [Chemical Formula 1-9]

[0211]

[0212] [Chemical Formula 1-10]

[0213]

[0214] [Chemical Formula 1-11]

[0215]

[0216] [Chemical Formula 1-12]

[0217]

[0218] [Chemical Formula 1-13]

[0219]

[0220] [Chemical Formula 1-14]

[0221]

[0222] [Chemical Formula 1-15]

[0223]

[0224] [Chemical Formula 1-16]

[0225]

[0226] In the above formula,

[0227] R a is a hydrogen or methyl group.

[0228] In particular, in terms of improving resistance to film abrasion and surface roughness during plasma treatment, at least one of R1 to R8 may be a group represented by the following chemical formula 1-14.

[0229] [Chemical Formula 1-14]

[0230]

[0231] In the above formula,

[0232] R a is a hydrogen or methyl group.

[0233] Specific examples of the above silsesquioxane compounds include allyl-heptaisobutyl substituted silsesquioxane (PSS-Allyl-Heptaisobutyl substituted), [2-(3,4-epoxycyclohexyl)ethyl]-heptaisobutyl substituted silsesquioxane (PSS-[2-(3,4-Epoxycyclohexyl)ethyl]-Heptaisobutyl substituted), (3-glycidyl)propoxy-heptaisobutyl substituted silsesquioxane (PSS-(3-Glycidyl)propoxy-Heptaisobutyl substituted), octa[(3-glycidyloxypropyl)dimethylsiloxy] substituted silsesquioxane (PSS-Octa[(3-glycidyloxypropyl)dimethylsiloxy] substituted), (3-mercapto)propyl-heptaisobutyl substituted Silsesquioxane (PSS-(3-Mercapto)propyl-Heptaisobutyl substituted), methacryl substituted silsesquioxane (PSS-Methacryl substituted), octa[(1,2-epoxy-4-ethylcyclohexyl)dimethylsiloxy] substituted silsesquioxane (PSS-Octavinyl substituted), (1-propylmethacrylate)-heptaisobutyl substituted silsesquioxane (PSS-(1-Propylmethacrylate)-Heptaisobutyl substituted), trivinylsilyloxy-heptacyclopentyl substituted silsesquioxane (PSS-Trivinylsilyloxy-Heptacyclopentyl substituted), vinyl-heptacyclopentyl substituted Examples include silsesquioxane (PSS-Vinyl-Heptacyclopentyl substituted), vinyl-heptaisobutyl substituted silsesquioxane (PSS-Vinyl-Heptaisobutyl substituted), etc. These can be used alone or in combination of two or more.

[0234]

[0235] The above silsesquioxane compound (D) is included in an amount of 50 wt% or more, preferably 70 wt% or more, for example, 70 to 99 wt%, based on 100 wt% of the total amount of the photopolymerizable compound (C) and the silsesquioxane compound (D). If the silsesquioxane compound (D) is included in an amount less than 50 wt% based on 100 wt% of the total amount of the photopolymerizable compound (C) and the silsesquioxane compound (D), film abrasion may become severe during plasma treatment and poor surface roughness may occur.

[0236] The above silsesquioxane compound (D) may be included in an amount of 1 to 50 wt%, preferably 10 to 50 wt%, based on 100 wt% of the total solid content of the colored photosensitive resin composition for a solid-state imaging device. When the silsesquioxane compound (D) is included in the above range, plasma resistance may be improved.

[0237]

[0238] Photopolymerization initiator (E)

[0239] In one embodiment of the present invention, the photopolymerization initiator (E) can be used without particular limitation on its type as long as it can polymerize the photopolymerizable compound (C). In terms of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, etc., it is preferable to use at least one compound selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, oxime compounds, and thioxanthone compounds as the photopolymerization initiator (E), and in particular, it is preferable to use an oxime compound in terms of pattern characteristics when forming an ultra-high-resolution pattern.

[0240] 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.

[0241] Examples of the above benzophenone compounds include benzophenone, 0-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

[0242] Specific examples of the above biimidazole compound 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 a biimidazole compound 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.

[0243] 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 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.

[0244] The above oxime compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9Hcarbazol-3-yl]-1-(O-acetyloxime), etc., and commercially available products include TR-PBG-305 (TRONLY), OXE-01 (BASF), OXE-02 (BASF), etc.

[0245] Examples of the above thioxanthone compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

[0246] In addition, the photopolymerization initiator (E) may be used in combination with a photopolymerization initiation auxiliary agent (e1) to improve the sensitivity of the colored photosensitive resin composition of the present invention. By containing the photopolymerization initiation auxiliary agent (e1), the colored photosensitive resin composition according to the present invention can further improve sensitivity and thus productivity.

