CN115202151A

CN115202151A - Photosensitive resin composition and layer thereof, adhesive composition and adhesive film thereof, color filter, polarizing plate and optical display device

Info

Publication number: CN115202151A
Application number: CN202211040189.8A
Authority: CN
Inventors: 柳娥凛; 金善大; 金圭泳; 郑喆; 高埰赫; 李英
Original assignee: Samsung SDI Co Ltd
Current assignee: Samsung SDI Co Ltd
Priority date: 2018-03-09
Filing date: 2018-10-12
Publication date: 2022-10-18
Also published as: TW201938694A; KR20190106411A; KR102219646B1; CN110244511A; CN115236935A; TWI707003B; CN110244511B

Abstract

The present invention relates to a photosensitive resin composition and an adhesive composition comprising a compound represented by chemical formula 1, a photosensitive resin layer and an adhesive film manufactured using the composition, a color filter comprising the photosensitive resin layer, a polarizing plate comprising the adhesive film, and an optical display device comprising the color filter and/or the polarizing plate. In chemical formula 1, each substituent is the same as defined in the specification. The compound has a pairThe characteristic that light in a very narrow region is strongly absorbed, and thus the spectrum of light in the corresponding region can be blocked, and blue color is achieved even with a very small amount. The adhesive film and the polarizing plate manufactured by using the adhesive composition have excellent durability and color stability.

Description

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

The invention is a divisional application of patent application with application number 201811188088.9, which is proposed in 2018, 10, 12 and named as photosensitive resin composition and layer thereof, adhesive composition and adhesive film thereof, color filter, polarizing plate and optical display device.

Technical Field

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

Background

Among the many kinds of displays, liquid crystal display devices have advantages of being light, thin, low in cost, low in operating power consumption, and high in support of integrated circuits, and have been more widely used for laptop computers, monitors, and television screens. The liquid crystal display device includes a lower substrate on which a black matrix (light blocking layer), a color filter, and an Indium Tin Oxide (ITO) pixel electrode are formed, and an upper substrate on which an active circuit portion including a liquid crystal layer, a thin film transistor, and a capacitor layer, and an ITO pixel electrode are formed.

A color filter is formed in a pixel region by sequentially stacking a plurality of color filters, generally, formed of three primary colors such as red (R), green (G), and blue (B), in a predetermined order to form each pixel, and a black matrix (light blocking layer) is disposed on a transparent substrate in a predetermined pattern to form a boundary between pixels.

A pigment dispersion method, which is one of various methods of forming a color filter, provides a colored thin film by repeating a series of the following processes: for example, a photopolymerizable composition containing a colorant is coated on a transparent substrate including a black matrix, a formed pattern is exposed, an unexposed portion is removed with a solvent, and heat curing is performed thereon. The colored photosensitive resin composition for manufacturing a color filter according to the pigment dispersion method generally includes an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, other additives, and the like. The pigment dispersion method is actively used in manufacturing Liquid Crystal Displays (LCDs) such as mobile phones, laptop computers, monitors, and televisions.

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 required to stabilize the dispersion even if dispersed, and a complicated process is required, and it is difficult to further maintain the optimum quality of the pigment dispersion under complicated storage conditions and transportation conditions.

In addition, a color filter manufactured using the pigment-type photosensitive resin composition has limitations in brightness and contrast due to the particle size of the pigment. A color image sensor device for an image sensor requires smaller dispersed particle diameters to form a fine pattern. In order to meet this requirement, attempts have been made to prepare a photosensitive resin composition by introducing a dye instead of or together with a pigment to realize a color filter having improved color characteristics such as brightness, contrast, etc., but the dye-type photosensitive resin composition has a problem of deteriorated durability as compared with the pigment-type photosensitive resin composition.

On the other hand, a Liquid Crystal Display (LCD) requires a liquid crystal cell including liquid crystal and a polarizing plate, and an appropriate adhesive layer or an adhesive layer for adhering the liquid crystal cell and the polarizing plate.

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

The release film is released from the adhesive layer during the process of adhering the polarizing plate having this structure to the liquid crystal cell, and also released and removed when the function of the surface protective film in the following process is completed. The release film and the surface protection film are formed of a plastic material, and thus exhibit high insulating properties and generate static electricity during detachment.

This static electricity may cause a surface contamination problem of the optical member due to impurities adsorbed on the optical member, a stain problem due to alignment distortion of the liquid crystal, and the like, and damage a Thin Film Transistor (TFT) circuit. In particular, since a Liquid Crystal Display (LCD) panel has recently become large-sized, a polarizing plate used to manufacture the Liquid Crystal Display (LCD) tends to become large-sized even through a high-speed process, and thus the amount of generated static electricity is continuously increased, thereby requiring more urgent solution.

Disclosure of Invention

Embodiments of the present invention provide a photosensitive resin composition including a compound having improved color reproducibility as a colorant.

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

Another embodiment provides a color filter comprising the photosensitive resin layer.

Another embodiment provides an adhesive composition comprising the compound as a colorant.

Another embodiment provides an adhesive film manufactured using the adhesive composition.

Another embodiment provides a polarizing plate comprising the adhesive film.

Another embodiment provides an optical display device comprising the color filter and/or the polarizing plate.

An embodiment of the present invention provides a photosensitive resin composition, including: (a) a colorant comprising a compound represented by chemical formula 1; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent.

[ chemical formula 1]

In the chemical formula 1, the reaction mixture is,

m is Zn, co or Cu, and

R ¹ to R ²⁰ 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,

with the proviso that R ¹ To R ⁵ At least one of R ⁶ To R ¹⁰ At least one of (1), R ¹¹ To R ¹⁵ At least one of (1) and R ¹⁶ To R ²⁰ Is independently not a hydrogen atom.

The compound may be represented by chemical formula 2.

[ chemical formula 2]

In the chemical formula 2, the first and second organic solvents,

m is Zn, co or Cu,

R ²¹ to R ²⁸ Independently 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,

n1 to n8 are independently integers of 0 or 1, 1. Ltoreq. N1+ n 2. Ltoreq.2, 1. Ltoreq. N3+ n 4. Ltoreq.2, 1. Ltoreq. N5+ n 6. Ltoreq.2, and 1. Ltoreq. N7+ n 8. Ltoreq.2.

The compound may be represented by one of chemical formulas 1-1 to 1-20.

[ chemical formula 1-1]

[ chemical formulas 1-2]

[ chemical formulas 1-3]

[ chemical formulas 1 to 4]

[ chemical formulas 1-5]

[ chemical formulas 1 to 6]

[ chemical formulas 1 to 7]

[ chemical formulas 1 to 8]

[ chemical formulas 1 to 9]

[ chemical formulas 1-10]

[ chemical formulas 1 to 11]

[ chemical formulas 1 to 12]

[ chemical formulas 1-13]

In the chemical formulae 1 to 13,

r is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

m1 and m2 are independently integers in the range of 0 to 20, and 4. Ltoreq. M1+ m 2. Ltoreq.20,

[ chemical formulas 1 to 14]

[ chemical formulas 1 to 15]

[ chemical formulas 1 to 16]

[ chemical formulas 1 to 17]

[ chemical formulas 1 to 18]

[ chemical formulas 1 to 19]

[ chemical formulas 1 to 20]

The compound represented by chemical formula 1 may be included in an amount of 0.01 to 7% by weight, based on the total amount of the photosensitive resin composition.

The colorant can also comprise a blue dye, a blue pigment, a red dye, a red pigment, or a combination thereof.

The blue dye may be represented by chemical formula 3.

