Photosensitive resin composition and layer thereof, adhesive composition and adhesive film thereof, color filter, polarizing plate, and optical display device

Abstract

The present invention relates to a photosensitive resin composition, an adhesive composition containing a compound represented by Chemical Formula 1, a photosensitive resin layer and an adhesive film manufactured using this composition, a color filter including this photosensitive resin layer, a polarizing plate including this adhesive film, and an optical display device including this color filter and / or polarizing plate. In Chemical Formula 1, each substituent is the same as defined in the specification. The compound has the property of strongly absorbing light in a very narrow region, and thus can block the spectrum of light in the corresponding region, and can achieve blue even with a very small amount. The adhesive film and its polarizing plate manufactured using this adhesive composition can have excellent durability and color stability.

Description

[0001] This invention is a divisional application of the patent application with the application number 201811188088.9 and the invention title "Photosensitive Resin Composition and Its Layer, Adhesive Composition and Its Adhesive Film, Color Filter, Polarizing Plate and Optical Display Device" filed on October 12, 2018. Technical Field

[0002] The present disclosure relates to a photosensitive resin composition, an adhesive composition, a photosensitive resin layer manufactured using this photosensitive resin composition, an adhesive film manufactured using this adhesive composition, a color filter including this photosensitive resin layer, a polarizing plate including this adhesive film, and an optical display device including this color filter and / or polarizing plate. Background Art

[0003] Among various types of displays, liquid crystal display devices have the advantages of being light, thin, low in cost, low in operating power consumption, and having high support for integrated circuits, and have been more widely used in laptop computers, monitors, and television screens. A liquid crystal display device includes a lower substrate and an upper substrate. A black matrix (light-blocking layer), a color filter, and indium tin oxide (ITO) pixel electrodes are formed on the lower substrate, and an active circuit portion including a liquid crystal layer, thin film transistors, and a capacitor layer and ITO pixel electrodes are formed on the upper substrate.

[0004] The color filter is formed in the pixel region by sequentially stacking a plurality of color filters (generally formed of three primary colors (e.g., red (R), green (G), and blue (B))) in a predetermined order to form each pixel, and the black matrix (light-blocking layer) is disposed on the transparent substrate in a predetermined pattern to form the boundaries between the pixels.

[0005] As one method among various methods for forming a color filter, the pigment dispersion method provides a colored film by repeating a series of processes such as coating a photopolymerizable composition containing a colorant on a transparent substrate including a black matrix, exposing the formed pattern, removing the unexposed portion with a solvent, and thermally curing it. The colored photosensitive resin composition used for manufacturing a color filter according to the pigment dispersion method generally contains an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, other additives, etc. The pigment dispersion method is actively applied to manufacturing liquid crystal displays (LCDs) such as mobile phones, laptop computers, monitors, and televisions.

[0006] However, the photosensitive resin composition for a color filter using a pigment dispersion method having many advantages has some disadvantages, because it is difficult to finely pulverize the powder, various additives are still required to stabilize the dispersion even if dispersion is achieved, a complex process is needed, and it is difficult to further maintain the optimal quality of the pigment dispersion under complex storage and transportation conditions.

[0007] In addition, color filters manufactured using pigment-type photosensitive resin compositions have limitations in terms of brightness and contrast due to the pigment particle size. Color image sensor devices for image sensors require smaller dispersion particle sizes to form fine patterns. To meet this requirement, attempts have been made to prepare photosensitive resin compositions by introducing dyes instead of pigments or by introducing dyes together with pigments, thereby achieving color filters with improved color characteristics such as brightness and contrast. However, dye-type photosensitive resin compositions have problems of deteriorated durability compared to pigment-type photosensitive resin compositions.

[0008] On the other hand, a liquid crystal display (LCD) needs to include a liquid crystal cell including liquid crystal, a polarizing plate, and an appropriate adhesive layer or adhesion layer for adhering the liquid crystal cell and the polarizing plate.

[0009] In addition, the polarizing plate includes a polyvinyl alcohol (PVA)-based polarizer (or 'polarizing film') and polarizer protective films for protecting both sides of the polarizer. The PVA-based polarizer (or 'polarizing film') is elongated in a predetermined direction, and an iodine-based compound or a polarizing mineral is adsorbed and aligned therein. Specifically, one surface of the polarizer is provided with a triacetyl cellulose (TAC)-based polarizer protective film and a similar film, and an adhesive layer that adheres to the liquid crystal cell and a release film on the polarizer protective film, while the other surface of the polarizer is provided with a multilayer composed of a polarizer protective film, a substrate film provided thereon, and a surface protective film provided on the adhesion film.

[0010] During the process of adhering the polarizing plate having this structure to the liquid crystal cell, the release film is detached from the adhesive layer, and the surface protective film is also detached and removed when its role in the following process is completed. The release film and the surface protective film are formed of a plastic material and thus exhibit high insulation properties and generate static electricity during detachment.

[0011] This static electricity can cause problems such as surface contamination of the optical member due to impurities adsorbed on the optical member, stain problems due to alignment distortion of the liquid crystal, etc., and damage to the thin film transistor (TFT) circuit. In particular, since liquid crystal display (LCD) panels have recently become large-sized, the polarizing plates used for manufacturing liquid crystal displays (LCDs) tend to be large-sized even through high-speed processes, and thus the amount of static electricity generated continuously increases, making it necessary to solve the problem more urgently. SUMMARY OF THE INVENTION

[0012] Embodiments of the present invention provide a photosensitive resin composition including a compound with improved color reproducibility as a colorant.

[0013] Another embodiment provides a photosensitive resin layer manufactured using this photosensitive resin composition.

[0014] Another embodiment provides a color filter including this photosensitive resin layer.

[0015] Another embodiment provides an adhesive composition including the compound as a colorant.

[0016] Another embodiment provides an adhesive film manufactured using this adhesive composition.

[0017] Another embodiment provides a polarizing plate including this adhesive film.

[0018] Another embodiment provides an optical display device including this color filter and / or polarizing plate.

[0019] Embodiments of the present invention provide a photosensitive resin composition, the photosensitive resin composition including: (A) a colorant including a compound represented by Chemical Formula 1; (B) an adhesive resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent.

[0020] [Chemical Formula 1]

[0021]

[0022] In Chemical Formula 1,

[0023] M is Zn, Co, or Cu, and

[0024] R 1 to R 20 are independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, a sulfonic acid group, a substituted or unsubstituted sulfonamide group, or a substituted or unsubstituted C1 to C20 alkyl ester group,

[0025] The limitation is that at least one of R 1 to R 5 , at least one of R 6 to R 10 , at least one of R 11 to R 15 , and at least one of R 16 to R 20 is independently not a hydrogen atom.

[0026] The compound can be represented by Chemical Formula 2.

[0027] [Chemical Formula 2]

[0028]

[0029] In Chemical Formula 2,

[0030] M is Zn, Co or Cu,

[0031] R 21 to R 28 are independently a halogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a sulfonic acid group, a substituted or unsubstituted sulfonamide group, or a substituted or unsubstituted C1-C20 alkyl ester group,

[0032] n1 to n8 are independently integers of 0 or 1, 1 ≤ n1 + n2 ≤ 2, 1 ≤ n3 + n4 ≤ 2, 1 ≤ n5 + n6 ≤ 2, and 1 ≤ n7 + n8 ≤ 2.

[0033] The compound can be represented by one of Chemical Formulas 1-1 to 1-20.

[0034] [Chemical Formula 1-1]

[0035]

[0036] [Chemical Formula 1-2]

[0037]

[0038] [Chemical Formula 1-3]

[0039]

[0040] [Chemical Formula 1-4]

[0041]

[0042] [Chemical Formula 1-5]

[0043]

[0044] [Chemical formula 1-6]

[0045]

[0046] [Chemical formula 1-7]

[0047]

[0048] [Chemical formula 1-8]

[0049]

[0050] [Chemical formula 1-9]

[0051]

[0052] [Chemical formula 1-10]

[0053]

[0054] [Chemical formula 1-11]

[0055]

[0056] [Chemical formula 1-12]

[0057]

[0058] [Chemical formula 1-13]

[0059]

[0060] In Chemical formula 1-13,

[0061] R is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[0062] m1 and m2 are independently integers in the range of 0 to 20, and 4 ≤ m1 + m2 ≤ 20,

[0063] [Chemical formula 1-14]

[0064]

[0065] [Chemical formula 1-15]

[0066]

[0067] [Chemical formula 1-16]

[0068]

[0069] [Chemical Formula 1-17]

[0070]

[0071] [Chemical Formula 1-18]

[0072]

[0073] [Chemical Formula 1-19]

[0074]

[0075] [Chemical Formula 1-20]

[0076]

[0077] Based on the total amount of the photosensitive resin composition, the compound represented by Chemical Formula 1 may be included in an amount of 0.01% to 7% by weight.

[0078] The colorant may further include a blue dye, a blue pigment, a red dye, a red pigment, or a combination thereof.

[0079] The blue dye may be represented by Chemical Formula 3.

[0080] [Chemical Formula 3]

[0081]

[0082] In Chemical Formula 3,

[0083] R 29 and R 30 are independently a substituted C1-C20 alkyl group or a substituted or unsubstituted C3-C20 cycloalkyl group,

[0084] R 31 is a hydrogen atom or a halogen,

[0085] R 32 is a hydrogen atom or a substituted or unsubstituted C1-C20 alkyl group,

[0086] R 33 is a C1-C20 alkyl group substituted or unsubstituted with an acrylate group, and

[0087] X- is represented by one of Chemical Formulas A to C.

[0088] [Chemical Formula A]

[0089] SO3 -

[0090] [Chemical Formula B]

[0091] F3C-(CF2) n3 -SO3

[0092] (In Chemical Formula B, n3 is an integer ranging from 0 to 10)

[0093] [Chemical Formula C]

[0094]

[0095] The blue dye can be represented by Chemical Formula 3-1 or Chemical Formula 3-2.

[0096] [Chemical Formula 3-1]

[0097]

[0098] [Chemical Formula 3-2]

[0099]

[0100] In Chemical Formula 3-1 and Chemical Formula 3-2,

[0101] X- is represented by one of Chemical Formulas A to C.