[0247] The above photopolymerization initiation auxiliary agent (e1) may preferably be at least one compound selected from the group consisting of, for example, an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group.

[0248] As the above amine compound, specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; aromatic amine compounds such as 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), and 4,4'-bis(diethylamino)benzophenone can be used, and in particular, use of an aromatic amine compound is preferable.

[0249] 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, etc.

[0250] Specific examples of the organic sulfur compound having the above 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), tetraethylene glycol bis(3-mercaptopropionate), etc.

[0251]

[0252] The above photopolymerization initiator (E) may be included in an amount of 0.01 to 10 wt%, preferably 1 to 7 wt%, based on 100 wt% of the total solid content of the colored photosensitive resin composition for a solid-state imaging device. When the photopolymerization initiator (E) is included in the above range, the colored photosensitive resin composition for a solid-state imaging device of the present invention has high sensitivity, shortens the exposure time, improves productivity, and maintains high resolution, which is preferable. In addition, the strength of the pixel portion formed using the composition under the above-described conditions and the smoothness on the surface of the pixel portion can be improved.

[0253] In addition, when the photopolymerization initiation aid (e1) is further used, it is preferable to use the photopolymerization initiation aid (e1) in an amount of typically 10 moles or less, preferably 0.01 to 5 moles per mole of the photopolymerization initiator. When the photopolymerization initiation aid is used within the above range, the polymerization efficiency can be increased, thereby improving productivity.

[0254]

[0255] Solvent (F)

[0256] In one embodiment of the present invention, the solvent (F) may be any solvent used in a conventional colored photosensitive resin composition without particular limitation, as long as it is effective in dissolving other components included in the colored photosensitive resin composition, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters, or amides are preferable.

[0257] The above solvent (F) specifically includes ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, and dipropylene glycol dibutyl ether; 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; Examples thereof include esters such as 3-ethoxypropionate ethyl, 3-methoxypropionate methyl, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and γ-butyrolactone. The above solvents can be used alone or in combination of two or more.

[0258] In particular, in terms of applicability and drying properties, the boiling point should be 100 to 200°C, and propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. are preferable.

[0259]

[0260] The above solvent (F) may be included in an amount of 60 to 90 wt%, preferably 70 to 87 wt%, based on 100 wt% of the total weight of the colored photosensitive resin composition. When the solvent (F) is included in the above range, the coating property may be improved when applied using a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes also called a die coater), or inkjet.

[0261]

[0262] Additive (G)

[0263] The colored photosensitive resin composition for a solid-state imaging device of the present invention may contain additives such as other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, and anti-coagulants, as needed.

[0264] Specific examples of the other polymer compounds include thermosetting 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.

[0265] The above hardener is used to increase deep hardening and mechanical strength, and specific examples of the hardener include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, etc.

[0266] Specific examples of the epoxy compound in the above curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine 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.

[0267] Specific examples of the oxetane compound in the above curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

[0268] The hardeners exemplified above can be used alone or in combination of two or more.

[0269] The above curing agent may be used in combination with a curing auxiliary compound that can cause ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic anhydrides may be commercially available as epoxy resin curing agents. Specific examples of the epoxy resin curing agent include Adekahadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Ricasiddo HH (manufactured by Shin Nippon Eika Co., Ltd.), and MH-700 (manufactured by Shin Nippon Eika Co., Ltd.).

[0270] The above surfactant can be used to further improve the film-forming property of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant can be preferably used.

[0271] Examples of the silicone-based surfactants include commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Silicone Co., Ltd., and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, and TSF-4452 from GE Toshiba Silicone Co., Ltd. As for the fluorine-based surfactants, commercially available products such as Megapis F-470, F-471, F-475, F-482, and F-489 from Dainippon Ink & Kagaku Kogyo Co., Ltd. The surfactants exemplified above may be used alone or in combination of two or more.

[0272] 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, 3-isocyanatopropyltriethoxysilane, etc. The adhesion promoters exemplified above can be used alone or in combination of two or more.

[0273] Specific examples of the above antioxidants include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, etc.

[0274] Specific examples of the above anti-coagulant include sodium polyacrylate, etc.

[0275]

[0276] A colored photosensitive resin composition for a solid-state imaging device according to one embodiment of the present invention can be manufactured, for example, by the following method.

