KR20200026592A - Adhesive composition, adhesive film using the same, polarizing plate and display device - Google Patents

Abstract

The present invention relates to an adhesive composition comprising: (A) a dye including a compound represented by chemical formula (1); (B) a resin; (C) a curing agent; and (D) a solvent, to an adhesive film produced using the composition, to a polarizing plate comprising the adhesive film, and to a display device comprising the polarizing plate. In the chemical formula 1, each substituent is the same as defined in the specification.

Description

Adhesive composition, adhesive film, polarizing plate, and display device using same {ADHESIVE COMPOSITION, ADHESIVE FILM USING THE SAME, POLARIZING PLATE AND DISPLAY DEVICE}

The present substrate relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive film produced using the pressure-sensitive adhesive composition, a polarizing plate including the pressure-sensitive adhesive film, and a display device including the polarizing plate.

The polarizing plate is an optical element for making natural light or arbitrary polarization into polarized light vibrating in a specific direction, and is applied to a display device such as a liquid crystal display (LCD), an organic light emitting device, or the like. Display devices including polarizing plates are used in various products such as portable, vehicle-mounted, outdoor metering machines, computers, televisions, and the like, and their applications are increasing. As the field of application is diversified, the environment in which the display device is used is also severe. Accordingly, it is required to have high durability even in an environment with high temperature, high humidity, and / or extreme change in temperature or humidity.

However, in the case of conventional display devices, defects such as light leakage are often caused under severe use environments. For example, in an environment where the temperature and / or humidity change is severe, each member included in the polarizing plate causes a dimensional change due to a change in the external environment, thereby causing an interfacial stress. When the stress is generated as described above, the photoelastic birefringence of the polarizing plate protective film or the adhesive layer is changed, and as a result, light leakage is generated while the retardation characteristic of the protective film is changed. In particular, since the dimensional change of each member becomes larger at the end of the screen than at the center of the screen, the light leakage phenomenon at the end tends to be remarkable.

In addition, in a high temperature and high humidity environment, the panel warpage occurs due to a difference in shrinkage between the upper polarizer and the lower polarizer, in particular, a shrinkage difference in the polarizing plate stretching direction. In a device in which the optical axes of the upper polarizer and the lower polarizer are attached to each other by 0 ° and 90 °, such as the liquid crystal display of the IPS mode or the VA mode, the stretching axes of the upper polarizer and the lower polarizer are asymmetrically arranged. As a result, curls of the upper polarizer and the lower polarizer are differently generated when shrinkage occurs, and warpage of the liquid crystal panel occurs in the direction in which the curls of the upper and lower polarizers are large. When the panel warpage occurs as described above, the panel is pressed by the case when the panel is fixed, which causes light leakage due to the occurrence of liquid crystal unevenness.

In order to solve the above problems, the pressure-sensitive adhesive film attaching the polarizing plate and the panel is formed of a flexible material to induce stress relaxation at the corners and to suppress the occurrence of panel warpage. However, when the adhesive film of the flexible material is formed in this way, a problem occurs that the surface hardness of the polarizing plate is lowered. In particular, in recent years, thin polarizing plates that reduce the thickness of the protective film and the polarizer or omit the protective film are applied according to the tendency of the display device to be slimmed down. When such a thin polarizing plate is applied, the surface hardness decreases further. There is a problem of getting worse.

Furthermore, in recent years, development of a wavelength absorbing adhesive film according to the development of a quantum dot display has been required. Accordingly, development of a low reflection film and application of a dye-type adhesive have been applied as important factors in order to improve luminous degradation.

One embodiment is to provide a pressure-sensitive adhesive composition comprising a compound capable of maximizing the brightness reduction problem improvement and color reproducibility improvement effect as a dye.

Another embodiment is to provide a pressure-sensitive adhesive film prepared using the pressure-sensitive adhesive composition.

Another embodiment is to provide a polarizing plate comprising the adhesive film.

Another embodiment is to provide a display device including the polarizing plate.

One embodiment of the present invention (A) a dye comprising a compound represented by the formula (1); (B) resins; (C) curing agent; And (D) provides a pressure-sensitive adhesive composition containing a solvent.

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁵ are each independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

R ⁶ is a halogen atom, cyano group, substituted or unsubstituted C1 to C20 alkoxy group, or substituted or unsubstituted C1 to C20 alkylester group.

The compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 1A.

[Formula 1A]

In Chemical Formula 1A,

R ¹ to R ⁵ are each independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

R ⁶ is a halogen atom, cyano group, substituted or unsubstituted C1 to C20 alkoxy group, or substituted or unsubstituted C1 to C20 alkylester group.

At least one of the R ² and R ³ may include a cyano group at the terminal.

R ⁴ and R ⁵ may each independently be a hydrogen atom, a halogen atom or a cyano group.

R ⁴ and R ⁵ may each independently be a hydrogen atom.

The compound represented by Chemical Formula 1 may have a maximum absorption peak at a wavelength of 490 nm to 600 nm.

The compound represented by Chemical Formula 1 may be represented by any one of the following Chemical Formulas 1-1 to 1-16.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

[Formula 1-15]

[Formula 1-16]

The dye may have a core-shell structure, the core may be represented by Chemical Formula 1, and the shell may be represented by Chemical Formula 2 or Chemical Formula 3 below.

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,

L ^a to L ^d are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

L ^a to L ^d may be each independently a substituted or unsubstituted C1 to C10 alkylene group.

