Infrared-transmissive photosensitive resin composition, infrared-transmissive pixel, color filter array, image sensor, and lidar sensor

Abstract

The present invention provides: an infrared-transmissive photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant comprises an azo compound having a specific structure, a blue colorant, and a violet colorant; an infrared-transmissive pixel formed using same; and a color filter array and an image sensor, each comprising same. The infrared-transmissive photosensitive resin composition according to the present invention has a low transmittance in a visible ray region while exhibiting a high transmittance in an infrared ray region, thereby allowing for the acquisition of high-quality images even with a low amount of light.

Description

Infrared-transmitting photosensitive resin composition, infrared-transmitting pixel, color filter array, image sensor, and lidar sensor

[0001] The present invention relates to an infrared-transmitting photosensitive resin composition, and more particularly, to an infrared-transmitting photosensitive resin composition having low transmittance in the visible light region and high transmittance in the infrared region, thereby enabling an image of excellent image quality to be obtained even with a low amount of light, and having excellent pattern linearity and residue characteristics, an infrared-transmitting pixel formed using the same, a color filter array including the same, an image sensor, and a lidar sensor.

[0002] In general, an image sensor is a semiconductor device that converts optical images into electrical signals. Image sensors include charge-coupled device (CCD) image sensors and complementary metal oxide semiconductor (CMOS) image sensors.

[0003] Among these, the CMOS image sensor utilizes CMOS manufacturing technology, resulting in low power consumption and a favorable integration path, enabling miniaturization of the product. Therefore, the CMOS image sensor is used in digital still cameras, digital video cameras, and other applications. Furthermore, the CMOS image sensor is being used in diverse fields, including vehicle black boxes, biometrics, augmented reality, autonomous driving, drones, and AI robots.

[0004] The above CMOS image sensor is configured by forming a photodiode, an interlayer insulating film, metal wiring and a metal interlayer insulating film, a passivation layer, a color filter array, a micro lens, etc. on a silicon substrate. Among these, the color filter array refers to color pixels (R, G, B) or color pixels (C, M, Y).

[0005] However, a conventional color filter array can obtain a color image by transmitting only the visible light region, but as the size of the unit pixel constituting the color filter array has decreased recently, the amount of light that can be received per unit area has also decreased, making it difficult to obtain a photo with excellent image quality in a place where there is insufficient light.

[0006] Accordingly, a technology has been proposed to add infrared-transmitting pixels to existing color pixels (R, G, B or C, M, Y). When adding infrared-transmitting pixels, when there is insufficient light, an infrared image can be obtained and synthesized with an existing visible-light image, thereby obtaining an image with excellent image quality in situations where there is insufficient light, and converting it into distance information to an object can secure a three-dimensional image.

[0007] Therefore, there is a need for development of an infrared-transmitting photosensitive resin composition that more effectively absorbs wavelengths in the visible light range and exhibits excellent transmittance for wavelengths in the infrared range.

[0008] Korean Patent Publication No. 10-2015-0064107 discloses a composition for a color filter having transmittance for light in the near-infrared region, but has the disadvantages of insufficient visible light shielding, difficulty in securing sufficient transmittance in the infrared region, and insufficient resolution.

[0009] One object of the present invention is to provide an infrared-transmitting photosensitive resin composition that has low transmittance in the visible light region and high transmittance in the infrared region, thereby enabling obtaining images with excellent image quality even under low light conditions.

[0010] Another object of the present invention is to provide an infrared transmitting pixel formed using the infrared transmitting photosensitive resin composition.

[0011] Another object of the present invention is to provide a color filter array including the above infrared transmitting pixels.

[0012] Another object of the present invention is to provide an image sensor including the color filter array.

[0013] On the one hand, the present invention provides an infrared-transmitting photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the colorant comprises an azo compound represented by the following chemical formula 1, a blue colorant, and a violet colorant.

[0014] [Chemical Formula 1]

[0015]

[0016] (In chemical formula 1, L 1 is a group represented by formula (ph1), A is a group represented by formula (ia), and B is a group represented by formula (ib).

[0017]

[0018] (In equation (ph1), X 1 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -NH2, -CONH2, -COOH, -CN, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a halogen atom, and -CH2- contained in the hydrocarbon group may be substituted with -O-, -CO-, or -NH-, and -CH= contained in the hydrocarbon group may be substituted with -N=.

[0019] n represents an integer from 0 to 4. If n is an integer greater than 2, multiple X 1 may be the same or different. n is an integer greater than or equal to 2, and also X 1 If it is bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 1 They can combine with each other to form rings.

[0020] * indicates the number of combinations with A, and ** indicates the number of combinations with B.)

[0021]

[0022] (In equations (ia) and (ib), X 6 ~X 9 Each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be substituted with -O-, -CO- or -NH-, -CH= contained in the hydrocarbon group may be substituted with -N=, -CH< contained in the hydrocarbon group may be substituted with -N<, and an oxygen atom, a nitrogen atom or a carbonyl group may be inserted between the carbon atoms constituting the hydrocarbon group.

[0023] X 6 and X 7 can be combined with each other to form a ring, and X 8 and X 9 They may be combined with each other to form a ring.

[0024] * is L 1 ) indicates the number of combinations with

[0025] In one embodiment of the present invention, the L 1 It can be expressed as a formula (ph2).

[0026]

[0027] (In equation (ph2), X 2 ~X 5 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -NH2, -CONH2, -COOH, -CN, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a halogen atom.

[0028] X 2 Wow X 3 And X 4 Wow X 5 They can be combined with each other to form a ring.

[0029] * indicates the number of combinations with A, and ** indicates the number of combinations with B.)

[0030] In one embodiment of the present invention, the azo compound represented by the chemical formula 1 may be included in an amount of 5 to 40 wt%, the blue colorant may be included in an amount of 30 to 70 wt%, and the purple colorant may be included in an amount of 5 to 30 wt%, based on 100 wt% of the total colorant.

[0031] In one embodiment of the present invention, the colorant may further include an orange colorant.

[0032] In one embodiment of the present invention, the colorant may further include a black colorant.

[0033] On the other hand, the present invention provides an infrared transmitting pixel formed using the infrared transmitting photosensitive resin composition.

[0034] In one embodiment of the present invention, the infrared transmitting pixel may have a transmittance of 10% or less in a range of 400 to 700 nm at a film thickness of 0.5 ㎛, and a transmittance of 90% or more in a range of 900 nm or more.

[0035] On the other hand, the present invention provides a color filter array including the above infrared transmitting pixels.

[0036] On the other hand, the present invention provides an image sensor including the color filter array.

[0037] On the other hand, the present invention provides a lidar sensor including the above infrared transmitting pixels.

[0038] The infrared-transmitting photosensitive resin composition according to the present invention has low transmittance in the visible light region and high transmittance in the infrared region, so that an image with excellent image quality can be obtained even with a low amount of light, and the linearity and residue characteristics of the pattern are excellent.

[0039] Hereinafter, the present invention will be described in more detail.

[0040]

[0041] One embodiment of the present invention relates to an infrared-transmitting 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 colorant comprises an azo compound having a specific structure, a blue colorant and a violet colorant.

[0042]

[0043] Hereinafter, each component of an infrared transmitting photosensitive resin composition according to one embodiment of the present invention will be described in detail.

[0044]

[0045] Colorant (A)

[0046] In one embodiment of the present invention, the colorant (A) is a colorant for performing an infrared transmitting function, and includes an azo compound represented by the following chemical formula 1, a blue colorant, and a violet colorant.

[0047] By including an azo compound represented by the following chemical formula 1 as the above coloring agent (A), a blue coloring agent and a violet coloring agent, it is possible to sufficiently absorb short-wavelength light in the visible light range while effectively transmitting long-wavelength light in the infrared range.

[0048]

[0049] The azo compound represented by the following chemical formula 1 can effectively reduce the transmittance of visible light, particularly at a point of about 500 nm, and has excellent tinting power, so that even if the thickness of the coating film is thin, excellent visible light shielding can be secured.

[0050] [Chemical Formula 1]

[0051]

[0052] (In chemical formula 1, L 1is a group represented by formula (ph1), A is a group represented by formula (ia), and B is a group represented by formula (ib).