[0277] First, the pigment among the above-mentioned colorants (A) is mixed with the solvent (F) and dispersed using a bead mill or the like until the average particle size of the pigment becomes 0.2 ㎛ or less. At this time, if necessary, a pigment dispersant, part or all of the alkali-soluble resin (B), or a dye can be mixed with the solvent (F) to dissolve or disperse it. To the mixed dispersion, the remainder of the alkali-soluble resin (B), a photopolymerization initiator (E), a photopolymerizable compound (C), a silsesquioxane compound (D), and an additive (G), and if necessary, a solvent (F), can be further added to a predetermined concentration to manufacture a colored photosensitive resin composition for a solid-state imaging device according to the present invention.

[0278] The colored photosensitive resin composition for a solid-state imaging device according to the present invention can be used to produce a colored pattern, and the colored pattern can be used, for example, in a color filter, particularly a color filter of a solid-state imaging device, as described below.

[0279] Accordingly, one embodiment of the present invention relates to a color filter formed using the above-described colored photosensitive resin composition for a solid-state imaging device. A color filter according to one embodiment of the present invention can be manufactured by applying the above-described colored photosensitive resin composition for a solid-state imaging device onto a substrate, exposing it to light in a predetermined pattern, and developing it to form a colored pattern.

[0280] For example, the above-described colored photosensitive resin composition for a solid-state imaging device can be applied onto a substrate and heated and dried to form a preliminary colored film.

[0281] The substrate may include a photoelectric conversion element substrate used in a solid-state imaging device (e.g., a silicon substrate for CCD or CMOS). The substrate may also include a black matrix or black stripes for isolating each pixel.

[0282] The above coating process may include a coating or printing process such as, for example, roll coating, spin coating, slit coating, inkjet printing, etc.

[0283] The above heat drying can be performed at 70 to 200°C, preferably 80 to 130°C.

[0284] After heat drying, the film thickness can be 0.5 to 8 μm.

[0285] Thereafter, the preliminary coloring film can be exposed and developed to form a coloring pattern corresponding to each pixel.

[0286] The above exposure process may include laser exposure using a mask that selectively exposes the pixel area. Thereafter, the unexposed area may be selectively removed using a developer to form the colored pattern.

[0287] The developer may include, for example, an inorganic or organic alkaline compound. Examples of the inorganic alkaline compound 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, ammonia, and the like. Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, and the like. These may be used alone or in combination of two or more.

[0288] After the above development process, a post-baking process can be performed, for example, at 150 to 230°C.

[0289]

[0290] One embodiment of the present invention relates to a solid-state imaging device equipped with the above-described color filter.

[0291] The solid-state imaging device may include, for example, a CMOS image sensor.

[0292] The above solid-state imaging device includes a support including a semiconductor device or a photoelectric conversion device and a micro lens, and the color filter may be arranged between the support and the micro lens.

[0293]

[0294] Hereinafter, the present invention will be described in more detail through examples and experimental examples. These examples and experimental examples are intended solely to illustrate the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not limited thereto.

[0295]

[0296] Manufacturing Example 1: Manufacturing of pigment dispersion

[0297] A pigment dispersion was prepared by mixing and dispersing 10 parts by weight of CI Pigment Blue 15:6 (Grade I) as a pigment, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 85.0 parts by weight of propylene glycol methyl ether acetate as a solvent using a bead mill for 12 hours.

[0298]

[0299] Synthesis Example 1: Synthesis of Alkali-Soluble Resin

[0300] 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 13.0 parts by weight of acrylic acid, 10 parts by weight of benzyl methacrylate, 57.0 parts by weight of 4-methylstyrene, 20 parts by weight of methyl methacrylate, and 3 parts by weight of n-dodecanethiol were charged into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, and nitrogen was purged. Then, the temperature of the reaction solution was raised to 110°C while stirring, and the reaction was carried out for 6 hours. The solid acid value of the alkali-soluble resin thus synthesized was 95.8 mgKOH / g, and the weight average molecular weight (Mw) measured by GPC was approximately 14,200.

[0301]

[0302] Examples 1 to 6 and Comparative Examples 1 to 3: Preparation of colored photosensitive resin compositions for solid-state imaging devices

[0303] A colored photosensitive resin composition for a solid-state imaging device was prepared by mixing each component according to the composition shown in Table 1 below (unit: weight %).