The shell may be represented by the following Chemical Formula 2-1 or Chemical Formula 3-1.

[Formula 2-1]

[Formula 3-1]

The shell may have a cage width of 6.5 mm to 7.5 mm.

The length of the core may be 1nm to 3nm.

The pressure-sensitive adhesive composition may further include a silane coupling agent, an antistatic agent, an ultraviolet absorber, a cationic initiator, a release agent, or a combination thereof.

Another embodiment provides an adhesive film prepared using the pressure-sensitive adhesive composition.

Yet another embodiment provides a polarizing plate including the adhesive film.

Yet another embodiment provides a display device including the polarizing plate.

Other details of aspects of the invention are included in the following detailed description.

Since the pressure-sensitive adhesive composition according to one embodiment includes a dye that absorbs the wavelength between the green and the red wavelengths to the maximum, the display device including the polarizing plate to which the pressure-sensitive adhesive film is applied using the same has improved color reproducibility, reduced external light reflection, and excellent black feeling. It is possible to implement, and furthermore, to reduce the luminance deterioration.

1 is a graph showing absorbance according to the wavelength of the compound represented by Chemical Formula 1-1 and azapopyrine dye.
FIG. 2 illustrates a cage width of a shell represented by Chemical Formula 3-1. FIG.
3 is a cross-sectional view of a polarizer according to an embodiment.
4 is another cross-sectional view of a polarizer according to an embodiment.
5 is a cross-sectional view of a display device according to an embodiment.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the present specification, "substituted" to "substituted" means that at least one hydrogen atom of the functional group of the present invention is a halogen atom (F, Br, Cl or I), hydroxy group, nitro group, cyano group, amino group ( NH ₂ , NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ), where R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different from each other, and are each independently C 1 to C 10 alkyl groups, amidino groups, Hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group, And it means substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group.

Unless stated otherwise in the specification, an "alkyl group" means a C1 to C20 alkyl group, specifically a C1 to C15 alkyl group, and a "cycloalkyl group" means a C3 to C20 cycloalkyl group, specifically C3 To C18 cycloalkyl group, "alkoxy group" means C1 to C20 alkoxy group, specifically C1 to C18 alkoxy group, "aryl group" means C6 to C20 aryl group, specifically C6 to Means an C18 aryl group, "alkenyl group" means a C2 to C20 alkenyl group, specifically means a C2 to C18 alkenyl group, "alkylene group" means a C1 to C20 alkylene group, specifically C1 To C18 alkylene group, the "arylene group" means a C6 to C20 arylene group, and specifically means a C6 to C16 arylene group.

Unless stated otherwise in the specification, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid". Both mean it's possible.

Unless otherwise defined herein, “combination” means mixed or copolymerized. In addition, "copolymerization" means block copolymerization to random copolymerization, and "copolymer" means block copolymer to random copolymerization.

Unless otherwise defined in the chemical formulas herein, when a chemical bond is not drawn at the position where the chemical bond is to be drawn, it means that a hydrogen atom is bonded at the position.

In addition, unless otherwise defined in the present specification, "*" means the part connected with the same or different atoms or formulas.

In addition, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

In addition, when any part of the specification is to "include" any component, which means that it may further include other components, except to exclude other components unless otherwise stated.

One embodiment includes (A) a dye comprising a compound represented by Formula 1; (B) resins; (C) curing agent; And (D) a solvent.

Each component is demonstrated concretely below.

dyes

Pressure-sensitive adhesive composition according to one embodiment includes a compound represented by the formula (1) as a dye.

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁵ are each independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

R ⁶ is a halogen atom, cyano group, substituted or unsubstituted C1 to C20 alkoxy group, or substituted or unsubstituted C1 to C20 alkylester group.

For example, the compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 1A.

[Formula 1A]

In Chemical Formula 1A,

R ¹ to R ⁵ are each independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

R ⁶ is a halogen atom, cyano group, substituted or unsubstituted C1 to C20 alkoxy group, or substituted or unsubstituted C1 to C20 alkylester group.

In order to improve color reproducibility, reduce external light reflection and realize neutral black, the characteristics required for display device materials are i) minimization of half width and ii) no absorption (fluorescence) outside the absorption wavelength, and iii) a certain level. Should be maintained. In order to satisfy the above characteristics, a material (dye) that absorbs the wavelength between the green and red wavelength ranges is maximized, and azaphophyrin-based compounds are usually used. This is because the azapopyrine-based compound is a dye which is very advantageous for improving color reproducibility with a half-width at a wavelength of 20 nm. However, as shown in FIG. 1, short wavelength absorbance (shoulder) exists at a wavelength of 580 nm or less, and as the amount of use is increased to increase color reproducibility, a decrease in green luminance due to short wavelength absorption increases.

According to one embodiment, by using the compound represented by Formula 1, specifically, the compound represented by Formula 1A to minimize the short wavelength absorption to improve the brightness degradation problem (short wavelength absorption at a wavelength of 580nm or less as shown in Figure 1 And the maximum absorption value in the wavelength range of about 590 nm to 600 nm at the same time as minimizing short wavelength absorption, thereby improving color reproducibility, minimizing external light reflection, and realizing excellent black feeling. The luminance deterioration problem implemented in the display device may also be solved. That is, the inventors of the present invention do not have short wavelength absorption in order to improve color reproducibility without decreasing luminance, and the compound represented by Chemical Formula 1 having a maximum absorption wavelength value λ _max in the wavelength range of about 590 nm to 600 nm (specifically, Compound represented by 1A) or a core-shell compound including the same as a core is used as a dye. In particular, the compound represented by Formula 1 (specifically, the compound represented by Formula 1A) has an asymmetric structure and has an essential substituent (halogen atom, cyano group, substituted or unsubstituted C1 to C20 alkoxy group or substituted or unsubstituted on one side). Ring having a C1 to C20 alkyl ester group), the above-mentioned effect than when using a compound having a different structure as a dye due to the presence of the essential substituent in the benzene ring constituting the indole substituent It will be easy to implement.