[ chemical formula 3]

In the chemical formula 3, the reaction mixture is,

R ²⁹ and R ³⁰ Independently a substituted C1 to C20 alkyl group or a substituted or unsubstituted C3 to C20 cycloalkyl group,

R ³¹ is a hydrogen atom or a halogen atom,

R ³² is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ³³ is a C1 to C20 alkyl group substituted or not with an acrylate group, and

x-is represented by one of chemical formula A to chemical formula C.

[ chemical formula A ]

SO ₃ ^-

[ chemical formula B ]

F ₃ C-(CF ₂ ) _n3 -SO ₃

(in the chemical formula B, n3 is an integer ranging from 0 to 10)

[ chemical formula C ]

The blue dye may be represented by chemical formula 3-1 or chemical formula 3-2.

[ chemical formula 3-1]

[ chemical formula 3-2]

In chemical formula 3-1 and chemical formula 3-2,

x-is represented by one of chemical formula A to chemical formula C.

[ chemical formula A ]

SO ₃ ^-

[ chemical formula B ]

F ₃ C-(CF ₂ ) _n3 -SO ₃

(in the chemical formula B, n3 is an integer ranging from 0 to 10)

[ chemical formula C ]

The blue pigment may be color index (c.i.) pigment blue 15.

The binder resin may include an acrylic binder resin.

The photopolymerization initiator may include oxime-based initiators and acetophenone-based initiators.

The photosensitive resin composition may include, based on the total amount of the photosensitive resin composition: 3 to 20% by weight of (a) a colorant comprising a compound represented by chemical formula 1; 1 to 10% by weight of (B) a binder resin; 1 to 10% by weight of (C) a photopolymerizable compound; 0.1 to 5% by weight of (D) a photopolymerization initiator; and the balance (E) solvent.

The photosensitive resin composition may further include an epoxy compound, a silane coupling agent, a surfactant, or a combination thereof.

Another embodiment provides an adhesive composition comprising: (1) a compound represented by chemical formula 1; (2) acrylic binder resins; (3) a hardener; and (4) a solvent.

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.

Another embodiment provides a polarizing plate comprising the adhesive film.

Another embodiment provides an optical display device including the polarizing plate.

Another embodiment provides an optical display device including the color filter and/or the polarizing plate.

Other embodiments of the invention are included in the following detailed description.

The photosensitive resin composition according to the embodiment includes a compound blocking a wavelength of a violet region (400 nm to 440 nm) to improve color reproducibility of a color filter constituting an optical display device such as a Liquid Crystal Display (LCD), and thus can achieve relatively high luminance at high color coordinates. In particular, the compound has a characteristic of strongly absorbing light in a very narrow region, and thus can block the spectrum of light in a corresponding region, and realize blue color even with a very small amount. In addition, the adhesive composition according to the embodiment does not discolor even when exposed to a high temperature/high humidity environment for a long time, and thus may exhibit excellent color stability, durability, heat resistance, or moisture resistance. Therefore, an adhesive film manufactured using the adhesive composition has excellent durability, and a polarizing plate including the adhesive film having excellent durability may also have excellent durability and color stability.

Drawings

Fig. 1 is a graph showing transmittance as a function of wavelength of the compound represented by chemical formula 1-1, yellow dye 1 and yellow dye 2.

Detailed Description

Hereinafter, examples of the present invention are explained in detail. These embodiments are exemplary, however, and the invention is not limited thereto and is defined by the scope of the claims.

In the present specification, when a specific definition is not otherwise provided, "substituted" means substituted with a substituent selected from: halogen (F, br, cl or I), hydroxy, nitro, cyano, amino (NH) ₂ 、NH(R ²⁰⁰ ) Or N (R) ²⁰¹ )(R ²⁰² ) Wherein R is ²⁰⁰ 、R ²⁰¹ And R ²⁰² Are the same or different and are independently C1 to C10 alkyl), amidino, hydrazine, hydrazone, carboxyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted alicyclic organic, substituted or unsubstituted aryl, and substituted or unsubstituted heterocyclic.

In this specification, when a specific definition is not otherwise provided, "alkyl" means C1 to C20 alkyl and especially C1 to C15 alkyl, "cycloalkyl" means C3 to C20 cycloalkyl and especially C3 to C18 cycloalkyl, "alkoxy" means C1 to C20 alkoxy and especially C1 to C18 alkoxy, "aryl" means C6 to C20 aryl and especially C6 to C18 aryl, "alkenyl" means C2 to C20 alkenyl and especially C2 to C18 alkenyl, "alkylene" means C1 to C20 alkylene and especially C1 to C18 alkylene, and "arylene" means C6 to C20 arylene and especially C6 to C16 arylene.

In the present specification, "(meth) acrylate" means "acrylate" and "methacrylate", and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid", when a specific definition is not otherwise provided.

In the present specification, the term "combination" means mixing or copolymerization when a definition is not otherwise provided. In addition, "copolymerization" refers to block copolymerization to random copolymerization, and "copolymer" refers to block copolymer to random copolymer.

In the chemical formulae of the present specification, unless a specific definition is otherwise provided, when a chemical bond is not drawn at a position that should be given, the hydrogen bonds at the position.

In the present specification, when a specific definition is not otherwise provided, ""' indicates a point connecting the same or different atoms or chemical formulae.

In addition, when any member is provided "on" another member in the present specification, the member may not only contact the other member, but also there may be another member between the two members.

In addition, in this specification, unless explicitly stated to the contrary, the word "comprise", and variations such as "comprises" or "comprising", will be understood to imply the inclusion of stated elements but not the exclusion of any other elements.

Hereinafter, each component is specifically described.

Colouring agent

The photosensitive resin composition according to the embodiment includes a compound represented by chemical formula 1 as a colorant.

[ chemical formula 1]

In the chemical formula 1, the first and second,

m is Zn, co or Cu, and

R ¹ to R ²⁰ 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(s),

For example, the compound may be represented by chemical formula 2.

[ chemical formula 2]

In the chemical formula 2, the reaction mixture is,

m is Zn, co or Cu,

n1 to n8 are independently an integer of 0 or 1, 1. Ltoreq. N1+ n 2. Ltoreq.2, 1. Ltoreq. N3+ n 4. Ltoreq.2, 1. Ltoreq. N5+ n 6. Ltoreq.2, and 1. Ltoreq. N7+ n 8. Ltoreq.2.

For example, the compound may be represented by one of chemical formulas 1-1 through 1-20.

[ chemical formula 1-1]

[ chemical formulas 1-2]

[ chemical formulas 1-3]

[ chemical formulas 1-4]

[ chemical formulas 1 to 5]

[ chemical formulas 1 to 6]

[ chemical formulas 1 to 7]

[ chemical formulas 1 to 8]

[ chemical formulas 1 to 9]

[ chemical formulas 1-10]

[ chemical formulas 1 to 11]

[ chemical formulas 1-12]

[ chemical formulas 1 to 13]

In the chemical formulae 1 to 13,

r is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

[ chemical formulas 1 to 14]

[ chemical formulas 1 to 15]

[ chemical formulas 1 to 16]

[ chemical formulas 1 to 17]

[ chemical formulas 1 to 18]

[ chemical formulas 1 to 19]

[ chemical formulas 1 to 20]

With respect to the blue resist among the conventional color filter resists, some violet colorant is generally added to the blue pigment to adjust the color coordinates and increase the brightness. However, bx of the color coordinates of novel blue tends to be much smaller recently to increase color reproducibility. In order to realize a blue color filter having such high color reproducibility, a narrow transmission spectrum should be formed around 450nm of the wavelength of a blue Light Emitting Diode (LED), i.e., a light source, and thus it is suggested to manufacture a resist by reducing the width of the transmission spectrum by using a beta blue (beta blue) pigment instead of an epsilon blue (epsilon blue) conventionally used but increasing a Pigment Weight Concentration (PWC). However, there is a problem of conventional luminance degradation.