[0102] [Chemical Formula A]

[0103] SO3 -

[0104] [Chemical Formula B]

[0105] F3C-(CF2) n3 -SO3

[0106] (In Chemical Formula B, n3 is an integer ranging from 0 to 10)

[0107] [Chemical Formula C]

[0108]

[0109] The blue pigment can be Color Index (C.I.) Pigment Blue 15:6.

[0110] The binder resin can include an acrylic binder resin.

[0111] The photoinitiator can include an oxime-based initiator and an acetophenone-based initiator.

[0112] Based on the total amount of the photosensitive resin composition, the photosensitive resin composition may comprise: 3 wt% to 20 wt% of (A) a colorant comprising a compound represented by Chemical Formula 1; 1 wt% to 10 wt% of (B) a binder resin; 1 wt% to 10 wt% of (C) a photopolymerizable compound; 0.1 wt% to 5 wt% of (D) a photopolymerization initiator; and the balance of (E) a solvent.

[0113] The photosensitive resin composition may further comprise an epoxy compound, a silane coupling agent, a surfactant, or a combination thereof.

[0114] Another embodiment provides a photosensitive resin layer manufactured using this photosensitive resin composition.

[0115] Another embodiment provides a color filter including this photosensitive resin layer.

[0116] Another embodiment provides an adhesive composition comprising: (1) a compound represented by Chemical Formula 1; (2) an acrylic adhesive resin; (3) a hardener; and (4) a solvent.

[0117] The adhesive composition may further comprise a silane coupling agent, an antistatic agent, an ultraviolet (UV) absorber, a cationic initiator, a release agent, or a combination thereof.

[0118] Another embodiment provides an adhesive film manufactured using this adhesive composition.

[0119] Another embodiment provides a polarizing plate including this adhesive film.

[0120] Another embodiment provides an optical display device including this polarizing plate.

[0121] Another embodiment provides an optical display device including this color filter and / or polarizing plate.

[0122] Other embodiments of the present invention are included in the following detailed description.

[0123] The photosensitive resin composition according to an embodiment includes a compound that blocks wavelengths in the violet region (400 nm to 440 nm) to improve the color reproducibility of a color filter that constitutes an optical display device such as a liquid crystal display (LCD), and thus relatively high brightness can be achieved at high color coordinates. In particular, the compound has the property of strongly absorbing light in a very narrow region, and thus can block the spectrum of light in the corresponding region, and blue can be achieved even with a very small amount. In addition, the adhesive composition according to an embodiment does not change color even when exposed to a high temperature / high humidity environment for a long time, and thus can exhibit excellent color stability, durability, heat resistance, or moisture resistance. Therefore, the adhesive film manufactured using this adhesive composition has excellent durability, and a polarizing plate including the adhesive film having excellent durability can also have excellent durability and color stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0124] Figure 1 is a graph showing the change in transmittance with respect to the wavelength of the compound represented by Chemical Formula 1-1, Yellow Dye 1, and Yellow Dye 2. DETAILED DESCRIPTION

[0125] Hereinafter, embodiments of the present invention will be described in detail. However, these embodiments are exemplary, and the present invention is not limited thereto and is defined by the scope of the claims.

[0126] In this specification, when no specific definition is provided otherwise, "substituted" means substituted with a substituent selected from the following: halogen (F, Br, Cl, or I), hydroxyl group, nitro group, cyano group, amino group (NH2, NH(R 200 ), or N(R 201 )(R 202 ), where R 200 , R 201 , and R 202 are the same or different and are independently C1 to C10 alkyl), amidino group, hydrazino group, hydrazono group, carboxyl group, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl, and substituted or unsubstituted heterocyclic group.

[0127] In this specification, unless otherwise provided with specific definitions, "alkyl" means C1 to C20 alkyl, especially C1 to C15 alkyl; "cycloalkyl" means C3 to C20 cycloalkyl, especially C3 to C18 cycloalkyl; "alkoxy" means C1 to C20 alkoxy, especially C1 to C18 alkoxy; "aryl" means C6 to C20 aryl, especially C6 to C18 aryl; "alkenyl" means C2 to C20 alkenyl, especially C2 to C18 alkenyl; "alkylene" means C1 to C20 alkylene, especially C1 to C18 alkylene; and "arylene" means C6 to C20 arylene, especially C6 to C16 arylene.

[0128] In this specification, unless otherwise provided with specific definitions, "(meth)acrylate" means "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid".

[0129] In this specification, unless otherwise provided with definitions, the term "combination" means mixing or copolymerization. In addition, "copolymerization" means from block copolymerization to random copolymerization, and "copolymer" means from block copolymer to random copolymer.

[0130] In the chemical formulas in this specification, unless otherwise provided with specific definitions, when a chemical bond is not drawn at the position where it should be given, a hydrogen bond is formed at that position.

[0131] In this specification, unless otherwise provided with specific definitions, "*" indicates a point connecting the same or different atoms or chemical formulas.

[0132] In addition, when any component is disposed "on" another component in this specification, the component may not only contact the other component, but there may also be another component between the two components.

[0133] In addition, in this specification, unless the contrary is explicitly stated, the terms "comprising" and variations such as "comprises or comprising" should be understood to mean including the recited elements without excluding any other elements.

[0134] An embodiment of the present invention provides a photosensitive resin composition, which comprises: (A) a colorant, comprising a compound represented by Chemical Formula 1; (B) a binder resin; (C) a photopolymerizable compound; (D) a photoinitiator; and (E) a solvent.

[0135] Hereinafter, each component will be specifically described.

[0136] Colorant

[0137] The photosensitive resin composition according to the embodiment contains a compound represented by Chemical Formula 1 as a colorant.

[0138] [Chemical Formula 1]

[0139]

[0140] In Chemical Formula 1,

[0141] M is Zn, Co or Cu, and

[0142] R 1 to R 20 are independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a sulfonic acid group, a substituted or unsubstituted sulfonamide group or a substituted or unsubstituted C1-C20 alkyl ester group,

[0143] with the proviso that at least one of R 1 to R 5 , at least one of R 6 to R 10 , at least one of R 11 to R 15 and at least one of R 16 to R 20 is independently not a hydrogen atom.

[0144] For example, the compound can be represented by Chemical Formula 2.

[0145] [Chemical Formula 2]

[0146]

[0147] In Chemical Formula 2,

[0148] M is Zn, Co or Cu,

[0149] R 21 to R 28 are independently a halogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a sulfonic acid group, a substituted or unsubstituted sulfonamide group or a substituted or unsubstituted C1-C20 alkyl ester group,

[0150] n1 to n8 are independently integers of 0 or 1, 1 ≤ n1 + n2 ≤ 2, 1 ≤ n3 + n4 ≤ 2, 1 ≤ n5 + n6 ≤ 2, and 1 ≤ n7 + n8 ≤ 2.

[0151] For example, the compound can be represented by one of Chemical Formulas 1-1 to 1-20.

[0152] [Chemical Formula 1-1]

[0153]

[0154] [Chemical Formula 1-2]

[0155]

[0156] [Chemical Formula 1-3]

[0157]

[0158] [Chemical Formula 1-4]

[0159]

[0160] [Chemical Formula 1-5]

[0161]

[0162] [Chemical Formula 1-6]

[0163]

[0164] [Chemical Formula 1-7]

[0165]

[0166] [Chemical Formula 1-8]

[0167]

[0168] [Chemical Formula 1-9]

[0169]

[0170] [Chemical Formula 1-10]

[0171]

[0172] [Chemical Formula 1-11]

[0173]

[0174] [Chemical Formula 1-12]

[0175]

[0176] [Chemical Formula 1-13]

[0177]

[0178] In Chemical Formula 1-13,

[0179] R is a hydrogen atom or a substituted or unsubstituted C1-C20 alkyl group,

[0180] m1 and m2 are independently integers in the range of 0 to 20, and 4 ≤ m1 + m2 ≤ 20,

[0181] [Chemical formula 1-14]

[0182]

[0183] [Chemical formula 1-15]

[0184]

[0185] [Chemical formula 1-16]

[0186]

[0187] [Chemical formula 1-17]

[0188]

[0189] [Chemical formula 1-18]

[0190]

[0191] [Chemical formula 1-19]

[0192]

[0193] [Chemical formula 1-20]

[0194]

[0195] Regarding the blue resist in traditional color filter resists, generally some purple colorants are added to the blue pigment to adjust the color coordinates and increase the brightness. However, the Bx of the color coordinates of the novel blue has recently tended to be much smaller to increase the color reproducibility. To achieve a blue color filter with such high color reproducibility, a narrow transmission spectrum should be formed near 450 nm, which is the wavelength of the light source, i.e., a blue light emitting diode (LED). Therefore, it is proposed to manufacture the resist by using beta blue pigment instead of the conventionally used epsilon blue but increasing the pigment weight concentration (PWC) to reduce the width of the transmission spectrum. However, there is a problem of deterioration of the traditional brightness.

[0196] According to an embodiment, a dye is used that reduces Bx compared to β blue but truncates the purple region to ensure sufficient brightness. The compound represented by Chemical Formula 1 strongly absorbs light in a very narrow region around 400 nm to 440 nm, especially around 420 nm to 440 nm, and truncates the spectrum in the corresponding region in a very small amount, thereby enabling blue. To achieve a similar purpose, conventional azo-based yellow dyes, etc. have been tried to absorb light in the region of 380 nm to 420 nm, but since a relatively large amount of azo-based yellow dye is incorporated, there is a problem that the process margin of the entire composition cannot be ensured. However, according to the embodiment, since a small amount of the compound represented by Chemical Formula 1 can be used to achieve sufficiently high color reproducibility, this problem can be solved. In addition, when a conventional azo-based yellow dye is used together with a conventional blue dye (ε blue), the transmission spectrum overlaps with the absorption spectrum, and thus the blue transmission region is damaged, and as a result, the brightness loss may increase. However, according to the embodiment, the brightness loss of the (main) spectrum of the light source can be minimized by adjusting the transmittance according to the wavelength of the yellow dye that absorbs light in the wavelength region around 400 nm to 440 nm, especially around 420 nm to 440 nm, and adjusting the transmittance in the wavelength region less than 400 nm and greater than or equal to 450 nm to be greater than or 80%, for example, greater than or equal to 95%. In addition, regarding a colorant (dye or pigment) that has high brightness compared to a conventional blue pigment but has a large Bx and is thus not suitable for high color coordinates, the compound (represented by Chemical Formula 1) according to the embodiment can be used to further increase the brightness and achieve high color coordinates.