[0053]

[0054] (In equation (ph1), X 1 represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -NH2, -CONH2, -COOH, -CN, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a halogen atom, and -CH2- contained in the hydrocarbon group may be substituted with -O-, -CO-, or -NH-, and -CH= contained in the hydrocarbon group may be substituted with -N=.

[0055] n represents an integer from 0 to 4. If n is an integer greater than 2, multiple X 1 may be the same or different. n is an integer greater than or equal to 2, and also X 1 If it is bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 1 They can combine with each other to form rings.

[0056] * indicates the number of combinations with A, and ** indicates the number of combinations with B.)

[0057] X 1 The monovalent hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be a saturated or unsaturated hydrocarbon group, and may be a chain or alicyclic hydrocarbon group. In addition, the alicyclic hydrocarbon group may be a monocyclic or polycyclic hydrocarbon group.

[0058]

[0059] (In equations (ia) and (ib), X 6 ~X 9Each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be substituted with -O-, -CO- or -NH-, -CH= contained in the hydrocarbon group may be substituted with -N=, -CH< contained in the hydrocarbon group may be substituted with -N<, and an oxygen atom, a nitrogen atom or a carbonyl group may be inserted between the carbon atoms constituting the hydrocarbon group.

[0060] X 6 and X 7 can be combined with each other to form a ring, and X 8 and X 9 They may be combined with each other to form a ring.

[0061] * is L 1 ) indicates the number of combinations with

[0062] Above X 6 Inland X 9 Examples of the monovalent saturated hydrocarbon group include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl; branched-chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, sec-butyl, tert-butyl, 1,3-dimethylbutyl, and 2-ethylbutyl; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl.

[0063] The hydrogen atoms contained in the above saturated hydrocarbon group of 1 may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group, a halogen atom such as a fluorine atom, a hydroxy group, etc.

[0064] Also, the above L 1 It can be expressed as a formula (ph2).

[0065]

[0066] (In equation (ph2), X 2 ~X 5 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -NH2, -CONH2, -COOH, -CN, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a halogen atom.

[0067] X 2 Wow X 3 And X 4 Wow X 5 They can be combined with each other to form a ring.

[0068] * indicates the number of combinations with A, and ** indicates the number of combinations with B.)

[0069] X 2 Inland X 5 Examples of the alkyl group having 1 to 4 carbon atoms include straight-chain alkyl groups such as methyl, ethyl, and propyl; and branched-chain alkyl groups such as n-butyl, isobutyl, and tert-butyl. Among them, a methyl group or an ethyl group is preferable.

[0070] The group represented by the above formula (ia) and the group represented by the formula (ib) can each independently be any one of the groups represented by formulas (t1) to (t5).

[0071]

[0072] (In equation (t1) to equation (t5), R 1 ~R 16 Each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, a heterocyclic group having a 3 to 10 membered ring, -CN, -OH or a halogen atom.

[0073] * is L 1 ) indicates the number of combinations with

[0074] R 1 ~R 16Examples of the monovalent saturated hydrocarbon group include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; branched-chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; and alicyclic saturated hydrocarbon groups having 3 to 10 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl.

[0075] The hydrogen atoms contained in the above saturated hydrocarbon group of 1 may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group, a halogen atom such as a fluorine atom, a hydroxy group, etc.

[0076] R 1 ~R 16 As the aromatic hydrocarbon group in , phenyl group, tolyl group, xylyl group, naphthyl group, etc. can be mentioned, and preferably phenyl group and tolyl group are mentioned. In addition, as the substituent that the aromatic hydrocarbon group may have, halogen atom such as fluorine atom, chlorine atom, iodine atom, bromine atom; C1-C6 alkoxy group such as methoxy group, ethoxy group; -OH; -SO3H; -SO3 - ; -SO2NR 17 R 18 ; Alkylsulfonyl group having 1 to 6 carbon atoms, such as a methylsulfonyl group; Alkoxycarbonyl group having 1 to 6 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group; etc. can be mentioned.

[0077] R 17 represents a C1-C10 aliphatic saturated hydrocarbon group which may have a halogen atom, -OH or -NH2 as a substituent; an C3-C10 alicyclic hydrocarbon group which may have a halogen atom, -OH, -NH2 or a C1-C10 aliphatic saturated hydrocarbon group as a substituent; or an C6-C10 aromatic hydrocarbon group which may have a halogen atom, -OH, -NH2 or a C1-C10 aliphatic saturated hydrocarbon group as a substituent.

[0078] R 18 Silver represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.

[0079] R 1 ~R 16 The heterocyclic group in may be a phenyl group or a heterocyclic group having a benzene ring which may have a substituent, and preferably may be a phenyl group or a benzimidazoline group which may have a halogen atom.

[0080] The azo compound represented by the above chemical formula 1 may include a counter ion as needed. The counter ion may be a cation containing an alkaline earth metal, and is preferably at least one selected from the group consisting of a magnesium cation, a calcium cation, a strontium cation, and a barium cation, and is more preferably a barium cation.

[0081]

[0082] The above blue colorant can be used to absorb short-wavelength light in the range of about 500 to 750 nm. Since light in a relatively wide wavelength range can be absorbed by the blue colorant, it is preferable to include the blue colorant essentially and include it in the largest amount.

[0083] The blue colorant may be a blue pigment and / or a blue dye. The pigment may be a compound classified as a pigment in the Color Index (published by The Society of Dyers and Colourists), and may include, but is not necessarily limited to, pigments having the color index (CI) numbers listed below as examples. The dye may be a compound classified as a dye in the Color Index (published by The Society of Dyers and Colourists), or a known dye listed in a dyeing note (color dyeing yarn), but is not necessarily limited to the above.

[0084] Examples of blue pigments include CI Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 16, 21, 28, 60, 64, 76, etc., and CI Pigment Blue 16, 15:6 are particularly preferable in terms of infrared transmittance.

[0085] Examples of blue dyes include CI solvent blue series dyes, CI acid blue series dyes, CI direct blue series dyes, and CI modanto blue series dyes.

[0086] Specific examples of the above blue dye include:

[0087] Blue dyes such as CI Solvent Blue 35, 37, 59, 67;

[0088] 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;

[0089] 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;

[0090] Examples include 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, etc.

[0091]

[0092] The above purple colorant can be used as a colorant to improve selective transmittance in the infrared region. Examples of the purple colorant include a purple pigment and / or a purple dye.

[0093] Examples of purple pigments include CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37, 38, etc., and CI Pigment Violet 29, 23 are particularly preferable in terms of infrared transmittance.

[0094] Examples of purple dyes include CI solvent violet series dyes, CI acid violet series dyes, CI direct violet series dyes, and CI modanto violet series dyes.

[0095] Specific examples of the above purple dye include:

[0096] Purple dyes such as CI Solvent Violet 8, 9, 13, 14, 36, 37, 47, 49;

[0097] Purple dyes such as CI Acid Violet 6B, 7, 9, 17, 19;

[0098] 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;

[0099] Examples include purple 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, and 58.

[0100]

[0101] In the infrared transmitting photosensitive resin composition according to the present invention, the azo compound of the chemical formula 1 may be included in an amount of 5 to 40 wt%, the blue colorant may be included in an amount of 30 to 70 wt%, and the purple colorant may be included in an amount of 5 to 30 wt%, based on 100 wt% of the total colorant. When each content is within the above range, an infrared transmitting pixel having very low visible light transmittance and high infrared transmittance can be formed, and the linearity and residue characteristics of the pattern may also be excellent.

[0102]

[0103] In one embodiment of the present invention, the colorant may further include an orange colorant. When an orange colorant is included, light having a wavelength of about 500 nm or less can be effectively absorbed.

[0104] Examples of the orange colorant include orange pigments and / or orange dyes.

[0105] Examples of orange pigments include CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71, with CI Pigment Orange 64 being particularly preferred in terms of infrared transmittance.

[0106] Examples of orange dyes include CI solvent orange dyes, CI acid orange dyes, CI direct orange dyes, and CI modanto orange dyes.

[0107] Specific examples of the above orange dye include:

[0108] Orange dyes such as CI Solvent Orange 2, 7, 11, 15, 26, 56;

[0109] 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;

[0110] Orange dyes such as CI Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

[0111] Examples include 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, and 48.