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 in the vicinity of 400 to 440nm, especially 420 to 440nm, and intercepts the spectrum in the corresponding region in a very small amount, so that blue color can be realized. In order to achieve the similar object, there has been an attempt to absorb light in the region of 380nm to 420nm using a conventional azo-based yellow dye or the like, but there is a problem in that a process margin of the entire composition cannot be secured since a relatively large amount of the azo-based yellow dye is put, but according to an embodiment, since a sufficiently high color reproducibility can be achieved using a small amount of the compound represented by chemical formula 1, 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 loss of brightness may increase. However, according to an embodiment, the loss of brightness of the (main) spectrum of the light source may be minimized by: the transmittance is adjusted depending on the wavelength of the yellow dye that absorbs light in a wavelength region near 400 to 440nm, and particularly near 420 to 440nm, and the transmittance in a wavelength region of less than 400nm and greater than or equal to 450nm is adjusted to be greater than or greater than 80%, for example, greater than or equal to 95%. In addition, with respect to a colorant (dye or pigment) having high brightness but Bx is large compared to a conventional blue pigment and thus is not suitable for high color coordinates, the compound according to the embodiment (represented by chemical formula 1) may be used to further increase brightness and achieve high color coordinates.

The compound represented by chemical formula 1 may be included in an amount of 0.01 to 7% by weight, based on the total amount of the photosensitive resin composition. Within this range, sufficiently high color reproducibility and improved process margin can be provided.

For example, the colorant can also include a blue dye, a blue pigment, a red dye, a red pigment, or a combination thereof.

The blue dye may be represented by chemical formula 3.

[ chemical formula 3]

In the chemical formula 3, the first and second,

R ³¹ is a hydrogen atom or a halogen atom,

X ^- is represented by one of chemical formulas a to C.

[ chemical formula A ]

SO ₃ ^-

[ chemical formula B ]

F ₃ C-(CF ₂ ) _n3 -SO ₃

(in the chemical formula B, n3 is an integer ranging from 0 to 10)

[ chemical formula C ]

For example, the blue dye may be represented by chemical formula 3-1 or chemical formula 3-2.

[ chemical formula 3-1]

[ chemical formula 3-2]

In chemical formula 3-1 and chemical formula 3-2,

x-is represented by one of chemical formula A to chemical formula C.

[ chemical formula A ]

SO ₃ ^-

[ chemical formula B ]

F ₃ C-(CF ₂ ) _n3 -SO ₃

(in the chemical formula B, n3 is an integer ranging from 0 to 10)

[ chemical formula C ]

Specifically, the blue dye may be represented by chemical formula 3-1.

Since the compound represented by chemical formula 3-1 includes a cyclohexyl group and thus can improve heat resistance, and also includes a methyl group in a phenyl group substituted with a nitrogen atom and thus can improve light resistance, a color filter having excellent durability (e.g., heat resistance, light resistance, etc.) and high luminance in color coordinates can be provided.

For example, the blue pigment can be an epsilon blue pigment. When a blue pigment is used as the blue colorant according to the embodiment, the epsilon blue pigment may more contribute to the improvement of the brightness than the beta blue pigment.

For example, the blue pigment can be c.i. pigment blue 15.

For example, the red pigment may be c.i. red pigment 254, c.i. red pigment 255, c.i. red pigment 264, c.i. red pigment 270, c.i. red pigment 272, c.i. red pigment 177, c.i. red pigment 179, c.i. red pigment 89, etc., but is not limited thereto.

The colorant may be included in an amount of 3 to 20% by weight, based on the total amount of the photosensitive resin composition according to the embodiment. When the colorant is contained in this range, high luminance can be achieved at high color coordinates.

Adhesive resin

The binder resin may include an acrylic binder resin. For example, the binder resin may be an acrylic binder resin.

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 comprising at least one acrylic repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer comprising at least one carboxyl and/or hydroxyl group, and the barrier of the monomer comprises acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or combinations thereof.

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

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, alpha-methylstyrene, vinyltoluene, vinylbenzyl methyl ether, or the like; unsaturated carboxylic acid ester compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, and the like; unsaturated aminoalkyl carboxylate compounds such as 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, and the like; vinyl carboxylate compounds such as vinyl acetate, vinyl benzoate and the like; unsaturated glycidyl carboxylate compounds such as glycidyl (meth) acrylate and the like; acrylonitrile compounds such as (meth) acrylonitrile and the like; unsaturated amide compounds such as (meth) acrylamide and the like; and the like, and the second ethylenically unsaturated monomer may be used alone or as a mixture of two or more.

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

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

The acid value of the acrylic adhesive resin may be from 15mgKOH/g to 60mgKOH/g, for example from 20mgKOH/g to 50mgKOH/g. When the acid value of the acrylic binder resin is within the range, excellent pixel resolution can be obtained.

The binder resin may be included in an amount of 1 to 10 wt%, for example, 3 to 7 wt%, based on the total amount of the photosensitive resin composition. When the binder resin is included within the range, developability may be improved, and excellent surface smoothness may be improved due to improved crosslinking during the manufacture of the color filter.

Photopolymerizable compounds

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

The photopolymerizable compound has an ethylenically unsaturated double bond, and thus can cause sufficient polymerization during exposure of the pattern forming process and form a pattern having excellent heat resistance, light resistance, and chemical resistance.

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 tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, quaternary pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol a epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate, and the like.

Commercially available examples of the photopolymerizable compounds are as follows. The monofunctional (meth) acrylate may include Aronix M-

M-

M-

(Toagosei Chemistry Industry Co., ltd.); kayarad (KAYARAD) TC-

TC-

(Nippon Kayaku Co., ltd.); v-

V-

(Osaka Organic Chemical Ind., ltd.) and the like. Examples of difunctional (meth) acrylates may include Aronix M-

M-

M-

(Toyata chemical Co., ltd.), kayarad (KAYARAD)

HX-

R-

(chemical Co., ltd., japan), V-

V-

V-335

(Osaka organic chemical Co., ltd.) and the like. Examples of trifunctional (meth) acrylates may include Aronix M-

M-

M-

M-

M-

M-

M-

(Toyata chemical Co., ltd.), kayarad (KAYARAD)

DPCA-

DPCA-

DPCA-

DPCA-

(chemical Co., ltd., japan), V-

V-

V-

V-

V-

V-

(Osaka Yoki Kayaku Kogyo Co., ltd.)) and the like. These photopolymerizable compounds may be used alone or in a mixture of two or more.

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

The photopolymerizable compound may be included in an amount of 1 to 10 wt%, for example, 1 to 5 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is contained within the range, the photopolymerizable compound is sufficiently cured during exposure of the pattern forming process and has excellent reliability, and the developability of the alkaline developer may be improved.

Photopolymerization initiator

The photopolymerization initiator may be a conventional initiator in a photosensitive resin composition, for example, 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.

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

Examples of the benzophenone-based compound may be benzophenone, benzoyl benzoate, benzoylmethyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4' -bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4' -dimethylaminobenzophenone, 4' -dichlorobenzophenone, 3' -dimethyl-2-methoxybenzophenone and the like.

Examples of the thioxanthone-based compound may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

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

Examples of the triazine-based compound 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- (naphthol 1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol 1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-s-triazine, 2, 4-bis (trichloromethyl) -6-methoxystyryl-s-triazine, and the like.