The alkyl ester group may be represented by * -OC (= O) R ⁷ (R ⁷ is a C1 to C20 alkyl group).

For example, in Formula 1, at least one of R ² and R ³ may include a cyano group at the terminal.

For example, in Formula 1, R ⁴ and R ⁵ may be each independently a hydrogen atom, a halogen atom or a cyano group.

For example, R ⁴ and R ⁵ may each independently be a hydrogen atom.

For example, the compound represented by Formula 1 (specifically, the compound represented by Formula 1A) may have a maximum absorption peak at a wavelength of 490 nm to 600 nm, such as 590 nm to 600 nm. Since the compound represented by Chemical Formula 1 (specifically, the compound represented by Chemical Formula 1A) has a maximum absorption peak at the wavelength in the above range, the problem of deterioration of visibility due to diffuse reflection generated by the light coming from the outside, that is, reflection Can be improved. Reflectance measurement for improved visibility may be measured through a spectrophotometer. That is, the reflectance may indicate the level at which light entering the panel from the outside decreases visibility due to diffuse reflection generated by particles inside the panel.

The compound represented by Chemical Formula 1 (specifically, the compound represented by Chemical Formula 1A) may be included in an amount of 0.01 wt% to 5 wt% based on the total amount of the pressure-sensitive adhesive composition (eg, the total amount of dye in the pressure-sensitive adhesive composition is 0.01 wt% to 5 wt%). Weight percent).

The compound represented by Chemical Formula 1 has three resonance structures, as shown in the following scheme, but for the sake of convenience, the compound represented by Chemical Formula 1 may be represented by only one resonance structure. That is, the compound represented by Chemical Formula 1 may be represented by any one of the three resonance structures.

[scheme]

For example, the compound represented by Chemical Formula 1 may be represented by any one of the following Chemical Formulas 1-1 to 1-16, but is not necessarily limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

[Formula 1-15]

[Formula 1-16]

The dye may be a dye of the core-shell structure. For example, the dye may be composed of a core represented by Chemical Formula 1 and a shell surrounding the core. Specifically, the shell may be a macrocyclic compound, the shell may form a coating layer surrounding the compound represented by the formula (1).

In one embodiment, the shell corresponding to the macrocyclic compound has a structure surrounding the compound represented by Formula 1, that is, the structure represented by the compound represented by Formula 1 exists in the macrocyclic ring, It is possible to improve the durability of the core-shell dye.

The length of the compound represented by Formula 1 included in the core or constituting the core may be 1 nm to 3 nm, for example, 1.5 nm to 2 nm. When the compound represented by Chemical Formula 1 has a length within the above range, a core-shell dye having a structure of a core and a shell surrounding the compound may be easily formed. In other words, as the compound represented by Formula 1 has a length within the above range, the macrocyclic compound shell may be obtained in a structure surrounding the compound represented by Formula 1. When using other compounds that do not fall within the range of the above range, the shell is difficult to form a structure surrounding the compound serving as a core, it is difficult to expect the improvement of durability.

For example, the shell surrounding the core including the compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 2 or Chemical Formula 3.

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,

L ^a to L ^d are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

In Formula 2 or Formula 3, L ^a to L ^d may be each independently a substituted or unsubstituted C1 to C10 alkylene group. In this case, it is excellent in solubility and it is easy to form the structure which a shell encloses the core containing the compound represented by said Formula (1).

For example, a core-shell dye according to one embodiment is a non-covalent bond, ie, a hydrogen bond, between an oxygen atom of a compound represented by Formula 1 and a nitrogen atom of a shell represented by Formula 2 or Formula 3 It may include.

The shell may be represented by, for example, the following Chemical Formula 2-1 or Chemical Formula 3-1.

[Formula 2-1]

[Formula 3-1]

The cage width of the shell may be 6.5 kPa to 7.5 kPa and the volume of the shell may be 10 kPa to 16 kPa. As used herein, the cage width refers to a shell internal distance, such as a distance between two different phenylene groups in which a methylene group is connected to both sides in a shell represented by Formula 2-1 or 3-1. (See Figure 2). When the shell has a cage width within the above range, it is possible to obtain a core-shell dye having a structure surrounding the core comprising the compound represented by the formula (1), thereby adding the core-shell dye to the pressure-sensitive adhesive composition In this case, durability and luminance improvement effects can be expected.

The core-shell dye may include a core including the compound represented by Chemical Formula 1 and the shell in a molar ratio of 1: 1. When the core and the shell are present in the molar ratio, a coating layer (shell) surrounding the core including the compound represented by Chemical Formula 1 may be well formed.

Suzy

The pressure-sensitive adhesive composition according to one embodiment may include a resin, such as an acrylic binder resin.

