Polymer, photosensitive resin composition containing the same, photosensitive resin film using the same, color filter and display device

Abstract

Provided are a polymer including a structural unit represented by a specific chemical formula, a photosensitive resin composition including the polymer, a photosensitive resin film including the photosensitive resin composition, a color filter including the photosensitive resin film, and a display device including the color filter.

Description

Technical Field

[0001] The present disclosure relates to a polymer, a photosensitive resin composition including the same, a photosensitive resin film manufactured using the photosensitive resin composition, a color filter including the photosensitive resin film, and a display device including the color filter. Background Art

[0002] Among many types of displays, liquid crystal display devices have the advantages of being light, thin, low cost, low operating power consumption, and improved adhesion to integrated circuits, and have been more widely used in laptop computers, monitors, and television screens. The liquid crystal display device includes: a lower substrate on which a light blocking layer, a color filter, and an ITO pixel electrode are formed; and an upper substrate on which an active circuit portion including a liquid crystal layer, a thin film transistor, and a capacitor layer and an ITO pixel electrode are formed. The color filter is formed in a pixel area by sequentially stacking a plurality of color filters (usually, formed of a plurality of colors (usually three primary colors of red (R), green (G), and blue (B)) in a predetermined order, and the light blocking layer is arranged on a transparent substrate in a predetermined pattern to form a boundary between pixels. Color filters are widely used in photographic devices, liquid crystal display devices (LCDs), field emission displays (FELs), light emitting displays (LEDs), etc., and their application range is rapidly expanding. In particular, recently, liquid crystal display devices have advantages of light weight, low power, low driving voltage, etc., and thus have been more variously applied recently, and therefore, color filters are considered to be one of the most important components in reproducing color tones of liquid crystal display devices.

[0003] Due to the nature of the display industry, high color reproducibility, high resolution, and obvious contrast are required, so the importance of color is emphasized in the key components of liquid crystal display devices. Since the pigments currently used for color filters have excellent properties such as heat resistance, light resistance, chemical resistance, etc., but insufficient solubility, they are dispersed and used in a particle state, and there is a disadvantage that the display may show poor colors due to insufficient color contrast and unclear light and dark. Due to this disadvantage, the need to use dyes instead of pigments is increasing. Compared with pigments, dyes have sufficient solubility and are advantageous for high color reproduction.

[0004] On the other hand, in order to use the dye for the color filter, the dye should satisfy appropriate conditions of wavelength, absorbance, transmittance, heat resistance, light resistance, chemical resistance, etc. Among red dyes, xanthene-based compounds have a high extinction coefficient and are therefore advantageous for coloring and also have excellent durability, and are therefore widely used as red dyes.

[0005] However, even if xanthene compounds are used as red dyes, since high brightness and high durability characteristics have not yet reached satisfactory levels compared with other dyes, attempts have been made to modify xanthene compounds and thereby achieve more excellent brightness and durability. Summary of the invention

[0006]

Technical issues

[0007] One embodiment provides a copolymer compound that can be used as a dye.

[0008] Another embodiment provides a photosensitive resin composition including the dye copolymer.

[0009] Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition.

[0010] Another embodiment provides a color filter including a photosensitive resin film.

[0011] Another embodiment provides a display device including a color filter.

[0012]

Technical solution

[0013] One embodiment provides a polymer including a structural unit represented by Chemical Formula 1.

[0014] [Chemical formula 1]

[0015]

[0016] In Chemical Formula 1,

[0017] R 1 and R 2 are each independently hydrogen, a halogen group, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof, and

[0018] n1 is an integer from 1 to 10.

[0019] R 1 and R 2 At least one of may be a substituted or unsubstituted C6 to C20 aryl group.

[0020] R 1 and R 2 Each independently may be a substituted or unsubstituted C6 to C20 aryl group.

[0021] The polymer may include two or more structural units represented by Chemical Formula 1.

[0022] The polymer may include a structural unit represented by Chemical Formula 2.

[0023] [Chemical formula 2]

[0024]

[0025] In chemical formula 2,

[0026] X 1 and X 2 Each independently is hydrogen, SO3 - A + , or SO2NHR 3 ,

[0027] R 3 is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

[0028] A + is a monovalent metal cation or a compound represented by Chemical Formula 3, and

[0029] n1 is an integer from 1 to 10.

[0030] [Chemical formula 3]

[0031]

[0032] In chemical formula 3,

[0033] R 4 To R 7 Each is independently hydrogen or substituted or unsubstituted C1 to C20 alkyl.

[0034] The polymer may include a functional group represented by Chemical Formula 4 at a terminal.

[0035] [Chemical formula 4]

[0036] *-(CH2) n2 -R 8

[0037] In chemical formula 4,

[0038] R 8 is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group, and

[0039] n2 is an integer from 1 to 10.

[0040] One of the two terminals of the polymer may be represented by Chemical Formula 5.

[0041] [Chemical formula 5]

[0042]

[0043] In Chemical Formula 5,

[0044] X 3 and X 4 Each independently is hydrogen, SO3 - A + , or SO2NHR 3 ,

[0045] A + is a monovalent metal cation or a compound represented by Chemical Formula 3,

[0046] R 3 is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

[0047] R 8 is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group, and

[0048] n2 is an integer from 1 to 10.

[0049] [Chemical formula 3]

[0050]

[0051] In chemical formula 3,

[0052] R 4 To R 7 Each is independently hydrogen or substituted or unsubstituted C1 to C20 alkyl.

[0053] The polymer may be represented by any one of Chemical Formula 2A to Chemical Formula 2D.

[0054] [Chemical Formula 2A]

[0055]

[0056] [Chemical formula 2B]

[0057]

[0058] [Chemical formula 2C]

[0059]

[0060] [Chemical Formula 2D]

[0061]

[0062] In Chemical Formulae 2A to 2D,

[0063] R 9 and R 10are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group,

[0064] n1 is an integer from 1 to 10,

[0065] n3 is an integer from 1 to 20,

[0066] n4 and n5 are each independently an integer from 1 to 10, provided that 2≤n4+n5≤20,

[0067] X 5 To X 7 Each independently is hydrogen, SO3 - A + , or SO2NHR 3 , the condition is X 5 and X 6 Different from each other,

[0068] A + is a monovalent metal cation or a compound represented by Chemical Formula 3, and

[0069] R 3 is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

[0070] The polymer may be represented by any one of Chemical Formulas 2-1 to 2-6.

[0071] [Chemical formula 2-1]

[0072]

[0073] [Chemical formula 2-2]

[0074]

[0075] [Chemical formula 2-3]

[0076]

[0077] [Chemical formula 2-4]

[0078]

[0079] [Chemical formula 2-5]

[0080]

[0081] [Chemical formula 2-6]

[0082]

[0083] In Chemical Formula 2-1 to Chemical Formula 2-6,

[0084] B + is [CH3(CH2) 11 ]2N + (CH3)2,

[0085] R 11 It is 2-hydroxypropyl,

[0086] n3 is an integer from 1 to 20, and

[0087] n4 and n5 are each independently an integer from 1 to 10, provided that 2≤n4+n5≤20.