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

The photopolymerization initiator may include both an oxime-based initiator and an acetophenone-based initiator. Herein, when the photopolymerization initiator includes an oxime-based initiator and an acetophenone-based initiator, an excellent process margin can be secured by improving curing efficiency, compared to when one photopolymerization initiator is used. In addition, a larger amount of the oxime-based initiator may be contained as compared with the amount of the acetophenone-based initiator. When an oxime-based initiator is contained in an amount equal to or less than that of the acetophenone-based initiator, a desired circular dichroism spectrum (CD) can be obtained due to low sensitivity (excellent sensitivity).

The photopolymerization initiator may further contain a carbazole-based compound, a diketone-based compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, a biimidazole-based compound, a fluorene-based compound, and the like, in addition to the above-mentioned compounds.

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

Examples of the photosensitizer may be tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

The photopolymerization initiator may be included in an amount of 0.1 to 5% by weight, for example, 0.1 to 1% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the range, sufficient photopolymerization occurs during exposure of the pattern forming process, excellent reliability can be achieved, heat resistance, light resistance and chemical resistance, resolution and close contact properties of the pattern can be improved, and transmittance can be prevented from being reduced by the non-reactive initiator.

Solvent(s)

The solvent is a material that is compatible with but does not react with the colorant, the binder resin, the photopolymerizable compound and the photopolymerization initiator.

Examples of the solvent may include alcohols such as methanol, ethanol, and the like; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, anisole, tetrahydrofuran, and the like; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like; cellosolves of acetic acid such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, and the like; 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, and the like; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and the like; 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-amyl ketone, 2-heptanone, and the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactates such as methyl lactate, ethyl lactate, and the like; alkyl oxyacetates such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc.; alkyl alkoxyacetates such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like; alkyl 3-oxopropanates such as methyl 3-oxopropanoate, ethyl 3-oxopropanoate and the like; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-oxopropanates such as methyl 2-oxopropanoate, ethyl 2-oxopropanoate, propyl 2-oxopropanoate, and the like; alkyl 2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-oxo-2-methylpropionates such as methyl 2-oxo-2-methylpropionate, ethyl 2-oxo-2-methylpropionate and the like; mono-oxo-monocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methylpropionates, such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, and the like; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate and the like; ketoesters such as ethyl pyruvate and the like. In addition, high boiling point solvents such as N-methylformamide, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetylacetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like can also be used.

In view of miscibility and reactivity, ketones such as cyclohexanone and the like; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate and the like; esters such as ethyl 2-hydroxypropionate and the like; carbitols such as diethylene glycol monomethyl ether and the like; propylene glycol alkyl ether acetates, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate.

The solvent is used in a balance of, for example, 40 to 80% by weight, for example, 50 to 75% by weight, based on the total amount of the photosensitive resin composition. When the solvent is included within the range, the photosensitive resin composition may have an appropriate viscosity, thereby improving coating characteristics of the color filter.

Other additives

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

Examples of the epoxy compound may include a phenol novolac epoxy compound, a tetramethyl biphenyl epoxy compound, a bisphenol a epoxy compound, an alicyclic epoxy compound, or a combination thereof.

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

In addition, the photosensitive resin composition may further include a silane coupling agent having a reactive substituent (e.g., a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, etc.) to improve adhesion to a substrate.

Examples of the silane-based coupling agent may include trimethoxysilylbenzoic acid, gamma-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-vinyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-3-aminopropyltriethoxysilane, 3-1-dimethylaminopropyltrimethoxysilane, 3-2- (aminopropyl) aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-1-dimethylaminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 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 admixture of two or more.

The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included within the range, close contact properties, storage properties, and the like may be excellent.

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

Examples of the surfactant may be commercially available fluorine-based surfacesActive agents, such as BM-

BM-

Etc.; meijia Method (MEGAFACE) F of Dainippon Ink Kagaku Kogyo Co., ltd., japan Ink chemical Co., ltd.)

F

F

F

F

Etc.; florade (FULORAD) FC-

FC-

FC-

FC-

Etc.; shafu Long (SURFLON) S-

S-

S-

S-

S-

Etc.; and SH-

SH-

SH-

SZ-

SF-

And so on.

The surfactant may be included in an amount of 0.001 parts by weight to 5 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the surfactant is contained in the range, coating uniformity is ensured, no stain is found, and wettability to the glass substrate is excellent.

In addition, unless the properties of the photosensitive resin composition deteriorate, the photosensitive resin composition may further contain predetermined amounts of other additives, such as an oxidation inhibitor, a stabilizer, and the like.

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

The patterning process of the photosensitive resin layer is as follows.

The process comprises the following steps: coating the photosensitive resin composition according to the embodiment on a supporting substrate by spin coating, slit coating, inkjet printing, or the like; drying the applied 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 aqueous alkali 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 related art and will not be described in detail in this specification.

According to an embodiment, there is provided a color filter including a photosensitive resin layer.

According to another embodiment, an adhesive composition comprises: (1) a compound represented by chemical formula 1; (2) acrylic binder resin; (3) a hardening agent; 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.

Hereinafter, adhesive compositions according to embodiments of the present invention are described.

The adhesive film formed using the adhesive composition according to the embodiment includes the compound represented by chemical formula 1 and having the maximum absorption wavelength of 400nm to 450nm, and thus may improve scattered reflection (spread reflection) generated by incident light in the panel, i.e., visibility deterioration due to reflection. A spectrophotometer can be used to measure the reflectance for improved visibility. In other words, the reflectivity may express the degree to which visibility is degraded by incident light in the panel and by divergent reflections generated by particles within the panel.

The compound represented by chemical formula 1 may be included in an amount of 0.001 to 0.01 wt% based on the total amount of the adhesive composition (0.01 to 0.03 wt% based on the solid content of the adhesive composition).

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

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

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

The first (meth) acrylate copolymer forms a matrix of the adhesive film and provides at least one of hydroxyl and carboxylic acid groups to render the adhesive composition self-curing.

The first (meth) acrylate copolymer may be a copolymer of: a monomer mixture including at least one of a (meth) acrylate monomer having a hydroxyl group, a (meth) acrylate monomer having a carboxylic acid group; and a monomer copolymerizable therewith (hereinafter, referred to as "first copolymerizable monomer"). At least one of the (meth) acrylate monomer having a hydroxyl group and the (meth) acrylate monomer having a carboxylic acid group may be included in an amount of less than or equal to 10mol% and particularly 0.01mol% 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 being suitable for a flexible device may be realized.

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

The (meth) acrylate monomer having a hydroxyl group may include at least one of: a (meth) acrylate monomer having at least one hydroxyl group and containing a C1 to C20 alkyl group, a (meth) acrylic monomer having at least one hydroxyl group and containing a C3 to C20 cycloalkyl group, and a (meth) acrylic monomer having at least one hydroxyl group and containing a C6 to C20 aromatic group. Specifically, the (meth) acrylate monomer having a hydroxyl group may include at least one of: 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 may be used alone or in the form of a mixture of two or more.

The (meth) acrylate monomer having a carboxylic acid group may be capable of achieving self-curing. The (meth) acrylate monomer having a carboxylic acid group may be included in an amount of less than or equal to 5mol% and especially 0.01mol% to 5mol% of the monomer mixture. In the range, the adhesive film does not have high acidity and thus does not risk to corrode the substrate, and thus has the effect of reducing resistance and increasing reliability. The (meth) acrylate monomer having a carboxylic acid group may include (meth) acrylic acid and the like, but is not limited thereto.

The first copolymerizable monomer may form the 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 carboxylic acid group, and may form a matrix of the adhesive film and may provide additional functions.