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

The acrylic binder resin constituting the pressure-sensitive 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 may form a matrix of the adhesive film, and may provide one or more of hydroxyl groups and carboxylic acid groups to allow the adhesive composition to self-cure.

The first (meth) acrylate copolymer is at least one of a (meth) acrylate monomer having a hydroxyl group, (meth) acrylic monomer having a carboxylic acid group; And it may be a copolymer of a monomer mixture comprising a monomer copolymerizable with these (hereinafter "first copolymer monomer"). At least one of the (meth) acrylate monomer having a hydroxyl group and the (meth) acrylate monomer having a carboxylic acid group in the monomer mixture may be included in an amount of 10 mol% or less, specifically 0.01 mol% to 5 mol%. In the above range, when included with the second (meth) acrylate copolymer, it is possible to implement an adhesive film that can be used in a flexible device having good flexibility and bending properties.

The (meth) acrylate monomer having a hydroxyl group can be self-curable and / or increase the adhesive force of the adhesive film and increase the durability of the adhesive film. The (meth) acrylate monomer having a hydroxyl group may be included in the monomer mixture of 5 mol% or less, specifically 0.01 mol% to 5 mol%. In the above range, the adhesive force and durability of the pressure-sensitive adhesive film is improved, there may be an effect that the aging of the pressure-sensitive adhesive composition is faster.

The (meth) acrylate monomer having a hydroxyl group is a (meth) acrylate monomer having a C1 to C20 alkyl group having at least one hydroxyl group, a (meth) acrylic monomer having a C3 to C20 cycloalkyl group having at least one hydroxyl group, at least one hydroxyl group It may include one or more of the (meth) acrylate monomer having a C6 to C20 aromatic group having. Specifically, the (meth) acrylate monomer having a hydroxyl group is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 1-chloro-2-hydroxypropyl (meth) acrylate, diethylene At least one of glycol mono (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclopentyl (meth) acrylate, and 4-hydroxycyclohexyl (meth) acrylate It may include. These may be included alone or in combination of two or more.

The (meth) acrylate monomer having a carboxylic acid group can be made self-curable. The (meth) acrylate monomer having a carboxylic acid group may be included in an amount of 5 mol% or less, specifically 0.01 mol% to 5 mol%, in the monomer mixture. In the above range, the acidity of the pressure-sensitive adhesive film is not high, there is no risk of corrosion on the adherend, the resistance can be lowered, there may be an effect that the reliability of the pressure-sensitive adhesive film is increased. The (meth) acrylate monomer having a carboxylic acid group may include (meth) acrylic acid and the like, but is not limited thereto.

The first copolymer monomer is copolymerized with at least one of a (meth) acrylate monomer having a hydroxyl group and a (meth) acrylate monomer having a carboxylic acid group to form a first (meth) acrylate copolymer, thereby forming a matrix of the adhesive film. Can form or provide additional functionality.

The first copolymerized monomer may include a (meth) acrylate monomer having an alkyl group. The (meth) acrylate monomer which has an alkyl group is contained in a (meth) acrylate copolymer, can form the matrix of an adhesive film, and can raise the mechanical strength of an adhesive film. The (meth) acrylate monomer having an alkyl group may be included in 50 mol% to 99.99 mol%, specifically 50 mol% to 95 mol%, 95 mol% to 99.9 mol%, 55 mol% to 90 mol%, 60 mol% to 85 mol% in the monomer mixture. . In the above range, the mechanical strength of the adhesive film can be increased. The (meth) acrylate monomer having an alkyl group may include a (meth) acrylic acid ester having an unsubstituted C4 to C12 alkyl group. Specifically, the (meth) acrylate monomer having an alkyl group is n-butyl (meth) acrylate, t-butyl (meth) acrylate, iso-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, iso-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate , But may include one or more of dodecyl (meth) acrylate, but is not limited thereto. These may be included alone or in mixture of two or more thereof.

The first copolymer monomer may further increase the pencil hardness of the polarizing plate including the adhesive film by further 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 which has the said alicyclic group is contained in the said 1st (meth) acrylate copolymer, and raises the pencil hardness of the polarizing plate containing an adhesive film with the said 2nd (meth) acrylate copolymer. Can be. Specifically, in the polarizing plate to which the pressure-sensitive adhesive film for polarizing plate is attached, the pencil hardness of the polarizing plate on the adhesive film may be 2H or more, more specifically 2H to 3H. In the above range, even when the polarizing plate is adhered to the liquid crystal panel such as a glass material with the adhesive film for the polarizing plate, the pencil hardness is not significantly reduced compared to the case where the polarizing plate is adhered to the liquid crystal panel without the adhesive film, the polarizing plate can be used in the display device. In addition, the (meth) acrylate monomer having an alicyclic group is included in the (meth) acrylate copolymer together with the (meth) acrylate monomer having the following heteroalicyclic group, so that the creep is lowered at 25 ° C. of the pressure-sensitive adhesive film for a polarizing plate. Creep can be increased at < RTI ID = 0.0 > In particular, the glass transition temperature of the (meth) acrylate monomer having an alicyclic group and the (meth) acrylate monomer having a heteroalicyclic group are respectively 40 ° C. to 180 ° C. when the homopolymer is used. You can lower the creep at ° C and increase the creep at 85 ° C. The (meth) acrylate monomer having the alicyclic group in the monomer mixture: The (meth) acrylic monomer having the heteroalicyclic group may be included in a molar ratio of 1: 0.25 to 1: 2. In the above range, there may be an effect of increasing the cohesion or strength at room temperature. Alternatively, there may be a stress relaxation effect and a warpage improvement effect of the polarizing film at a high temperature.