[0088] The polymer may have a weight average molecular weight (Mw) of about 1,000 to about 15,000 g / mol.

[0089] The polymer may have a maximum absorbance in the wavelength range of 500 nm to 600 nm.

[0090] Another embodiment provides a photosensitive resin composition including a colorant including a red dye, wherein the red dye includes a polymer.

[0091] The photosensitive resin composition further includes a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

[0092] The binder resin may include an acrylic binder resin, a cardo-based binder resin, or a combination thereof.

[0093] The photosensitive resin composition may further include a pigment as a colorant.

[0094] The photosensitive resin composition may include 1 wt % to 50 wt % of a colorant, 1 wt % to 30 wt % of a binder resin, 1 wt % to 15 wt % of a photopolymerizable monomer, 0.01 wt % to 10 wt % of a photopolymerization initiator, and the balance of a solvent, based on the total amount of the photosensitive resin composition.

[0095] The photosensitive resin composition may further include malonic acid, 3-amino-1,2-propanediol, a silane coupling agent containing a vinyl group or a (meth)acryloyloxy group, a leveling agent, a surfactant, a free radical polymerization initiator, or a combination thereof.

[0096] Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition.

[0097] Another embodiment provides a color filter including the photosensitive resin composition.

[0098] Another embodiment provides a display device including a color filter.

[0099] Other embodiments of the invention are included in the detailed description below.

[0100]

Beneficial Effects

[0101] The polymer according to the embodiment has improved solubility, fluorescence control characteristics, and spectral consistency in an organic solvent, and thus a photosensitive resin composition including a colorant including the polymer as a constituent unit may provide a color filter having improved brightness, heat resistance, chemical resistance, and the like. DETAILED DESCRIPTION

[0102] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the present invention is not limited thereto, and the present invention is defined by the scope of the claims.

[0103] As used herein, when no specific definition is provided otherwise, "substituted" means that at least one hydrogen in the functional group of the present invention is replaced by a halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group (NH2, NH(R 200 ), or N(R 201 )(R 202 )) is replaced by at least one substituent, wherein R 200 , R 201 and R 202 are the same or different and are each independently a C1 to C10 alkyl group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group.

[0104] As used herein, when a specific definition is not otherwise provided, “alkyl” refers to a C1 to C20 alkyl group, and specifically a C1 to C15 alkyl group, “cycloalkyl” refers to a C3 to C20 cycloalkyl group, and specifically a C3 to C18 cycloalkyl group, “alkoxy” refers to a C1 to C20 alkoxy group, and specifically a C1 to C18 alkoxy group, “aryl” refers to a C6 to C20 aryl group, and specifically a C6 to C18 aryl group, “alkenyl” refers to a C2 to C20 alkenyl group, and specifically a C2 to C18 alkenyl group, “alkylene” refers to a C1 to C20 alkylene group, and specifically a C1 to C18 alkylene group, and “arylene” refers to a C6 to C20 arylene group, and specifically a C6 to C16 arylene group.

[0105] As used herein, when specific definition is not otherwise provided, “(meth)acrylate” refers to both “acrylate” and “methacrylate”, and “(meth)acrylic acid” refers to both “acrylic acid” and “methacrylic acid”.

[0106] As used herein, when no definition is otherwise provided, the term "combination" refers to mixing or copolymerization. In addition, "copolymerization" refers to block copolymerization or random copolymerization, and "copolymer" refers to block copolymerization or random copolymerization.

[0107] In the chemical formulae in the present specification, unless a specific definition is otherwise provided, hydrogen is bonded to a position where a chemical bond is not drawn (at a position where it should be given).

[0108] As used herein, when a specific definition is not otherwise provided, "*" indicates a point of attachment of the same or different atoms or chemical formulas.

[0109] One embodiment provides a polymer including a structural unit represented by Chemical Formula 1.

[0110] [Chemical formula 1]

[0111]

[0112] In Chemical Formula 1,

[0113] R 1 and R 2 are each independently hydrogen, a halogen group, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof, and

[0114] n1 is an integer from 1 to 10.

[0115] * indicates the point of attachment to another atom.

[0116] Due to the pigment particle size, the color filter manufactured by using the pigment type photosensitive resin composition has limitations in brightness and contrast. In addition, the color image sensor device used for the image sensor requires a smaller dispersed particle size to form a fine pattern. In order to meet the requirements, attempts have been made to achieve a color filter with improved brightness and contrast by introducing a dye that does not form particles instead of a pigment to prepare a photosensitive resin composition suitable for a dye.

[0117] Generally, xanthene compounds undergo charge separation, and a photosensitive resin composition including the same has low solubility in an organic solvent such as PGMEA and exhibits deteriorated durability such as heat resistance and chemical resistance, and thus, there is a limit to using xanthene compounds as a colorant in a photosensitive resin composition.

[0118] However, the compound according to the embodiment, that is, the polymer containing the structural unit represented by Chemical Formula 1 can improve solubility in organic solvents, and further, since the structural unit has a polymer structure in a polymerized form, the fluorescence control characteristics and spectral consistency can be better than those of the monomer compound. In addition, a color filter with further improved brightness and contrast can be manufactured by using a photosensitive resin composition containing the compound.

[0119] R 1 and R 2 It may be a substituted or unsubstituted C6 to C20 aryl group, for example, a C6 to C18 aryl group, a C6 to C14 aryl group, or a C6 to C10 aryl group. 1 and R 2 When it is an aromatic group such as a phenyl group, the durability of the dye can be improved, and a color filter made of a photosensitive resin composition including the same can have high brightness and high contrast.

[0120] R 1 and R 2 At least one of may be a substituted or unsubstituted C6 to C20 aryl group. 1 and R 2 At least one of them may be a substituent represented by Chemical Formula A.

[0121] [Chemical formula A]

[0122]

[0123] In chemical formula A,

[0124] Y 1 To Y 4 are each independently hydrogen or C1 to C10 alkyl,

[0125] X is SO3 - A + or SO2NHR 3 ,

[0126] R 3 is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

[0127] A + is a monovalent metal cation or a compound represented by Chemical Formula 3, and

[0128] n1 is an integer from 1 to 10;

[0129] [Chemical formula 3]

[0130]

[0131] In chemical formula 3,

[0132] R 4 To R 7 Each is independently hydrogen or substituted or unsubstituted C1 to C20 alkyl.

[0133] Here, R 1 and R 2 may be independently substituted or unsubstituted C6 to C20 aryl groups, for example, R 1 and R 2 Any of them may be a substituent represented by Chemical Formula A.

[0134] The polymer may include two or more structural units represented by Chemical Formula 1. That is, when the polymer is represented by Chemical Formula 1, it may be formed by copolymerization between different structural units.

[0135] The polymer may be a polymer including a structural unit represented by Chemical Formula 2.