The first copolymerizable monomer may 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 ester monomer having an alkyl group may be included in an amount of 50 to 99.99mol%, particularly 50 to 95mol%, 95 to 99.9mol%, 55 to 90mol%, or 60 to 85mol% of the monomer mixture. Within the range, the mechanical strength of the adhesive film may be increased. The (meth) acrylate monomer having an alkyl group may include a (meth) acrylate having an unsubstituted C4 to C12 alkyl group. Specifically, the (meth) acrylate monomer having an alkyl group may include at least one of: n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (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 are not limited thereto. These monomers may be used alone or in a mixture of two or more.

The first copolymerizable monomer may increase the pencil hardness of the 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 heteroalicyclic group.

The (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 the pencil hardness of the polarizing plate on the adhesive film of greater than or equal to 2H, more specifically, 2H to 3H. Within the range, even if 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, as compared to when the polarizing plate is adhered to the liquid crystal panel without the adhesive film, and thus, the polarizing plate can be used for an optical display device. In addition, a (meth) acrylate monomer having an alicyclic group is included in the (meth) acrylate copolymer together with a (meth) acrylate monomer having a heteroalicyclic group, and may reduce creep of the adhesive film of the polarizing plate at 25 ℃ but increase creep thereof at 85 ℃. In particular, when the (meth) acrylate monomer having an alicyclic group and the (meth) acrylate monomer having a heteroalicyclic group are homopolymers, respectively, the glass transition temperature becomes greater than or equal to 30 ℃, and particularly 40 ℃ to 180 ℃, and thus it is possible to deteriorate the creep of the adhesive film at 25 ℃ and enhance the creep thereof at 85 ℃. The molar ratio of (meth) acrylate monomer having an alicyclic group to (meth) acrylate monomer having a heteroalicyclic group in the monomer mixture may range from 1. Within the range, there may be an effect of increasing cohesion or strength at room temperature. Alternatively, there may be a stress relaxation effect at a high temperature and a bending improvement effect of the polarizing film.

The (meth) acrylate ester monomer having an alicyclic group may be contained in an amount of 1 to 30mol% and particularly 5 to 20mol% of the monomer mixture. Within the above range, the pencil hardness and cohesion of the polarizing plate on the adhesive film can be increased.

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

"cycloaliphatic radical" means a non-heteroalicyclic radical that does not contain a heteroatom of nitrogen, oxygen, or sulfur. "heterocycle" refers to at least two alicyclic groups attached to each other that share at least one carbon atom.

In particular, the (meth) acrylate having a substituted or unsubstituted C5 to C20 monocyclic or heterocyclic cycloaliphatic group can include at least one of: cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, methylcyclohexyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. These (meth) acrylates may be used alone or in a mixture of two or more.

The (meth) acrylate monomer having a heteroalicyclic group together with the (meth) acrylate monomer having an alicyclic group can degrade creep at 25 ℃ and enhance creep at 85 ℃.

The (meth) acrylate ester monomer having a heteroalicyclic group may be included in the monomer mixture in an amount of 1 to 30mol% and particularly 5 to 20 mol%. Within the range, there may be an effect of increasing the modulus of the adhesive film at 30 ℃ and improving the cohesive force.

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

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

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

The second (meth) acrylate copolymer forms a matrix of the adhesive film and provides at least one of an epoxy group and an oxetane group, and thus the adhesive composition is self-curable without a crosslinking agent.

The second (meth) acrylate copolymer may 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 may be included in an amount of less than or equal to 10mol% and particularly 0.01mol% to 5 mol%. Within the range, when the 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, an adhesive film having excellent flexibility, bending property, hardness, workability and reliability and thus being suitable for a flexible device may be realized.

The (meth) acrylate monomer having an epoxy group can make the adhesive composition self-cure and/or achieve the effect of improving cohesion and reliability. In the monomer mixture, the (meth) acrylic monomer having an epoxy group may be contained in an amount of 5mol% or less, and particularly 0.01mol% to 5 mol%. Within the range, there may be effects of accelerating curing and improving reliability. The (meth) acrylic monomer having an epoxy group may be glycidyl (meth) acrylate or the like.

The (meth) acrylate monomer having an oxetanyl group can make the adhesive composition self-cure and/or achieve the effect of improving cohesion and reliability. In the monomer mixture, the (meth) acrylate monomer having an oxetanyl group may be contained in an amount of 5mol% or less and especially 0.01mol% to 5 mol%. Within the range, there may be effects of accelerating curing and improving reliability. The (meth) acrylate monomer having an oxetanyl group may be oxetanyl (meth) acrylate, methyl 3-methyl-3-oxetanyl (meth) acrylate, methyl 3-ethyl-3-oxetanyl (meth) acrylate, or the like.

The second copolymerizable monomer is copolymerized with at least one of the (meth) acrylate monomer having an epoxy group and the (meth) acrylate monomer having an oxetanyl group, and thus may form a substrate of the adhesive film or provide additional functions.

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 heteroalicyclic group, and thus may 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 heteroalicyclic group are specifically the same species as mentioned in the first copolymerizable monomer.

In exemplary embodiments, the second (meth) acrylate copolymer may be a copolymer of: 0.01 to 5mol% of at least one of a (meth) acrylate monomer having an epoxy group and a (meth) acrylate monomer having an oxetanyl group; and 95 to 99.9mol% of a (meth) acrylate monomer having an alkyl group. In another exemplary embodiment, the second (meth) acrylate copolymer may be a copolymer of: 0.01 to 5mol% of at least one of a (meth) acrylate monomer having an epoxy group and a (meth) acrylate monomer having an oxetanyl group; 50 to 95mol% of a (meth) acrylate monomer having an alkyl group; 1 to 30mol% of a (meth) acrylate monomer having an alicyclic group; and 1 to 30mol% of a (meth) acrylate monomer having a heteroalicyclic group. Within the range, there may be effects of accelerating curing and improving reliability.

The first and second (meth) acrylate copolymers each have a glass transition temperature of-55 ℃ to-5 ℃ and in particular-50 ℃ to-30 ℃. The first and second (meth) acrylate copolymers can each have a weight average molecular weight of 200,000g/mol to 1,500,000g/mol and especially 500,000g/mol to 1,000,000g/mol. The first and second (meth) acrylate copolymers can each have an acid value of less than or equal to 5mgKOH/g, and more specifically, 0.01mgKOH/g to 3 mgKOH/g. Within the above range, the effect of directly preventing and suppressing the corrosion of the substrate can be achieved.

The first (meth) acrylate copolymer and the second (meth) acrylate copolymer can be prepared by polymerizing each monomer mixture using a general polymerization method. The polymerization process may include general methods known to those of ordinary skill in the art. For example, the (meth) acrylate copolymer may be prepared by adding an initiator to a monomer mixture and performing general copolymer polymerization (e.g., suspension polymerization, emulsion polymerization, solution polymerization, etc.). The polymerization temperature may range from 65 ℃ to 70 ℃ and the polymerization time may range from 6 hours to 8 hours. The initiator may be an azo polymerization initiator; and/or peroxides such as benzoyl peroxide or acetyl peroxide.

The hardener may be a thermal hardener, and may enhance cohesive force of the adhesive by appropriately crosslinking the acrylic adhesive resin, but is not particularly limited. For example, the hardener may be an isocyanate-based compound, an aziridine-based compound, etc., and may be used alone or in a mixture of two or more.

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

The aziridine compound may be N, N ' -toluene-2, 4-bis (1-aziridinecarboxamide), N ' -diphenylmethane-4, 4' -bis (1-aziridinecarboxamide), triethylenemelamine, bis-isophthaloyl-1- (2-methylaziridine), tris-1-aziridinylphosphine oxide, or the like.

In addition, the melamine-based compound may be used alone or in a mixture of two or more of them together with the isocyanate-based compound and the aziridine-based compound.

The melamine compound may be hexamethylolmelamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, or the like.