[0197] Based on the total amount of the photosensitive resin composition, the compound represented by Chemical Formula 1 may be included in an amount of 0.01% by weight to 7% by weight. Within this range, sufficiently high color reproducibility and improved process margin can be provided.

[0198] For example, the colorant may further include a blue dye, a blue pigment, a red dye, a red pigment, or a combination thereof.

[0199] The blue dye may be represented by Chemical Formula 3.

[0200] [Chemical Formula 3]

[0201]

[0202] In Chemical Formula 3,

[0203] R 29 and R 30 are independently a substituted C1 to C20 alkyl group or a substituted or unsubstituted C3 to C20 cycloalkyl group,

[0204] R 31is a hydrogen atom or a halogen,

[0205] R 32 is a hydrogen atom or a substituted or unsubstituted C1-C20 alkyl group,

[0206] R 33 is a C1-C20 alkyl group substituted or unsubstituted with an acrylate group, and

[0207] X - is represented by one of Chemical Formula A to Chemical Formula C.

[0208] [Chemical Formula A]

[0209] SO3 -

[0210] [Chemical Formula B]

[0211] F3C-(CF2) n3 -SO3

[0212] (In Chemical Formula B, n3 is an integer in the range of 0 to 10)

[0213] [Chemical Formula C]

[0214]

[0215] For example, the blue dye can be represented by Chemical Formula 3-1 or Chemical Formula 3-2.

[0216] [Chemical Formula 3-1]

[0217]

[0218] [Chemical Formula 3-2]

[0219]

[0220] In Chemical Formula 3-1 and Chemical Formula 3-2,

[0221] X- is represented by one of Chemical Formula A to Chemical Formula C.

[0222] [Chemical Formula A]

[0223] SO3 -

[0224] [Chemical Formula B]

[0225] F3C-(CF2) n3 -SO3

[0226] (In Chemical Formula B, n3 is an integer in the range of 0 to 10)

[0227] [Chemical formula C]

[0228]

[0229] Specifically, the blue dye can be represented by Chemical Formula 3-1.

[0230] Since the compound represented by Chemical Formula 3-1 contains a cyclohexyl group and thus can improve heat resistance, and also contains a methyl group in the phenyl group substituted with a nitrogen atom and thus can improve light resistance, a color filter having excellent durability (such as heat resistance, light resistance, etc.) and high brightness under color coordinates can be provided.

[0231] For example, the blue pigment can be an ε blue pigment. When using the blue pigment as the blue colorant according to the embodiment, the ε blue pigment can contribute more to improving brightness compared to the β blue pigment.

[0232] For example, the blue pigment can be C.I. Pigment Blue 15:6.

[0233] For example, the red pigment can be C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment Red 270, C.I. Pigment Red 272, C.I. Pigment Red 177, C.I. Pigment Red 179, C.I. Pigment Red 89, etc., but is not limited thereto.

[0234] Based on the total amount of the photosensitive resin composition according to the embodiment, a colorant can be included in an amount of 3% to 20% by weight. When the colorant is included within this range, high brightness can be achieved under high color coordinates.

[0235] Binder resin

[0236] The binder resin can include an acrylic binder resin. For example, the binder resin can be an acrylic binder resin.

[0237] 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 containing at least one acrylic repeating unit.

[0238] The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group and / or hydroxyl group, and the monomers include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

[0239] Based on the total amount of the acrylic binder resin, the first ethylenically unsaturated monomer can be included in an amount of 5% to 50% by weight, for example, 10% to 40% by weight.

[0240] The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl methyl ether, etc.; an unsaturated carboxylic acid ester compound 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, phenyl (meth)acrylate, etc.; an unsaturated aminoalkyl carboxylic acid ester compound such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, etc.; a vinyl carboxylate compound such as vinyl acetate, vinyl benzoate, etc.; an unsaturated glycidyl carboxylate compound such as glycidyl (meth)acrylate, etc.; an acrylonitrile compound such as (meth)acrylonitrile, etc.; an unsaturated amide compound such as (meth)acrylamide, etc., and the second ethylenically unsaturated monomer may be used alone or in the form of a mixture of two or more of them.

[0241] Specific examples of the acrylic binder resin may be a (meth)acrylic acid / benzyl methacrylate copolymer, a (meth)acrylic acid / benzyl methacrylate / styrene copolymer, a (meth)acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, a (meth)acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc., but are not limited thereto, and these binder resins may be used alone or in the form of a mixture of two or more of them.

[0242] The weight average molecular weight of the acrylic binder resin may be from 3,000 g / mol to 150,000 g / mol, such as from 5,000 g / mol to 50,000 g / mol, such as from 20,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the photosensitive resin composition may have excellent physical and chemical properties and an appropriate viscosity, maintain appropriate developability and sensitivity, and exhibit excellent properties of close contact with the substrate during the manufacture of the color filter.

[0243] The acid value of the acrylic binder resin may be from 15 mgKOH / g to 60 mgKOH / g, such as from 20 mgKOH / g to 50 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, excellent pixel resolution can be obtained.

[0244] Based on the total amount of the photosensitive resin composition, the binder resin may be contained in an amount of 1% by weight to 10% by weight, such as 3% by weight to 7% by weight. When the binder resin is contained within the above range, the developability can be improved, and excellent surface smoothness can be improved due to improved crosslinking during the manufacture of the color filter.

[0245] Photopolymerizable compound

[0246] The photopolymerizable compound may be a monofunctional or polyfunctional (meth)acrylate containing at least one ethylenically unsaturated double bond.

[0247] The photopolymerizable compound has an ethylenically unsaturated double bond and can thus cause sufficient polymerization during the exposure in the patterning process to form a pattern with excellent heat resistance, light resistance, and chemical resistance.

[0248] Specific examples of the photopolymerizable compound may be 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 tetra(meth)acrylate, dipentaerythritol 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, tris(acryloyloxyethyl) phosphate, phenolic epoxy (meth)acrylate, etc.

[0249] Commercially available examples of the photopolymerizable compound are as follows. Monofunctional (meth)acrylate may include Aronix M- M- M- (Toagosei Chemistry Industry Co., Ltd.); KAYARAD TC- TC- (Nippon Kayaku Co., Ltd.); V- V- (Osaka Organic Chemical Ind., Ltd.), etc. Examples of difunctional (meth)acrylate may include Aronix M- M- M- (Toagosei Chemistry Industry Co., Ltd.), KAYARAD HX- R- (Nippon Kayaku Co., Ltd.), V- V- V-335 (Osaka Organic Chemical Industry Co., Ltd.) and the like. Examples of trifunctional (meth)acrylate esters may include Aronix M- M- M- M- M- M- M- (Toagosei Co., Ltd.), KAYARAD DPCA- DPCA- DPCA- DPCA- (Nippon Kayaku Co., Ltd.), V- V- V- V- V- V- (Osaka Yuki Kayaku Kogyo Co., Ltd.) and the like. These photopolymerizable compounds may be used alone or in the form of a mixture of two or more of them.

[0250] The photopolymerizable compound may be treated with an acid anhydride to improve developability.

[0251] Based on the total amount of the photosensitive resin composition, the photopolymerizable compound may be included in an amount of 1 wt% to 10 wt%, for example, 1 wt% to 5 wt%. When the photopolymerizable compound is included within the said range, the photopolymerizable compound is sufficiently cured during the exposure in the patterning process and has excellent reliability, and the developability with an alkaline developer can be improved.

[0252] Photopolymerization initiator

[0253] The photopolymerization initiator may be a commonly used initiator in the photosensitive resin composition, such as an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, or a combination thereof.

[0254] Examples of acetophenone compounds may be 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, etc.

[0255] Examples of benzophenone compounds may be 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, 3,3'-dimethyl-2-methoxybenzophenone, etc.

[0256] Examples of thioxanthone compounds may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0257] Examples of benzoin compounds may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0258] Examples of triazine compounds may be 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-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, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, etc.

[0259] Examples of the oxime-based compounds may be O-acyl oxime-based compounds, 2-(o-benzoylhydroxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetylhydroxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, and the like. Specific examples of the O-acyl oxime-based compounds may be 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)-octan-1-one oxime-O-acetate, 1-(4-phenylthiophenyl)-butan-1-one oxime-O-acetate, and the like.

[0260] The photopolymerization initiator may include an oxime-based initiator and an acetophenone-based initiator at the same time. In this article, when the photopolymerization initiator includes an oxime-based initiator and an acetophenone-based initiator, excellent process margins can be ensured by improving the curing efficiency compared with when using one photopolymerization initiator. In addition, a larger amount of the oxime-based initiator may be included compared with the amount of the acetophenone-based initiator. When an amount of the oxime-based initiator equal to or less than the amount of the acetophenone-based initiator is included, a desired circular dichroism spectrum (CD) can be obtained due to low sensitivity (excellent sensitivity).

[0261] In addition to the above compounds, the photopolymerization initiator may further include carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds, biimidazole-based compounds, fluorene-based compounds, and the like.

[0262] The photopolymerization initiator may be used together with a photosensitizer capable of causing a chemical reaction by absorbing light, being excited, and then transferring its energy.

[0263] Examples of the photosensitizer may be tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, dipentaerythritol tetra-3-mercaptopropionate, and the like.

[0264] Based on the total amount of the photosensitive resin composition, the photopolymerization initiator may be included in an amount of 0.1% by weight to 5% by weight, for example, 0.1% by weight to 1% by weight. When the photopolymerization initiator is included within the above range, sufficient photopolymerization occurs during the exposure in the pattern forming process, excellent reliability can be achieved, the heat resistance, light resistance, chemical resistance, resolution, and close contact properties of the pattern can be improved, and the transmittance can be prevented from decreasing due to unreacted initiators.

[0265] Solvent

[0266] A solvent is a material that is compatible with but does not react with a colorant, binder resin, photo-polymerizable compound, and photo-polymerization initiator.