[0136] [Chemical formula 2]

[0137]

[0138] In chemical formula 2,

[0139] X 1 and X 2 Each independently is hydrogen, SO3 - A + , or SO2NHR 3 ,

[0140] R 3 is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

[0141] A + is a monovalent metal cation or a compound represented by Chemical Formula 3, and

[0142] n1 is an integer from 1 to 10;

[0143] [Chemical formula 3]

[0144]

[0145] Among them, in chemical formula 3,

[0146] R 4 To R 7 Each is independently hydrogen or substituted or unsubstituted C1 to C20 alkyl.

[0147] The monovalent metal cation may be, for example, a monovalent metal cation such as Na + or K +, and is not particularly limited as long as it is capable of reacting with SO3 - Monovalent metal cations that form salts are sufficient.

[0148] R 4 To R 7 Each independently may be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl.

[0149] The polymer may include a functional group represented by Chemical Formula 4 at a terminal.

[0150] [Chemical formula 4]

[0151] *-(CH2) n2 -R 8

[0152] In chemical formula 4,

[0153] R 8 is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group, and

[0154] n2 is an integer from 1 to 10.

[0155] R 8 It may be, for example, an alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

[0156] The substituted or unsubstituted acrylate group may be represented by Chemical Formula E, for example.

[0157] [Chemical formula E]

[0158]

[0159] In chemical formula E,

[0160] R a is hydrogen or substituted or unsubstituted C1 to C10 alkyl, and

[0161] R b is a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

[0162] When R 8 When R is a substituted or unsubstituted acrylate group, 8 It may be an acrylate group such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, or the like.

[0163] Since the polymer includes the functional group represented by Chemical Formula 4 at the terminal, the light absorption characteristics of the photosensitive resin composition including the polymer may be improved. For example, when the terminal of the polymer is an alkyl group such as an ethyl group, the light absorption characteristics may be greatly improved.

[0164] One of the two terminals of the polymer may be represented by Chemical Formula 5.

[0165] [Chemical formula 5]

[0166]

[0167] In Chemical Formula 5,

[0168] X 3 and X 4 Each independently is hydrogen, SO3 - A + , or SO2NHR 3 ,

[0169] A + is a monovalent metal cation or a compound represented by Chemical Formula 3,

[0170] R 3 is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

[0171] R 8 is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group, and

[0172] n2 is an integer from 1 to 10.

[0173] [Chemical formula 3]

[0174]

[0175] In chemical formula 3,

[0176] R 4 To R 7 Each is independently hydrogen or substituted or unsubstituted C1 to C20 alkyl.

[0177] The monovalent metal cation may be, for example, a monovalent metal cation such as Na + or K + , and is not particularly limited as long as it is capable of reacting with SO3 - Monovalent metal cations that form salts are sufficient.

[0178] R 4 To R 7Each independently may be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl.

[0179] R 8 It may be, for example, an alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, or the like.

[0180] R 8 It may be an acrylate group such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, or the like.

[0181] The polymer may be represented by any one of Chemical Formula 2A to Chemical Formula 2D.

[0182] [Chemical Formula 2A]

[0183]

[0184] [Chemical formula 2B]

[0185]

[0186] [Chemical formula 2C]

[0187]

[0188] [Chemical Formula 2D]

[0189]

[0190] In Chemical Formulae 2A to 2D,

[0191] R 9 and R 10 are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group,

[0192] n1 is an integer from 1 to 10,

[0193] n3 is an integer from 1 to 20,

[0194] n4 and n5 are each independently an integer from 1 to 10, provided that 2≤n4+n5≤20,

[0195] X 5 To X 7 Each independently is hydrogen, SO3 - A + , or SO2NHR 3, the condition is X 5 and X 6 Different from each other,

[0196] A + is a monovalent metal cation or a compound represented by Chemical Formula 3, and

[0197] R 3 is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group,

[0198] That is, due to X 5 and X 6 The polymer may include two or more different monomers, each of which has different substituents.

[0199] The polymer may be a polymer represented by any one of Chemical Formulae 2-1 to 2-9, but is not limited thereto.

[0200] [Chemical formula 2-1]

[0201]

[0202] [Chemical formula 2-2]

[0203]

[0204] [Chemical formula 2-3]

[0205]

[0206] [Chemical formula 2-4]

[0207]

[0208] [Chemical formula 2-5]

[0209]

[0210] [Chemical formula 2-6]

[0211]

[0212] [Chemical formula 2-7]

[0213]

[0214] [Chemical formula 2-8]

[0215]

[0216] [Chemical formula 2-9]

[0217]

[0218] In Chemical Formula 2-1 to Chemical Formula 2-9,

[0219] B + is [CH3(CH2) 11 ]2N + (CH3)2,

[0220] R 11 It is 2-hydroxypropyl,

[0221] n3 is an integer from 1 to 20, and

[0222] n4 and n5 are each independently an integer from 1 to 10, provided that 2≤n4+n5≤20.

[0223] The weight average molecular weight (Mw) of the polymer can be 1,000 g / mol to 15,000 g / mol, for example 1,000 g / mol to 14,000 g / mol, for example 1,000 g / mol to 13,000 g / mol, for example 1,000 g / mol to 12,000 g / mol, for example 1,000 g / mol to 10,000 g / mol, for example 1,000 g / mol to 9,000 g / mol, for example 1,000 g / mol to 7,000 g / mol, for example 1,000 g / mol to / mol to 6,000g / mol, for example, 1,000g / mol to 4,000g / mol, for example, 2,000g / mol to 15,000g / mol, for example, 3,000g / mol to 15,000g / mol, for example, 4,000g / mol to 15,000g / mol, for example, 5,000g / mol to 6,000g / mol, for example, 7,000g / mol to 15,000g / mol, or for example, 8,000g / mol to 15,000g / mol, but not limited to this. When the weight average molecular weight of the polymer is outside the above range, the solubility in the solvent can be reduced. In addition, when the polymer has a weight average molecular weight (Mw) value within the above range, the brightness of the color filter manufactured using the photosensitive resin composition including it can be improved. Furthermore, when the polymer has a weight average molecular weight value within the above range and simultaneously has a butene linking group, the intensity of the peak at a wavelength of 580 nm with respect to red brightness increases, thereby further improving brightness.

[0224] Since the polymer according to the embodiment includes the structural unit represented by Chemical Formula 1, even a small amount can show a brighter color, so that when used as a colorant, a display device with excellent color characteristics, such as brightness and contrast, can be manufactured. When used as a colorant, a display device with excellent color characteristics (such as brightness and contrast) can be manufactured. For example, the dye compound represented by Chemical Formula 1 can have a maximum absorbance (λ) in the wavelength range of 500nm to 600nm. max ).

[0225] Generally, dyes are the most expensive components used in color filters. Therefore, expensive dyes may need to be used more to achieve desired effects, such as high brightness, high contrast, etc., and thus, increase the unit cost of production. However, when the polymer according to the embodiment is used as a dye in a color filter, even if used in small amounts, the polymer can achieve excellent color properties, such as high brightness, high contrast, etc. and reduce unit production costs.