The hardener may be included in an amount of 0.1 to 1 wt%, for example 0.1 to 0.5 wt%, based on the total amount of the adhesive composition (0.3 to 1.0 wt% based on the solid content of the adhesive composition) to improve adhesive strength or cohesion. When the hardener is included in an amount of less than 0.1 wt% based on the total amount of the adhesive composition, the adhesive strength or cohesion of the adhesive is slightly deteriorated (incomplete curing) due to insufficient degree of crosslinking, and thus durability may be deteriorated (e.g., floating), and brittleness may be damaged, but when the hardener is included in an amount of 1 wt% based on the total amount of the adhesive composition, compatibility may be slightly deteriorated, and thus surface transition may be caused, crosslinking reaction excessively proceeds, and adhesive strength may be slightly deteriorated, and thus there may be a residual stress relaxation problem.

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

The silane coupling agent is the same as described above, and may be included in an amount of 0.01 to 0.1 wt%, such as 0.01 to 0.05 wt%, based on the total adhesive composition (0.1 to 0.3 wt% based on adhesive composition solids).

The antistatic agent suppresses generation of static electricity during rework of the adhesive film, and may be a commonly used antistatic agent. The antistatic agent may be included in an amount of 1 to 5 wt%, such as 1 to 3 wt%, based on the total weight of the adhesive composition (1.0 to 5.0 wt% based on the adhesive composition solids). When the antistatic agent is contained in the range, it is advantageous in terms of charging. When the antistatic agent is included in an amount of less than 1% by weight based on the total amount of the adhesive composition, the antistatic effect is slightly deteriorated, and when the antistatic agent is included in an amount of more than 5% by weight based on the total amount of the adhesive composition, the properties of the adhesive composition are deteriorated and the manufacturing cost may be increased.

For example, the antistatic agent can be an ionic antistatic agent. The ionic antistatic agent can be alkali metal salt and ionic liquid or solid. However, the alkali metal salt has a slightly low compatibility with the adhesive, and the alkali metal salt may lack durability, and the ionic liquid has a large fluidity in the sintered product of the adhesive and thus may have slightly deteriorated antistatic performance with the change of the passage time. Briefly, an ionic liquid having a solid phase at room temperature of 25 ℃ may be included in consideration of stability of change in durability and antistatic property according to change with passage time.

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

The Ultraviolet (UV) absorber may have an absorption wavelength of 380nm to 420 nm. Herein, "absorption wavelength" refers to "maximum absorption wavelength".

When the adhesive composition includes an Ultraviolet (UV) absorber having the absorption wavelength range, a transmittance of 5% or less may be obtained in a wavelength region of 400nm or less, and the polarizing plate and the device including the polarizing plate may be prevented from being damaged by external Ultraviolet (UV).

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-benzo [ d ] [1,2,3] triazol-2-yl) benzyl methacrylate, but is not limited thereto as long as it satisfies an absorption wavelength.

The cationic initiator may be a cationic photopolymerization initiator, but is not limited thereto and includes any cationic photoinitiator commonly used in the related art. For example, onium salts that release lewis acids due to photoradicals or derivatives thereof may be included. Such compounds may be of the formula [ X ]] ^x+ [Y] ^x- As the salt composed of the cation and the anion, aromatic diazonium salt, aromatic iodonium salt, aromatic halonium salt and aromatic sulfonium salt may be exemplified as the cation, and tetrafluoroborate (BF) may be exemplified as the anion ₄ ) Hexafluorophosphate (PF) ₆ ) Hexafluoroantimonate (SbF) ₆ ) Hexafluoroarsenate (AsF) ₆ ) Hexachloroantimonate (SbCl) ₆ ) And the like. These cationic photopolymerization initiators may be used alone or as a mixture of two or more thereof.

The amount of the cationic initiator is not particularly limited, but may be, for example, 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on the total amount of the adhesive composition, based on the solid content. When the cationic initiator is included in an amount of less than 0.01 parts by weight based on the total amount of the adhesive composition, the colored adhesive composition is insufficiently cured, and thus it is difficult to obtain sufficient adhesiveness and close contact force, but when the cationic initiator is included in an amount of more than 10 parts by weight based on the total amount of the adhesive composition, hygroscopicity is increased due to an excessive amount of ionic material in the adhesive layer, and thus durability may be slightly deteriorated.

The release agent may 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, or the like. For example, when the release agent is an alkyd-based release agent, a silicon-based release agent, or a fluorine-based release agent, excellent heat resistance can be obtained, but the present invention is not limited thereto. The release agent may be included in an amount of 0.01 wt% to 0.1 wt% based on the total amount of the adhesive composition.

In addition to these components, the adhesive composition may further include additives such as reworkers, adhesive applying resins, antioxidants, leveling agents, surface lubricants, defoamers, fillers, light stabilizers, etc. to adjust adhesiveness, cohesion, viscosity, elasticity, glass transition temperature, etc., depending on the desired use.

The additive may be contained in an amount appropriately adjusted within a range not to impair the effects of the present invention.

The adhesive composition according to the embodiment may have a viscosity of 1,000cps to 4,000cps at 25 ℃. Within the range, the thickness of the adhesive film can be easily adjusted, and the adhesive film has no stain on the surface and has a uniform coating effect.

Another embodiment provides a polarizing plate comprising the adhesive film.

The method of producing the adhesive film is not particularly limited, but may include a conventional method. For example, adhesive compositions can be used to make adhesive films.

For example, the above adhesive composition may be directly coated on the polarizer protective film by using fluid casting, bar coater, air knife, gravure printing, reverse roll, kiss roll, spray, blade, etc., and then dried (thermally cured) to form an adhesive layer, and the adhesive layer may be laminated with the polarizer.

In addition, an adhesive film is formed on the silicon-coated release film in the same coating method as above, and is laminated with the silicon-coated release film having a different peeling force from the adhesive film using a roll press to manufacture an adhesive transfer tape, and the adhesive transfer tape may be adhered to a polarizing plate.

The adhesive film may be formed by thermal curing, but when an Ultraviolet (UV) curing compound and a photopolymerization initiator (the above cationic photopolymerization initiator, etc.) are used as a crosslinking agent, the adhesive film may be formed by: the polarizing plate is laminated, and then ultraviolet rays (UV) are irradiated from the side of the release film or silicon-coated release films having different peeling forces are laminated using a roll press and then irradiated with ultraviolet rays (UV) (photo-curing).

The thickness of the adhesive film is not particularly limited, but may 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 may have excellent adhesion and durability, and may be applied to a thin device.

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

Since the polarizing plate has a transmittance of 5% or less at a wavelength of 400nm or less, the polarizing plate or the device to which the polarizing plate is adhered can be prevented from being damaged, and since the polarizing plate has a transmittance of 40% or more at a wavelength of 455nm or more, the blue luminance can be prevented from being deteriorated.

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

The optical display device may include, but is not limited to, a Liquid Crystal Display (LCD), an Organic Light Emitting Diode (OLED), a flexible display, etc. as an image display device, and may include all image display devices known in the related art.

For example, the optical display device may be a Liquid Crystal Display (LCD). Generally, a Liquid Crystal Display (LCD) is composed of a Backlight (BLU), a polarizing plate, a Thin Film Transistor (TFT), a liquid crystal cell, a color filter, and a polarizing plate, and herein, the polarizing plate may be a polarizing plate according to an embodiment, and the color filter may be a color filter according to an embodiment. For example, an optical display device may be equipped with a polarizing plate laminated with the adhesive layer according to the embodiment on at least one surface of the color filter according to the embodiment.

The present invention is described in more detail below with reference to examples, which, however, should not be construed as limiting the scope of the present invention in any way.