The (meth) acrylate monomer having an alicyclic group may be included in 1 mol% to 30 mol%, specifically 5 mol% to 20 mol% in the monomer mixture. In the above range, the pencil hardness of the polarizing plate on the pressure-sensitive adhesive film may be increased, and cohesion may be increased.

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

By "cycloaliphatic group" is meant a non-heteroalicyclic group containing no heteroatoms of nitrogen, oxygen or sulfur. The "heterocycle" means that two or more alicyclic groups are linked and share one or more carbon atoms.

Specifically, the (meth) acrylic acid ester having a substituted or unsubstituted C5 to C20 monocyclic or heterocyclic alicyclic group is cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) And one or more of acrylate, methylcyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate. These may be included alone or in combination of two or more.

The (meth) acrylate monomer having a heteroalicyclic group may be creep lowered at 25 ° C. and creep at 85 ° C. together with the (meth) acrylate monomer having an alicyclic group.

The (meth) acrylate monomer having a heteroalicyclic group may be included in 1 mol% to 30mol%, specifically 5mol% to 20mol% in the monomer mixture. In the above range, the modulus at 30 ° C of the pressure-sensitive adhesive film may be high, the cohesive force may be increased.

The (meth) acrylate monomer having a heteroalicyclic group may include a (meth) acrylic acid ester 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 (meth) acryloyl morpholine, but is not limited thereto.

The first copolymerized monomer may further include one or more monomers of (meth) acrylic acid ester 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 methyl (meth) acrylate, (meth) acrylamide, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, and the like, but is not limited thereto.

In one embodiment, the first (meth) acrylate copolymer is 0.01 mol% to 5 mol% of at least one of the (meth) acrylate monomer having the hydroxyl group and the (meth) acrylate monomer having the carboxylic acid group and the alkyl group It may be a copolymer of 95 mol% to 99.99 mol% having a (meth) acrylate monomer. In another embodiment, the first (meth) acrylate copolymer is 0.01 mol% to 5 mol% of at least one of the (meth) acrylate monomer having the hydroxyl group and the (meth) acrylate monomer having the carboxylic acid group, the alkyl group Copolymer of 50 mol%-95 mol% of (meth) acrylate monomer which has, 1 mol%-30 mol% of (meth) acrylate monomer which has the said alicyclic group, 1 mol%-30 mol% of (meth) acrylate monomer which has the said heteroalicyclic group Can be. In the above range, there may be a high cohesive force and a high strength effect.

The second (meth) acrylate copolymer may form a matrix of the pressure-sensitive adhesive film and provide one or more of an epoxy group and an oxetane group to allow the pressure-sensitive adhesive composition to self-cure without a crosslinking agent.

The second (meth) acrylate copolymer is at least one of a (meth) acrylic monomer having an epoxy group and a (meth) acrylic monomer having an oxetane group; And it may be a copolymer of a monomer mixture comprising a monomer copolymerizable with these (hereinafter "second copolymer monomer"). At least one of the (meth) acrylate monomer having an epoxy group and the (meth) acrylate monomer having an oxetane group in the monomer mixture may be included in an amount of 10 mol% or less, specifically 0.01 mol% to 5 mol%. In the above range, when included with the first (meth) acrylate copolymer, it is possible to implement an adhesive film that can be used in a flexible device having good flexibility, bending properties, hardness, fairness, reliability.

The (meth) acrylate monomer having the epoxy group may realize the effect of enabling self curing and / or improving cohesion and reliability. The (meth) acrylic monomer having the epoxy group may be included in 5 mol% or less, specifically 0.01 mol% to 5 mol% in the monomer mixture. In the above range, there may be an effect that the rapid curing and reliability is improved. The (meth) acrylic monomer having the epoxy group may be glycidyl (meth) acrylate.

The (meth) acrylate monomer having the oxetane group may realize an effect of making it self-curable and / or improving cohesion and reliability. The (meth) acrylate monomer having the oxetane group may be included in 5 mol% or less, specifically 0.01 mol% to 5 mol% in the monomer mixture. In the above range, there may be an effect that the rapid curing and reliability is improved. (Meth) acrylate monomer which has the said oxetane group is oxetanyl (meth) acrylate, oxetanyl methyl (meth) acrylate, (3-methyl-3- oxetanyl) methyl (meth) acrylate, ( 3-ethyl-3-oxetanyl) methyl (meth) acrylate, and the like.

The second copolymer monomer may be copolymerized with one or more of the (meth) acrylate monomer having the epoxy group and the (meth) acrylate monomer having the oxetane group to form a matrix of the adhesive film or provide an additional function.

The second copolymer monomer may include a (meth) acrylate monomer having an alkyl group. The second copolymerization monomer may further increase the pencil hardness of the pressure-sensitive adhesive film-containing polarizing plate by further including at least one of a (meth) acrylate monomer having an alicyclic group and a (meth) acrylate monomer having a heteroalicyclic group. Specific types of 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 as described above in the first copolymerization monomer.