[0226] Another embodiment provides a photosensitive resin composition including a colorant including a red dye, wherein the red dye includes the polymer according to an embodiment.

[0227] The polymer according to an embodiment may be used as a red dye (colorant) in a photosensitive resin composition, thereby exhibiting excellent color characteristics.

[0228] The photosensitive resin composition may further include a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent. That is, the photosensitive resin composition may include the polymer according to the embodiment as a colorant, and other binder resins, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

[0229] Hereinafter, the components will be described in detail.

[0230] Colorants

[0231] The photosensitive resin composition may further include a pigment as a colorant in addition to the polymer as a red dye.

[0232] The colorant may be included in an amount of 1 wt % to 50 wt %, such as 1 wt % to 45 wt %, such as 1 wt % to 40 wt %, such as 1 wt % to 35 wt %, such as 1 wt % to 30 wt %, such as 1 wt % to 25 wt %, such as 1 wt % to 20 wt %, such as 1 wt % to 15 wt %, or such as 1 wt % to 10 wt %, based on the total amount of the photosensitive resin composition, but is not limited thereto. When the colorant according to an embodiment is included within the above range, color reproducibility and contrast may be improved.

[0233] The pigment may include a blue pigment, a purple pigment, a red pigment, a green pigment, a yellow pigment, and the like.

[0234] Examples of the blue pigment may be CI blue pigment 15:6, CI blue pigment 15, CI blue pigment 15:1, CI blue pigment 15:2, CI blue pigment 15:3, CI blue pigment 15:4, CI blue pigment 15:5, CI blue pigment 16, CI blue pigment 22, CI blue pigment 60, CI blue pigment 64, CI blue pigment 80, or a combination thereof.

[0235] Examples of violet pigments may be CI violet pigment 1, CI violet pigment 19, CI violet pigment 23, CI violet pigment 27, CI violet pigment 28, CI violet pigment 29, CI violet pigment 30, CI violet pigment 32, CI violet pigment 37, CI violet pigment 40, CI violet pigment 42, CI violet pigment 50, or combinations thereof.

[0236] Examples of red pigments may include perylene pigments, anthraquinone pigments, azo pigments, diazo pigments, quinacridone pigments, anthracene pigments, etc. Specific examples of red pigments may include perylene pigments, quinacridone pigments, naphthol AS, silcomin pigments, anthraquinone (Sudan I, II, III, R), dianthraquinone, vis azo, benzopyran, etc.

[0237] Examples of green pigments may be halogenated phthalocyanine pigments, such as CI Pigment Green 58, CI Pigment Green 59, and the like.

[0238] Examples of the yellow pigment may include CI Pigment Yellow 139, CI Pigment Yellow 138, CI Pigment Yellow 150, and the like, and may be used alone or as a mixture of two or more.

[0239] The pigment may be included in the photosensitive resin composition in the form of a pigment dispersion.

[0240] The pigment dispersion may include a solid pigment, a solvent, and a dispersant so as to uniformly disperse the pigment in the solvent.

[0241] The pigment may be included at a solid content of 1 to 20 wt %, such as 8 to 20 wt %, such as 8 to 15 wt %, such as 10 to 20 wt %, or such as 10 to 15 wt %, based on the total amount of the pigment dispersion.

[0242] The dispersant may be a nonionic dispersant, anionic dispersant, cationic dispersant, etc. Specific examples of the dispersant may be polyalkylene glycols and esters thereof, polyoxyalkylenes, polyol ester oxyalkylene addition products, alcohol oxyalkylene addition products, sulfonic acid esters, sulfonic acid salts, carboxylates, carboxylates, alkylamide oxyalkylene addition products, alkylamines, etc., and may be used alone or as a mixture of two or more.

[0243] For example, a commercially available product for dispersants is BYK Co., Ltd.'s DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPER BYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. from Chemicals Co.; Zeneka Co.'s Solsperse5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc.; or Ajinomoto Inc.'s PB711, PB821, etc.

[0244] The dispersant may be included in an amount of 1 wt % to 20 wt % based on the total amount of the pigment dispersion. When the dispersant is included within this range, dispersion of the photosensitive resin composition is improved due to appropriate viscosity, and thus, when the photosensitive resin composition is applied to a product, optical, physical and chemical qualities may be maintained.

[0245] The solvent used to form the pigment dispersion may be ethylene glycol acetate, ethyl cellosolve, propylene glycol (mono) methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, or the like.

[0246] Binder resin

[0247] The binder resin may include an acrylic binder resin, a cardo-type binder resin, or a combination thereof. For example, the binder resin may be an acrylic binder resin.

[0248] The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin including at least one acrylic acid repeating unit.

[0249] The first ethylenically unsaturated monomer may be an ethylenically unsaturated monomer including one or more carboxyl groups, and specific examples thereof may include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

[0250] The first ethylenically unsaturated monomer may be included in an amount of 5 wt % to 50 wt %, for example 10 wt % to 40 wt %, based on the total amount of the acrylic binder resin.

[0251] The second ethylenically unsaturated monomer may include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzyl methyl ether; unsaturated carboxylic acid ester compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, benzyl(meth)acrylate, cyclohexyl(meth)acrylate, and phenyl(meth)acrylate; unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl(meth)acrylate and 2-dimethylaminoethyl(meth)acrylate; carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl(meth)acrylate; vinyl cyanide compounds such as (meth)acrylonitrile; unsaturated amide compounds such as (meth)acrylamide; these may be used alone or in combination of two or more.

[0252] Specific examples of the acrylic binder resin may be (meth) acrylic acid / benzyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene copolymer, (meth) acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc., but the present invention is not limited thereto. These may be used alone or as a mixture of two or more.

[0253] The weight average molecular weight of the acrylic binder resin may be 3,000 g / mol to 150,000 g / mol, for example, 5,000 g / mol to 50,000 g / mol, for example, 20,000 g / mol to 30,000 g / mol. When the acrylic binder resin has a weight average molecular weight within this range, the photosensitive resin composition has good physical and chemical properties, appropriate viscosity, and close contact performance with a substrate during the manufacturing process of a color filter.

[0254] The acid value of the acrylic binder resin may be 15 mgKOH / g to 60 mgKOH / g, for example 20 mgKOH / g to 50 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern may be improved.

[0255] The cardo-based binder resin may include a repeating unit represented by Chemical Formula 6.

[0256] [Chemical formula 6]

[0257]

[0258] In Chemical Formula 6,

[0259] R 12 and R 13 are each independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxyalkyl group,

[0260] R 14 and R 15 are each independently hydrogen, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and

[0261] Z 1 It is a single bond, O, CO, SO2, CR 16 R 17 、SiR 18 R 19 (Among them, R 16 To R 19 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group), or one of the linking groups represented by Chemical Formula 6-1 to Chemical Formula 6-11,

[0262] [Chemical formula 6-1]

[0263]

[0264] [Chemical formula 6-2]

[0265]

[0266] [Chemical formula 6-3]

[0267]

[0268] [Chemical formula 6-4]

[0269]

[0270] [Chemical formula 6-5]

[0271]

[0272] (In chemical formula 6-5,

[0273] R a is a hydrogen atom, an ethyl group, C2H4Cl, C2H4OH, CH2CH=CH2, or a phenyl group) [Chemical Formula 6-6]

[0274]

[0275] [Chemical formula 6-7]

[0276]

[0277] [Chemical formula 6-8]

[0278]

[0279] [Chemical formula 6-9]

[0280]

[0281] [Chemical formula 6-10]

[0282]

[0283] [Chemical formula 6-11]

[0284]

[0285] Z 2 is a dianhydride residue, and

[0286] p1 and p2 are each independently an integer of 0 to 4.