[0267] Examples of solvents can include alcohols such as methanol, ethanol, etc.; ethers such as dichloroethyl ether, n-butyl ether, diisopentyl ether, anisole, tetrahydrofuran, etc.; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.; cellosolves 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 methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-pentyl ketone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactate esters such as methyl lactate, ethyl lactate, etc.; alkoxyacetic acid alkyl esters such as methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate, etc.; methoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; 3-oxopropionic acid alkyl esters such as methyl 3-oxopropionate, ethyl 3-oxopropionate, etc.; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; 2-oxopropionic acid alkyl esters such as methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, etc.; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-oxo-2-methylpropionic acid esters such as methyl 2-oxo-2-methylpropionate, ethyl 2-oxo-2-methylpropionate, etc.; mono-oxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, etc.; keto acid esters such as ethyl pyruvate, etc. Additionally, high-boiling 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, caproic acid, caprylic 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. can also be used.

[0268] In view of miscibility and reactivity, ketones such as cyclohexanone, etc.; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, etc.; esters such as ethyl 2-hydroxypropionate, etc.; carbitols such as diethylene glycol monomethyl ether, etc.; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate can be preferably used.

[0269] Based on the total amount of the photosensitive resin composition, the solvent is used as the balance, for example, 40% to 80% by weight, for example, 50% to 75% by weight. When the solvent within the said range is included, the photosensitive resin composition can have an appropriate viscosity, thereby improving the coating characteristics of the color filter.

[0270] Other additives

[0271] The photosensitive resin composition according to another embodiment may further contain an epoxy compound to improve the close contact property with the substrate.

[0272] Examples of the epoxy compound may include phenol novolac epoxy compounds, tetramethylbiphenyl epoxy compounds, bisphenol A epoxy compounds, alicyclic epoxy compounds or combinations thereof.

[0273] Based on 100 parts by weight of the photosensitive resin composition, the epoxy compound can be included in an amount of 0.01 part to 20 parts by weight, for example, 0.1 part to 10 parts by weight. When the epoxy compound within the said range is included, the close contact property, storage property, etc. can be improved.

[0274] In addition, the photosensitive resin composition may further contain a silane coupling agent having reactive substituents (such as carboxyl group, methacryloyl group, isocyanate group, epoxy group, etc.) to improve its adhesiveness to the substrate.

[0275] Examples of silane coupling agents may include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc., and these coupling agents may be used alone or in the form of a mixture of two or more of them.

[0276] Based on 100 parts by weight of the photosensitive resin composition, a silane coupling agent may be included in an amount of 0.01 part by weight to 10 parts by weight. When the silane coupling agent is included within the said range, properties such as close contact property and storage property may be excellent.

[0277] In addition, if necessary, the photosensitive resin composition may further include a surfactant to improve coating properties and prevent defects.

[0278] Examples of surfactants may be commercially available fluorine-based surfactants, such as BM- of BM Chemie Inc. BM- etc.; MEGAFACE F of Dainippon Ink Kagaku Kogyo Co., Ltd. F F F F etc.; FULORAD FC- of Sumitomo 3M Co., Ltd. FC- FC- FC- etc.; SURFLON S- of Asahi Glass Co., Ltd. S- S- S- S- etc.; and SH- SH- SH- SZ- SF- etc.

[0279] Based on 100 parts by weight of the photosensitive resin composition, it may contain 0.001 to 5 parts by weight of a surfactant. When the surfactant is included within the said range, the coating uniformity is ensured, no stains are found, and the wettability to the glass substrate is excellent.

[0280] In addition, unless the properties of the photosensitive resin composition deteriorate, the photosensitive resin composition may also contain a predetermined amount of other additives, such as oxidation inhibitors, stabilizers, etc.

[0281] According to another embodiment, there is provided a photosensitive resin layer manufactured using the photosensitive resin composition according to the embodiment.

[0282] The pattern formation process of the photosensitive resin layer is as follows.

[0283] The said process includes: coating the photosensitive resin composition according to the embodiment on a support substrate by methods such as spin coating, slit coating, inkjet printing, etc.; drying the coated positive photosensitive resin composition to form a photosensitive resin composition film; exposing the positive photosensitive resin composition film; developing the exposed positive photosensitive resin composition film in an alkaline aqueous solution to obtain a photosensitive resin layer; and performing heat treatment on the photosensitive resin layer. The conditions of the patterning process are well known in the relevant art and will not be described in detail in this specification.

[0284] According to the embodiment, there is provided a color filter including a photosensitive resin layer.

[0285] According to another embodiment, an adhesive composition includes: (1) a compound represented by Chemical Formula 1; (2) an acrylic adhesive resin; (3) a hardener; and (4) a solvent. That is, the adhesive composition may include the compound represented by Chemical Formula 1 as a colorant, and the compound represented by Chemical Formula 1 is the same as described above.

[0286] Hereinafter, the adhesive composition according to an embodiment of the present invention will be described.

[0287] The adhesive film formed using the adhesive composition according to the embodiment includes a compound represented by Chemical Formula 1 and having a maximum absorption wavelength of 400 nm to 450 nm, and thus can improve the spread reflection caused by incident light in the panel, that is, the visibility deterioration caused by reflection. A spectrophotometer can be used to measure the reflectance for improving visibility. In other words, the reflectance can represent the degree of visibility deterioration caused by the spread reflection generated by the incident light in the panel and the particles in the panel.

[0288] Based on the total amount of the adhesive composition, the compound represented by Chemical Formula 1 may be included in an amount of 0.001 wt% to 0.01 wt% (0.01 wt% to 0.03 wt% based on the solid content of the adhesive composition).

[0289] Based on the total amount of the adhesive composition, the acrylic adhesive resin may be included in an amount of 70 wt% to 85 wt%, for example, 70 wt% to 80 wt% (90 wt% to 97 wt% based on the solid content of the adhesive composition).

[0290] The acrylic adhesive resin of the adhesive composition may include a first (meth)acrylate copolymer and / or a second (meth)acrylate copolymer.

[0291] The first (meth)acrylate copolymer and the second (meth)acrylate copolymer may have different functional groups.

[0292] The first (meth)acrylate copolymer forms a matrix of the adhesive film and provides at least one of a hydroxyl group and a carboxylic acid group to self-cure the adhesive composition.

[0293] The first (meth)acrylate copolymer can be a copolymer of a monomer mixture including at least one of a (meth)acrylate monomer having a hydroxyl group and a (meth)acrylate monomer having a carboxyl group; and a monomer copolymerizable therewith (hereinafter referred to as "the first copolymerizable monomer"). It may contain a hydroxyl group-containing (meth)acrylate monomer and at least one of a carboxyl group-containing (meth)acrylate monomer in an amount of less than or equal to 10 mol%, and especially 0.01 mol% to 5 mol%. Within this range, when the at least one monomer is included together with the second (meth)acrylate copolymer, an adhesive film having excellent flexibility and bending properties and thus suitable for flexible devices can be achieved.

[0294] The hydroxyl group-containing (meth)acrylate monomer may be capable of achieving self-curing and / or increasing the adhesion strength of the adhesive film, and thus increasing the durability of the adhesive film. It may contain a hydroxyl group-containing (meth)acrylate monomer in an amount of less than or equal to about 5 mol%, and especially 0.01 mol% to 5 mol% of the monomer mixture. Within this range, the adhesion strength and durability of the adhesive film become better, and the aging of the adhesive composition becomes faster.

[0295] The hydroxyl group-containing (meth)acrylate monomer may include at least one of the following: a (meth)acrylate monomer having a C1 to C20 alkyl group containing at least one hydroxyl group, a (meth)acrylic monomer having a C3 to C20 cycloalkyl group containing at least one hydroxyl group, a (meth)acrylic monomer having a C6 to C20 aromatic group containing at least one hydroxyl group. Specifically, the hydroxyl group-containing (meth)acrylate monomer may include at least one of the following: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 1-chloro-2-hydroxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, 4-hydroxycyclopentyl (meth)acrylate, and 4-hydroxycyclohexyl (meth)acrylate. These monomers can be used alone or in the form of a mixture of two or more.

[0296] The carboxyl group-containing (meth)acrylate monomer may be capable of achieving self-curing. It may contain a carboxyl group-containing (meth)acrylate monomer in an amount of less than or equal to 5 mol%, and especially 0.01 mol% to 5 mol% of the monomer mixture. Within this range, the adhesive film does not have high acidity, and thus does not have the risk of corroding the substrate, and thus has the effect of reducing resistance and increasing reliability. The carboxyl group-containing (meth)acrylate monomer may include (meth)acrylic acid, etc., but is not limited thereto.

[0297] The first copolymerizable monomer can form a first (meth)acrylate copolymer by copolymerizing with at least one of a (meth)acrylate monomer having a hydroxyl group and a (meth)acrylate monomer having a carboxyl group, and can form a matrix of the adhesive film and provide additional functions.

[0298] The first copolymerizable monomer can include a (meth)acrylate monomer having an alkyl group. The (meth)acrylate monomer having an alkyl group is included in the (meth)acrylate copolymer to form a matrix of the adhesive film and increase the mechanical strength of the adhesive film. The (meth)acrylate monomer having an alkyl group can be included in an amount of 50 mol% to 99.99 mol%, particularly 50 mol% to 95 mol%, 95 mol% to 99.9 mol%, 55 mol% to 90 mol%, or 60 mol% to 85 mol% of the monomer mixture. Within this range, the mechanical strength of the adhesive film can be increased. The (meth)acrylate monomer having an alkyl group can include a (meth)acrylate having an unsubstituted C4 to C12 alkyl group. Specifically, the (meth)acrylate monomer having an alkyl group can include at least one of the following: n-butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, and dodecyl (meth)acrylate, but is not limited thereto. These monomers can be used alone or in the form of a mixture of two or more.

[0299] The first copolymerizable monomer can increase the pencil hardness of a polarizing plate including the adhesive film by including at least one of a (meth)acrylate monomer having an alicyclic group and a (meth)acrylate monomer having a heterocyclic alicyclic group.