[0112]

[0113] The above pigments and / or dyes may be used alone or in combination of two or more.

[0114]

[0115] In the infrared-transmitting photosensitive resin composition according to the present invention, the content of the orange colorant may be 5 to 30 wt% based on 100 wt% of the total colorant. When the content of the orange colorant is within the above range, light having a wavelength of about 500 nm or less can be effectively absorbed.

[0116]

[0117] In one embodiment of the present invention, the colorant may further include a black colorant. When a black colorant is included, wavelengths in the visible light range can be effectively absorbed.

[0118] The above black colorant may include a black pigment. The type of black pigment is not particularly limited as long as it has light-blocking properties in visible light, but examples include lactam black, aniline black, perylene black, titanium black, and carbon black. Among these, organic blacks such as lactam black, aniline black, and perylene black are particularly preferred.

[0119] In the infrared-transmitting photosensitive resin composition according to the present invention, the content of the black colorant may be 5 to 30 wt% based on 100 wt% of the total colorant. When the content of the black colorant is within the above range, wavelengths in the visible light range can be effectively absorbed.

[0120]

[0121] The above colorant may further include organic pigments, inorganic pigments, dyes, etc. commonly used in the field within a range that does not harm the purpose of the present invention.

[0122] As organic pigments, various pigments used in printing inks, inkjet inks, etc. can be used, 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, or diketopyrroropyrrole pigments.

[0123] Examples of the above inorganic pigment include metal compounds such as metal oxides or metal complexes, and specifically, oxides or composite metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, or antimony.

[0124] In particular, examples of the organic pigments and inorganic pigments include:

[0125] CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255, 264, and 277;

[0126] CI Pigment Green 7, 10, 15, 25, 36, 47, 58, 59, 62 and 63;

[0127] Examples include, but are not limited to, CI Pigment Brown 28.

[0128]

[0129] Pigments may be subjected to surface treatment using, as necessary, resin treatment, pigment derivatives with acidic or basic groups introduced, grafting treatment on the pigment surface using polymer compounds, atomization treatment using, for example, sulfuric acid atomization, or washing treatment using organic solvents or water to remove impurities, or removal treatment of ionic impurities using, for example, ion exchange.

[0130] When the colorant contains a pigment, a dispersant may be added to facilitate deagglomeration and maintain stability of the pigment. Any dispersant commonly used in the art may be used without limitation. Examples include cationic, anionic, nonionic, zwitterionic, polyester, and polyamine surfactants, and these may be used singly or in combination of two or more.

[0131] The above dispersant preferably includes 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, and DISPER BYK-2150. The above acrylate-based dispersants may be used alone or in combination of two or more.

[0132] In addition to the above-mentioned acrylate-based dispersant, a pigment dispersant of a resin type other than the above-mentioned acrylate-based dispersant may also be used. The pigment dispersant of the above other resin type includes a known resin type pigment dispersant, in particular, a polycarboxylic acid ester represented by polyurethane, polyacrylate, an unsaturated polyamide, a polycarboxylic acid, an amine salt of a polycarboxylic acid, an ammonium salt of a polycarboxylic acid, an alkylamine salt of a polycarboxylic acid, a polysiloxane, a long-chain polyaminoamide phosphate salt, an ester of a polycarboxylic acid substituted with a hydroxyl group and a modified product thereof, an amide formed by the reaction of a polyester having a free carboxyl group and a poly(lower alkylene imine) or a salt thereof, a water-soluble resin or water-soluble polymer compound such as a (meth)acrylic acid-styrene copolymer, a (meth)acrylic acid-(meth)acrylate ester copolymer, a styrene-maleic acid copolymer, polyvinyl alcohol, or polyvinyl pyrrolidone; a polyester; a modified polyacrylate; Examples include adducts of ethylene oxide / propylene oxide and phosphate esters.

[0133] Commercially available products of the above resin type pigment 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.

[0134] In addition to the above-mentioned acrylate-based dispersant, other resin-type pigment dispersants may be used alone or in combination of two or more, and may also be used in combination with the acrylate-based dispersant.

[0135]

[0136] Any dye that is soluble in an organic solvent may be additionally used without limitation. Preferably, a dye that is soluble in an organic solvent and can secure reliability such as solubility in an alkaline developer, heat resistance, and solvent resistance is 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. In addition, azo, xanthene, and phthalocyanine acid dyes and their derivatives may also be selected.

[0137]

[0138] The above colorant may be included in an amount of 30 to 80 wt% based on 100 wt% of the total solid content of the infrared-transmitting photosensitive resin composition. When the content of the colorant is within the above range, the visible light shielding property and infrared transmittance are excellent.

[0139]

[0140] Alkali-soluble resin (B)

[0141] In one embodiment of the present invention, the alkali-soluble resin (B) typically has reactivity and alkali solubility under the action of light or heat, and acts as a dispersion medium for a colorant.

[0142]

[0143] The above alkali-soluble resin (B) may be, for example, a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the monomer.

[0144] Examples of the above carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated tricarboxylic acids, and unsaturated polycarboxylic acids having two or more carboxyl groups in the molecule. Here, examples of the unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acids may be acid anhydrides, and specific examples include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polycarboxylic acid may be its mono(2-methacryloyloxyalkyl)ester, and examples thereof include mono(2-acryloyloxyethyl succinic acid), mono(2-methacryloyloxyethyl succinic acid), mono(2-acryloyloxyethyl phthalic acid, and mono(2-methacryloyloxyethyl phthalic acid). The unsaturated polycarboxylic acid may also be a mono(meth)acrylate of a dicarboxylic polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate, and monomethacrylate of ω-carboxypolycaprolactone. These carboxyl group-containing monomers may be used alone or in combination of two or more.

[0145] Other monomers copolymerizable with the above carboxyl group-containing monomer include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; unsaturated carboxylate compounds such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexylacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, and benzyl methacrylate; unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; unsaturated glycidyl carboxylate compounds such as glycidyl (meth)acrylate; vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; Examples thereof include unsaturated oxetane carboxylate compounds such as 3-methyl-3-acryloxymethyl oxetane, 3-methyl-3-methacryloxy methyl oxetane, 3-ethyl-3-acryloxy methyl oxetane, 3-ethyl-3-methacryloxy methyl oxetane, 3-methyl-3-acryloxy ethyl oxetane, 3-methyl-3-methacryloxy ethyl oxetane, 3-methyl-3-acryloxy ethyl oxetane, and 3-methyl-3-methacryloxy ethyl oxetane. These may be used alone or in combination of two or more.

[0146]

[0147] The alkali-soluble resin (B) may have an acid value of 10 to 200 (KOH mg / g), preferably 10 to 150 (KOH mg / g). When the acid value of the alkali-soluble resin satisfies the above range, the infrared-transmitting photosensitive resin composition can secure a sufficient development speed and improve adhesion to the substrate, thereby preventing the occurrence of pattern short-circuiting. 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.

[0148] The 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 the alkali-soluble resin (B) may be 3,000 to 200,000, preferably 5,000 to 100,000. When the molecular weight is within the above range, the hardness of the coating film is improved, the film residue ratio is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution tends to be improved.

[0149] The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the above alkali-soluble resin (B) may be 1.5 to 6.0, preferably 1.8 to 4.0. If the molecular weight distribution is within the above range, the developability may be excellent.

[0150] The content of the alkali-soluble resin (B) may be included in an amount of 5 to 80 wt%, preferably 5 to 70 wt%, based on 100 wt% of the total solid content of the infrared-transmitting photosensitive resin composition. When the content of the alkali-soluble resin (B) is less than 5 wt%, the sensitivity of the non-exposed portion to be dissolved in the developer may be reduced, resulting in the generation of residues. When the content exceeds 80 wt%, the degree of photocuring may be reduced, resulting in the exposure portion being dissolved in the developer.

[0151]

[0152] Photopolymerizable compound (C)

[0153] 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 below, and may include a monofunctional photopolymerizable compound, a difunctional photopolymerizable compound, or a trifunctional or more polyfunctional photopolymerizable compound.