[0287] The cardo-based binder resin may include a functional group represented by Chemical Formula 7 at at least one of both ends.

[0288] [Chemical formula 7]

[0289]

[0290] In Chemical Formula 7,

[0291] Z 3 It can be represented by Chemical Formula 7-1 to Chemical Formula 7-7.

[0292] [Chemical formula 7-1]

[0293]

[0294] (In Chemical Formula 7-1, R b and R care each independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, ester, or ether)

[0295] [Chemical formula 7-2]

[0296]

[0297] [Chemical formula 7-3]

[0298]

[0299] [Chemical formula 7-4]

[0300]

[0301] [Chemical formula 7-5]

[0302]

[0303] (In Chemical Formula 7-5, R d is O, S, NH, substituted or unsubstituted C1 to C20 alkylene, C1 to C20 alkylamino, or C2 to C20 alkenylamino).

[0304] [Chemical formula 7-6]

[0305]

[0306] [Chemical formula 7-7]

[0307]

[0308] The cardo-type binder resin may include, for example, one prepared by mixing at least two of the following: a fluorene-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene, etc.; an anhydride compound such as benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, tetrahydrofurantetracarboxylic dianhydride, tetrahydrophthalic anhydride, etc.; a diol compound such as ethylene glycol, propylene glycol, polyethylene glycol, etc.; an alcohol compound such as methanol, ethanol, propanol, n-butanol, cyclohexanol, benzyl alcohol, etc.; a solvent compound such as propylene glycol methyl ethyl acetate, N-methylpyrrolidone, etc.; a phosphorus compound such as triphenylphosphine, etc.; and an amine or ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, etc.

[0309] When the cardo-based binder resin is used together with the acryl-based binder resin, a photosensitive resin composition having improved close contact force, high resolution, and high light emitting characteristics may be obtained.

[0310] The weight average molecular weight of the cardo-based binder resin may be 500 g / mol to 50,000 g / mol, for example 3,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the cardo-based binder resin is within this range, a satisfactory pattern may be formed without residues during color filter manufacturing and without loss of film thickness during development.

[0311] The cardo-based binder resin may have an acid value of about 100 mgKOH / g to about 140 mgKOH / g.

[0312] The binder resin may be included in an amount of 1 wt % to 30 wt %, such as 1 wt % to 25 wt %, such as 1 wt % to 20 wt %, such as 1 wt % to 15 wt %, such as 1 wt % to 10 wt %, such as 1 wt % to 7 wt %, such as 1 wt % to 5 wt %, based on the total amount of the photosensitive resin composition, but is not limited thereto. When the binder resin is included within the above range, excellent developability and improved crosslinking properties may be obtained when manufacturing a color filter, thereby obtaining excellent surface smoothness.

[0313] Photopolymerizable monomers

[0314] The photopolymerizable monomer may be a monofunctional ester or a polyfunctional ester of (meth)acrylic acid including at least one vinyl unsaturated double bond.

[0315] The photopolymerizable monomer has an ethylenically unsaturated double bond, and thus, can cause sufficient polymerization during light exposure in a pattern forming process and form a pattern having excellent heat resistance, light resistance, and chemical resistance.

[0316] Specific examples of the photopolymerizable monomers may include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol bis(meth)acrylate, and bis(meth)acrylate. Tetraol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylolpropane tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, and the like.

[0317] Commercially available examples of photopolymerizable monomers are as follows. Monofunctional (meth)acrylates may include Aronix (Toagosei Chemistry Industry Co., Ltd.); KAYARAD (Nippon Kayaku Co., Ltd.)); (Osaka Organic Chemical Ind., Ltd.), etc. Examples of difunctional (meth)acrylates may include Aronix (Toagosei Chemistry Industry Co., Ltd.), KAYARAD (Nippon Kayaku Co., Ltd.), (Osaka Organic Chemical Ind., Ltd.), etc. Examples of trifunctional (meth)acrylates may include: Aronix from Toagosei Chemistry Industry Co., Ltd. etc.; KAYARAD of Nippon Kayaku Co., Ltd. Osaka YukiKayaku Kogyo Co., Ltd. etc. These may be used alone or as a mixture of two or more.

[0318] The photopolymerizable monomers may be treated with anhydrides to improve developability.

[0319] The photopolymerizable compound may be included in an amount of 1 wt % to 15 wt %, for example, 1 wt % to 10 wt %, for example, 1 wt % to 7 wt %, for example, 1 wt % to 5 wt %, based on the total amount of the photosensitive resin composition, but is not limited thereto. When the photopolymerizable monomer is included within a range, the photopolymerizable monomer is sufficiently cured during exposure in a pattern forming process and has excellent reliability, and developability with respect to an alkaline developer can be improved.

[0320] Photopolymerization initiator

[0321] The photopolymerization initiator may be an initiator commonly used in a photosensitive resin composition, such as an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, or a combination thereof.

[0322] Examples of acetophenone compounds may include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

[0323] Examples of benzophenone compounds may include benzophenone, benzoyl benzoate, benzoyl methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dimethyl-2-methoxybenzophenone, and the like.

[0324] Examples of thioxanthone compounds may include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0325] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

[0326] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-phenylvinyl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxyphenylvinyl)-s-triazine, etc.

[0327] Examples of oxime compounds may be O-acyl oxime compounds, 2-(o-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyl oxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, and the like. Specific examples of O-acyl oxime compounds can be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-one oxime-O-acetate, 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate, and the like.

[0328] In addition to these compounds, the photopolymerization initiator may also include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, fluorene compounds, and the like.

[0329] The photopolymerization initiator may be used together with a photosensitizer capable of causing a chemical reaction by absorbing light and becoming excited and then transferring its energy.

[0330] Examples of the photosensitizer may include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

[0331] The photopolymerization initiator may be included in an amount of 0.01 wt % to 10 wt %, such as 0.01 wt % to 9 wt %, such as 0.01 wt % to 7 wt %, such as 0.01 wt % to 5 wt %, such as 0.01 wt % to 3 wt %, such as 1 wt % to 10 wt %, such as 3 wt % to 10 wt %, based on the total amount of the photosensitive resin composition, but is not limited thereto. When the photopolymerization initiator is included within this range, sufficient curing occurs during exposure during pattern formation, excellent reliability can be achieved, heat resistance, light resistance and chemical resistance, resolution and close contact characteristics of the pattern can be improved, and a reduction in transmittance due to a non-reactive initiator can be prevented.

