Photosensitive resin composition, photosensitive resin layer and color filter using the same

Abstract

The present invention discloses a photosensitive resin composition, a photosensitive resin layer manufactured using the photosensitive resin composition, and a color filter including the photosensitive resin layer. The photosensitive resin composition includes: (A) a binder resin including an acryl-based binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant including a phthalocyanine dye; and (E) a solvent, wherein the acryl-based binder resin includes a structural unit represented by Chemical Formula 2, the acryl-based binder resin further includes at least one structural unit selected from the group consisting of Chemical Formula 1 and Chemical Formula 3, and the acryl-based binder resin includes 5 wt % to 25 wt % of the structural unit represented by Chemical Formula 2 based on the total amount of solids constituting the acryl-based binder resin.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2020-0108055 filed in the Korean Intellectual Property Office on August 26, 2020, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to a photosensitive resin composition, a photosensitive resin layer manufactured using the photosensitive resin composition, and a color filter including the photosensitive resin layer. Background Art

[0004] Among many types of displays, liquid crystal display devices have advantages in brightness, thinness, low cost, low operating power consumption, and improved adhesion to integrated circuits, and have been more widely used in laptop computers, monitors, and TV screens. The liquid crystal display device includes: a lower substrate on which a black matrix, 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 the ITO pixel electrode are formed.

[0005] A color filter is formed in a pixel area by sequentially stacking a plurality of color filters (generally, formed of a plurality of colors (usually three primary colors of red (R), green (G) and blue (B)) in a predetermined order to form each pixel, and a black matrix layer is placed in a predetermined pattern on a transparent substrate to form a boundary between pixels.

[0006] The pigment dispersion method, which is one of the methods for forming a color filter, provides a color film by repeating a series of processes such as coating a photopolymerizable composition containing a colorant on a transparent substrate containing a black matrix, exposing the formed pattern to light, removing unexposed portions with a solvent, and thermally curing the same.

[0007] The colored photosensitive resin composition used to manufacture a color filter according to the pigment dispersion method generally contains a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a colorant, a solvent, and other additives. The pigment dispersion method having such characteristics is actively used to manufacture LCDs for mobile phones, laptop computers, monitors, and TVs.

[0008] However, in recent years, even in the photosensitive resin composition for color filters using the pigment dispersion method having various advantages, there are still various problems, such as the need for a powder refinement process, the need for additives for stable dispersion, and the difficulty in storage and transportation of the pigment dispersion. That is, although the pigment has excellent processability, there is still a limit to finely dispersing the pigment particles that affect brightness improvement. In recent years, it also serves as a cause of ACC failure, which is a problem of LCD displays.

[0009] Therefore, there has been a demand for developing dyes that do not require separate refining and dispersion processes, rather than pigments.

[0010] Compared with pigment, the dye in the monomolecular state can have high solubility, high brightness and high contrast ratio. Since the dye has weaker heat resistance and durability than the pigment, it may be susceptible to the influence of the processing solvent used in the LCD panel manufacturing process. Therefore, it is limited to completely replace the pigment with the dye, and in order to solve this situation, the method such as limiting the amount of the dye or applying the epoxy adhesive resin with good chemical resistance has been used. However, if the amount of the dye in the composition is high, the developability may deteriorate, and therefore, it may not be developed or residues may be produced on the organic layer after development. Summary of the invention

[0011] The embodiment provides a photosensitive resin composition that achieves high brightness and excellent chemical resistance, improves residue characteristics on an organic layer after development, and does not cause pattern tearing.

[0012] Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.

[0013] Another embodiment provides a color filter including a photosensitive resin layer.

[0014] The embodiment provides a photosensitive resin composition, which includes: (A) a binder resin containing an acryl-based binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant containing a phthalocyanine dye; and (E) a solvent, wherein the acryl-based binder resin includes a structural unit represented by Chemical Formula 2, the acryl-based binder resin further includes at least one structural unit selected from the group consisting of Chemical Formula 1 and Chemical Formula 3, and the acryl-based binder resin includes 5 wt % to 25 wt % of the structural unit represented by Chemical Formula 2 based on the total amount of solids constituting the acryl-based binder resin.

[0015] [Chemical formula 1]

[0016]

[0017] [Chemical formula 2]

[0018]

[0019] [Chemical formula 3]

[0020]

[0021] In Chemical Formula 1 to Chemical Formula 3,

[0022] R 0 and R 1 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0023] R 2 is a substituted or unsubstituted C3 to C20 cycloalkyl group or a condensed ring of two or more C3 to C20 cycloalkane rings, and

[0024] L 1 is a substituted or unsubstituted C1 to C20 alkylene group.

[0025] The phthalocyanine dye may be included in an amount of 30 wt % or more based on the total amount of the photosensitive resin composition.

[0026] The structural unit represented by Chemical Formula 1 may be at least one selected from the structural units represented by Chemical Formula 1-1 to Chemical Formula 1-3.

[0027] [Chemical formula 1-1]

[0028]

[0029] [Chemical formula 1-2]

[0030]

[0031] [Chemical formula 1-3]

[0032]

[0033] The structural unit represented by Chemical Formula 3 may be a structural unit represented by Chemical Formula 3-1 or Chemical Formula 3-2.

[0034] [Chemical formula 3-1]

[0035]

[0036] [Chemical formula 3-2]

[0037]

[0038] In Chemical Formula 3-1 and Chemical Formula 3-2,

[0039] R 1 is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0040] The acryl-based binder resin may further include a structural unit represented by Chemical Formula 4.

[0041] [Chemical formula 4]

[0042]

[0043] In chemical formula 4,

[0044] R 1 is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and

[0045] L 2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0046] The acrylic-based binder resin may further include a structural unit represented by Chemical Formula 5.

[0047] [Chemical formula 5]

[0048]

[0049] In Chemical Formula 5,

[0050] R 3 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclyl group, or a substituted or unsubstituted C6 to C20 aryl group, and

[0051] n is an integer from 0 to 5.

[0052] The acryl-based binder resin may include a structural unit represented by Chemical Formula 1-2, a structural unit represented by Chemical Formula 1-3, a structural unit represented by Chemical Formula 2, and a structural unit represented by Chemical Formula 4, and may include the structural unit represented by Chemical Formula 2 in an amount less than the amount of the structural unit represented by Chemical Formula 4, based on the total amount of solids constituting the acryl-based binder resin.