[0154] Specific examples of the above monofunctional photopolymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc., and commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), or Viscote 158 (Osaka Yukigagaku High School).

[0155] Specific examples of the above-mentioned bifunctional photopolymerizable compounds 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, 3-methylpentanediol di(meth)acrylate, etc., and commercially available products include Aronix M-210, M-1100, M-1200 (Toagosei), KAYARAD HDDA (Nippon Kayaku), Viscote 260 (Osaka Yuki Kagaku Kogyo), AH-600, AT-600, or UA-306H (Kyoeisha Kagakusha).

[0156] Specific examples of the above trifunctional or more multifunctional photopolymerizable compounds 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, propoxylated dipentaerythritol hexa(meth)acrylate, etc., and commercially available products include NK ESTER ATM-4E (Shin-Nakamura) and Aronix. Examples include M-309, M-520 (Toagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku).

[0157] The photopolymerizable compounds exemplified above can be used alone or in combination of two or more.

[0158] The above photopolymerizable compound (C) may be included in an amount of 0.5 to 20 wt% based on 100 wt% of the total solid content of the infrared-transmitting photosensitive resin composition. When the content is within the above range, the strength and smoothness of the pixel portion are improved, which is preferable.

[0159]

[0160] Photopolymerization initiator (D)

[0161] In one embodiment of the present invention, the photopolymerization initiator (D) can be used without particular limitation on its type as long as it is capable of polymerizing a photopolymerizable compound.

[0162] In particular, it is preferable to use as the photopolymerization initiator at least one compound selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, oxime compounds, and thioxanthone compounds from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, etc.

[0163] 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.

[0164] Examples of the above benzophenone compounds include benzophenone, O-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, or 2,4,6-trimethylbenzophenone.

[0165] 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.

[0166] Specific examples of the above biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and biimidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted by a carboalkoxy group. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc. are preferably used.

[0167] Specific examples of the above oxime compounds include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and representative commercial products include BASF's Irgacure OXE-01 and OXE-02.

[0168] Examples of the above thioxanthone compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0169] In addition, within a range that does not impair the effects of the present invention, a photopolymerization initiator other than the above may be additionally used in combination. Examples thereof include benzoin-based compounds and anthracene-based compounds, and these may be used singly or in combination of two or more.

[0170] Examples of the above benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.

[0171] Examples of the above anthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, or 2-ethyl-9,10-diethoxyanthracene.

[0172] In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, or titanocene compounds can be additionally used in combination as photopolymerization initiators.

[0173]

[0174] In addition, the photopolymerization initiator may further include a photopolymerization initiation aid to improve the sensitivity of the infrared-transmitting photosensitive resin composition of the present invention. By including the photopolymerization initiation aid, the infrared-transmitting photosensitive resin composition according to the present invention can further increase sensitivity and improve productivity.

[0175] As the photopolymerization initiation auxiliary agent, 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 can be preferably used.

[0176] Specific examples of amine compounds include 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, and it is preferable to use aromatic amine compounds.

[0177] The 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.

[0178] Specific examples of organic sulfur compounds 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).

[0179]

[0180] The above photopolymerization initiator (D) may be included in an amount of 0.1 to 5 wt% based on 100 wt% of the total solid content of the infrared-transmitting photosensitive resin composition. When the content is within the above range, the infrared-transmitting photosensitive resin composition becomes highly sensitive, thus shortening the exposure time, thereby improving productivity and maintaining 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.

[0181] In addition, when further using the above photopolymerization initiator, it is preferable to use the same content range as the photopolymerization initiator, and when used in the above-described content, the sensitivity of the infrared transmitting photosensitive resin composition is further increased, and the productivity of the color filter formed using the composition is improved.

[0182]

[0183] Solvent (E)

[0184] In one embodiment of the present invention, the solvent (E) can be used without particular limitation as long as it is effective in dissolving other components included in the infrared-transmitting photosensitive resin composition, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters, or amides are preferable.

[0185]

[0186] The solvent is specifically an ether 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, dipropylene glycol dibutyl ether, etc.;

[0187] Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene;

[0188] Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone;

[0189] Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin;

[0190] 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,

[0191] Examples thereof include esters such as diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, or γ-butyrolactone.

[0192] In terms of applicability and drying properties, the solvent is preferably an organic solvent having a boiling point of 100°C to 200°C, and examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate. These may be used singly or in combination of two or more.

[0193] The above solvent may be included in an amount of 30 to 90 wt%, preferably 30 to 85 wt%, based on 100 wt% of the total infrared-transmitting photosensitive resin composition. When the above solvent is included in the above range, it provides an effect of improving the applicability when applied using an application device such as a roll coater, spin coater, slit-and-spin coater, slit coater (die coater), spray coater, reverse printing, gravure printing, screen printing, pad printing, and inkjet.

[0194]

[0195] Additive (F)

[0196] The infrared-transmitting photosensitive resin composition of the present invention may contain additives such as other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-coagulants, as needed.

[0197] Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

[0198] 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.

[0199] 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.

[0200] Specific examples of the oxetane compound in the above curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

[0201] The hardeners exemplified above can be used alone or in combination of two or more.

[0202] 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.).

[0203] 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.

[0204]

[0205] 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.

[0206] 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.

[0207] Specific examples of the above antioxidants include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, etc.

[0208] Specific examples of the above ultraviolet absorbent include 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, etc.

[0209] Specific examples of the above anti-coagulant include sodium polyacrylate, etc.

[0210]

[0211] An infrared-transmitting photosensitive resin composition according to one embodiment of the present invention has low transmittance in the visible light region and high transmittance in the infrared region, so that it can produce an image with excellent image quality even under a weak light amount, and thus can be usefully used in the manufacture of pixels constituting a color filter array of an image sensor.

[0212]

[0213] Accordingly, one embodiment of the present invention relates to an infrared transmitting pixel formed using the above-described infrared transmitting photosensitive resin composition.

[0214] The above infrared transmitting pixel may be manufactured by, for example, applying an infrared transmitting photosensitive resin composition to a substrate as described below, and photocuring and developing to form a pattern.

[0215] First, the infrared-transmitting photosensitive resin composition is applied onto a substrate (usually silicon) or a layer formed of the solid content of the previously formed infrared-transmitting photosensitive resin composition, and then heated and dried to remove volatile components such as solvents, thereby obtaining a smooth coating film.

[0216] The coating method may be, for example, spin coating, flexible coating, roll coating, slit-and-spin coating, or slit coating. After coating, the coating is heated and dried (prebaked), or after drying under reduced pressure, heated to volatilize volatile components such as solvents. At this time, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C. The thickness of the coating film after heating and drying is usually about 0.5 to 1.5 μm. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming the desired pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel rays are uniformly irradiated to the entire exposed area and accurate alignment of the mask and the substrate is achieved. When irradiated with ultraviolet rays, curing occurs in the area irradiated with ultraviolet rays.

[0217] The above ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), etc. The amount of ultraviolet ray may be appropriately selected as needed. By contacting the cured film with a developer to dissolve the unexposed area and developing it, a pattern having the desired shape can be obtained.

[0218] The above-mentioned developing method may be any of a liquid addition method, a dipping method, a spray method, etc. In addition, the substrate may be tilted at an arbitrary angle during development. The above-mentioned developing solution is usually an aqueous solution containing an alkaline compound and a surfactant. The above-mentioned alkaline compound may be any of an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium dihydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia, etc. In addition, specific examples of organic alkaline compounds include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, etc.

[0219] These inorganic and organic alkaline compounds may be used singly or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10 mass%, and more preferably 0.03 to 5 mass%.

[0220] The surfactant in the above alkaline developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

[0221] Specific examples of the above nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and the like.

[0222] Specific examples of the above anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate ester or sodium oleyl alcohol sulfate ester, alkyl sulfate salts such as sodium lauryl sulfate or ammonium lauryl sulfate, and alkyl aryl sulfate salts such as sodium dodecylbenzenesulfonate or sodium dodecylnaphthalenesulfonate.

[0223] Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride or lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactants may be used singly or in combination of two or more.