[0300] An (meth)acrylate monomer having an alicyclic group is included in the first (meth)acrylate copolymer and thus, together with the second (meth)acrylate copolymer, increases the pencil hardness of the polarizing plate on the adhesive film of the polarizing plate, which is adhered to the adhesive film of the polarizing plate. Specifically, the polarizing plate adhered to the adhesive film of the polarizing plate may have a pencil hardness of the polarizing plate on the adhesive film of 2H or more, more specifically, 2H to 3H. Within this range, compared with when the polarizing plate is adhered to the liquid crystal panel without an adhesive film, even when the polarizing plate is adhered to the liquid crystal panel formed of a glass material or the like through the adhesive film of the polarizing plate, the pencil hardness is not greatly reduced, and thus, this polarizing plate can be used for an optical display device. In addition, an (meth)acrylate monomer having an alicyclic group is included in the (meth)acrylate copolymer together with an (meth)acrylate monomer having a heterocyclic alicyclic group, and can reduce the creep of the adhesive film of the polarizing plate at 25°C but increase its creep at 85°C. In particular, when the (meth)acrylate monomer having an alicyclic group and the (meth)acrylate monomer having a heterocyclic alicyclic group are each a homopolymer, the glass transition temperature becomes 30°C or more, and in particular, 40°C to 180°C, and thus, the creep of the adhesive film can be deteriorated at 25°C and the creep can be enhanced at 85°C. The molar ratio of the (meth)acrylate monomer having an alicyclic group: the (meth)acrylate monomer having a heterocyclic alicyclic group in the monomer mixture may be in the range of 1:0.25 to 1:2. Within this range, there can be an effect of increasing the cohesion or strength at room temperature. Alternatively, there can be a stress relaxation effect at high temperature and an effect of improving the bending of the polarizing film.

[0301] The (meth)acrylate monomer having an alicyclic group may be included in an amount of 1 mol% to 30 mol%, and in particular, 5 mol% to 20 mol% of the monomer mixture. Within this range, the pencil hardness and the cohesion of the polarizing plate on the adhesive film can be increased.

[0302] The (meth)acrylate monomer having an alicyclic group may include an (meth)acrylate having a substituted or unsubstituted C5 to C20 monocyclic or heterocyclic alicyclic group.

[0303] "Alicyclic group" means a non-heterocyclic alicyclic group that does not contain a heteroatom of nitrogen, oxygen, or sulfur. "Heterocycle" means at least two alicyclic groups that are connected to each other and share at least one carbon atom.

[0304] Specifically, the (meth)acrylate having a substituted or unsubstituted C5 to C20 monocyclic or heterocyclic alicyclic group may include at least one of the following: cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, methylcyclohexyl (meth)acrylate, and dicyclopentenyl (meth)acrylate. These (meth)acrylates may be used alone or in the form of a mixture of two or more of them.

[0305] The (meth)acrylate monomer having a heterocyclic alicyclic group and the (meth)acrylate monomer having an alicyclic group together may cause creep degradation at 25°C and enhance creep at 85°C.

[0306] The (meth)acrylate monomer having a heterocyclic alicyclic group may be included in an amount of 1 mol% to 30 mol%, and especially 5 mol% to 20 mol% in the monomer mixture. Within this range, there may be an effect of increasing the modulus of the adhesive film and improving the cohesion at 30°C.

[0307] The (meth)acrylate monomer having a heterocyclic alicyclic group may include the (meth)acrylate having a C4 to C9 heterocyclic alicyclic group containing at least one of nitrogen, oxygen, or sulfur. Specifically, the (meth)acrylate monomer having a heterocyclic alicyclic group may include (meth)acryloylmorpholine, but is not limited thereto.

[0308] The first copolymerizable monomer may further include at least one monomer among the (meth)acrylate having a C1 to C3 alkyl group, the monomer having an amide group, and the monomer having an aromatic group. Specifically, the monomer may include methyl (meth)acrylate, (meth)acrylamide, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc., but is not limited thereto.

[0309] In an exemplary embodiment, the first (meth)acrylate copolymer may be a copolymer of: at least one of a (meth)acrylate monomer having a hydroxyl group and a (meth)acrylate monomer having a carboxylic acid group in an amount of 0.01 mol% to 5 mol%; and a (meth)acrylate monomer having an alkyl group in an amount of 95 mol% to 99.99 mol%. In another exemplary embodiment, the first (meth)acrylate copolymer may be a copolymer of: at least one of a (meth)acrylate monomer having a hydroxyl group and a (meth)acrylate monomer having a carboxylic acid group in an amount of 0.01 mol% to 5 mol%; a (meth)acrylate monomer having an alkyl group in an amount of 50 mol% to 95 mol%; a (meth)acrylate monomer having an alicyclic group in an amount of 1 mol% to 30 mol%; and a (meth)acrylate monomer having a heterocyclic alicyclic group in an amount of 1 mol% to 30 mol%. Within this range, there may be an effect of high cohesion and high strength.

[0310] The second (meth)acrylate copolymer forms the matrix of the pressure-sensitive adhesive film and provides at least one of an epoxy group and an oxetanyl group, and thus the pressure-sensitive adhesive composition can be self-cured without a crosslinking agent.

[0311] The second (meth)acrylate copolymer can be a copolymer of: a monomer mixture including at least one of a (meth)acrylic monomer having an epoxy group and a (meth)acrylic monomer having an oxetanyl group; and a monomer copolymerizable therewith (hereinafter referred to as "second copolymerizable monomer"). In the monomer mixture, at least one of the (meth)acrylate monomer having an epoxy group and the (meth)acrylate monomer having an oxetanyl group can be included in an amount of less than or equal to 10 mol%, and particularly 0.01 mol% to 5 mol%. Within this range, when at least one of the (meth)acrylate monomer having an epoxy group and the (meth)acrylate monomer having an oxetanyl group is included together with the first (meth)acrylate copolymer, a pressure-sensitive adhesive film having excellent flexibility, bending properties, hardness, processability, and reliability and thus suitable for flexible devices can be achieved.

[0312] The (meth)acrylate monomer having an epoxy group can self-cure the pressure-sensitive adhesive composition and / or achieve the effect of improving cohesion and reliability. In the monomer mixture, the (meth)acrylic monomer having an epoxy group can be included in an amount of less than or equal to 5 mol%, and particularly 0.01 mol% to 5 mol%. Within this range, the effects of accelerating curing and improving reliability can be present. The (meth)acrylic monomer having an epoxy group can be glycidyl (meth)acrylate or the like.

[0313] The (meth)acrylate monomer having an oxetanyl group can self-cure the pressure-sensitive adhesive composition and / or achieve the effect of improving cohesion and reliability. In the monomer mixture, the (meth)acrylate monomer having an oxetanyl group can be included in an amount of less than or equal to 5 mol%, and particularly 0.01 mol% to 5 mol%. Within this range, the effects of accelerating curing and improving reliability can be present. The (meth)acrylate monomer having an oxetanyl group can be oxetanyl (meth)acrylate, methyl oxetanyl (meth)acrylate, methyl (3-methyl-3-oxetanyl)(meth)acrylate, methyl (3-ethyl-3-oxetanyl)(meth)acrylate, or the like.

[0314] The second copolymerizable monomer copolymerizes with at least one of the (meth)acrylate monomer having an epoxy group and the (meth)acrylate monomer having an oxetanyl group, and thus can form the matrix of the pressure-sensitive adhesive film or provide additional functions.

[0315] The second copolymerizable monomer may include a (meth)acrylate monomer having an alkyl group. The second copolymerizable monomer further includes at least one of a (meth)acrylate monomer having an alicyclic group and a (meth)acrylate monomer having a heterocycloaliphatic group, and thus can further increase the pencil hardness of the polarizing plate including the adhesive film. The (meth)acrylate monomer having an alkyl group, the (meth)acrylate monomer having an alicyclic group, and the (meth)acrylate monomer having a heterocycloaliphatic group are specifically the same types as those mentioned in the first copolymerizable monomer.

[0316] In an exemplary embodiment, the second (meth)acrylate copolymer may be a copolymer of: at least one of a (meth)acrylate monomer having an epoxy group and a (meth)acrylate monomer having an oxetanyl group in an amount of 0.01 mol% to 5 mol%; and a (meth)acrylate monomer having an alkyl group in an amount of 95 mol% to 99.9 mol%. In another exemplary embodiment, the second (meth)acrylate copolymer may be a copolymer of: at least one of a (meth)acrylate monomer having an epoxy group and a (meth)acrylate monomer having an oxetanyl group in an amount of 0.01 mol% to 5 mol%; a (meth)acrylate monomer having an alkyl group in an amount of 50 mol% to 95 mol%; a (meth)acrylate monomer having an alicyclic group in an amount of 1 mol% to 30 mol%; and a (meth)acrylate monomer having a heterocycloaliphatic group in an amount of 1 mol% to 30 mol%. Within the above ranges, the effects of accelerating curing and improving reliability can be achieved.

[0317] The first (meth)acrylate copolymer and the second (meth)acrylate copolymer each have a glass transition temperature of -55°C to -5°C, and particularly -50°C to -30°C. The first (meth)acrylate copolymer and the second (meth)acrylate copolymer may each have a weight average molecular weight of 200,000 g / mol to 1,500,000 g / mol, and particularly 500,000 g / mol to 1,000,000 g / mol. The first (meth)acrylate copolymer and the second (meth)acrylate copolymer may each have an acid value of less than or equal to 5 mgKOH / g, and more specifically 0.01 mgKOH / g to 3 mgKOH / g. Within the above ranges, the effects of directly preventing and inhibiting corrosion of the substrate can be achieved.

[0318] The first (meth)acrylate copolymer and the second (meth)acrylate copolymer can be prepared by polymerizing each monomer mixture using general polymerization methods. The polymerization method can include general methods known to those skilled in the art. For example, the (meth)acrylate copolymer can be prepared by adding an initiator to the monomer mixture and performing general copolymer polymerization (such as suspension polymerization, emulsion polymerization, solution polymerization, etc.). The polymerization temperature can range from 65°C to 70°C, and the polymerization time can range from 6 hours to 8 hours. The initiator can generally be an azo-based polymerization initiator; and / or a peroxide such as benzoyl peroxide or acetyl peroxide.

[0319] The hardener can be a heat hardener, and the cohesion of the adhesive can be enhanced by appropriately crosslinking the acrylic adhesive resin, but there is no particular limitation. For example, the hardener can be an isocyanate-based compound, an aziridine-based compound, etc., and can be used alone or in the form of a mixture of two or more of them.

[0320] The isocyanate-based compound can be a diisocyanate compound, such as toluene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate, etc.; an addition product obtained by reacting 1 mol of a polyol-based compound (such as trimethylolpropane, etc.) with 3 mol of a diisocyanate compound, an isocyanurate product obtained by self-condensing 3 mol of a diisocyanate compound, a titration product obtained by condensing a diisocyanurate obtained from 2 mol of 3 mol of a diisocyanate compound with 1 mol of a diisocyanate, a polyfunctional isocyanate compound including three functional groups, such as triphenylmethane triisocyanate, methylene bis triisocyanate, etc.