(Synthesis of dye)

Synthesis example 1: synthesis of dye represented by chemical formula 1-1

[ reaction scheme 1]

(1) 4-Tert-butylbenzaldehyde (16.2g, 0.1mol), 100g propionic acid and pyrrole (6.71g, 0.1mol) were placed in a round bottom flask, then heated to 130 ℃ and stirred for 6 hours. When the reaction was completed, the resultant was cooled to room temperature, 100g 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 (4.2g, 20%).

(2) The intermediate (4.2g, 5 mmol) and 80g of chloroform were put into a round-bottom flask and stirred at 60 ℃, and in another round-bottom flask, zinc acetate (2.75g, 15 mmol) was put into it, 53g of methanol was added thereto, and the obtained mixture was stirred. Herein, stirring should be continuously performed until zinc acetate is completely dissolved, and when zinc acetate is completely dissolved, this solution is added to the intermediate, and after stirring the obtained mixture at 60 ℃ for 3 hours, the reaction is completed. An extract was obtained using chloroform, washed with water, and filtered. The filtrate was subjected to distillation, 50g 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).

Synthesis example 2: synthesis of blue dye represented by chemical formula 3-1

1. Synthesis of Compound 1

Reacting NaBH ₄ (3.8g, 0.1mol) was placed in a round-bottom flask, to which 100g of 1, 2-dichloroethane was added, and the resulting mixture was cooled to 0 ℃ and stirred. Next, acetic acid (21.6 g, 0.36mol) was added thereto, the obtained mixture was stirred for 2 hours while slowly heating to room temperature, and then cyclohexanone (8.8 g, 0.09mol) was added dropwise thereto. The reaction was stirred at room temperature for 1 hour, aniline (7.9 g, 0.85mol) was added thereto, and the obtained mixture was allowed to stand at room temperature for one night. When it is reversedAfter completion, an extract was obtained by using methylene chloride and washed with distilled water and a 10% aqueous NaCl solution. Using MgSO ₄ Water was removed therefrom, and the resultant was filtered and dried to synthesize compound 1 (4.5 g, yield 97%).

[ Compound 1]

2. Synthesis of Compound 2

4,4' -dichlorobenzophenone (10g, 39.8mmol) and Pd were mixed in a nitrogen atmosphere ₂ (dba) ₃ (220mg, 0.002mol%), XPhos (230mg, 0.005mol%) and sodium t-butoxide (11.48g, 119.5 mmol) were put in a round-bottom flask, 50g of toluene was added thereto, the obtained mixture was stirred at room temperature for 10 minutes, and Compound 1 (14g, 79.6 mmol) was added thereto. The reaction was slowly heated to 80 ℃ and stirred for 2 hours. When the reaction was completed, the temperature was lowered to room temperature, 50g of isopropyl alcohol was added thereto, and the obtained mixture was stirred. The precipitate therein was filtered, washed with water and added to acetonitrile, and the obtained mixture was stirred at 80 ℃ 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%).

[ Compound 2]

3. Synthesis of Compounds 3 to 6

[ reaction scheme 2]

(Synthesis of Compound 3)

Sodium ethoxide (34.2g, 0.503mol) and 250g ethanol were placed in a round bottom flask and stirred at room temperature for 30 minutes, to which ethyl cyanoacetate (45.5g, 0.402mol) was slowly added, and the obtained mixture was stirred at room temperature for 30 minutes. O-tolylisocyanate (50g, 0.335mol) was slowly added thereto, and the resulting mixture was heated to 80 ℃ and stirred for 3 hours. When 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, 200g of MeOH was added to the solid compound produced therein, and the obtained mixture was stirred at 0 ℃ for 30 minutes and filtered to synthesize compound 3 (73.8 g, yield 84%).

[ Compound 3]

(Synthesis of Compound 4)

NaOH (45.7g, 1.14mol) and 240g water were placed in a round bottom flask and stirred at 0 ℃ for 30 minutes, to which was added compound 3 (30g, 0.114mol) and the reaction was heated to 80 ℃ and stirred for 3 hours. When the reaction was complete, the temperature was lowered to 0 ℃ and the reaction was acidified (pH: about 6) with concentrated HCl. The precipitate was filtered, washed and dried to synthesize compound 4 (19.7 g, yield 90%).

[ Compound 4]

(Synthesis of Compound 5)

KOH (8.71g, 0.155mol) and 200g MeOH were placed in a round-bottom flask and stirred at room temperature for 30 minutes, to which compound 4 (20.5g, 0.108mol) and 2' -chlorobenzoylmethyl bromide (26.6 g, 0.114mol) were added, respectively, and the obtained mixture was stirred at room temperature for 2 hours. When the reaction was completed, 200g of water was added thereto, the obtained 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%).

[ Compound 5]

(Synthesis of Compound 6)

KOH (10.4 g, 0.185mol), 170g of acetone and 80g of water were placed in a round-bottom flask and stirred at room temperature, compound 5 (30g, 92.4 mmol) and 2-iodopropane (31.5 g, 0.185mol) were added thereto, respectively, and the resulting mixture was stirred at 60 ℃ for 12 hours. When 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%).

[ Compound 6]

4. Synthesis of Compound represented by chemical formula 3-1

Compound 2 (1.50g, 2.83mmol) and compound 6 (1.0g, 2.83mmol) were placed in a round-bottom flask under nitrogen, and 7.5g of toluene and POCl were added thereto ₃ (2.6g, 17.0 mmol), and the obtained mixture was stirred for 5 hours while slowly heating to 110 ℃. When the reaction was completed, the temperature was lowered to room temperature, and an extract was obtained using Methyl Ethyl Ketone (MEK) and washed with 10% NaCl, water, and 10% HCl, respectively. After removing the organic layer, the remaining one was dried, lithium bis (trifluoromethane) sulfonimide (1.2g, 4.2mmol) was added thereto, 10g dimethyl sulfoxide (DMSO) was added thereto, and the obtained mixture was stirred at room temperature for 30 minutes (anion)An exchange process). The reactant was dropped into water to form a precipitate, and the precipitate was separated by a filter. The solid compound obtained by the filter was dissolved in 40g of acetonitrile, 3g of activated carbon was added thereto, and the obtained mixture was stirred for 30 minutes. Subsequently, the activated carbon was removed through a filter, and the filtrate was removed by distillation and dried to obtain the compound represented by chemical formula 3-1 (2.69 g, yield 82%). The chemical formula X is represented by chemical formula C.

[ chemical formula 3-1]

Liquid Chromatography (LC) -mass spectrometry (MC): 1003m/z

[ chemical formula C ]

Synthesis example 3: synthesis of blue dye represented by chemical formula 3-2

The blue dye represented by chemical formula 3-2 was synthesized using 2-aminopropane instead of aniline and the like with reference to synthesis example 1. The chemical formula X is represented by chemical formula C.

[ chemical formula 3-2]

LC-MC：735m/z

[ chemical formula C ]

Synthesis example 4: synthesis of yellow dye 1

Hydrochloric acid (2.5 mL) and sodium nitrate (2m 1.25m aqueous solution) were added to 4-aminophthalitrile (2.5 mmol), and azonium obtained therefrom was put into a weakly basic aqueous solution prepared by dissolving barbituric acid (2.5 mmol) in NaOH aqueous solution to obtain an azo compound. Herein, the solid obtained therefrom was filtered, purified and vacuum-dried, followed by reaction with 1-iodobutane (5.5 mmol) and potassium carbonate (7.5 mmol) in the presence of Dimethylformamide (DMF) solvent, and then purification and vacuum-drying were performed to obtain yellow dye 1.