In one embodiment, the second (meth) acrylate copolymer is 0.01 mol% to 5 mol% of at least one of the (meth) acrylate monomer having the epoxy group, the (meth) acrylate monomer having the oxetane group, the alkyl group It may be a copolymer of 95 mol% to 99.9 mol% of (meth) acrylate monomer having a. In another embodiment, the second (meth) acrylate copolymer is 0.01 mol% to 5 mol% of at least one of the (meth) acrylate monomer having the epoxy group and the (meth) acrylate monomer having the oxetane group, the alkyl group 50 mol% to 95 mol% of a (meth) acrylate monomer having a, 1 mol% to 30 mol% of a (meth) acrylate monomer having an alicyclic group, and 1 mol% to 30 mol% of a (meth) acrylate monomer having a heteroalicyclic group It may be coalescing. In the above range, there may be an effect that the rapid curing and reliability is improved.

The glass transition temperature of the first (meth) acrylate copolymer and the second (meth) acrylate copolymer may be -55 ° C to -5 ° C, specifically -50 ° C to -30 ° C. The weight average molecular weight of the first (meth) acrylate copolymer and the second (meth) acrylate copolymer may be 200,000 g / mol to 1,500,000 g / mol, specifically 500,000 g / mol to 1,000,000 g / mol. have. The first (meth) acrylate copolymer and the second (meth) acrylate copolymer may each have an acid value of 5 mgKOH / g or less, more specifically 0.01 mgKOH / g to 3 mgKOH / g. Within this range, it is possible to implement a corrosion protection inhibitory effect directly or indirectly on the adherend.

The first (meth) acrylate copolymer and the second (meth) acrylate copolymer may be prepared by polymerizing a monomer mixture, respectively, by a conventional polymerization method. Polymerization methods can include conventional methods known to those skilled in the art. For example, the (meth) acrylate copolymer can be prepared by adding an initiator to the monomer mixture, followed by conventional copolymer polymerization, such as suspension polymerization, emulsion polymerization, solution polymerization, and the like. The polymerization temperature may be 65 ° C to 70 ° C and the polymerization time may be 6 hours to 8 hours. The initiator may be an azo polymerization initiator; And / or conventional ones including peroxides such as benzoyl peroxide or acetyl peroxide and the like.

Hardener

The curing agent may be a thermosetting agent, which is used to strengthen the cohesive force of the pressure-sensitive adhesive by appropriately crosslinking the acrylic binder resin, and the type thereof is not particularly limited. For example, an isocyanate type compound, an aziridine type compound, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

As the isocyanate compound, tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, Diisocyanate compounds such as naphthalene diisocyanate; Diisocyanate obtained from 2 mol of the adduct which reacted 3 mol of diisocyanate compounds with 1 mol of polyhydric alcohol compounds, such as trimethylol propane, the isocyanurate body which self-condensed 3 mol of diisocyanate compounds, and 3 mol of diisocyanate compounds The polyfunctional isocyanate compound containing three functional groups, such as the biuret body, triphenylmethane triisocyanate, and methylene bistriisocyanate which the remaining 1 mol of diisocyanate condensed to urea, is mentioned.

Examples of the aziridine compounds include N, N'-toluene-2,4-bis (1-aziridinecarboxamide), and N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxes). Mead), triethylene melamine, bisisoprotaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, and the like.

In addition, a melamine compound may be used alone or in combination of two or more kinds together with the isocyanate compound and the aziridine compound.

Hexamethylol melamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, etc. are mentioned as said melamine type compound.

The curing agent may be included in an amount of 0.1 wt% to 1 wt%, such as 0.1 wt% to 0.5 wt% (including 0.3 wt% to 1.0 wt% based on the adhesive composition solid content) based on the total amount of the pressure-sensitive adhesive composition. It is preferable at the point. When the curing agent is less than 0.1% by weight based on the total amount of the pressure-sensitive adhesive composition, the adhesiveness or cohesive force of the pressure-sensitive adhesive may be slightly lowered due to insufficient crosslinking (incomplete curing), leading to deterioration of durability such as moxibustion and damage to cutting properties. When the amount exceeds 1% by weight based on the total amount of the pressure-sensitive adhesive composition, the compatibility may be slightly lowered and surface migration may occur, the crosslinking reaction may proceed too much, and the adhesive force may be slightly lowered, and problems may occur in reducing residual stress.

solvent

The solvent can improve the coating property of the pressure-sensitive adhesive composition, and can inhibit the self-curing reaction of the pressure-sensitive adhesive composition. The solvent can be used a conventional solvent known to those skilled in the art. For example, the solvent may include any one or more of methyl ethyl ketone, ethyl acetate, toluene, and the amount of the residue relative to the pressure-sensitive adhesive composition, such as 10% to 40% by weight, such as 10% by weight, based on the total amount of the pressure-sensitive adhesive composition. % To 30% by weight may be included.

Other ingredients

The pressure-sensitive adhesive composition may further include a silane coupling agent, an antistatic agent, an ultraviolet absorber, a cationic initiator, a release agent, or a combination thereof.

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

The antistatic agent inhibits the generation of static electricity during rework of the pressure-sensitive adhesive film, and may include a conventional antistatic agent. The antistatic agent may be included in an amount of 1% by weight to 5% by weight, such as 1% by weight to 3% by weight, based on the total amount of the pressure-sensitive adhesive composition (including 1.0% by weight to 5.0% by weight based on the amount of the adhesive composition). When the antistatic agent is included in the above range is preferable in terms of chargeability. When the antistatic agent is included in less than 1% by weight relative to the total amount of the pressure-sensitive adhesive composition may be somewhat less antistatic effect, when included in more than 5% by weight relative to the total amount of the pressure-sensitive adhesive composition to lower the physical properties of the pressure-sensitive adhesive composition It will increase the cost.