[0053] The acryl-based binder resin may include 1 to 10 wt % of the structural unit represented by Chemical Formula 1-2, 20 to 50 wt % of the structural unit represented by Chemical Formula 1-3, 15 to 25 wt % of the structural unit represented by Chemical Formula 2, and 30 to 50 wt % of the structural unit represented by Chemical Formula 4, based on the total amount of solids constituting the acryl-based binder resin.

[0054] The acryl-based binder resin may include 15 to 25 wt % of the structural unit represented by Chemical Formula 1-1, 5 to 15 wt % of the structural unit represented by Chemical Formula 2, 25 to 35 wt % of the structural unit represented by Chemical Formula 3-1, 15 to 30 wt % of the structural unit represented by Chemical Formula 3-2, and 15 to 25 wt % of the structural unit represented by Chemical Formula 5, based on the total amount of solids constituting the acryl-based binder resin.

[0055] The acryl-based binder resin may have a weight average molecular weight of about 10,000 g / mol to about 20,000 g / mol.

[0056] The phthalocyanine dye can be represented by Chemical Formula 6.

[0057] [Chemical formula 6]

[0058]

[0059] In Chemical Formula 6,

[0060] R 4 to R 11 are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryloxy group,

[0061] R 12 to R 19 are each independently a hydrogen atom, and

[0062] R 4 to R 7 At least one of R 8 to R 11 At least one of them is independently represented by Chemical Formula 7,

[0063] [Chemical formula 7]

[0064]

[0065] Among them, in chemical formula 7,

[0066] R 20 and R 21 are each independently a C1 to C10 alkyl group which may be substituted with or without a C1 to C5 alkyl group, and

[0067] o and p are each independently an integer from 0 to 5, provided that 1≤op≤5.

[0068] In Chemical Formula 6, R 6 and R 9 can be independently represented by Chemical Formula 7, and R 4, R 5 , R 7 , R 8 , R 10 and R 11 Each may independently be a halogen atom.

[0069] The colorant may further comprise green and yellow pigments.

[0070] The photosensitive resin composition may include 1 wt % to 10 wt % of (A) a binder resin, 1 wt % to 10 wt % of (B) a photopolymerizable monomer, 0.1 wt % to 5 wt % of (C) a photopolymerization initiator, 30 wt % to 65 wt % of (D) a colorant, and 20 wt % to 60 wt % of (E) a solvent, based on the total amount of the photosensitive resin composition.

[0071] The photosensitive resin composition may further include an additive of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.

[0072] Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.

[0073] Another embodiment provides a color filter including a photosensitive resin layer.

[0074] Other embodiments of the invention are included in the detailed description below.

[0075] When a color filter pattern is manufactured while using a substantially conventional process, the photosensitive resin composition according to the embodiment can achieve excellent brightness and chemical resistance, and can improve the organic layer (SiN x ) and may not cause pattern tearing. BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Figure 1 is used to determine the organic layer (SiN x ) on an optical microscope photograph of the residue characteristics.

[0077] Figure 2 is used to determine the organic layer (SiN x ) on an optical microscope photograph of the residue characteristics.

[0078] Figure 3 is used to determine the organic layer (SiN x ) on an optical microscope photograph of the residue characteristics.

[0079] Figure 4 and Figure 5 is an optical micrograph of a pattern obtained by using the photosensitive resin composition according to Example 1.

[0080] Figure 6 and Figure 7 is an optical micrograph of a pattern obtained by using the photosensitive resin composition according to Comparative Example 2. DETAILED DESCRIPTION

[0081] Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, and the present invention is not limited thereto and the present invention is defined by the scope of the claims.

[0082] As used herein, when no specific definition is otherwise provided, "substituted" refers to replacing at least one hydrogen of a functional group of the present invention by at least one substituent selected from the group consisting of 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 ), where R 200 , R 201 and R 202 The invention also includes the following: (i) an alkyl group, ...

[0083] 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.

[0084] As used herein, when a specific definition is not otherwise provided, the term "hetero" means that at least one heteroatom selected from N, O, S and P is included in a chemical formula.

[0085] As used herein, when a 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”.

[0086] In the chemical formulae of the present specification, unless a specific definition is otherwise provided, when a chemical bond is not drawn at a position where it should be given, hydrogen bonds are formed at the position.

[0087] As used herein, when a specific definition is not otherwise provided, an “ethylenically unsaturated double bond” refers to a “carbon-carbon double bond”, and an ethylenically unsaturated monomer refers to a monomer containing an ethylenically unsaturated double bond.

[0088] As used herein, when a specific definition is not otherwise provided, "*" indicates a point of bonding to the same or different atoms or chemical formulas.

[0089] The photosensitive resin composition according to an embodiment includes: (A) a binder resin including an acryl-based binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant including a phthalocyanine dye; and (E) a solvent, wherein the acryl-based binder resin includes a structural unit represented by Chemical Formula 2, the acryl-based binder resin further includes at least one structural unit selected from the group consisting of Chemical Formula 1 and Chemical Formula 3, and the acryl-based binder resin includes 5 wt % to 25 wt % of the structural unit represented by Chemical Formula 2 based on the total amount of solids constituting the acryl-based binder resin.

[0090] [Chemical formula 1]

[0091]

[0092] [Chemical formula 2]

[0093]

[0094] [Chemical formula 3]

[0095]

[0096] In Chemical Formula 1 to Chemical Formula 3,

[0097] R 0 and R 1 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0098] R 2 is a substituted or unsubstituted C3 to C20 cycloalkyl group or a condensed ring of two or more C3 to C20 cycloalkane rings, and

[0099] L 1is a substituted or unsubstituted C1 to C20 alkylene group.

[0100] As described above, the color filter manufactured by using the pigment type photosensitive resin composition has limitations in brightness and contrast ratio due to the pigment particle size. In addition, the color image sensor device for the image sensor requires a smaller dispersed particle diameter to form a fine pattern. In order to meet the requirements, attempts have been made to achieve color filters with improved brightness and contrast ratio by introducing non-particle-forming dyes instead of pigments to prepare photosensitive resin compositions suitable for dyes.