[0332] Solvents

[0333] The solvent is a material having compatibility with the (dye) compound according to the embodiment, the pigment, the binder resin, the photopolymerizable monomer, and the photopolymerization initiator but not reacting therewith.

[0334] Examples of the solvent may include alcohols such as methanol, ethanol, etc.; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, tetrahydrofuran, etc.; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, etc.; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, etc.; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; ketones such as Such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-amyl ketone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactic acid alkyl esters, such as methyl lactate, ethyl lactate, etc.; oxyethyl acetate esters, such as oxymethyl acetate, oxyethyl acetate, oxybutyl acetate, etc.; alkoxyalkyl acetate esters, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, etc.; 3-oxypropionic acid alkyl esters, such as 3-oxypropionic acid methyl ester, 3-oxypropionic acid ethyl ester, etc.; 3-alkoxypropionic acid alkyl esters, such as 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, etc.; 2-oxopropionic acid alkyl esters, such as 2-oxopropionic acid methyl ester, 2-oxopropionic acid ethyl ester, 2-oxopropionic acid propyl ester, etc.; 2-alkoxy propionic acid alkyl esters, such as 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-ethoxypropionic acid ethyl ester, 2-ethoxypropionic acid methyl ester, etc.; 2-oxy-2-methylpropionic acid esters, such as 2-oxy-2-methylpropionic acid methyl ester, 2-oxy-2-methylpropionic acid ethyl ester, etc.; 2-alkoxy-2-methylpropionic acid alkyl esters, such as 2-methoxy-2-methylpropionic acid methyl ester, 2-ethoxy-2-methylpropionic acid ethyl ester, etc.; Ethyl propionate, etc.; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, etc.; ketoesters such as ethyl pyruvate, etc.; high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc.

[0335] Taking into account the compatibility and reactivity, ketones such as cyclohexanone, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, esters such as ethyl 2-hydroxypropionate, carbitols such as diethylene glycol monomethyl ether, propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate.

[0336] The solvent may be included in a balance amount, for example, 40 wt % to 90 wt % based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, since the photosensitive resin composition has appropriate viscosity, processability when manufacturing a color filter may be improved.

[0337] Other additives

[0338] The photosensitive resin composition may also include malonic acid; 3-amino-1,2-propanediol; a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, etc.; a leveling agent; a fluorine-based surfactant; a free radical polymerization initiator, etc., to prevent stains or spots during coating, improve leveling properties, or prevent residues generated due to non-development.

[0339] Examples of the silane coupling agent may be trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, and these may be used alone or in mixture of 2 or more types.

[0340] The silane-based coupling agent may be used in an amount of 0.01 parts by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane-based coupling agent is included within this range, close contact characteristics, storage capacity, and the like may be improved.

[0341] The photosensitive resin composition may further include an epoxy compound to improve close contact characteristics with a substrate.

[0342] Examples of the epoxy compound include phenol novolac epoxy compounds, tetramethylbiphenyl epoxy compounds, bisphenol A type epoxy compounds, alicyclic epoxy compounds, or combinations thereof.

[0343] The photosensitive resin composition may include the epoxy compound in an amount of 0.01 to 20 parts by weight, for example 0.1 to 10 parts by weight, based on 100 parts by weight. When the epoxy compound is included within the above range, close contact characteristics and storage capacity may be improved.

[0344] Furthermore, if necessary, the photosensitive resin composition may further include a surfactant to improve coating properties and prevent defect formation.

[0345] The surfactant may be a fluorine-based surfactant, and examples of the fluorine-based surfactant may be F-482, F-484, F-478, F-554, etc. from DIC Co., Ltd., but are not limited thereto.

[0346] The surfactant may be used in an amount of 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included within this range, excellent wetting and coating uniformity on a glass substrate may be ensured, but stains may not be generated.

[0347] In addition, the photosensitive resin composition may further include a predetermined amount of other additives such as an oxidation inhibitor, a stabilizer, etc. unless the performance is deteriorated.

[0348] According to another embodiment, a photosensitive resin film manufactured using the photosensitive resin composition according to the embodiment is provided.

[0349] According to another embodiment, a color filter including the photosensitive resin film according to the embodiment is provided.

[0350] The patterning process of the color filter is as follows.

[0351] The process includes coating the photosensitive resin composition according to the embodiment on a supporting substrate by spin coating, slit coating, inkjet printing, etc.; drying the coated positive photosensitive resin composition to form a photosensitive resin composition layer; exposing the positive photosensitive resin composition layer to light; developing the exposed positive photosensitive resin composition layer in an alkaline aqueous solution to obtain a photosensitive resin film; and heat treating the photosensitive resin film. The conditions of the patterning process are prior art and are not described in detail herein.

[0352] According to another embodiment, a display device including the color filter according to the embodiment is provided. For example, the display device may be a liquid crystal display (LCD).

[0353] Hereinafter, the present invention is described in more detail with reference to Examples. However, these Examples should not be construed as limiting the scope of the present invention in any sense.

[0354] Synthesis example: Synthesis of polymer

[0355] Synthesis Example 1: Synthesis of the polymer represented by Chemical Formula 2-1

[0356]

[0357] Acid Red 289 (1 mol) and dilauryl dimethyl ammonium bromide (1.5 mol) were added to H2O, then heated at 70°C, stirred for 24 hours, cooled to room temperature, and the organic layer was extracted therefrom with MC to obtain an intermediate. The intermediate (1 mol), 1,2-diiodoethane (1 mol) and K2CO3 (10 mol) were added to NMP (N-methylpyrrolidone), then heated at 100°C and stirred for 24 hours, and iodoethane was added thereto, and then quenched in a mixed state. Subsequently, dichloromethane was added to the solution, and then washed twice with water to extract the organic layer. The extracted organic layer was distilled under reduced pressure, then purified by column chromatography and solidified with hexane to synthesize a polymer represented by Chemical Formula 2-1.

[0358] [Chemical formula 2-1]

[0359]

[0360] GPC MS: 5,003m / z

[0361] Synthesis Example 2: Synthesis of the polymer represented by Chemical Formula 2-2

[0362]

[0363] A polymer represented by Chemical Formula 2-2 was synthesized in the same manner as in Synthesis Example 1, except that 1,4-diiodobutane was used as a linking chain instead of 1,2-diiodoethane in the reaction of Synthesis Example 1.

[0364] [Chemical formula 2-2]

[0365]

[0366] GPC MS: 5,003m / z

[0367] Synthesis Example 3: Synthesis of the polymer represented by Chemical Formula 2-3

[0368]

[0369] 3',6'-dichlorospiro[3H-2,1-benzooxathiol-3,9'-[9H]xanthene]-1,1-dioxide (1 mol), 2,6-dimethylaniline (2 mol), and ZnCl2 (1.7 mol) were placed in DMF and then stirred at room temperature for 24 hours. Subsequently, dichloromethane was added to the solution, which was then washed twice with water to extract the organic layer. The extracted organic layer was distilled under reduced pressure and solidified with hexane to obtain Intermediate 1. Then, the polymer represented by Chemical Formula 2-3 was synthesized by replacing Acid Red 289 with Intermediate 1 but performing the same method as in Synthesis Example 1.