[0304] Composition (% by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Colorant (A) A-150 50 50 50 50 50 50 50 50 Alkali-soluble resin (B) B-18.8 8.8 8.8 8.8 8.8 8.8 8.8 8.8 Photopolymerizable compound (C) C-10.1 1234569 10 Silsesquioxane compound (D) D-19.99 87654 10 Photopolymerizable Initiator (E) E-12.12.12.12.12.12.12.12.12.1 Additive (G) G-10.10.10.10.10.10.10.10.10.1 Solvent (F) F-1292929292929292929

[0305]

[0306] A-1: Pigment dispersion of manufacturing example 1

[0307] B-1: Alkali-soluble resin of Synthesis Example 1

[0308] C-1: A-DPH-12E NS (Shin-Nakamura)

[0309] D-1: SY-ASO 101 (cage type, mixture, Suyang Chemtech)

[0310] E-1: OXE-01 (BASF)

[0311] G-1: SH-8400 (Dow Corning Korea)

[0312] F-1: Propylene glycol monomethyl ether acetate (KH NEOCHEM)

[0313]

[0314] Experimental Example 1:

[0315] The film abrasion resistance and surface roughness characteristics of the colored photosensitive resin compositions for solid-state imaging devices manufactured in the above examples and comparative examples were measured during plasma treatment using the following methods. The measurement results are shown in Table 2 below.

[0316]

[0317] (1) Resistance to scratching

[0318] In a clean room at 23°C, the colored photosensitive resin compositions of Examples and Comparative Examples were applied by spin coating on the surface of a glass substrate (manufacturer: Corning, product name: No. 1737, thickness: 0.7 mm). Then, the substrate was placed on a heating plate and maintained at a temperature of 100°C for 3 minutes to form a thin film. After the formed colored photosensitive resin layer was cooled to 23°C, the entire surface was selectively exposed to i-line (wavelength 365 nm) using a photomask. At this time, an ultra-high pressure mercury lamp was used as the light source of i-line, and the irradiation amount was 150 mJ / cm2. Subsequently, the selectively exposed colored photosensitive resin layer was developed by immersing it in an aqueous solution containing 0.04 wt% of tetramethylammonium hydroxide as a developer at 23°C, and post-heated at 220°C for 180 seconds to form a colored pattern.

[0319] Afterwards, the coloring pattern was subjected to O2 plasma ashing using PSK's DAS2000 equipment under the conditions of 1500w / 800mT / 1000sccm O2 / 25℃.

[0320] At this time, the film thickness of the coloring pattern before and after O2 plasma ashing treatment was measured using a DEKTAK 6M film measuring device, and the film thickness reduction rate was calculated according to the following mathematical equation 1. The film abrasion resistance was evaluated according to the following evaluation criteria.

[0321] [Mathematical Formula 1]

[0322] Film thickness reduction rate (%): (ab) / a × 100

[0323] In the above formula,

[0324] a is the film thickness before plasma treatment,

[0325] b is the film thickness after plasma treatment.

[0326]

[0327] <Evaluation Criteria>

[0328] Very good: less than 15%

[0329] Good: 15% or more but less than 20%

[0330] Normal: 20% or more but less than 25%

[0331] Defective: 25% or more but less than 30%

[0332] Very poor: 30% or more

[0333]

[0334] (2) Surface roughness characteristics

[0335] In a clean room at 23°C, the colored photosensitive resin compositions of Examples and Comparative Examples were applied by spin coating on the surface of a glass substrate (manufacturer: Corning, product name: No. 1737, thickness: 0.7 mm). Then, the substrate was placed on a heating plate and maintained at a temperature of 100°C for 3 minutes to form a thin film. After the formed colored photosensitive resin layer was cooled to 23°C, the entire surface was selectively exposed to i-line (wavelength 365 nm) using a photomask. At this time, an ultra-high pressure mercury lamp was used as the light source of i-line, and the irradiation amount was 150 mJ / cm2. Subsequently, the selectively exposed colored photosensitive resin layer was developed by immersing it in an aqueous solution containing 0.04 wt% of tetramethylammonium hydroxide as a developer at 23°C, and post-heated at 220°C for 180 seconds to form a colored pattern.

[0336] Afterwards, the coloring pattern was subjected to O2 plasma ashing using PSK's DAS2000 equipment under the conditions of 1500w / 800mT / 1000sccm O2 / 25℃.

[0337] At this time, the average roughness (Ra - Average Roughness) value was obtained in non-contact mode using an atomic force electron microscope (manufacturer: Park system, model name: NX10) for the coloring pattern before and after O2 plasma ashing treatment, and the difference in surface roughness was calculated according to the following mathematical equation 2. The surface roughness characteristics were evaluated according to the evaluation criteria below.