[0321] The aziridine-based compound can be N,N'-toluene-2,4-bis(1-aziridinecarboxamide), N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), triethylenetrismelamine, bisisophthaloyl-1-(2-methylaziridine), and tris-1-aziridinylphosphine oxide, etc.

[0322] In addition, the melamine-based compound can also be used alone or in the form of a mixture of two or more of them together with the isocyanate-based compound and the aziridine-based compound.

[0323] The melamine-based compound can be hexahydroxymethylmelamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, etc.

[0324] Based on the total amount of the adhesive composition, a curing agent may be included in an amount of 0.1 wt% to 1 wt%, for example, 0.1 wt% to 0.5 wt% (0.3 wt% to 1.0 wt% based on the solid content of the adhesive composition), so as to improve the adhesion strength or cohesion. When the amount of the curing agent included is less than 0.1 wt% based on the total amount of the adhesive composition, the adhesion strength or cohesion of the adhesive is slightly deteriorated (incomplete curing) due to insufficient crosslinking degree, and thus durability deterioration (such as floating) may be caused, and the friability may be damaged. However, when the amount of the curing agent included is 1 wt% based on the total amount of the adhesive composition, the compatibility may be slightly deteriorated, and thus surface transformation may be caused, the crosslinking reaction proceeds excessively and the adhesion strength may be slightly deteriorated, and thus there may be a problem of residual stress relaxation.

[0325] The solvent can improve the coating property of the adhesive composition but prevent the self-curing reaction of the adhesive composition. The solvent can be any solvent known to those of ordinary skill in the art. For example, the solvent may include at least one of methyl ethyl ketone, ethyl acetate, and toluene, and can be used in the balance based on the total amount of the adhesive composition, for example, 10 wt% to 40 wt%, for example, 10 wt% to 30 wt%.

[0326] The adhesive composition may further include a silane coupling agent, an antistatic agent, an ultraviolet (UV) absorber, a cationic initiator, a release agent, or a combination thereof.

[0327] The silane coupling agent is the same as that described above, and based on the total amount of the adhesive composition, a silane coupling agent may be included in an amount of 0.01 wt% to 0.1 wt%, for example, 0.01 wt% to 0.05 wt% (0.1 wt% to 0.3 wt% based on the adhesive composition solid).

[0328] The antistatic agent inhibits the generation of static electricity during the reprocessing of the adhesive film and can be a commonly used antistatic agent. Based on the total amount of the adhesive composition, an antistatic agent may be included in an amount of 1 wt% to 5 wt%, for example, 1 wt% to 3 wt% (1.0 wt% to 5.0 wt% based on the adhesive composition solid). When the antistatic agent within the said range is included, it is advantageous in terms of charging. When the amount of the antistatic agent included is less than 1 wt% based on the total amount of the adhesive composition, the antistatic effect is slightly deteriorated, and when the amount of the antistatic agent included is greater than 5 wt% based on the total amount of the adhesive composition, the properties of the adhesive composition are deteriorated, and the manufacturing cost may be increased.

[0329] For example, the antistatic agent may be an ionic antistatic agent. The ionic antistatic agent may be an alkaline metal salt and an ionic liquid or solid. However, the alkaline metal salt has slightly lower compatibility with the adhesive, and the alkaline metal salt may lack durability, and the ionic liquid has great fluidity in the product of the sintered adhesive and thus may have slightly deteriorated antistatic performance over time. Simply put, considering the change stability of durability and the antistatic property that changes over time, an ionic liquid having a solid phase at room temperature of 25 °C may be included.

[0330] For example, the antistatic agent may be dodecylpyridinium hexafluorophosphate (KOEI), lithium bis(trifluoromethanesulfonyl)imide (3M), tri-n-butylmethylammonium bis(trifluoromethanesulfonyl)imide (3M), etc., but is not limited thereto, and may be used in the form of a mixture of two or more thereof.

[0331] The ultraviolet (UV) absorber may have an absorption wavelength of 380 nm to 420 nm. In this text, "absorption wavelength" means "maximum absorption wavelength".

[0332] When the adhesive composition contains an ultraviolet (UV) absorber having the absorption wavelength range, a transmittance of less than or equal to 5% can be obtained in the wavelength region of less than or equal to 400 nm, and the polarizing plate and the device including the polarizing plate can be prevented from being damaged by external ultraviolet (UV).

[0333] When the ultraviolet (UV) absorber satisfies the above absorption wavelength range, the present invention is not limited thereto, but includes any ultraviolet (UV) absorber commonly used in the related art. For example, the ultraviolet (UV) absorber may be 2-hydroxy-3((4-methoxyphenyl)diazenyl)-5-methylbenzyl methacrylate or 2-hydroxy-5-methoxy-3-(5-trifluoromethyl)-2H-benzotriazol-2-yl)benzyl methacrylate, but is not limited thereto as long as it satisfies the absorption wavelength.

[0334] The cationic initiator may be a cationic photoinitiator, but is not limited thereto, and includes any cationic photoinitiator commonly used in the related art. For example, it may include an onium salt that releases a Lewis acid due to a photo radical or its derivative. Such a compound may be represented by the general formula [X] x+ [Y] x-A salt composed of the represented cations and anions. Specific examples of the cations can be aromatic diazonium salts, aromatic iodonium salts, aromatic halonium salts, and aromatic sulfonium salts, and specific examples of the anions can be tetrafluoroborate (BF4), hexafluorophosphate (PF6), hexafluoroantimonate (SbF6), hexafluoroarsenate (AsF6), hexachloroantimonate (SbCl6), etc. These cationic photoinitiators can be used alone or in the form of a mixture of two or more of them.

[0335] The amount of the cationic initiator is not particularly limited, but based on the solid content, it can be, for example, 0.01 parts by weight to 10 parts by weight, for example, 0.1 parts by weight to 5 parts by weight based on the total amount of the adhesive composition. When the amount of the cationic initiator contained is less than 0.01 parts by weight based on the total amount of the adhesive composition, the colored adhesive composition is not sufficiently cured, and thus it is difficult to obtain sufficient adhesiveness and close contact force. However, when the amount of the cationic initiator contained is greater than 10 parts by weight based on the total amount of the adhesive composition, the hygroscopicity increases due to the excessive ionic materials in the adhesive layer, and thus the durability may be slightly deteriorated.

[0336] The release agent can be an alkyd-based release agent, a silicone-based release agent, a fluorine-based release agent, an unsaturated ester-based release agent, a polyolefin-based release agent, a wax-based release agent, etc. For example, when the release agent is an alkyd-based release agent, a silicone-based release agent, or a fluorine-based release agent, excellent heat resistance can be obtained, but the present invention is not limited thereto. Based on the total amount of the adhesive composition, the release agent can be contained in an amount of 0.01% by weight to 0.1% by weight.

[0337] In addition to these components, the adhesive composition can also contain additives such as a reprocessing agent, an adhesiveness-imparting resin, an antioxidant, a leveling agent, a surface lubricant, a defoaming agent, a filler, a light stabilizer, etc. according to the desired use to adjust the adhesiveness, cohesion, viscosity, elasticity, glass transition temperature, etc.

[0338] Additives in an appropriately adjusted amount within the range that does not interfere with the effects of the present invention can be included.

[0339] The adhesive composition according to the embodiment can have a viscosity of 1,000 cPs to 4,000 cPs at 25°C. Within this range, it is easy to adjust the thickness of the adhesive film, and the adhesive film has no stains on the surface and has a uniform coating effect.

[0340] Another embodiment provides an adhesive film manufactured using this adhesive composition.

[0341] Another embodiment provides a polarizing plate including this adhesive film.

[0342] The method for manufacturing the adhesive film is not particularly limited, but can include common methods. For example, the adhesive film can be manufactured using the adhesive composition.

[0343] For example, the above adhesive composition can be directly coated on the polarizing plate protective film by using fluid casting, a bar coater, an air knife, gravure printing, a reverse roll, a kiss roll, spraying, a blade, etc., and then dried (thermally cured) to form an adhesive layer, and the adhesive layer can be laminated with the polarizing plate.

[0344] In addition, an adhesive film is formed on a silicone-coated release film by the same coating method as above, and laminated with a silicone-coated release film having a different peel force from the adhesive film by using a roll press to manufacture an adhesive transfer tape, and the adhesive transfer tape can be adhered to the polarizing plate.

[0345] The adhesive film can be formed by thermal curing, but when using an ultraviolet (UV) curing compound and a photoinitiator (such as the above cationic photoinitiator, etc.) as a crosslinking agent, the adhesive film can be formed in the following manner: laminating the polarizing plate, and then irradiating ultraviolet (UV) light from the release film side or laminating a silicone-coated release film having a different peel force by using a roll press and then irradiating ultraviolet (UV) light thereto (photo-curing).

[0346] The thickness of the adhesive film is not particularly limited, and can be 5 μm to 30 μm, for example, 7 μm to 20 μm, for example, 10 μm to 15 μm. When the adhesive film has a thickness within this range, the adhesive film can have excellent adhesiveness and durability, and can be applied to thin devices.

[0347] In a polarizing plate equipped with an adhesive film on at least one surface, the polarizing plate can have a transmittance of less than or equal to 5% at a wavelength of less than or equal to 400 nm and a transmittance of greater than or equal to 40% at a wavelength of greater than or equal to 455 nm.

[0348] Since the polarizing plate has a transmittance of less than or equal to 5% at a wavelength of less than or equal to 400 nm, damage to the polarizing plate or the device adhered with the polarizing plate can be prevented, and since the polarizing plate has a transmittance of greater than or equal to 40% at a wavelength of greater than or equal to 455 nm, blue brightness deterioration can be prevented.

[0349] In addition, another embodiment provides a color filter including a photosensitive resin layer and / or an optical display device including a polarizing plate.

[0350] The optical display device can include a liquid crystal display (LCD), an organic light-emitting diode (OLED), a flexible display, etc. as an image display, but is not limited thereto, and can include all image display devices known in the related art.

[0351] For example, the optical display device may be a liquid crystal display (LCD). Generally, a liquid crystal display (LCD) is composed of a backlight unit (BLU), polarizing plates, thin film transistors (TFTs), liquid crystal cells, color filters, and polarizing plates. In this document, the polarizing plates may be polarizing plates according to embodiments, and the color filters may be color filters according to embodiments. For example, the optical display device may be equipped with a polarizing plate laminated with an adhesive layer according to an embodiment on at least one surface of the color filter according to an embodiment.