[0370] [Chemical formula 2-3]

[0371]

[0372] GPC MS: 6,705 m / z

[0373] Synthesis Example 4: Synthesis of the polymer represented by Chemical Formula 2-4

[0374] The polymer represented by Chemical Formula 2-4 was synthesized in the same manner as in Synthesis Example 1 except that the intermediate reaction was omitted, and Acid Red 289 and ethyl methacrylate were used as the quenching material instead of ethyl iodide.

[0375] [Chemical formula 2-4]

[0376]

[0377] GPC MS: 8,550 m / z

[0378] Synthesis Example 5: Synthesis of the polymer represented by Chemical Formula 2-5

[0379] The polymer represented by Chemical Formula 2-5 was synthesized in the same manner as in Synthesis Example 3, except that 2-iodobutane was used instead of iodoethane as the quenching material in the reaction of Synthesis Example 3.

[0380] [Chemical formula 2-5]

[0381]

[0382] GPC MS: 6,502 m / z

[0383] Synthesis Example 6: Synthesis of a polymer represented by Chemical Formula 2-6

[0384] A polymer represented by Chemical Formula 2-6 was synthesized in the same manner as in Synthesis Example 3, except that 1-bromo-2-propanol was used instead of dilauryldimethylammonium bromide in the reaction of Synthesis Example 2.

[0385] [Chemical formula 2-6]

[0386]

[0387] GPC MS: 7,782 m / z

[0388] In chemical formula 2-6,

[0389] R 11 It is 2-hydroxypropyl

[0390] Synthesis Example 7: Synthesis of the polymer represented by Chemical Formula 2-7

[0391] A polymer represented by Chemical Formula 2-7 was synthesized in the same manner as in Synthesis Example 2 except that the intermediate reaction was omitted (n4 and n5 had a ratio of 1:1), and 2-iodobutane was used instead of iodoethane as a quenching material in a mixture state of Acid Red 289 and the intermediate of Chemical Formula 2-2.

[0392] [Chemical formula 2-7]

[0393]

[0394] Maldi-tof MS: 8,264m / z

[0395] Synthesis Example 8: Synthesis of the polymer represented by Chemical Formula 2-8

[0396] A polymer represented by Chemical Formula 2-8 was synthesized in the same manner as in Synthesis Example 1, except that 1,6-diiodohexane was used instead of 1,2-diiodoethane as a linking chain in the reaction of Synthesis Example 1.

[0397] [Chemical formula 2-8]

[0398]

[0399] Maldi-tof MS: 8,264m / z

[0400] Synthesis Example 9: Synthesis of the polymer represented by Chemical Formula 2-9

[0401] A polymer represented by Chemical Formula 2-9 was synthesized in the same manner as in Synthesis Example 1, except that 1,8-diiodooctane was used instead of 1,2-diiodoethane as a linking chain in the reaction of Synthesis Example 1.

[0402] [Chemical formula 2-9]

[0403]

[0404] Maldi-tof MS: 8,264m / z

[0405] Comparative Synthesis Example 1: Synthesis of Compound X

[0406]

[0407] 10 g of compound A (CAS No. 77545-45-0) was placed in a reactor and dissolved in 100 g of 2-propanol. 7.2 g of diethylamine was added thereto, and then stirred at 80° C. for 8 hours. The reactant was cooled, and 800 mL of water was added thereto to produce a precipitate. The obtained precipitate was filtered by suction and washed with water. The filtrate was dried to obtain 9.9 g (yield: 84%) of compound X.

[0408] Maldi-tof MS: 478.2m / z

[0409] Comparative Synthesis Example 2: Synthesis of Compound Y

[0410]

[0411] Acid Red 289 (1 mol) and dilauryl dimethyl ammonium bromide (1.5 mol) were added to H2O, then heated at 70°C for 24 hours, stirred, and cooled to room temperature, and an organic layer was extracted therefrom with MC to obtain an intermediate. The intermediate (1 mol), 1,12-diiododecane (1 mol) and K2CO3 (10 mol) were added to NMP (N-methylpyrrolidone), then heated to 100°C, stirred for 24 hours, and quenched by adding iodoethane thereto in a mixed state. Subsequently, dichloromethane was added to the solution, and then, the organic layer was extracted by washing with water twice. The extracted organic layer was distilled under reduced pressure, then purified by column chromatography and solidified with hexane to synthesize a polymer represented by compound Y.

[0412] Example: Synthesis of photosensitive resin composition

[0413] (Examples 1 to 9 and Comparative Examples 1 and 2)

[0414] Photopolymerization initiator is added to the solvent with each composition shown in Table 1, and the mixture is stirred at room temperature for 1 hour and dissolved therein. Then, binder resin and photopolymerization monomer are added thereto, and the mixture is stirred at room temperature for 1 hour. Other additives are added thereto, and the resultant is stirred at room temperature for 1 hour. Subsequently, the compound according to Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 and 2 (or together with red pigment) is added thereto respectively, then stirred at room temperature for 2 hours, and the solution is filtered three times to remove impurities, thereby preparing the photosensitive resin composition according to Examples 1 to 9 and Comparative Examples 1 and 2. Photosensitive resin composition is prepared by using the following components.

[0415] (A) Binder resin

[0416] (A-1) Acrylic binder resin (RY-25, Showadenko)

[0417] (A-2) Acrylic binder resin (CRG-1000S, SMS)

[0418] (B) Photopolymerizable monomer

[0419] (B-1)DPHA(Nippon KAYAKU)

[0420] (B-2)ABPE-20(Shin-nakamura)

[0421] (C) Photopolymerization initiator

[0422] (C-1)SPI-03(Samyang Corporation)

[0423] (C-2)OXE-01(Basf)

[0424] (D) Colorant

[0425] (D-1) Polymer according to Synthesis Example 1

[0426] (D-2) Polymer according to Synthesis Example 2

[0427] (D-3) Polymer according to Synthesis Example 3

[0428] (D-4) Polymer according to Synthesis Example 4

[0429] (D-5) Polymer according to Synthesis Example 5

[0430] (D-6) Polymer according to Synthesis Example 6

[0431] (D-7) Polymer according to Synthesis Example 7

[0432] (D-8) Polymer according to Synthesis Example 8

[0433] (D-9) Polymer according to Synthesis Example 9

[0434] (D-10) Monomer according to Comparative Synthesis Example 1

[0435] (D-11) Monomer according to Comparative Synthesis Example 2

[0436] (D-12) CI Pigment Red 254 (SANYO)

[0437] (E) Solvent

[0438] Propylene glycol monomethyl ether acetate (PGMEA, Sigma-Aldrich)

[0439] (F) Other additives

[0440] Fluorine surfactant (F-554, DIC Co., Ltd.)