For example, the antistatic agent may be an ionic antistatic agent. The ionic antistatic agent may be an alkali metal salt, an ionic liquid or an ionic solid. However, the alkali metal salt may be insufficient in durability due to its low compatibility with the pressure-sensitive adhesive, and the ionic liquid may have a low fluidity in the pressure-sensitive adhesive plastic, and thus, the antistatic performance may decrease slightly with time. In short, in consideration of the stability of the durability and antistatic properties over time, it is preferable to include an ionic solid that is a solid at room temperature (25 ° C).

For example, the antistatic agent is 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 by mixing two or more kinds.

The ultraviolet absorber may have an absorption wavelength of absorption wavelength of 380 to 420 nm. Here, the "absorption wavelength" may refer to "maximum absorption wavelength."

The pressure-sensitive adhesive composition may exhibit a transmittance of 5% or less in a region of 400 nm or less when including the ultraviolet absorbent having the absorption wavelength range, thereby preventing a polarizer and a device including the same from being damaged by external ultraviolet rays. There is an advantage to this.

The ultraviolet absorbent is not limited to the above if it satisfies the above-described absorption wavelength range, it is possible to apply the ultraviolet absorber commonly used in the art. For example, the ultraviolet absorbent 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 so long as the absorption wavelength is satisfied.

The cationic initiator may be a cationic photopolymerization initiator, but is not limited thereto. A cationic photoinitiator generally used in the art may be used. For example, the onium salt or its derivative which releases a Lewis acid by light irradiation is mentioned. Such compounds are in the form of salts consisting of cations and anions represented by the general formula [X] ^{x +} [Y] ^x- , and specific examples of the cations include aromatic diazonium salts, aromatic iodonium salts, aromatic halonium salts, aromatic sulfonium salts, and the like. Specific examples of the anion include tetrafluoroborate (BF ₄ ), hexafluorophosphate (PF ₆ ), hexafluoroantimonate (SbF ₆ ), hexafluoroarsenate (AsF ₆ ), hexa Chloro antimonate (SbCl ₆ ) and the like. These cationic photoinitiators can be used 1 type or in mixture of 2 or more types.

The content of the cationic initiator is not particularly limited, but may be included in an amount of 0.01 parts by weight to 10 parts by weight, such as 0.1 parts by weight to 5 parts by weight, based on the total amount of the adhesive composition. When the cationic initiator is less than 0.01 parts by weight based on the total amount of the pressure-sensitive adhesive composition, curing of the colored adhesive composition may be insufficient to obtain sufficient adhesion and adhesion, and the adhesive when the cationic initiator exceeds 10 parts by weight based on the total amount of the pressure-sensitive adhesive composition. The hygroscopicity may be increased by excessive content of the ionic substance in the layer, and the durability may be somewhat reduced.

The release agent may be an alkyd release agent, a silicone release agent, a fluorine release agent, an unsaturated ester release agent, a polyolefin release agent or a wax release agent. For example, it may be preferable to use an alkyd-based release agent, a silicone-based release agent or a fluorine-based release agent in terms of heat resistance, but is not necessarily limited thereto. The release agent may be included in an amount of 0.01% by weight to 0.1% by weight based on the total amount of the pressure-sensitive adhesive composition.

In addition to the above components, the pressure-sensitive adhesive composition is a reworking agent (adhesive agent), adhesion imparting resin, antioxidant, leveling agent in order to adjust the adhesion, cohesion, viscosity, elastic modulus, glass transition temperature, etc. required according to the application And additives such as surface lubricants, antifoams, fillers, and light stabilizers.

The additive may be added by appropriately adjusting the content within the range that does not inhibit the effect of the present invention.

Pressure-sensitive adhesive composition according to one embodiment may have a viscosity of 1,000 cPs to 4,000 cPs at 25 ℃. In the above range, it may be easy to adjust the thickness of the adhesive film, there is no stain on the adhesive film, the coating surface may have a uniform effect.

Another embodiment provides a pressure-sensitive adhesive film prepared using the pressure-sensitive adhesive composition described above.

Yet another embodiment provides a polarizing plate including the adhesive film.

The manufacturing method of the adhesive film is not particularly limited, and may be prepared by a conventional method. For example, it can be applied to the production of the adhesive film using the pressure-sensitive adhesive composition.

For example, the above-mentioned pressure-sensitive adhesive composition on the polarizer protective film is flow casted, bar coater, air knife, gravure, reverse roll, kiss roll, spray ( It can be manufactured by directly applying in an appropriate development method using a coating method such as a spray or blade method, followed by drying (thermal curing) to form an adhesive layer, and laminating with a polarizing plate.

In addition, after the pressure-sensitive adhesive film was formed on the silicone-coated release film by the same coating method as described above, a silicone-coated release film having a different peeling force was laminated using a roll pressing device to prepare an adhesive transfer tape, and then to a polarizing plate. It can be used by sticking.

The pressure-sensitive adhesive film may be formed through heat curing, but when an ultraviolet curable compound and a photopolymerization initiator (such as the cationic photopolymerization initiator described above) are used as a crosslinking agent, after the polarizing plate is laminated, ultraviolet rays are irradiated from the release film, or roll compression is performed. The device may be manufactured by laminating a silicone-coated release film having a different peel force and then irradiating (photocuring) ultraviolet rays.