[0101] Therefore, in the case where the photosensitive resin composition is used for a green filter, a general method for improving brightness is to improve the color characteristics of the green dye, which does not mean that in addition to brightness, heat resistance properties, chemical resistance properties, residue properties, and pattern properties, etc. are not improved together, and thus there has been a demand for a photosensitive resin composition for a (green) filter that can continuously maintain stable pattern processability and high brightness characteristics. In addition, as the content of the dye increases, the residue problem on the organic layer after development tends to become more serious.

[0102] Therefore, the inventors have tried many times to find a pigment with improved brightness characteristics and patternability, but could not ensure the effect of improving brightness and patternability by any novel pigment. Therefore, when a high content of green phthalocyanine dye is used, it may be mixed with a binder resin having a specific structure to obtain a high brightness green photoresist, and at the same time, it can be ensured that the organic layer (SiN x ) to develop a photosensitive resin composition having excellent properties and patternability onto the residue on the organic layer.

[0103] Hereinafter, each component is described in detail.

[0104] (A) Binder resin

[0105] Specifically, the photosensitive resin composition according to the embodiment includes an acryl-based binder resin including "a structural unit represented by Chemical Formula 2" and simultaneously including "a structural unit represented by Chemical Formula 1" and / or "a structural unit represented by Chemical Formula 3", and includes the structural unit represented by Chemical Formula 2 in an amount of 5 wt % to 25 wt % based on the total amount of solids constituting the acryl-based binder resin, and thus even if the dye in the composition is included at a high content, it is possible to very neatly solve the phenomenon of residues on the organic layer after development.

[0106] For example, the structural unit represented by Chemical Formula 1 may be at least one selected from the structural units represented by Chemical Formula 1-1 to Chemical Formula 1-3.

[0107] [Chemical formula 1-1]

[0108]

[0109] [Chemical formula 1-2]

[0110]

[0111] [Chemical formula 1-3]

[0112]

[0113] For example, the structural unit represented by Chemical Formula 2 can be used to increase the acid value of the photosensitive resin composition. When the acrylic binder resin is composed of the above composition, the acid value can be imparted to the acrylic binder resin and the effect of improving the developability can be achieved at the same time, and thus, regardless of the high dye content in the composition, the pattern tearing does not occur while maintaining the excellent residue characteristics on the organic layer. In the composition of the acrylic binder resin as described above, when the structural unit represented by Chemical Formula 2 is included in an amount of less than 5% by weight based on the total amount of solids constituting the acrylic binder resin, the residue characteristics on the organic layer cannot be improved, but when the structural unit represented by Chemical Formula 2 is included in an amount of more than 25% by weight based on the total amount of solids constituting the acrylic binder resin, the pattern tearing phenomenon may seriously occur.

[0114] For example, the structural unit represented by Chemical Formula 3 may be a structural unit represented by Chemical Formula 3-1 or Chemical Formula 3-2.

[0115] [Chemical formula 3-1]

[0116]

[0117] [Chemical formula 3-2]

[0118]

[0119] In Chemical Formula 3-1 and Chemical Formula 3-2,

[0120] R 1 is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

[0121] For example, the acrylic-based binder resin may further include a structural unit represented by Chemical Formula 5.

[0122] [Chemical formula 5]

[0123]

[0124] In Chemical Formula 5,

[0125] R3 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclyl group, or a substituted or unsubstituted C6 to C20 aryl group, and

[0126] n is an integer from 0 to 5.

[0127] For example, the acryl-based binder resin may include 15 to 25 wt % of the structural unit represented by Chemical Formula 1-1, 5 to 15 wt % of the structural unit represented by Chemical Formula 2, 25 to 35 wt % of the structural unit represented by Chemical Formula 3-1, 15 to 30 wt % of the structural unit represented by Chemical Formula 3-2, and 15 to 25 wt % of the structural unit represented by Chemical Formula 5, based on the total amount of solids constituting the acryl-based binder resin.

[0128] For example, the acrylic-based binder resin may further include a structural unit represented by Chemical Formula 4.

[0129] [Chemical formula 4]

[0130]

[0131] In chemical formula 4,

[0132] R 1 is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and

[0133] L 2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

[0134] Even when the content of the dye is high, the structural unit represented by Chemical Formula 4 may realize a photosensitive resin composition having high brightness and excellent chemical resistance by imparting thermosetting properties to the acryl-based binder resin.

[0135] For example, the acryl-based binder resin may include a structural unit represented by Chemical Formula 1-2, a structural unit represented by Chemical Formula 1-3, a structural unit represented by Chemical Formula 2, and a structural unit represented by Chemical Formula 4, wherein the structural unit represented by Chemical Formula 2 may be included in an amount less than the amount of the structural unit represented by Chemical Formula 4, based on the total amount of solids constituting the acryl-based binder resin.

[0136] For example, the acryl-based binder resin may include 1 to 10 wt % of the structural unit represented by Chemical Formula 1-2, 20 to 50 wt % of the structural unit represented by Chemical Formula 1-3, 15 to 25 wt % of the structural unit represented by Chemical Formula 2, and 30 to 50 wt % of the structural unit represented by Chemical Formula 4, based on the total amount of solids constituting the acryl-based binder resin.

[0137] When the composition of the acrylic binder resin is the same as above, the photosensitive resin composition including the composition has excellent brightness and chemical resistance, and can maintain excellent residue characteristics on the organic layer after development despite high dye content. In addition, the occurrence of pattern tearing phenomenon can be prevented as much as possible.

[0138] The acryl-based binder resin may have a weight average molecular weight of 10,000 to 20,000 g / mol. For example, when the acryl-based binder resin includes structural units represented by Chemical Formulas 1 to 3 and 5, it may have a weight average molecular weight of 10,000 to 13,000 g / mol. When the acryl-based binder resin includes structural units represented by Chemical Formulas 1, 2, and 4, the acryl-based binder resin may have a weight average molecular weight of 14,000 to 20,000 g / mol. When the weight average molecular weight of the acryl-based binder resin is within the above range, the photosensitive resin composition may have excellent physical and chemical properties, appropriate viscosity, and excellent close contact properties with a substrate when manufacturing a color filter.