[0352] Hereinafter, the present invention will be 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.

[0353] (Synthesis of Dye)

[0354] Synthesis Example 1: Synthesis of the dye represented by Chemical Formula 1-1

[0355] [Reaction Scheme 1]

[0356]

[0357] (1) 4-tert-Butylbenzaldehyde (16.2 g, 0.1 mol), 100 g of propionic acid, and pyrrole (6.71 g, 0.1 mol) were placed in a round-bottom flask, and then heated to 130 °C and stirred for 6 hours. After the reaction was completed, the product was cooled to room temperature, 100 g of acetone was added thereto, and the obtained mixture was stirred. The solid compound formed therein was filtered, washed with acetone, and dried to synthesize a porphyrin intermediate (4.2 g, 20%).

[0358] (2) The intermediate (4.2 g, 5 mmol) and 80 g of chloroform were placed in a round-bottom flask and stirred at 60 °C. In another round-bottom flask, zinc acetate (2.75 g, 15 mmol) was placed, 53 g of methanol was added thereto, and the obtained mixture was stirred. Herein, the stirring should be continued until the zinc acetate is completely dissolved. After the zinc acetate was completely dissolved, this solution was added to the intermediate, and the obtained mixture was stirred at 60 °C for 3 hours, and then the reaction was completed. An extract was obtained using chloroform, washed with water, and filtered. The filtrate was distilled, 50 g of acetone was added thereto, and the obtained mixture was stirred at room temperature for 1 hour and filtered again to obtain a porphyrin-based dye (3.1 g, 69%) (900 m / z).

[0359] Synthesis Example 2: Synthesis of the blue dye represented by Chemical Formula 3-1

[0360] 1. Synthesis of Compound 1

[0361] NaBH4 (3.8 g, 0.1 mol) was placed in a round-bottom flask, 100 g of 1,2-dichloroethane was added thereto, and the resulting mixture was cooled to 0 °C and stirred. Subsequently, acetic acid (21.6 g, 0.36 mol) was added thereto, and the resulting mixture was stirred for 2 hours while slowly heating to room temperature, and then cyclohexanone (8.8 g, 0.09 mol) was added dropwise thereto. The reaction mixture was stirred at room temperature for 1 hour, aniline (7.9 g, 0.85 mol) was added thereto, and the resulting mixture was allowed to stand at room temperature overnight. When the reaction was completed, an extract was obtained using dichloromethane and washed with distilled water and 10% aqueous NaCl solution. Water was removed therefrom using MgSO4, and the product was filtered and dried to synthesize Compound 1 (4.5 g, yield 97%).

[0362] [Compound 1]

[0363]

[0364] 2. Synthesis of Compound 2

[0365] Under a nitrogen atmosphere, 4,4'-dichlorobenzophenone (10 g, 39.8 mmol), Pd2(dba)3 (220 mg, 0.002 mol%), XPhos (230 mg, 0.005 mol%), and sodium tert-butoxide (11.48 g, 119.5 mmol) were placed in a round-bottom flask, 50 g of toluene was added thereto, the resulting mixture was stirred at room temperature for 10 minutes, and Compound 1 (14 g, 79.6 mmol) was added thereto. The reaction mixture was slowly heated to 80 °C and stirred for 2 hours. When the reaction was completed, the temperature was lowered to room temperature, 50 g of isopropanol was added thereto, and the resulting mixture was stirred. The precipitate therein was filtered, washed with water and added to acetonitrile, and the resulting mixture was stirred at 80 °C for 30 minutes. The temperature was lowered to room temperature, and the precipitate therein was filtered and dried to synthesize Intermediate 2 (27.3 g, yield 65%).

[0366] [Compound 2]

[0367]

[0368] 3. Synthesis of Compounds 3 to 6

[0369] [Reaction Scheme 2]

[0370]

[0371] (Synthesis of Compound 3)

[0372] Sodium ethoxide (34.2 g, 0.503 mol) and 250 g of ethanol were placed in a round-bottom flask and stirred at room temperature for 30 minutes. Ethyl cyanoacetate (45.5 g, 0.402 mol) was slowly added thereto, and the resulting mixture was stirred at room temperature for 30 minutes. o-Tolyl isothiocyanate (50 g, 0.335 mol) was slowly added thereto, and the resulting mixture was heated to 80 °C and stirred for 3 hours. After the reaction was completed, the solvent was removed therefrom, and an extract was obtained using dichloromethane and washed with 10% HCl and water, respectively. After removing the organic solvent therefrom, 200 g of MeOH was added to the resulting solid compound, and the resulting mixture was stirred at 0 °C for 30 minutes and filtered to synthesize Compound 3 (73.8 g, yield 84%).

[0373] [Compound 3]

[0374]

[0375] (Synthesis of Compound 4)

[0376] NaOH (45.7 g, 1.14 mol) and 240 g of water were placed in a round-bottom flask and stirred at 0 °C for 30 minutes. Compound 3 (30 g, 0.114 mol) was added thereto, and the reactants were heated to 80 °C and stirred for 3 hours. After the reaction was completed, the temperature was lowered to 0 °C, and the reactants were acidified with concentrated HCl (pH: about 6). The precipitate therein was filtered, then washed and dried to synthesize Compound 4 (19.7 g, yield 90%).

[0377] [Compound 4]

[0378]

[0379] (Synthesis of Compound 5)

[0380] KOH (8.71 g, 0.155 mol) and 200 g of MeOH were placed in a round-bottom flask and stirred at room temperature for 30 minutes. Compound 4 (20.5 g, 0.108 mol) and 2'-chlorobenzoylmethyl bromide (26.6 g, 0.114 mol) were added thereto, respectively, and the resulting mixture was stirred at room temperature for 2 hours. After the reaction was completed, 200 g of water was added thereto, the resulting mixture was stirred at room temperature for 1 hour, and the precipitate therein was filtered, then washed with MeOH and dried to synthesize Compound 5 (29.8 g, yield 89%).

[0381] [Compound 5]

[0382]

[0383] (Synthesis of Compound 6)

[0384] KOH (10.4 g, 0.185 mol), 170 g of acetone and 80 g of water were placed in a round-bottom flask and stirred at room temperature. Compound 5 (30 g, 92.4 mmol) and 2-iodopropane (31.5 g, 0.185 mol) were added thereto, and the resulting mixture was stirred at 60 °C for 12 hours. After the reaction was completed, acetone was removed by distillation, and an extract was obtained using dichloromethane and washed with 10% HCl and saturated sodium thiosulfate. After removing the organic solvent therefrom, a precipitate was obtained using ethyl acetate / hexane to synthesize Compound 6 (19 g, yield 56%).

[0385] [Compound 6]

[0386]

[0387] 4. Synthesis of the compound represented by Chemical Formula 3-1

[0388] Under nitrogen conditions, Compound 2 (1.50 g, 2.83 mmol) and Compound 6 (1.0 g, 2.83 mmol) were placed in a round-bottom flask, 7.5 g of toluene and POCl3 (2.6 g, 17.0 mmol) were added thereto, and the resulting mixture was stirred while slowly heating to 110 °C for 5 hours. After the reaction was completed, the temperature was lowered to room temperature, and an extract was obtained using methylethyl ketone (MEK) and washed with 10% NaCl, water and 10% HCl, respectively. After removing the organic layer, the remainder was dried, lithium bis(trifluoromethane)sulfonimide (1.2 g, 4.2 mmol) was added thereto, 10 g of dimethylsulfoxide (DMSO) was added thereto, and the resulting mixture was stirred at room temperature for 30 minutes (anion exchange process). The reaction product was dropped into water to form a precipitate, and the precipitate was separated by filtration. The solid compound obtained by filtration was dissolved in 40 g of acetonitrile, 3 g of activated carbon was added thereto, and the resulting mixture was stirred for 30 minutes. Subsequently, the activated carbon was removed by filtration, and the filtrate was removed by distillation and dried to obtain the compound represented by Chemical Formula 3-1 (2.69 g, yield 82%). Chemical Formula X is represented by Chemical Formula C.

[0389] [Chemical Formula 3-1]

[0390]

[0391] Liquid Chromatography (LC) - Mass Spectrometry (MC): 1003 m / z

[0392] [Chemical formula C]

[0393]

[0394] Synthesis Example 3: Synthesis of the blue dye represented by Chemical formula 3-2

[0395] Using 2-aminopropane instead of aniline etc. as in Synthesis Example 1, the blue dye represented by Chemical formula 3-2 was synthesized. Chemical formula X is represented by Chemical formula C.

[0396] [Chemical formula 3-2]

[0397]

[0398] LC - MC: 735 m / z

[0399] [Chemical formula C]

[0400]

[0401] Synthesis Example 4: Synthesis of Yellow Dye 1

[0402] Hydrochloric acid (2.5 mL) and sodium nitrate (2 mL of 1.25 M aqueous solution) were added to 4-aminophthalonitrile (2.5 mmol), and the obtained diazonium was placed in a weakly basic aqueous solution prepared by dissolving barbituric acid (2.5 mmol) in an aqueous NaOH solution to obtain an azo compound. Herein, the obtained solid was filtered, purified, and vacuum dried, and then reacted with 1-iodobutane (5.5 mmol) and potassium carbonate (7.5 mmol) under dimethylformamide (DMF) solvent conditions, and then purified and vacuum dried to obtain Yellow Dye 1.

[0403] Synthesis Example 5: Synthesis of Yellow Dye 2

[0404] (1) Synthesis of Intermediate 1

[0405]

[0406] 4-Methoxyphenyl isocyanate (5 g, 33.5 mmol) was placed in a round-bottom flask, to which 50 g of toluene and 4-methoxyaniline (4.13 g, 33.5 mmol) were added, and the resulting mixture was stirred at room temperature for 5 hours. After the reaction was completed, the product was filtered, and the solid compound obtained therefrom was washed several times with methanol and dried to synthesize Intermediate 1 (8.9 g, 97%).