[0441] [Table 1]

[0442] (Unit: wt%)

[0443]

[0444] Evaluation 1: Evaluation of color change before and after baking

[0445] The color characteristics of the color filter samples manufactured in Examples 1 to 9 and Comparative Examples 1 and 2 were measured by baking the color filter samples three times in a forced convection oven at 230°C for 20 minutes and comparing the color changes before and after baking using a spectrophotometer (Otsuka Electronics Co., Ltd., MCPD3000). The results are shown in Table 2.

[0446] Evaluation 2: Evaluation of luminescence characteristics

[0447] The photosensitive resin compositions according to Examples 1 to 9 and Comparative Examples 1 and 2 were coated on a 1 mm thick degreased glass substrate to a thickness of 1 μm to 3 μm, respectively, and then dried on a 90° C. hot plate for 2 minutes to obtain films. The films were prepared by using a high pressure mercury lamp having a main wavelength of 365 nm at 50 mJ / cm 2 The entire surface of each film was exposed under the conditions of . Subsequently, the film was dried in a hot air circulation drying oven at 230° C. for 20 minutes to obtain samples of the same thickness. The brightness of the pixel layer was measured by using a spectrophotometer (MCPD3000, Otsuka Electronics Co., Ltd.), and the results are shown in Table 2.

[0448] Evaluation 3: Evaluation of chemical resistance

[0449] The patterns of the color filter samples manufactured in Examples 1 to 9, Comparative Examples 1 and 2 were immersed in a 90°C NMP solution for 10 minutes, and then the PI solution chemical resistance was evaluated. The chemical resistance was evaluated by the color change of the color filter pattern before and after immersion in the NMP solution and the peeling of the color filter pattern after immersion in the stripper. The color change of the color filter pattern was measured using a spectrophotometer (Otsuka Electronics Co., Ltd., MCPD3000), and the peeling of the color filter pattern was evaluated by an optical microscope. The evaluation results are shown in Table 2.

[0450] Evaluation 4: Evaluation of heat resistance

[0451] TGA (spot) was used to evaluate the heat resistance of the dye dissolved in the photosensitive resin composition according to Examples 1 to 9 and Comparative Examples 1 and 2. Here, the experiment was conducted by setting the temperature range of 30°C to 400°C at 5°C / min under air conditions. The evaluation results are shown in Table 2.

[0452] Assessment 5: Evaluation of Fluorescence Control

[0453] The dyes of Examples 1 to 9 and Comparative Examples 1 and 2 were diluted in a solvent. Herein, the concentration thereof was set to less than 0.02 AU in UV-vis. Subsequently, the fluorescence characteristics were evaluated by using an integrating hemispherical measurement device for the solution.

[0454] The evaluation items are QY (quantum yield), FWHM (full width at half maximum), fluorescence intensity, λ_emission, other surface abnormalities, appearance problems of each process, etc. QY is an index indicating the ratio of emitted light to incident light, showing how much fluorescence is emitted. FWHM is full width at half maximum, which is measured by the width between two wavelengths of the portion corresponding to half of the maximum intensity on the emission spectrum of light, where the narrower, the better. The fluorescence intensity is measured by the value corresponding to the y-axis on the emission spectrum, and is judged as a value taking into account the thickness correction value by multiplying QY by Abs (absorbance).

[0455] [Table 2]

[0456]

[0457] Referring to Table 2, the photosensitive resin compositions of Examples 1 to 9 including the polymer (red dye) according to the embodiment exhibited excellent heat resistance, chemical resistance, and fluorescence control performance as well as excellent color characteristics such as brightness, etc., compared with the photosensitive resin compositions of Comparative Examples 1 and 2 not including the polymer.

[0458] In the above, some embodiments of the present invention have been described and shown, however, it is obvious to those skilled in the art that the present invention is not limited to the described embodiments, and various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications or changes in embodiments cannot be understood separately from the technical concepts and aspects of the present invention, and the modified embodiments are within the scope of the claims of the present invention.

Claims

1. A polymer, wherein The polymer is represented by any one of Chemical Formula 2A to Chemical Formula 2D: [Chemical Formula 2A] [Chemical formula 2B] [Chemical formula 2C] [Chemical Formula 2D] Wherein, in Chemical Formulae 2A to 2D, R 9 and R 10 are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted acrylate group, n1 is an integer from 1 to 10, n3 is an integer from 1 to 20, n4 and n5 are each independently an integer from 1 to 10, provided that 2≤n4+n5≤20, X 5 To X 7 Each independently is hydrogen, SO3 - A + , or SO2NHR 3 , the condition is X 5 and X 6 Different from each other, A + is a monovalent metal cation or a compound represented by Chemical Formula 3, and R 3 is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group, [Chemical formula 3] Wherein, in Chemical Formula 3, R 4 To R 7 Each is independently hydrogen or substituted or unsubstituted C1 to C20 alkyl.

2. The polymer according to claim 1, wherein The polymer is represented by any one of Chemical Formulas 2-1 to 2-6: [Chemical Formula 2-1] [Chemical formula 2-2] [Chemical formula 2-3] [Chemical formula 2-4] [Chemical formula 2-5] [Chemical formula 2-6] Among them, in Chemical Formula 2-1 to Chemical Formula 2-6, B + is [CH3(CH2) 11 ]2N + (CH3)2, R 11 It is 2-hydroxypropyl, n3 is an integer from 1 to 20, and n4 and n5 are each independently an integer from 1 to 10, provided that 2≤n4+n5≤20.

3. The polymer according to claim 1, wherein The weight average molecular weight (Mw) of the polymer is 1,000 g / mol to 15,000 g / mol.

4. The polymer according to claim 1, wherein The polymer has a maximum absorbance in a wavelength range of 500 nm to 600 nm.

5. A photosensitive resin composition comprising: Coloring agent containing red dye, in, The red dye comprises the polymer according to any one of claims 1 to 4.

6. The photosensitive resin composition according to claim 5, wherein The photosensitive resin composition further includes a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

7. The photosensitive resin composition according to claim 6, wherein The binder resin includes an acrylic binder resin, a cardo-based binder resin, or a combination thereof.

8. The photosensitive resin composition according to claim 5, wherein The colorants also include pigments.

9. The photosensitive resin composition according to claim 6, wherein Based on the total amount of the photosensitive resin composition, the photosensitive resin composition comprises: 1wt% to 50wt% of the colorant; 1wt% to 30wt% of the binder resin; 1 wt % to 15 wt % of the photopolymerizable monomer; 0.01 wt % to 10 wt % of the photopolymerization initiator; and The remaining amount of solvent.

10. The photosensitive resin composition according to claim 6, wherein The photosensitive resin composition further comprises malonic acid, 3-amino-1,2-propylene glycol, a silane coupling agent containing a vinyl group or a (meth)acryloyloxy group, a leveling agent, a surfactant, a free radical polymerization initiator, or a combination thereof. 11 . A photosensitive resin film manufactured using the photosensitive resin composition according to claim 5 . 12 . A color filter comprising the photosensitive resin film according to claim 11 .

13. A display device comprising the color filter according to claim 12.

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