[0139] The acryl-based binder resin may have an acid value of about 110 mg KOH / g to about 130 mg KOH / g. When the acid value of the acryl-based binder resin is within the above range, the resolution of the pixel pattern may be improved.

[0140] For example, when the acryl-based binder resin consists of v and the structural unit represented by Chemical Formula 5, the photosensitive resin composition according to the embodiment may further include an epoxy-based binder resin as the binder resin in addition to the acryl-based binder resin.

[0141] The epoxy-based binder resin may help ensure dispersion stability of dyes and pigments, which will be described later, and help form pixels having a desired resolution during a development process.

[0142] When the photosensitive resin composition according to an embodiment further includes an epoxy-based binder resin, heat resistance can be improved. The epoxy-based binder resin may include, for example, phenol novolac epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin or a combination thereof, but is not limited thereto.

[0143] For example, the epoxy-based adhesive resin may be represented by Chemical Formula X.

[0144] [Chemical formula X]

[0145]

[0146] The epoxy equivalent of the epoxy-based binder resin may be 200 g / equivalent to 150 g / equivalent. When the epoxy-based binder resin having the epoxy equivalent within the above range is used, the curing degree of the formed pattern may be improved and the dye may need to be fixed in the structure in which the pattern is formed.

[0147] The acryl-based binder resin may be included in an amount greater than that of the epoxy-based binder resin.

[0148] The epoxy-based binder resin may be included in an amount of 0.1 wt % to 1 wt %, for example 0.1 wt % to 0.7 wt %, based on the total amount of the photosensitive resin composition.

[0149] For example, when the acryl-based binder resin consists of structural units represented by Chemical Formula 1, Chemical Formula 2, and Chemical Formula 4, the photosensitive resin composition according to an embodiment may further include an acrylic resin having another structure as a binder resin in addition to the acryl-based binder resin.

[0150] The binder resin may be included in an amount of 1 wt % to 10 wt %, for example, 3 wt % to 10 wt %, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, brightness, heat resistance, and developability when manufacturing a color filter are improved, and crosslinking properties are improved to obtain excellent surface smoothness.

[0151] (D) Colorant

[0152] The photosensitive resin composition according to an embodiment includes a phthalocyanine dye as a colorant, and the phthalocyanine dye may be represented by Chemical Formula 6 as a green dye.

[0153] [Chemical formula 6]

[0154]

[0155] In Chemical Formula 6,

[0156] R 4 to R 11 are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryloxy group,

[0157] R 12 to R 19 are each independently a hydrogen atom, and

[0158] R 4 to R 7 At least one of R 8 to R 11 At least one of them is independently represented by Chemical Formula 7,

[0159] [Chemical formula 7]

[0160]

[0161] In Chemical Formula 7,

[0162] R 20 and R 21 are each independently a C1 to C10 alkyl group which may be substituted with or without a C1 to C5 alkyl group, and

[0163] o and p are each independently an integer from 0 to 5, provided that 1≤op≤5.

[0164] The compound represented by Chemical Formula 6 has excellent green spectrum characteristics and high brightness. In addition, the compound represented by Chemical Formula 6 includes an aryloxy group represented by Chemical Formula 7, and the aryloxy group includes an alkyl group as a substituent, and the alkyl group is not substituted with an alkyl group or is substituted with an alkyl group, and thus can have excellent solubility in an organic solvent.

[0165] R 20 and R 21 Any one of them may be an unsubstituted alkyl group, and the other may be a substituent including an isopropyl group or a tert-butyl group at the terminal, such as a tert-butyl group. Thus, the solubility in an organic solvent can be increased, and the brightness can be improved.

[0166] Each of o and p may be an integer of 1. The aryloxy group represented by Chemical Formula 7 includes two alkyl groups (specifically, one unsubstituted alkyl group and one alkyl group-substituted alkyl group) which may be substituted with or without an alkyl group as a substituent, and thus, the aryloxy group may have better solubility in an organic solvent than the case of including one alkyl group as a substituent.

[0167] For example, Chemical Formula 7 can be represented by Chemical Formula 7-1.

[0168] [Chemical formula 7-1]

[0169]

[0170] In chemical formula 7-1,

[0171] R 20 is an alkyl-substituted or unsubstituted C1 to C10 alkyl group, and

[0172] R 21 is an unsubstituted C1 to C10 alkyl group.

[0173] R 20 may be present at the ortho position relative to the oxygen atom constituting the aryloxy group, and R 21 It may be present in the para position relative to the oxygen atom constituting the aryloxy group. When the alkyl substituent is present in the ortho and para positions, respectively, relative to the oxygen atom constituting the aryloxy group, this case has a favorable effect on solubility and brightness compared to other cases.

[0174] In addition, in Chemical Formula 6, R 4 to R 11 is not a hydrogen atom, and R 12 to R 19 Each is independently a hydrogen atom, and thus the photosensitive resin composition according to the embodiment may have more improved brightness and chemical resistance than the case where a phthalocyanine-based dye having a different structure is used alone.

[0175] For example, in Chemical Formula 6, R 6 and R 9 can be independently represented by Chemical Formula 7, and R 4 , R 5 , R 7 , R 8 , R 10 and R 11 Each may independently be a halogen atom.

[0176] For example, green phthalocyanine dyes can be used in combination with auxiliary dyes.

[0177] Examples of the auxiliary dye may include triarylmethane-based dyes, anthraquinone-based dyes, benzylidene-based dyes, cyanine-based dyes, phthalocyanine-based dyes (having another structure), azaporphyrin-based dyes, indigo-based dyes, and dibenzopyran-based dyes.

[0178] The colorant may further include a green pigment (dispersion liquid) and a yellow pigment (dispersion liquid).

[0179] Can use and green dye, for example phthalocyanine green dye has the pigment of excellent compatibility as yellow pigment dispersion liquid.For example, yellow pigment dispersion liquid can have 20 milligrams of potassium hydroxide / gram to 60 milligrams of potassium hydroxide / gram amine value.In general, yellow pigment dispersion liquid has 100 milligrams of potassium hydroxide / gram to 120 milligrams of potassium hydroxide / gram amine value.When the amine value of yellow pigment dispersion liquid is limited as described above (limited to have amine value lower than conventional amine value), maximize the compatibility with aforementioned green dye, and can greatly improve brightness.