Synthesis example 5: synthesis of yellow dye 2

(1) Synthesis of intermediate 1

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

(2) Synthesis of intermediate 2

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

(3) Synthesis of yellow dye 2

4-Aminophthalonitrile (4.21g, 29.4mmol) was placed in a round-bottomed flask, 30g of water were added thereto, and the temperature was lowered to 0 ℃. Then, 30g of HCl was added thereto, and the obtained mixture was stirred at 0 ℃. Adding NaNO into the reactant ₂ (2.03g, 29.4 mmol) in 20g of water, and the resulting mixture was stirred at 0 ℃ for 2 hours.

In another round-bottom flask, sodium carbonate (9.35g, 88.2mmol) was placed, 500g of water was added thereto, and the obtained mixture was stirred. After sodium carbonate was dissolved in water, intermediate 2 (10g, 29.4 mmol) was added thereto, and the obtained mixture was stirred at room temperature for 1 hour. This reaction was slowly added dropwise to the above reaction stirred over 2 hours, and when the addition was complete, the resulting mixture was stirred for 12 hours. When the reaction is complete, the product is filtered and the solid compound obtained therefrom is washed with water and dried. Then, 100g of MeCN was added to the dried compound, and the obtained mixture was stirred at 80 ℃ for 2 hours, followed by filtration and drying to synthesize yellow dye 2 (12.3g, 85%).

(Synthesis of photosensitive resin composition)

Examples 1 to 3, comparative examples 1 and 1, and reference example 1

The following components were mixed in the compositions shown in table 1 to prepare photosensitive resin compositions according to examples 1 to 3, comparative example 1, comparative example 2 and reference example 1.

Specifically, a photopolymerization initiator was dissolved in a solvent, the solution was stirred at room temperature for 2 hours, a binder resin and a photopolymerizable compound were added thereto, and the obtained mixture was stirred at room temperature for 2 hours. Subsequently, a coloring agent and other additives were added to the reaction mixture, and the obtained 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.

(Table 1)

(unit: g)

(A) Coloring agent

(A-1) Synthesis of the Compound of example 1 (blue dye represented by chemical formula 1-1)

(A-2) Synthesis example 2 Compound (blue dye represented by chemical formula 3-1)

(A-3) Compound of Synthesis example 3 (blue dye represented by chemical formula 3-2)

(A-4) Compound of Synthesis example 4 (yellow dye 1)

(a-5) c.i. pigment blue 15

(B) Adhesive resin

Acrylic adhesive resin (RY-25, showa electrician K.K.)

(C) Photopolymerizable compounds

Dipentaerythritol hexaacrylate (DPHA) (Nippon Chemicals Co., ltd.)

(D) Photopolymerization initiator

(D-1) Oxime-based Compound (NCI 831, adeka Corporation)

(D-2) acetophenone Compound (IRG 369, basf Corporation)

(E) Solvent(s)

(E-1) Propylene Glycol Monomethyl Ether Acetate (PGMEA) (Kyowa Co., ltd.)

(E-2) EDM (Co., ltd.)

(F) Additive agent

Gamma-glycidoxypropyltrimethoxysilane (S-510, chisso Corporation)

Evaluation 1: transmittance of dye

The transmittance of the films was measured by forming three 2 μm thick films using 2 wt% of each dye of synthetic example 1, synthetic example 4 and synthetic example 5 based on 100 wt% of the composition but the other conditions were set in the same manner, and the results are shown in fig. 1.

Referring to fig. 1, unlike the yellow dyes of synthesis examples 4 and 5, the blue dye of synthesis example 1 exhibited a maximum absorption wavelength in a very narrow wavelength region of 420nm to 440nm, and thus proved to be able to sufficiently block the spectrum of the wavelength region of 420nm to 440 nm.

Evaluation 2: brightness of photosensitive resin layer

The photosensitive resin compositions of examples 1 to 3, comparative examples 1 and 2, and reference example 1 were each coated to a thickness of 1 μm to 3 μm on a degreased and washed glass substrate of 1mm thickness at 250rpm to 350rpm, and then dried on a hot plate of 90 ℃ for 2 minutes to obtain a film. Subsequently, a high-pressure mercury lamp having a main wavelength of 365mm was used at 50mJ/cm ² The film was exposed and developed for 60 seconds and washed for another 60 seconds using KOH developing solution (111-fold diluted solution) under the conditions of wash solution/developing solution = 1/0.8. Next, the film was dried in a forced convection drying oven at 230 ℃ for 20 minutes to obtain each color sample (color chip).

Color characteristics of the color samples were evaluated with respect to the C light source using a spectrophotometer (MCPD 3000, tsukamur Electronics co., ltd.), luminance Y was calculated based on color coordinates (Bx/By = 0.148/0.048), and the results are shown in table 2.

(Table 2)

	Luminance (%)
		Example 1	7.72
Example 2	8.89
		Example 3	8.94
Comparative example 1	-
		Comparative example 2	-
Reference example 1	3.23

(with respect to comparative example 1 and comparative example 2, compositions could not be prepared because all components were not dissolved in the specified solvent due to an excess of yellow dye, and thus brightness could not be measured.)

Referring to evaluation 1 and evaluation 2, when the compound represented by chemical formula 1-1 was used, excellent luminance and blue color were sufficiently achieved with a small amount. In addition, referring to examples and reference examples, even though the compound represented by chemical formula 1-1 is included in an excessive amount, luminance and blue characteristics are not further improved.

(Synthesis of adhesive composition)

Example 4

An adhesive composition for a polarizing plate according to example 4 was prepared by mixing the following components: 78.583% by weight of an acrylic binder resin (PL-8540; saiden Chemical Industry Co., ltd.; ltd.)), 0.236% by weight of an isocyanate-based hardener (H-AL, zeka ceramics Inc.; 0.145% by weight of an aziridine-based hardener (HDU-P25), 0.028% by weight of a mold release agent (MAC-2101; soken Chemical Co., ltd.; ltd.)), 1.336% by weight of an antistatic agent (FC-440L 3M), 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).

Comparative example 3

An adhesive composition for a polarizing plate according to comparative example 3 was prepared according to the same method as example 4, except that the compound of synthesis example 1 was not used.

Evaluation 3: color reproducibility and reflectance of adhesive film

1. Measurement of color reproducibility

Each of the compositions according to example 4 and comparative example 3 was coated, dried at 90 ℃ for 4 minutes and aged at 23 ℃ for 24 hours at 55% relative humidity to form adhesive films, respectively, and then adhered to one surface of a panel (opposite side of a backlight), and then its color reproducibility was measured using a spectrophotometer (SR-3, topcon Technohouse corp.) and the results are shown in table 3.

2. Measurement of reflectance

Each adhesive film formed of the adhesive composition according to example 4 and comparative example 3, respectively, was adhered to a QD panel, the reflectance thereof was measured by applying a C-light spectrum using a spectrophotometer (CM-2600D, minolta co., ltd.), and the results are shown in table 3.

(Table 3)

(unit:%)

	Color reproducibility	Reflectivity of light
			Example 4	89.7	10.85
Comparative example 3	88.2	12.04

As shown in table 3, example 4 using the compound of synthesis example 1 showed high color reproducibility and decreased reflectance, compared to comparative example 3 using no compound of synthesis example 1.

While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, 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:

a compound represented by chemical formula 1;

an acrylic binder resin;

a hardening agent; and

a solvent;

[ chemical formula 1]

Wherein, in chemical formula 1,

m is Zn, co or Cu, and

2. The adhesive composition of claim 1, wherein the compound represented by chemical formula 1 is included in an amount of 0.001 to 0.01 wt% based on the total amount of the adhesive composition.

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

4. An adhesive film produced using the adhesive composition according to any one of claims 1 to 3.

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

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