[0407] (2) Synthesis of Intermediate 2

[0408]

[0409] Intermediate 1 (8.87 g, 32.6 mmol) was placed in a round-bottom flask, to which malonic acid (3.83 g, 36.8 mmol) and 80 g of acetic anhydride were added, and the resulting mixture was stirred at 90 °C for 5 hours. After the reaction was completed, the temperature was lowered to room temperature, and the solvent was removed therefrom by distillation. Subsequently, an extract was obtained therefrom using dichloromethane and washed with a 10% aqueous sodium hydroxide solution. After removing the organic layer, a 10% aqueous HCl solution was slowly added to the 10% aqueous NaOH solution layer to adjust the pH to 6, and an extract was obtained therefrom using dichloromethane. After removing the solvent therefrom, 50 g of isopropanol was added thereto, and the resulting mixture was stirred at 50 °C for 1 hour. The solid compound obtained therefrom was washed with isopropanol and dried to synthesize Intermediate 2 (5.99 g, 54%).

[0410] (3) Synthesis of Yellow Dye 2

[0411]

[0412] 4-Aminophthalonitrile (4.21 g, 29.4 mmol) was placed in a round-bottom flask, to which 30 g of water was added, and the temperature was lowered to 0 °C. Then, 30 g of HCl was added thereto, and the resulting mixture was stirred at 0 °C. A solution obtained by dissolving NaNO2 (2.03 g, 29.4 mmol) in 20 g of water was added to the reactant, and the resulting mixture was stirred at 0 °C for 2 hours.

[0413] In another round-bottom flask, sodium carbonate (9.35 g, 88.2 mmol) was placed, 500 g of water was added thereto, and the resulting mixture was stirred. After the sodium carbonate was dissolved in water, intermediate 2 (10 g, 29.4 mmol) was added thereto, and the resulting mixture was stirred at room temperature for 1 hour. This reactant was slowly added dropwise to the reactant stirred for 2 hours above, and after the addition was completed, the resulting mixture was stirred for 12 hours. After the reaction was completed, the product was filtered, and the solid compound obtained therefrom was washed with water and dried. Then, 100 g of MeCN was added to the dried compound, and the resulting mixture was stirred at 80 °C for 2 hours, and then filtered and dried to synthesize yellow dye 2 (12.3 g, 85%).

[0414] (Synthesis of photosensitive resin composition)

[0415] Examples 1 to 3, Comparative Example 1, Comparative Example 2, and Reference Example 1

[0416] The following components were mixed in the compositions shown in Table 1 to prepare the photosensitive resin compositions according to Examples 1 to 3, Comparative Example 1, Comparative Example 2, and Reference Example 1.

[0417] Specifically, the photoinitiator was dissolved in a solvent, the solution was stirred at room temperature for 2 hours, the binder resin and the photopolymerizable compound were added thereto, and the resulting mixture was stirred at room temperature for 2 hours. Subsequently, a colorant and other additives were added to the reactant, and the resulting mixture was stirred at room temperature for 1 hour. Then, the product obtained therefrom was filtered three times to remove impurities to prepare each photosensitive resin composition.

[0418] (Table 1)

[0419] (Unit: g)

[0420]

[0421] (A) Colorant

[0422] (A-1) Compound of Synthesis Example 1 (blue dye represented by Chemical Formula 1-1)

[0423] (A-2) Compound of Synthesis Example 2 (blue dye represented by Chemical Formula 3-1)

[0424] (A-3) Compound of Synthesis Example 3 (blue dye represented by Chemical Formula 3-2)

[0425] (A-4) Compound of Synthesis Example 4 (yellow dye 1)

[0426] (A-5)C.I. Pigment Blue 15:6 Pigment Dispersion (SANYO ELECTRIC Co., Ltd.)

[0427] (B)Binder Resin

[0428] Acrylic Binder Resin (RY-25, Showadenko K.K.)

[0429] (C)Photopolymerizable Compound

[0430] Dipentaerythritolhexaacrylate (DPHA) (Nippon Kayaku Co., Ltd.)

[0431] (D)Photopolymerization Initiator

[0432] (D-1)Oxime Compound (NCI831, Adeka Corporation)

[0433] (D-2)Acetophenone Compound (IRG369, Basf Corporation)

[0434] (E)Solvent

[0435] (E-1)Propylene Glycol Monomethyl Ether Acetate (PGMEA) (Kyowa Co., Ltd.)

[0436] (E-2)EDM (Kyowa Co., Ltd.)

[0437] (F)Additive

[0438] γ-Glycidoxypropyltrimethoxysilane (S-510, Chisso Corporation)

[0439] Evaluation 1: Transmittance of Dye

[0440] Three 2-μm-thick films were formed by using 2% by weight of each of the dyes of Synthesis Example 1, Synthesis Example 4, and Synthesis Example 5 based on 100% by weight of the composition while setting other conditions in the same manner, and the transmittance of the films was measured, and the results are shown in Figure 1 in.

[0441] Refer to Figure 1, unlike the yellow dyes of Synthesis Example 4 and Synthesis Example 5, the blue dye of Synthesis Example 1 exhibits a maximum absorption wavelength in a very narrow wavelength region of 420 nm to 440 nm, and thus proves to be able to sufficiently block the spectrum in the wavelength region of 420 nm to 440 nm.

[0442] Evaluation 2: Brightness of the photosensitive resin layer

[0443] Each of the photosensitive resin compositions of Examples 1 to 3, Comparative Example 1, Comparative Example 2, and Reference Example 1 was coated on a degreased and washed glass substrate having a thickness of 1 mm to a thickness of 1 μm to 3 μm at 250 rpm to 350 rpm, and then dried on a hot plate at 90 °C for 2 minutes to obtain a film. Subsequently, using a high-pressure mercury lamp having a main wavelength of 365 mm at 50 mJ / cm 2 The film was exposed, developed for 60 seconds, and further washed for 60 seconds using a KOH developing solution (a solution diluted 111 times) under the condition of washing solution / developing solution = 1 / 0.8. Then, the film was dried in a forced convection drying oven at 230 °C for 20 minutes to obtain each color sample (color chip).

[0444] The color characteristics of the color samples were evaluated using a spectrophotometer (MCPD3000, Otsuka Electronics Co., Ltd.) based on a C light source, and the brightness Y was calculated based on the color coordinates (Bx / By = 0.148 / 0.048), and the results are shown in Table 2.

[0445] (Table 2)

[0446] Brightness (%) Example 1 7.72 Example 2 8.89 Example 3 8.94 Comparative Example 1 - Comparative Example 2 - Reference Example 1 3.23

[0447] (Regarding Comparative Example 1 and Comparative Example 2, the compositions could not be prepared because all components were insoluble in the specified solvent due to an excess of the yellow dye, and thus the brightness could not be measured.)

[0448] Referring to Evaluation 1 and Evaluation 2, when using the compound represented by Chemical Formula 1-1, a small amount is sufficient to achieve excellent brightness and blue. In addition, referring to the examples and reference examples, even when an excess of the compound represented by Chemical Formula 1-1 is included, the brightness and blue characteristics are not further improved.

[0449] (Synthesis of the adhesive composition)

[0450] Example 4

[0451] The adhesive composition for a polarizing plate according to Example 4 was prepared by mixing the following components: 78.583% by weight of an acrylic adhesive resin (PL-8540; Saiden Chemical Industry Co., Ltd.), 0.236% by weight of an isocyanate-based curing agent (H-AL, Zircar Ceramic Inc.), 0.145% by weight of an aziridine-based curing agent (HDU-P25), 0.028% by weight of a release agent (MAC-2101; Soken Chemical Co., Ltd.), 1.336% by weight of an antistatic agent (FC-4400L; 3M Company), 0.024% by weight of a silane coupling agent (KBM-403; Shin-Etsu Co., Ltd.), 0.004% by weight of the compound according to Synthesis Example 1, and the balance (19.644% by weight) of a solvent (MEK).

[0452] Comparative Example 3

[0453] The adhesive composition for a polarizing plate according to Comparative Example 3 was prepared in the same manner as in Example 4, except that the compound according to Synthesis Example 1 was not used.

[0454] Evaluation 3: Color reproducibility and reflectance of the adhesive film

[0455] 1. Measurement of color reproducibility

[0456] Each of the compositions according to Example 4 and Comparative Example 3 was coated, dried at 90 °C for 4 minutes, and aged at 23 °C and 55% relative humidity for 24 hours to form an adhesive film, respectively, and then adhered to one surface (the side opposite to the backlight) of the panel, and then its color reproducibility was measured using a spectrophotometer (SR-3, Topcon Technohouse Corp.), and the results are shown in Table 3.

[0457] 2. Measurement of reflectance

[0458] Each of the adhesive films formed from the adhesive compositions according to Example 4 and Comparative Example 3 was adhered to a QD panel, and its reflectance was measured by applying a C-light spectrum using a spectrophotometer (CM-2600D, Minolta Co., Ltd.), and the results are shown in Table 3.

[0459] (Table 3)

[0460] (Unit: %)

[0461] Color reproducibility Reflectance Example 4 89.7 10.85 Comparative Example 3 88.2 12.04

[0462] As shown in Table 3, Example 4 in which the compound of Synthesis Example 1 was applied showed high color reproducibility with a reduced reflectance as compared with Comparative Example 3 in which the compound of Synthesis Example 1 was not applied.

[0463] Although the present invention has been described in connection with exemplary embodiments that are presently considered to be practical, it is to be understood that the invention is not limited to the disclosed embodiments, but on the contrary, the invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. An adhesive composition, comprising: 0.001% to 0.01% by weight of a compound represented by Chemical Formula 1; an acrylic adhesive resin; a hardener; and a solvent; [Chemical Formula 1] Among them, In Chemical Formula 1, M is Zn, Co or Cu, and R 1 to R 20 independently is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C6-C20 aryl group, a sulfonic acid group, a substituted or unsubstituted sulfonamide group or a substituted or unsubstituted C1-C20 alkyl ester group, The limitation is R 1 to R 5 at least one of, R 6 to R 10 at least one of, R 11 to R 15 at least one of, and R 16 to R 20 at least one of is independently not a hydrogen atom.

2. The adhesive composition according to claim 1, wherein the adhesive composition further comprises a silane coupling agent, an antistatic agent, an ultraviolet absorber, a cationic initiator, a release agent, or a combination thereof.

3. An adhesive film manufactured using the adhesive composition according to claim 1 or 2.

4. A polarizing plate comprising the adhesive film according to claim 3.

5. An optical display device comprising the polarizing plate according to claim 4.

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