[0180] Since the colorant has the above composition, the photosensitive resin composition according to the embodiment may achieve high brightness.

[0181] Examples of the yellow pigment may be CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 53, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 99, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 167, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 199, CI Pigment Yellow 215, CI Pigment Yellow 231, and the like.

[0182] Examples of the green pigment may include green pigments CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 62, and the like.

[0183] The pigment may be used alone or in admixture of two or more, but is not limited thereto.

[0184] The pigment dispersion may include a pigment, a dispersant, and a dispersing resin. For example, the pigment dispersion may further include a solvent.

[0185] The solvent of the pigment dispersion may be ethylene glycol acetate, ethyl glycol ethyl ether, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc., and is desirably propylene glycol methyl ether acetate.

[0186] The dispersant helps to evenly disperse the pigment, and may include a nonionic dispersant, an anionic dispersant, or a cationic dispersant. Specific examples may be polyalkylene glycol or its ester, polyoxyalkylene, polyol ester alkylene oxide addition product, alcohol alkylene oxide addition product, sulfonic acid ester, sulfonate, carboxylic acid ester, carboxylic acid salt, alkylamide alkylene oxide addition product, alkylamine, and may be used alone or in the form of a mixture of two or more.

[0187] The dispersion resin may be an acryl-based resin including a carboxyl group, and improves the stability of the pigment dispersion and the pattern properties of pixels.

[0188] The pigment may be used after pretreatment with a water-soluble inorganic salt and a wetting agent. When the pigment is used after pretreatment, the primary particle diameter of the yellow pigment may become finer.

[0189] The pretreatment may be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and then filtering and washing the kneaded pigment.

[0190] Kneading may be performed at a temperature within a range of 40° C. to 100° C., and filtering and washing may be performed by filtering the pigment after washing away the inorganic salt with water or the like.

[0191] Examples of water-soluble inorganic salts may be sodium chloride, potassium chloride, etc., but are not limited thereto. The wetting agent may uniformly mix the pigment with the water-soluble inorganic salt and pulverize it. Examples of wetting agents may include alkylene glycol monoalkyl ethers, such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, or diethylene glycol monomethyl ether; alcohols, such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol polyethylene glycol. These may be used alone or in combination of two or more.

[0192] The pigment may have an average particle diameter of 30 nm to 100 nm after kneading. When the average particle diameter of the pigment is within the above range, a fine pattern having excellent heat resistance and light resistance may be effectively formed.

[0193] Based on the total amount of the photosensitive resin composition, the colorant can be included in an amount of 30% by weight to 65% by weight. When the colorant within the above range is used, high brightness can be achieved in the desired color coordinates. For example, based on the total amount of the photosensitive resin composition, a phthalocyanine dye can be included in an amount greater than or equal to 30% by weight. In general, in the case where the photosensitive resin composition has an extremely high dye content, it is easy to cause problems such as residues on the organic layer after undeveloped or developed due to poor developability. However, in the photosensitive resin composition according to the embodiment, even if the total amount of the composition is calculated, including a dye content greater than or equal to 30% by weight, residue generation (one of the conventional problems) will not occur. This is because the acryl-based binder resin has the same composition as the composition described above.

[0194] (B) Photopolymerizable monomer

[0195] The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth)acrylic acid containing at least one ethylenically unsaturated double bond.

[0196] Since the photopolymerizable monomer has an ethylenically unsaturated double bond, it is possible to form a pattern having excellent heat resistance, light resistance, and chemical resistance by causing sufficient polymerization during light exposure in the pattern formation process.

[0197] Specific examples of the photopolymerizable monomer 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, phenolic epoxy (meth)acrylate, and the like.

[0198] 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 the bifunctional (meth)acrylate may include Aronix (Toa Synthetic Chemical Industry Co., Ltd.); KAYARAD (Nippon Kayaku Co., Ltd.); V-335 (Osaka Organic Chemical Industry Co., Ltd.) etc. Examples of trifunctional (meth)acrylates may include Aronix (Toa Synthetic Chemical Industry Co., Ltd.); KAYARAD (Nippon Kayaku Co., Ltd.); (Osaka Yuki Kayaku Kogyo Co. Ltd.), etc. These may be used alone or in admixture of two or more.

[0199] The photopolymerizable monomers may be treated with anhydrides to improve developability.

[0200] The photopolymerizable monomer may be included in an amount of 1 wt % to 10 wt % based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, curing occurs sufficiently during exposure during pattern formation to provide excellent reliability and excellent developability by an alkaline developer.

[0201] (C) Photopolymerization initiator

[0202] The photopolymerization initiator may include acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, and the like.

[0203] 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.

[0204] Examples of benzophenone compounds may include benzophenone, benzoylbenzoic acid, benzoylbenzoic acidmethyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

[0205] Examples of the thioxanthone-based compound may include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

[0206] Examples of the benzoin-based compound may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

[0207] Examples of triazine compounds may 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-(naphthol 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol 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.

[0208] Examples of oxime compounds may include O-acyloxime compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetoxiime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-hydroxyamino-1-phenylpropan-1-one, and the like. Specific examples of O-acyloxime compounds may include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octan-1-one oxime-O-acetate, 1-(4-phenylthiophenyl)-butan-1-one oxime-O-acetate, and the like.

[0209] In addition to the above compounds, the photopolymerization initiator may include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, and the like.

[0210] The photopolymerization initiator may be used together with a photosensitizer capable of causing a chemical reaction by absorbing light and becoming an excited state and then transferring its energy.

[0211] Examples of the photosensitizer may include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

[0212] The photopolymerization initiator may be included in an amount of 0.1 wt % to 5 wt % based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, excellent reliability may be ensured due to sufficient curing during exposure during pattern formation, and transmittance degradation may be prevented due to the non-reactive initiator.

[0213] (E) Solvent

[0214] The solvent may be a material having compatibility with the binder resin, the photopolymerizable monomer, the photopolymerization initiator, and the colorant but not reacting therewith.