[0224] The concentration of the surfactant in the developer is usually 0.01 to 10 wt%, preferably 0.05 to 8 wt%, and more preferably 0.1 to 5 wt%. After development, washing is performed, and, if necessary, post-baking may be performed at 150 to 230°C for 3 to 10 minutes.

[0225]

[0226] The infrared transmitting pixel of the present invention exhibits low transmittance in the visible light region and high transmittance in the infrared region. Specifically, when the film thickness of the infrared transmitting pixel is 0.5 ㎛, the light transmittance may have a maximum value of 10% or less at a wavelength ranging from 400 to 700 nm, and a minimum value of 90% or more at a wavelength of 900 nm or more.

[0227]

[0228] One embodiment of the present invention relates to a color filter array including the above-described infrared transmitting pixels.

[0229] In addition, one embodiment of the present invention relates to an image sensor or camera sensor including the above-described color filter array.

[0230] The image sensor may include, for example, a CMOS Image Sensor (CIS).

[0231] The image sensor includes a support including a semiconductor element or a photoelectric conversion element and a micro lens, and the color filter array may be arranged between the support and the micro lens.

[0232] The above image sensor can be applied to various fields such as smartphone cameras, vehicle black boxes, biometrics, augmented reality, autonomous driving, drones, and AI robots.

[0233] The above camera sensor includes an image sensor and an image processing module, and can process still images or moving images obtained by the image sensor.

[0234]

[0235] One embodiment of the present invention relates to a lidar sensor including the above infrared transmitting pixel.

[0236] The above LiDAR (Light Detection And Ranging) sensor can be widely used in fields such as aerospace, satellite, and atmospheric analysis, as well as autonomous driving, long-distance measurement, speed enforcement, 3D reverse engineering, and personal AR / VR.

[0237]

[0238] Hereinafter, the present invention will be described in more detail through examples, comparative examples, and experimental examples. These examples, comparative 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.

[0239] Synthesis Example 1: Synthesis of an azo compound represented by Chemical Formula 1

[0240] Synthesis Example 1-1: Synthesis of azo compound (A-1)

[0241] To 5.0 parts of 2,5-dichloro-4-nitroaniline, 4.0 parts of water, 10 parts of acetic acid, 10 parts of methanol, and 25 parts of 98% sulfuric acid were added and stirred. After ice-cooling, an aqueous solution of 2.0 parts of sodium nitrite dissolved in 3.0 parts of water was added to the reaction solution, and the mixture was stirred for 2 hours to obtain a suspension containing a diazonium salt. Meanwhile, 3.0 parts of barbituric acid (α) and 15 parts of methanol were added, and then 100 parts of an ice-cooled 25% aqueous sodium hydroxide solution was added and stirred. The suspension containing the diazonium salt was added dropwise thereto. After completion of the dropping, the mixture was stirred at room temperature for 1 hour to obtain an orange suspension. The orange solid obtained by filtration was dried at 60°C under reduced pressure to obtain a compound represented by the formula (1).

[0242]

[0243] Next, 97 parts of water, 4.1 parts of sodium bicarbonate, and 3.8 parts of sodium sulfide hydrate were added to 8.4 parts of the compound represented by formula (1), and stirred at 85°C for 2 hours. After cooling the reaction solution to room temperature, the reaction solution was neutralized to pH 6 with 35% hydrochloric acid and precipitated to obtain a solid. The obtained solid was washed with water and filtered, and the obtained red solid was dried under reduced pressure at 60°C to obtain 6.3 parts of the compound represented by formula (2).

[0244]

[0245] Next, 2.1 parts of the compound represented by formula (2) were added with 20 parts of water, 6.7 parts of acetic acid, and 33 parts of 98% sulfuric acid, and stirred. After cooling the reaction mixture on ice, 0.6 parts of sodium nitrite was dissolved in 3.3 parts of water. The aqueous solution was added to the reaction solution and stirred for 2 hours to obtain a suspension containing a diazonium salt. Meanwhile, 0.8 parts of barbituric acid (β) and 0.8 parts of methanol were added, and then 15 parts of a 25% aqueous sodium hydroxide solution was added under ice cooling, and stirred. To this was added dropwise the suspension containing the diazonium salt described above.

[0246] After completion of the addition, the mixture was stirred at room temperature for 1 hour to obtain a red suspension. The suspension was filtered and washed, and the obtained solid was dried at 60°C under reduced pressure to obtain 1.7 parts (57% yield) of an azo compound represented by the formula (A-1).

[0247] (Mass Spectrometry) Ionization Mode = ESI: m / z = 453.0 [MH] -

[0248]

[0249]

[0250] Synthesis Example 1-2: Synthesis of azo compound (A-2)

[0251] A compound represented by the formula (A-2) was obtained in the same manner as in Synthesis Example 1-1, 0.4 parts (yield 15%), except that 3.0 parts of barbituric acid (α) was replaced with 5.1 parts of 1,3-dicyclohexyl barbituric acid (α), and 0.8 parts of barbituric acid (β) was replaced with 0.7 parts of 1,3-dicyclohexylbarbituric acid (β).

[0252] (Mass Spectrometry) Ionization Mode = ESI: m / z = 783.4 [M+H] +

[0253]

[0254]

[0255] Synthesis Example 1-3: Synthesis of azo compound (A-3)

[0256] A compound represented by the formula (A-3) was obtained in 3.9 parts (yield: 66%) in the same manner as in Synthesis Example 1-1, except that 3.0 parts of barbituric acid (α) was replaced with 1.8 parts of 3-cyano-1-butyl-6-hydroxy-4-methyl-2-pyridone (α), and 0.8 parts of barbituric acid (β) was replaced with 1.4 parts of 3-cyano-1-butyl-6-hydroxy-4-methyl-2-pyridone (β).

[0257] (Mass Spectrometry) Ionization Mode = ESI: m / z = 609.2 [MH] -

[0258]

[0259]

[0260] Synthesis Example 1-4: Synthesis of azo compound (A-4)

[0261] A compound represented by the formula (A-4) was obtained in the same manner as in Synthesis Example 1-1, 0.8 parts (yield: 53%), except that 3.0 parts of barbituric acid (α) was replaced with 4.2 parts of 3-methyl-1-phenyl-5-pyrazolone (α), and 0.8 parts of barbituric acid (β) was replaced with 0.5 parts of 3-methyl-1-phenyl-5-pyrazolone (β).

[0262] (Mass Spectrometry) Ionization Mode = ESI: m / z = 547.2 [M+H] +

[0263]

[0264]

[0265] Synthesis Example 1-5: Synthesis of azo compound (A-5)

[0266] A compound represented by the formula (A-5) was obtained in the same manner as in Synthesis Example 1-1, 1.2 parts (yield: 58%), except that 3.0 parts of barbituric acid (α) was replaced with 4.9 parts of 3-methyl-1-(4-sulfophenyl)-2-pyrazolin-5-one (α), and 0.8 parts of barbituric acid (β) was replaced with 0.7 parts of 3-methyl-1-(4-sulfophenyl)-2-pyrazolin-5-one (β).

[0267] (Mass Spectrometry) Ionization Mode = ESI: m / z = 705.0 [MH] +

[0268]

[0269]

[0270] Synthesis Example 1-6: Synthesis of azo compound (A-6)

[0271] A compound represented by formula (A-6) (yield: 56%) was obtained in the same manner as in Synthesis Example 1-1, except that 0.8 parts of barbituric acid (β) was replaced with 1.2 parts of 3-cyano-1-butyl-6-hydroxy-4-methyl-2-pyridone.

[0272] (Mass Spectrometry) Ionization Mode = ESI: m / z = 533.0 [M+H] +

[0273]

[0274]

[0275] Synthesis Example 1-7: Synthesis of azo compound (A-7)

[0276] A compound represented by formula (A-7) (yield: 54%) was obtained in the same manner as in Synthesis Example 1-1, except that 0.8 part of barbituric acid (β) was replaced with 1.0 part of 3-methyl-1-phenyl-5-pyrazolone.

[0277] (Mass Spectrometry) Ionization Mode = ESI: m / z = 499.1 [MH] -

[0278]

[0279]

[0280] Synthesis Example 1-8: Synthesis of azo compound (A-8)

[0281] A compound represented by formula (A-8) (yield: 37%) was obtained in the same manner as in Synthesis Example 1-1, except that 0.8 part of barbituric acid (β) was replaced with 0.5 part of 3-methyl-1-(4-sulfophenyl)-2-pyrazolin-5-one.