[0338] [Equation 2]

[0339] Surface roughness difference (nm) = dc

[0340] In the above formula,

[0341] c is the Ra value before plasma treatment,

[0342] d is the Ra value after plasma treatment.

[0343]

[0344] <Evaluation Criteria>

[0345] Very good: less than 5 nm

[0346] Good: 5 nm or more but less than 8 nm

[0347] Normal: 8 nm or more and less than 13 nm

[0348] Defective: 13 nm or more and less than 20 nm

[0349] Very poor: 20 nm or more

[0350]

[0351] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Surface roughness characteristics Very good Very good Very good Good Good Good Average Poor Poor Very bad Scratch resistance Very good Very good Good Good Average Average Poor Very bad Very bad

[0352]

[0353] As shown in Table 2 above, it can be confirmed that the colored photosensitive resin compositions for solid-state imaging devices of Examples 1 to 6, in which the silsesquioxane compound is included in an amount of 50 wt% or more based on 100 wt% of the total amount of the photopolymerizable compound and the silsesquioxane compound according to the present invention, can reduce film peeling during plasma treatment and improve surface roughness defects, compared to the colored photosensitive resin compositions for solid-state imaging devices of Comparative Examples 1 to 3, in which the silsesquioxane compound is included in an amount of less than 50 wt% based on 100 wt% of the total amount of the photopolymerizable compound and the silsesquioxane compound.

[0354]

[0355] While specific aspects of the present invention have been described in detail above, it should be apparent to those skilled in the art that these specific descriptions are merely preferred embodiments and do not limit the scope of the present invention. Those skilled in the art will be able to make various applications and modifications within the scope of the present invention based on the above description.

[0356] Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims

1. Containing a coloring agent, an alkali-soluble resin, a photopolymerizable compound, a silsesquioxane compound, a photopolymerization initiator and a solvent, A colored photosensitive resin composition for a solid-state imaging device, wherein the above silsesquioxane compound is included in an amount of 50 wt% or more based on 100 wt% of the total amount of the photopolymerizable compound and the silsesquioxane compound.

2. A colored photosensitive resin composition for a solid-state imaging device, wherein the silsesquioxane compound in the first paragraph comprises a caged silsesquioxane compound.

3. In the first paragraph, the silsesquioxane compound is a colored photosensitive resin composition for a solid-state imaging device comprising a compound represented by the following chemical formula 1: [Chemical Formula 1] In the above formula, R1 to R8 are each independently a hydrogen atom, a substituted or unsubstituted C1~C30 alkyl group, a substituted or unsubstituted C2~C30 alkenyl group, a substituted or unsubstituted C2~C30 alkynyl group, a substituted or unsubstituted C1~C30 alkoxy group, a substituted or unsubstituted C3~C10 cycloalkyl group, a substituted or unsubstituted C1~C30 silyloxy group, or a substituted or unsubstituted aryl group.

4. A colored photosensitive resin composition for a solid-state imaging device, wherein in the third paragraph, the substituents of the C1 to C30 alkyl group, the C2 to C30 alkenyl group, the C2 to C30 alkynyl group, the C1 to C30 alkoxy group, the C3 to C10 cycloalkyl group, the C1 to C30 silyloxy group and the aryl group are each independently a hydroxy group, an epoxy group, a thiol group, a (meth)acryloxy group, a trivinylsilyl group or a diphenylvinylsilyl group.

5. In the third paragraph, R1 to R8 are each independently a hydrogen atom or a group represented by any one of the following chemical formulas 1-1 to 1-16, wherein the solid-state imaging device is a colored photosensitive resin composition: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] [Chemical Formula 1-5] [Chemical Formula 1-6] [Chemical Formula 1-7] [Chemical Formula 1-8] [Chemical Formula 1-9] [Chemical Formula 1-10] [Chemical Formula 1-11] [Chemical Formula 1-12] [Chemical Formula 1-13] [Chemical Formula 1-14] [Chemical Formula 1-15] [Chemical Formula 1-16] In the above formula, R a is a hydrogen or methyl group.

6. A colored photosensitive resin composition for a solid-state imaging device, wherein the photopolymerizable compound in the first paragraph comprises a pentafunctional or more multifunctional photopolymerizable compound.

7. A color filter formed using a colored photosensitive resin composition for a solid-state imaging device according to any one of claims 1 to 6.

8. A solid-state imaging device including the color filter of paragraph 7.

9. A solid-state imaging device comprising a CMOS image sensor according to claim 8.