[0215] Examples of the solvent may include: alcohols such as methanol, ethanol, etc.; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran, etc.; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, etc.; ethylene glycol ethyl acetate ethers such as methyl ethylene glycol ethyl acetate ether, ethyl ethylene glycol ethyl acetate ether, diethyl ethylene glycol ethyl acetate ether, 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 methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl n-acetone, methyl n-butyl ketone, methyl n-pentanone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; alkyl lactates, such as methyl lactate, ethyl lactate, etc.; alkyl hydroxyacetates, such as methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, etc.; alkoxyalkyl acetates, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, etc.; 3-hydroxyalkyl propionates, such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc.; 3-alkoxyalkyl propionic acid Esters, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; 2-hydroxyalkyl propionates, such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc.; 2-alkoxyalkyl propionates, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-hydroxy-2-methylalkyl propionates, such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, etc.; 2-alkoxy-2-methylalkyl propionates, such as methyl 2-methoxy-2-methylpropionate, methyl 2-ethoxy-2- ethyl methylpropionate, etc.; esters such as 2-hydroxyethylpropionate, 2-hydroxy-2-methylethylpropionate, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutyrate, etc.; or ketoesters such as ethyl pyruvate, etc., 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, ethylene glycol ethyl ether phenyl acetate, etc. These may be used alone or in a mixture of two or more.

[0216] In view of miscibility and reactivity, it is desirable to use: glycol ethers, such as ethylene glycol monoethyl ether, etc.; ethylene glycol alkyl ether acetates, such as ethylene glycol ethyl ether ethyl acetate, etc.; esters, such as 2-hydroxyethyl propionate, etc.; diethylene glycol, such as diethylene glycol monomethyl ether, etc.; propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc.

[0217] The solvent is used in a balance amount, for example, 20 to 60 wt % based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, a coating film having excellent applicability of the photosensitive resin composition and excellent flatness may be obtained.

[0218] (F) Other additives

[0219] The photosensitive resin composition may further include other additives such as malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a fluorine-based surfactant, a free radical polymerization initiator, or a combination thereof, in order to prevent stains or spots during coating, improve leveling properties, or prevent the generation of residues due to non-development.

[0220] Examples of the silane coupling agent may be trimethoxysilylbenzoic acid, γ-methacryloylpropoxytrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-epoxycyclohexylethyltrimethoxysilane, etc. These may be used alone or in a mixture of two or more.

[0221] Examples of fluorine-based surfactants include commercially available fluorine-based surfactants, such as and (BM Chemie Inc.); MEGAFACE F F F and F (Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORAD FULORAD FULORAD and FULORAD (Sumitomo 3M Co., Ltd.); SURFLON SURFLON SURFLON and SURFLON (Asahi Glass Co., Ltd.); and as well as etc. (Toray Silicone Co., Ltd.).

[0222] The amount of additives used can be controlled depending on the desired properties.

[0223] Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.

[0224] Another embodiment provides a color filter including a photosensitive resin layer.

[0225] The method of manufacturing the color filter is as follows.

[0226] The above photosensitive resin composition is coated on a glass substrate by a suitable method, such as spin coating, roll coating, spray coating, etc., to form a resin composition layer with a thickness of 0.5 μm to 10 μm.

[0227] Subsequently, the substrate having the resin composition layer is irradiated with light to form a pattern required for the color filter. As a light source for irradiation, UV, electron beam or X-ray can be used, and for example, UV in the region of 190 nanometers to 450 nanometers, specifically 200 nanometers to 400 nanometers can be irradiated. During the irradiation process, a photoresist mask can be further used. After the irradiation process is performed in this way, the resin composition layer irradiated with the light source is treated with a developing solution. At this time, the unexposed portion of the resin composition layer is dissolved to form a pattern required for the color filter. By repeating this process according to a large amount of desired pigments, a color filter having a desired pattern can be obtained. In addition, when the image pattern obtained by development in the above process is cured by heating again or by irradiation with actinic rays, crack resistance and solvent resistance can be improved.

[0228] Another embodiment provides a display device or a complementary metal-oxide semiconductor (CMOS) image sensor (CIS) including a color filter.

[0229] Hereinafter, the present invention is described in more detail with reference to examples. However, these examples should not be interpreted as limiting the scope of the present invention in any sense.

[0230] (Preparation of Acryl Binder Resin)

[0231] Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3

[0232] 7 parts by weight of AIBN (based on the total amount (100 parts by weight) of monomers for polymerization other than AIBN) as an initiator is placed in a flask equipped with a cooler and a stirring rod, and the monomers for polymerization are added thereto in sequence according to the weight % ratio shown in Table 1, and 200 parts by weight of propylene glycol monomethylether acetate (PGMEA) solvent and initiator are added thereto based on 100 parts by weight of the total weight of the monomers, and then slowly stirred under a nitrogen atmosphere. The reaction solution is heated to 85°C and stirred for 6 hours to polymerize the acryl-based binder resin. The acryl-based binder resin solution obtained in the above method has a solid concentration of 30% by weight, wherein its weight average molecular weight is reduced to the molecular weight of polystyrene, which is measured by using gel permeation chromatography (Gel Permeation Chromatography; GPC).

[0233] (Table 1)

[0234] (Unit: weight %, based on solid content)

[0235]

[0236] Synthesis Examples 6 to 10 and Comparative Synthesis Examples 4 and 5

[0237] 10 parts by weight of AIBN (based on the total amount (100 parts by weight) of monomers for polymerization other than AIBN) as an initiator is placed in a flask equipped with a cooler and a stirring rod, and the monomers for polymerization are added thereto in sequence according to the weight % ratio shown in Table 2, and 200 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) solvent and initiator are added thereto based on 100 parts by weight of the total weight of the monomers, and then slowly stirred under a nitrogen atmosphere. The reaction solution is heated to 85° C. and stirred for 6 hours to polymerize the acryl-based binder resin. The acryl-based binder resin solution obtained in the above method has a solid concentration of 30% by weight, wherein its weight average molecular weight is reduced to the molecular weight of polystyrene, which is measured by using gel permeation chromatography (GPC).