[0282] (Mass Spectrometry) Ionization Mode = ESI: m / z = 579.0 [MH] -

[0283]

[0284]

[0285] Synthesis Example 1-9: Synthesis of azo compound (A-9)

[0286] A compound represented by the formula (A-9) (yield: 31%) was obtained in the same manner as in Synthesis Example 1-2, except that 0.7 part of 1,3-dicyclohexylbarbituric acid (β) was replaced with 0.2 part of 3-methyl-1-phenyl-5-pyrazolone.

[0287] (Mass spectrometry) Ionization mode = ESI: m / z = 664.0 [M] -

[0288]

[0289]

[0290] Synthesis Example 1-10: Synthesis of azo compound (A-10)

[0291] A compound represented by the formula (A-10) was obtained in 35 parts (yield 73%) in the same manner as in Synthesis Example 1-4, except that 4.2 parts of 3-methyl-1-phenyl-5-pyrazolone (α) was replaced with 18 parts of 3-methyl-1-(4-sulfophenyl)-2-pyrazolin-5-one.

[0292] (Mass Spectrometry) Ionization Mode = ESI: m / z = 625.1 [MH] -

[0293]

[0294]

[0295] Synthesis Example 1-11: Synthesis of azo compound (A-11)

[0296] To 1.5 parts of the azo compound represented by the formula (A-10), 15 parts of chloroform and 0.4 parts of N,N-dimethylformamide were added, stirred, and 0.6 parts of thionyl chloride were added dropwise while maintaining the temperature below 20°C. After completion of the dropping, the temperature was raised to 50°C, reacted at the same temperature for 3 hours, and then cooled to 20°C. After cooling, a mixture of 0.5 parts of 2-methylcyclohexylamine and 1.9 parts of triethylamine was added dropwise while maintaining the reaction solution below 20°C while stirring. Thereafter, the reaction was carried out at the same temperature for 5 hours. Subsequently, the solvent was removed from the obtained reaction mixture using an evaporator, and a small amount of methanol was added and stirred vigorously. This mixture was added dropwise to 45 parts of a 20% aqueous sodium chloride solution while stirring to precipitate crystals. The precipitated crystals were washed with water and dried at 60°C under reduced pressure to obtain 1.2 parts (74% yield) of a compound represented by the formula (A-11).

[0297] (Mass Spectrometry) Ionization Mode = ESI: m / z = 720.2 [MH] -

[0298]

[0299]

[0300] Synthesis Example 1-12: Synthesis of azo compound (A-12)

[0301] A compound represented by the formula (A-12) was obtained in 0.8 parts (yield 58%) in the same manner as in Synthetic Example 1-11, except that 0.5 parts of 2-methylcyclohexylamine was replaced with 2.1 parts of 3,5-di-tert-butylaniline.

[0302] (Mass spectrometry) Ionization mode = ESI: m / z = 813.2 [M] -

[0303]

[0304]

[0305] Synthesis Example 1-13: Synthesis of azo compound (A-13)

[0306] A compound represented by the formula (A-13) was obtained in 1.2 parts (yield 74%) using the same method as in Synthesis Example 1-11, except that 0.5 parts of 2-methylcyclohexylamine was replaced with 1.3 parts of aniline.

[0307] (Mass Spectrometry) Ionization Mode = ESI: m / z = 701.1 [M] -

[0308]

[0309]

[0310] Synthesis Example 1-14: Synthesis of azo compound (A-14)

[0311] A compound represented by the formula (A-14) was obtained in 0.9 parts (yield 59%) in the same manner as in Synthetic Example 1-11, except that 0.5 parts of 2-methylcyclohexylamine was replaced with 1.8 parts of 1-adamantaneamine.

[0312] (Mass Spectrometry) Ionization Mode = ESI: m / z = 759.2 [M] -

[0313]

[0314]

[0315] Synthesis Example 1-15: Synthesis of azo compound (A-15)

[0316] A compound represented by the formula (A-15) was obtained in 0.9 parts (yield 62%) in the same manner as in Synthetic Example 1-11, except that 0.5 parts of 2-methylcyclohexylamine was replaced with 1.2 parts of 1,3-dimethylbutylamine.

[0317] (Mass spectrometry) Ionization mode = ESI: m / z = 709.2 [M] -

[0318]

[0319]

[0320] Synthesis Example 1-16: Synthesis of azo compound (A-16)

[0321] To 0.5 parts of the azo compound represented by formula (A-10), 60 parts of water and 60 parts of N,N-dimethylformamide were added, stirred, and 1.2 parts of barium acetate were added. The temperature was raised to 60°C, reacted at the same temperature for 2 hours, and then cooled to 20°C. After cooling, the reaction solution was filtered, washed with methanol, and dried under reduced pressure at 60°C, thereby obtaining 0.4 parts (yield 76%) of the compound represented by formula (A-16).

[0322]

[0323]

[0324] Synthesis Example 1-17: Synthesis of azo compound (A-17)

[0325] A compound represented by the formula (A-17) was obtained in the same manner as in Synthesis Example 1-11, except that 1.5 parts of the azo compound represented by the formula (A-10) were replaced with 12 parts of the azo compound represented by the formula (A-5), 0.4 parts of N,N-dimethylformamide were replaced with 0.3 parts, 0.6 parts of thionyl chloride were replaced with 9.4 parts, 0.5 parts of 2-methylcyclohexylamine were replaced with 2.3 parts, and 1.9 parts of triethylamine were replaced with 5.3 parts, thereby obtaining 0.4 parts (yield: 28%) of the compound represented by the formula (A-17).

[0326] (Mass Spectrometry) Ionization Mode = ESI: m / z = 895.2 [MH] -

[0327]

[0328]

[0329] Synthesis Example 1-18: Synthesis of azo compound (A-18)

[0330] A compound represented by the formula (A-18) was obtained in 3.2 parts (yield: 65%) in the same manner as in Synthesis Example 1-7, except that 5.0 parts of 2,5-dichloro-4-nitroaniline was replaced with 3.0 parts of 2-methyl-4-nitroaniline.

[0331] (Mass Spectrometry) Ionization Mode = ESI: m / z = 445.2 [MH] -

[0332]

[0333]

[0334] Synthesis Example 1-19: Synthesis of azo compound (A-19)

[0335] A compound represented by the formula (A-19) was obtained in 4.0 parts (yield: 90%) in the same manner as in Synthesis Example 1-10, except that 5.0 parts of 2,5-dichloro-4-nitroaniline was replaced with 6.0 parts of 2-methyl-4-nitroaniline.

[0336] (Mass Spectrometry) Ionization Mode = ESI: m / z = 571.2 [MH] -

[0337]

[0338]

[0339] Synthesis Example 1-20: Synthesis of azo compound (A-20)

[0340] Except that 1.5 parts of the azo compound represented by formula (A-10) were replaced with 1.5 parts of the azo compound represented by formula (A-19), 0.3 parts (20% yield) of the compound represented by formula (A-20) was obtained in the same manner as in Synthesis Example 1-11.

[0341] (Mass Spectrometry) Ionization Mode = ESI: m / z = 666.3 [MH] -

[0342]

[0343]

[0344] Synthesis Example 1-21: Synthesis of azo compound (A-21)

[0345] A compound represented by the formula (A-21) was obtained in 1.3 parts (yield 40%) in the same manner as in Synthesis Example 1-4, except that 5.0 parts of 2,5-dichloro-4-nitroaniline was replaced with 3.0 parts of 2-chloro-4-nitroaniline.

[0346] (Mass Spectrometry) Ionization Mode = ESI: m / z = 513.3 [M+H] +

[0347]

[0348]

[0349] Synthesis Example 1-22: Synthesis of azo compound (A-22)

[0350] A compound represented by the formula (A-22) was obtained in 0.3 parts (yield 21%) in the same manner as in Synthesis Example 1-4, except that 5.0 parts of 2,5-dichloro-4-nitroaniline was replaced with 3 parts of 2,6-dichloro-4-nitroaniline.