[0238] (Table 2)

[0239] (Unit: weight %, based on solid content)

[0240]

[0241] (Preparation of photosensitive resin composition)

[0242] Examples 1 to 10 and Comparative Examples 1 to 6

[0243] The photosensitive resin compositions according to Examples 1 to 10 and Comparative Examples 1 to 6 were prepared by using the components described below to have each composition shown in Table 3 and Table 4.

[0244] Specifically, after accurately measuring the content of the photopolymerization initiator, a solvent is added thereto, and then sufficiently stirred until the photopolymerization initiator is completely dissolved (30 minutes or more). Subsequently, an acrylic binder resin and a photopolymerizable monomer are sequentially added thereto, and then stirred again for about 1 hour. Next, a colorant is added thereto, and an antioxidant and other additives are added thereto, and then finally stirred for 2 hours or more, thereby preparing a photosensitive resin composition.

[0245] The components used to prepare the photosensitive resin composition are as follows.

[0246] (A) Binder resin

[0247] (A-1) Acryl-based binder resin (Synthesis Example 1)

[0248] (A-2) Acrylic Binder Resin (Synthesis Example 2)

[0249] (A-3) Acrylic Binder Resin (Synthesis Example 3)

[0250] (A-4) Acryl-based binder resin (Synthesis Example 4)

[0251] (A-5) Acrylic Binder Resin (Synthesis Example 5)

[0252] (A-6) Acryl-based binder resin (Synthesis Example 6)

[0253] (A-7) Acryl-based binder resin (Synthesis Example 7)

[0254] (A-8) Acrylic Binder Resin (Synthesis Example 8)

[0255] (A-9) Acryl-based binder resin (Synthesis Example 9)

[0256] (A-10) Acryl-based binder resin (Synthesis Example 10)

[0257] (A-11) Acrylic Binder Resin (Comparative Synthesis Example 1)

[0258] (A-12) Acrylic Binder Resin (Comparative Synthesis Example 2)

[0259] (A-13) Acrylic Binder Resin (Comparative Synthesis Example 3)

[0260] (A-14) Acryl-based binder resin (Comparative Synthesis Example 4)

[0261] (A-15) Acrylic Binder Resin (Comparative Synthesis Example 5)

[0262] (A-16) Epoxy binder resin (epoxy equivalent: 177 g / equivalent) (EHPE-3150, DAICEL CHEMICAL)

[0263] (A-17) Acrylic binder resin (NPR-5216, Miwon)

[0264] (B) Photopolymerizable monomer

[0265] (B-1) DPHA (Nippon KAYAKU)

[0266] (B-2) ABPE-20 (Shin-nakamura)

[0267] (C) Photopolymerization initiator

[0268] (C-1) SPI-03 (Samyang Corp.)

[0269] (C-2) IRG369 (BASF)

[0270] (D) Colorant

[0271] (D-1) CI Pigment Green 58 (SANYO company)

[0272] (D-2) CI Pigment Yellow 138 (Sanyo Co., Ltd.) (amine value of 20 mg KOH / g to 60 mg KOH / g)

[0273] (D-3) Phthalocyanine green dye represented by chemical formula P (Kyungin Corporation)

[0274] [Chemical formula P]

[0275]

[0276] (E) Solvent

[0277] Propylene glycol methyl ether acetate (PGMEA, Sigma-Aldrich Corporation)

[0278] (F) Other additives

[0279] Fluorinated surfactant (F-554, DIC Co., Ltd.)

[0280] (Table 3)

[0281] (Unit: weight %)

[0282]

[0283] (Table 4)

[0284] (Unit: weight %)

[0285]

[0286] Assessment 1: Color Characteristics

[0287] The photosensitive resin compositions according to Examples 1 to 10 and Comparative Examples 1 to 6 were coated at a rotation / minute (rpm) capable of presenting a predetermined thickness by using a coater (Opticoat MS-A150, Mikasa Co., Ltd.), respectively, and pre-baked on a 90° C. hot plate for 2 minutes. Subsequently, the front surface of the coated photosensitive resin composition was exposed using a high-pressure mercury lamp with a total wavelength of 365 nm under an exposure condition of 40 mJ / cm2, and then baked in an oven at 230° C. for 20 minutes to obtain a sample. The brightness of the sample was measured by using an MCPD3000 device before and after oven baking, and the results are shown in Table 5.

[0288] Assessment 2: Chemical Resistance

[0289] After immersing the sample obtained under the same conditions as in Evaluation 1 in an N-methylpyrrolidone (NMP) solution at room temperature for 10 minutes, the transmittance spectra of the samples before and after immersion were obtained by using a spectrophotometer (MCPD3000, Otsuka Electronics Co., Ltd.) and used to calculate ΔEab* according to Equation 1, and the results are shown in Table 5.

[0290] [Equation 1]

[0291] ΔEab*=√{(ΔL*) 2 +(Δa*) 2 +(Δb*) 2}

[0292] (The smaller the ΔEab* value, the better the chemical resistance)

[0293] Assessment 3: Residue Characteristics

[0294] By using the lower 1000 angstrom SiN x A red pattern substrate was prepared on the coated glass and subjected to extreme ultra violet (EUV) de-doping by using excimer UV debonding, each green photosensitive resin composition according to Examples 1 to 10 and Comparative Examples 1 to 6 was coated and developed, and the SiN x The residues on the substrate were evaluated for residues, and the results are shown in Tables 5 and Figures 1 to 3 Displayed in.

[0295] <Evaluation Criteria for Residue Characteristics on Organic Layer>

[0296] ○: No residue on the organic layer under an optical microscope

[0297] ×: There are residues on the organic layer under an optical microscope

[0298] Assessment 4: Patternability

[0299] Whether the pattern formed in the sample obtained under the same conditions as Evaluation 1 was torn or not was measured by an optical microscope with 500x zoom, and the results are shown in Tables 5 and Figures 4 to 7 Displayed in.

[0300] <Patternability Evaluation Criteria>

[0301] ○: The pattern is not torn but formed as a single outline

[0302] ×: The pattern is torn and formed into a 2-step outline

[0303] (Table 5)

[0304]

[0305] Refer to Table 5 and Figures 1 to 7 , compared with the photosensitive resin compositions according to Comparative Examples 1 to 6, the photosensitive resin compositions according to Examples 1 to 10 exhibited high brightness and excellent chemical resistance and simultaneously exhibited excellent residue characteristics and pattern characteristics on the organic layer.