[0351] (Mass Spectrometry) Ionization Mode = ESI: m / z = 545.3 [MH] -

[0352]

[0353]

[0354] Synthesis Example 1-23: Synthesis of azo compound (A-23)

[0355] A compound represented by the formula (A-23) was obtained in 2.4 parts (yield: 73%) in the same manner as in Synthesis Example 1-4, except that 5.0 parts of 2,5-dichloro-4-nitroaniline was replaced with 2.0 parts of 4-nitroaniline.

[0356] (Mass Spectrometry) Ionization Mode = ESI: m / z = 479.5 [M+H] +

[0357]

[0358]

[0359] Synthesis Example 1-24: Synthesis of azo compound (A-24)

[0360] A compound represented by the formula (A-24) was obtained in 0.3 parts (yield 15%) in the same manner as in Synthesis Example 1-4, except that 5.0 parts of 2,5-dichloro-4-nitroaniline was replaced with 1.0 parts of 2,5-dimethoxy-4-nitroaniline.

[0361] (Mass Spectrometry) Ionization Mode = ESI: m / z = 537.2 [MH] -

[0362]

[0363]

[0364] Synthesis Example 2: Synthesis of alkali-soluble resin (B)

[0365] A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube was prepared, and meanwhile, as a monomer dropping funnel, 11.82 g (0.1 mol) of vinyltoluene, 73.71 g (0.4 mol) of 2-ethylhexyl acrylate, 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 charged and mixed while stirring to prepare, and as a chain transfer agent dropping funnel, 6 g of n-dodecanethiol and 24 g of PGMEA were added and mixed while stirring to prepare. After that, 395 g of PGMEA was introduced into the flask, and the atmosphere inside the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90°C while stirring.

[0366] Next, the addition of monomer and chain transfer agent was initiated from each loading lot. The addition was carried out for 2 hours while maintaining 90°C, and after 1 hour, the temperature was increased to 110°C and maintained for 3 hours. Then, a gas introduction tube was introduced to initiate bubbling of a mixed gas of oxygen / nitrogen = 5 / 95 (v / v).

[0367] Next, 23.74 g (0.167 mol) of glycidyl methacrylate (33 mol% based on the carboxyl group of the acrylic acid used in this reaction), 0.4 g of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 g of triethylamine were placed in a flask and reacted at 110°C for 4 hours. Then, 7 g (0.07 mol) of succinic anhydride was added and the reaction was continued at 110°C for 4 hours to obtain an alkali-soluble resin (B-1). The alkali-soluble resin thus synthesized had an acid value of 39.5 mgKOH / g, a weight-average molecular weight in terms of polystyrene measured by GPC of 8,800, and a molecular weight distribution (Mw / Mn) of 1.9.

[0368]

[0369] Manufacturing Example 1: Manufacturing of azo compound dispersion (a1-1)

[0370] 15 parts of the compound represented by the formula (A-1) obtained in Synthesis Example 1-1, 4 parts of a dispersant (BYK, BYKLPN-6919) (converted to solid content), 3 parts of a dispersing resin (copolymer of 30 parts by weight of methacrylic acid and 70 parts by weight of benzyl methacrylate, acid value 80 mgKOH / g, weight average molecular weight 11,000) (converted to solid content), 73 parts of propylene glycol monomethyl ether acetate, and 5 parts of diacetone alcohol were mixed, and 300 parts of 0.2 mm zirconia beads were added, mixed, and dispersed to obtain an azo compound dispersion (a1-1).

[0371]

[0372] Manufacturing Example 2: Manufacturing of azo compound dispersion (a1-2)

[0373] An azo compound dispersion (a1-2) was obtained in the same manner as in Manufacturing Example 1, except that the compound represented by Formula (A-1) was replaced with the compound represented by Formula (A-2) obtained in Synthesis Example 1-2.

[0374]

[0375] Manufacturing Example 3: Manufacturing of azo compound dispersion (a1-3)

[0376] An azo compound dispersion (a1-3) was obtained in the same manner as in Manufacturing Example 1, except that the compound represented by Formula (A-1) was replaced with the compound represented by Formula (A-4) obtained in Synthesis Example 1-4.

[0377]

[0378] Manufacturing Example 4: Manufacturing of azo compound dispersion (a1-4)

[0379] An azo compound dispersion (a1-4) was obtained in the same manner as in Manufacturing Example 1, except that the compound represented by Formula (A-1) was replaced with the compound represented by Formula (A-15) obtained in Synthesis Example 1-15.

[0380]

[0381] Manufacturing Example 5: Manufacturing of azo compound dispersion (a1-5)

[0382] An azo compound dispersion (a1-5) was obtained in the same manner as in Manufacturing Example 1, except that the compound represented by Formula (A-1) was replaced with the compound represented by Formula (A-21) obtained in Synthesis Example 1-21.

[0383]

[0384] Manufacturing Example 6: Manufacturing of azo compound dispersion (a1-6)

[0385] An azo compound dispersion (a1-6) was obtained in the same manner as in Manufacturing Example 1, except that the compound represented by Formula (A-1) was replaced with the compound represented by Formula (A-24) obtained in Synthesis Example 1-24.

[0386]

[0387] Examples 1 to 11 and Comparative Examples 1 to 4: Preparation of infrared-transmitting photosensitive resin compositions

[0388] An infrared-transmitting photosensitive resin composition was prepared by mixing each component according to the compositions in Tables 1 and 2 below (unit: weight %).

[0389]

[0390] (Unit: wt%)Example 1234567891011Colorant (A)(a1-1)8.3 2.716.78.38.38.3(a1-2) 8.3 (a1-3) 8.3 (a1-4) 8.3 (a1-5) 8.3 (a1-6) 8.3 (a2)24.724.724.724.724.724.730.324.719.124.724.7(a3)11111111111111116.88.3 11(a4)11111111111111116.88.3115.5(a5) 115.5 (a6) 5.5 (a7) 5.5Alkali-soluble resin (B)(B)3.43.43.43.43.43.43.43.43.43.43.43.4Photopolymerizable compound(C)(C)1.21.21.21.21.21.21.21.21.21.21.21.2Photopolymerization initiator(D)(D)0.30.30.30.30.30.30.30.30.30.30.30.30.30.30.3Solvent (E)(E)4040404040404040404040Additive(F)(F)0.10.10.10.10.10.10.10.10.10.10.10.1

[0391] (Unit: weight%) Comparative example 1234 Colorant (A) (a1-1) 8.3 16.5 22 (a1-2) (a1-3) (a1-4) (a1-5) (a1-6) (a2) 33 30.2 (a3) ​​11 16.5 16.5 (a4) 11 16.5 (a5) (a6) (a7) 38.5 Alkali-soluble resin (B) (B) 3.4 3.4 3.4 3.4 3.4 Photopolymerizable compound (C) (C) 1.2 1.2 1.2 1.2 Photopolymerization initiator (D) (D) 0.3 0.3 0.3 0.3 Solvent (E) (E) 40 40 40 40 Additive (F) (F) 0.1 0.1 0.1 0.1

[0392] a1-1: Azo compound dispersion according to Manufacturing Example 1 (pigment content 15 wt%, solid content 22 wt%)

[0393] a1-2: Azo compound dispersion according to Manufacturing Example 2 (pigment content 15 wt%, solid content 22 wt%)

[0394] a1-3: Azo compound dispersion according to Manufacturing Example 3 (pigment content 15 wt%, solid content 22 wt%)

[0395] a1-4: Azo compound dispersion according to Manufacturing Example 4 (pigment content 15 wt%, solid content 22 wt%)

[0396] a1-5: Azo compound dispersion according to Manufacturing Example 5 (pigment content 15 wt%, solid content 22 wt%)

[0397] a1-6: Azo compound dispersion according to Manufacturing Example 6 (pigment content 15 wt%, solid content 22 wt%)

[0398] a2: Blue colorant (CI Pigment Blue 16, pigment content 15 wt%, solid content 22 wt%)

[0399] a3: Orange colorant (CI Pigment Orange 64, pigment content 15 wt%, solid content 22 wt%)

[0400] a4: Purple colorant (CI Pigment Violet 23, pigment content 15 wt%, solid content 22 wt%)

[0401] a5: Red colorant (CI Pigment Red 254, pigment content 15 wt%, solid content 22 wt%)

[0402] a6: Green colorant (CI Pigment Green 58, pigment content 15 wt%, solid content 22 wt%)

[0403] a7: Black colorant (lactam black, pigment content 15 wt%, solid content 22 wt%)

[0404] B: Alkali-soluble resin of Synthesis Example 2 (solid content 38.4 wt%)

[0405] C: Ethoxylated pentaerythritol tetraacrylate (NK ESTER ATM-4E, SHIN-NAKAMURA CHEMICAL CO.,LTD.)