[0306] Although the present invention has been described in conjunction with what are presently considered to be practical example embodiments, it should be understood that the present invention is not limited to the disclosed embodiments, but on the contrary, the present invention is intended to cover various modifications and equivalent arrangements included in the spirit and scope of the appended claims. Therefore, the foregoing embodiments should be understood as illustrative and not limiting the present invention in any way.

Claims

1. A photosensitive resin composition comprising A binder resin comprising an acryl-based binder resin; photopolymerizable monomers; Photopolymerization initiator; Colorants comprising phthalocyanine dyes; and Solvents wherein the acrylic adhesive resin comprises a structural unit represented by Chemical Formula 2, The acrylic adhesive resin further includes at least one structural unit selected from the group consisting of the structural units represented by Chemical Formula 1 and Chemical Formula 3, and The acrylic binder resin includes 5 wt % to 25 wt % of the structural unit represented by Chemical Formula 2, based on the total amount of solids constituting the acrylic binder resin: [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] in, In Chemical Formula 1 to Chemical Formula 3, R 0 and R 1 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, R 2 is a substituted or unsubstituted C3 to C20 cycloalkyl group or a condensed ring of two or more C3 to C20 cycloalkane rings, and L 1 is a substituted or unsubstituted C1 to C20 alkylene group, The phthalocyanine dye is represented by Chemical Formula 6: [Chemical formula 6] Among them, in chemical formula 6, R 4 to R 11 are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryloxy group, R 12 to R 19 are each independently a hydrogen atom, and R 4 to R 7 At least one of R 8 to R 11 At least one of them is independently represented by Chemical Formula 7, [Chemical formula 7] Among them, in chemical formula 7, R 20 and R 21 are each independently a C1 to C10 alkyl group which is unsubstituted or substituted with a C1 to C5 alkyl group, and o and p are each independently an integer from 0 to 5, provided that 1≤o+p≤5, The photosensitive resin composition comprises 30 wt % to 65 wt % of the colorant based on the total amount of the photosensitive resin composition. 2 . The photosensitive resin composition according to claim 1 , wherein the phthalocyanine dye is contained in an amount greater than or equal to 30 wt % based on the total amount of the photosensitive resin composition.

3. The photosensitive resin composition according to claim 1, wherein the structural unit represented by Chemical Formula 1 is at least one selected from the structural units represented by Chemical Formula 1-1 to Chemical Formula 1-3: [Chemical formula 1-1] [Chemical formula 1-2] [Chemical formula 1-3] 4. The photosensitive resin composition according to claim 3, wherein the structural unit represented by Chemical Formula 3 is represented by Chemical Formula 3-1 or Chemical Formula 3-2: [Chemical formula 3-1] [Chemical formula 3-2] in, In Chemical Formula 3-1 and Chemical Formula 3-2, R 1 is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

5. The photosensitive resin composition according to claim 3, wherein the acrylic binder resin further comprises a structural unit represented by Chemical Formula 4: [Chemical formula 4] in, In chemical formula 4, R 1 is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and L 2 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

6. The photosensitive resin composition according to claim 4, wherein the acrylic binder resin further comprises a structural unit represented by Chemical Formula 5: [Chemical formula 5] in, In Chemical Formula 5, R 3 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclyl group, or a substituted or unsubstituted C6 to C20 aryl group, and n is an integer from 0 to 5.

7. The photosensitive resin composition according to claim 5, wherein The acrylic adhesive resin includes the structural unit represented by Chemical Formula 1-2, the structural unit represented by Chemical Formula 1-3, the structural unit represented by Chemical Formula 2, and the structural unit represented by Chemical Formula 4, and The structural unit represented by Chemical Formula 2 is included in an amount smaller than an amount of the structural unit represented by Chemical Formula 4 based on the total amount of solids constituting the acrylic-based binder resin.

8. The photosensitive resin composition according to claim 5, wherein Based on the total amount of solids constituting the acrylic binder resin, The acrylic adhesive resin comprises 1 wt % to 10 wt % of the structural unit represented by Chemical Formula 1-2; 20 wt % to 50 wt % of the structural unit represented by Chemical Formula 1-3; 15 wt % to 25 wt % of the structural unit represented by Chemical Formula 2; as well as 30 wt % to 50 wt % of the structural unit represented by Chemical Formula 4.

9. The photosensitive resin composition according to claim 6, wherein Based on the total amount of solids constituting the acrylic binder resin, The acrylic adhesive resin comprises 15 wt % to 25 wt % of the structural unit represented by Chemical Formula 1-1; 5 wt % to 15 wt % of the structural unit represented by Chemical Formula 2; 25 wt % to 35 wt % of the structural unit represented by Chemical Formula 3-1; 15 wt % to 30 wt % of the structural unit represented by Chemical Formula 3-2; as well as 15 wt % to 25 wt % of the structural unit represented by Chemical Formula 5. 10 . The photosensitive resin composition according to claim 1 , wherein the acrylic-based binder resin has a weight average molecular weight of 10,000 to 20,000 g / mol.

11. The photosensitive resin composition according to claim 1, wherein In Chemical Formula 6, R 6 and R 9 are each independently represented by Chemical Formula 7, and R 4 , R 5 , R 7 , R 8 , R 10 and R 11 are each independently a halogen atom. 12 . The photosensitive resin composition according to claim 1 , wherein the colorant further comprises a green pigment and a yellow pigment.

13. The photosensitive resin composition according to claim 1, wherein Based on the total amount of the photosensitive resin composition, The photosensitive resin composition comprises 1 wt % to 10 wt % of said binder resin; 1 wt % to 10 wt % of said photopolymerizable monomer; 0.1 wt % to 5 wt % of the photopolymerization initiator; and 20 wt % to 60 wt % of said solvent. 14 . The photosensitive resin composition according to claim 1 , wherein the photosensitive resin composition further comprises an additive of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine-based surfactant, a free radical polymerization initiator, or a combination thereof.

15. A photosensitive resin layer produced using the photosensitive resin composition according to any one of claims 1 to 14. 16 . A color filter comprising the photosensitive resin layer according to claim 15 .

Images