[0406] D: Irgacure OXE-01 (BASF Korea Co., Ltd.)

[0407] E: PGMEA (Propylene glycol methyl ether acetate, KH NEOCHEM CO., LTD.)

[0408] F: SH-8400 (Dow Corning Korea) (solids content 10 wt%)

[0409]

[0410] Experimental Example 1:

[0411] Using the infrared-transmitting photosensitive resin compositions manufactured in the above examples and comparative examples, the visible light and infrared transmittance and pattern characteristics were measured by the following methods, and the results are shown in Table 3 below.

[0412]

[0413] (1) Measurement of visible light and infrared transmittance

[0414] In a clean room at 23°C, the infrared-transmitting photosensitive resin compositions obtained in the above examples and comparative examples were applied by spin coating on the surface of a 4-inch glass wafer, and then dried at 100°C for 90 seconds to volatilize volatile components to form a photosensitive resin composition layer. The substrate on which the photosensitive resin composition layer was formed was cooled to 23°C and then exposed using MA6. The substrate on which the exposed coating film was formed was developed with a 0.2 wt% tetramethylammonium hydroxide (TMAH) aqueous solution, and then heated (post-baked) at 220°C for 180 seconds to form a coating film. The thickness of the obtained coating films was all 0.5 μm. The transmittance of the manufactured substrate in the wavelength range of 300 to 1100 nm was measured at 1 nm intervals using a UV-Vis-NIR spectrophotometer (Cary5000, Agilent).

[0415]

[0416] (2) Pattern characteristic evaluation

[0417] In a clean room at 23°C, the infrared-transmitting photosensitive resin compositions obtained in the above examples and comparative examples were applied by spin coating on the surface of a 6-inch silicon wafer, and then dried at 100°C for 90 seconds to volatilize volatile components to form a photosensitive resin composition layer. The wafer on which the photosensitive resin composition layer was formed was cooled to 23°C and then exposed using an i-line stepper. The wafer on which the exposed film was formed was developed with a 0.2 wt% tetramethylammonium hydroxide (TMAH) aqueous solution and then heated at 220°C for 180 seconds to form pixels. The thickness of the formed pixels was all 0.5 μm. The minimum line width (resolution) of the formed pixels was 1.0 μm. The pattern size of the formed pattern was measured using a CD-SEM, and the pattern characteristics (linearity and residue) were evaluated as follows.

[0418]

[0419] <Linearity Evaluation Criteria>

[0420] 5: All four side walls of the pattern are straight

[0421] 4: The four side walls of the pattern are substantially straight, although they include some protrusions.

[0422] 3: Some of the four side walls of the pattern are actually uneven.

[0423] 2: All four side walls of the pattern are substantially convex.

[0424] 1: Non-formation of a consistent pattern shape

[0425]

[0426] <Residue Evaluation Criteria>

[0427] 5: No residue observed between the coloring patterns

[0428] 4: Residue distribution between coloring patterns exceeding 0% and less than 10% of the total area

[0429] 3: Residue distribution of 10% or more but less than 20% of the total area between the coloring patterns

[0430] 2: Residue distribution of 20% or more but less than 30% of the total area between the coloring patterns

[0431] 1: Residue distribution of more than 30% of the total area between the coloring patterns

[0432]

[0433] Transmittance (%) pattern characteristics T max (400-700)T min (900) Linearity Residue Example 13.195.455 Example 23.295.254 Example 33.595.555 Example 43.295.945 Example 52.995.654 Example 62.696.255 Example 74.592.444 Example 81.995.755 Example 96.894.545 Example 109.790.555 Example 116.595.344 Comparative Example 122.290.545 Comparative Example 211.388.533 Comparative Example 328.391.712 Comparative Example 464.291.832

[0434] As shown in Table 3 above, it was confirmed that the infrared-transmitting photosensitive resin compositions of Examples 1 to 11 containing the azo compound represented by the above-described chemical formula 1, the blue colorant, and the purple colorant as colorants had a transmittance of 10% or less in the range of 400 to 700 nm at a film thickness of 0.5 ㎛, a transmittance of 90% or more at 900 nm or more, and excellent linearity and residue characteristics of the pattern. On the other hand, it was confirmed that the infrared-transmitting photosensitive resin compositions of Comparative Examples 1 to 4 not containing at least one of the above-described azo compound represented by the above-described chemical formula 1 had a transmittance of more than 10% in the range of 400 to 700 nm at a film thickness of 0.5 ㎛, a transmittance of less than 90% at 900 nm or poor linearity or residue characteristics of the pattern.

[0435]

[0436] 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.

[0437] Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims

1. An infrared-transmitting photosensitive resin composition comprising a coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, The above colorant is an infrared-transmitting photosensitive resin composition comprising an azo compound represented by the following chemical formula 1, a blue colorant, and a purple colorant: [Chemical Formula 1] (In chemical formula 1, L 1 is a group represented by formula (ph1), A is a group represented by formula (ia), and B is a group represented by formula (ib). (In equation (ph1), X 1 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -NH2, -CONH2, -COOH, -CN, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a halogen atom, and -CH2- contained in the hydrocarbon group may be substituted with -O-, -CO-, or -NH-, and -CH= contained in the hydrocarbon group may be substituted with -N=. n represents an integer from 0 to 4. If n is an integer greater than 2, multiple X 1 may be the same or different. n is an integer greater than or equal to 2, and also X 1 If it is bonded to an adjacent carbon atom, X bonded to the adjacent carbon atom 1 They can combine with each other to form rings. * indicates the number of combinations with A, and ** indicates the number of combinations with B.) (In equations (ia) and (ib), X 6 ~X 9 Each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be substituted with -O-, -CO- or -NH-, -CH= contained in the hydrocarbon group may be substituted with -N=, -CH< contained in the hydrocarbon group may be substituted with -N<, and an oxygen atom, a nitrogen atom or a carbonyl group may be inserted between the carbon atoms constituting the hydrocarbon group. X 6 and X 7 can be combined with each other to form a ring, and X 8 and X 9 They may be combined with each other to form a ring. * is L 1 ) indicates the number of combinations with 2. In paragraph 1, Above L 1 A photosensitive resin composition having an infrared transmission property, represented by the formula (ph2): (In equation (ph2), X 2 ~X 5 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -NH2, -CONH2, -COOH, -CN, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or a halogen atom. X 2 Wow X 3 And X 4 Wow X 5 They can be combined with each other to form a ring. * indicates the number of combinations with A, and ** indicates the number of combinations with B.) 3. In paragraph 1, An infrared-transmitting photosensitive resin composition, wherein the azo compound represented by the chemical formula 1 is contained in an amount of 5 to 40 wt%, the blue colorant is contained in an amount of 30 to 70 wt%, and the purple colorant is contained in an amount of 5 to 30 wt%, based on 100 wt% of the total colorant.

4. In paragraph 1, The above colorant is an infrared-transmitting photosensitive resin composition further comprising an orange colorant.

5. In paragraph 1, The above colorant is an infrared-transmitting photosensitive resin composition further comprising a black colorant.

6. An infrared-transmitting pixel formed using an infrared-transmitting photosensitive composition according to any one of claims 1 to 5.

7. In paragraph 6, An infrared transmitting pixel having a transmittance of 10% or less in the range of 400 to 700 nm and a transmittance of 90% or more in the range of 900 nm or more at a film thickness of 0.5 ㎛.

8. A color filter array comprising an infrared transmitting pixel according to Article 6.

9. An image sensor comprising a color filter array according to Article 8.

10. A lidar sensor comprising an infrared transmitting pixel according to Article 6.

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