The thickness of the adhesive film is not particularly limited, but may be 5 μm to 30 μm, such as 7 μm to 20 μm, such as 10 μm to 15 μm. When the thickness of the pressure-sensitive adhesive film is in the above range is preferable in terms of adhesion and durability, there is an advantage that can be applied to a thin device.

In the polarizing plate having an adhesive film on at least one surface, the polarizing plate may have a transmittance of 5% or less of a wavelength of 400 nm or less, and a transmittance of 40% or more of a wavelength of 455 nm or more.

The polarizing plate can prevent damage occurring to the polarizing plate or the device to which the polarizing plate is bonded because the transmittance of the wavelength of 400 nm or less is 5% or less, and the blue luminance decreases because the transmittance of the wavelength of 455 nm or more is 40% or more. There is an advantage that can be prevented.

3 and 4 illustrate embodiments of the polarizer according to one embodiment. Hereinafter, a polarizer according to an embodiment will be described with reference to FIGS. 3 and 4.

First, referring to FIG. 3, the polarizer 100 according to the embodiment is a polarizer 110, a first optical film 120 formed on the upper surface of the polarizer 110, the adhesive formed on the lower surface of the polarizer 110. It includes a film 130, wherein the adhesive film 130 is formed by the pressure-sensitive adhesive composition according to the above-described embodiment. Since the adhesive composition has been described above, components other than the adhesive film will be described below.

The polarizer is made of a polyvinyl alcohol-based film, and is not particularly limited as long as it is a polyvinyl alcohol-based film regardless of the production method. For example, the polarizer can use modified polyvinyl alcohol films, such as a partially formalized polyvinyl alcohol film and an acetoacetyl-group modified polyvinyl alcohol film. Specifically, it is prepared by dyeing iodine or dichroic dye on a polyvinyl alcohol film and stretching it in a predetermined direction. Specifically, it is prepared through the swelling process, the dyeing step, the stretching step. Methods of performing each step are commonly known to those skilled in the art. The polarizer 110 may have a thickness of 5 μm to 50 μm. It can be used for the display device in the above range.

The first optical film is an optically transparent resin, specifically, a cyclic polyolefin-based, poly (meth) acrylate-based, polycarbonate-based, polyethylene terephthalate (PET) including an amorphous cyclic polyolefin (cyclic olefin polymer, COP), etc. Cellulose ester, polyether sulfone, polysulfone, polyamide, polyimide, polyolefin, polyarylate, polyvinyl alcohol It may be formed of one or more of the polyvinyl chloride-based, polyvinylidene chloride-based resin. The first optical film 120 may have a thickness of 10 μm to 200 μm, for example, 20 μm to 120 μm, and may be used for the display device in the above range.

Next, referring to FIG. 4, the polarizer 200 according to another embodiment of the present invention includes a polarizer 110, a first optical film 120 formed on an upper surface of the polarizer 110, and a lower part of the polarizer 110. It includes a second optical film 140 formed on the surface, a pressure-sensitive adhesive film 130 formed on the lower surface of the second optical film 140, the adhesive film is formed by the pressure-sensitive adhesive composition according to the above-described embodiment. It is substantially the same as the polarizing plate described above except that the second optical film 140 is further formed between the polarizer 110 and the adhesive film 130. The second optical film 140 may be formed of the same or different kinds of resin as the first optical film 120. The second optical film 140 may have the same or different thickness as the first optical film 120.

Meanwhile, although not shown in FIGS. 3 and 4, an adhesive layer formed of an adhesive for a polarizing plate may be included between the polarizer and the first optical film and between the polarizer and the second optical film, and the adhesive for the polarizing plate may be an aqueous adhesive, a pressure-sensitive adhesive, or an ultraviolet ray. It may include a curable adhesive.

The polarizing plate may be prepared by coating the pressure-sensitive adhesive composition according to the embodiment described above on one surface of the polarizing plate to a predetermined thickness and then aging, or by adhering the pressure-sensitive adhesive sheet including the pressure-sensitive adhesive film made of the pressure-sensitive adhesive composition to the polarizing plate. .

Yet another embodiment provides a display device including the polarizing plate.

Hereinafter, a display device according to an embodiment is described.

The display device may be, for example, a liquid crystal display, an organic light emitting display, or the like, but is not limited thereto.

5 illustrates an embodiment of a display device according to an embodiment. As shown in FIG. 5, the display device according to the embodiment includes a liquid crystal display panel 310, a first polarizing plate 320 formed on an upper surface of the liquid crystal display panel 310, and a lower portion of the liquid crystal display panel 310. It may include a second polarizing plate 330 formed on the surface, the backlight unit 340 formed under the second polarizing plate 330, wherein at least one of the first polarizing plate 320 and the second polarizing plate 330 It may be a polarizing plate according to one embodiment. Since the polarizer is described above, only the liquid crystal display panel 310 and the backlight unit 340 will be described below.

The liquid crystal display panel includes an upper substrate, a lower substrate, and a liquid crystal cell interposed between the upper substrate and the lower substrate. In the present invention, the upper substrate means a substrate disposed on the observer side of the liquid crystal display panel, and the lower substrate means a substrate disposed on the backlight unit side.

The material, configuration, and the like of the upper substrate, the lower substrate, and the liquid crystal cell are not particularly limited, and various upper substrates, lower substrates, and liquid crystal cells that are used for the liquid crystal display panel configuration in the art may be used without limitation. In addition, the driving mode of the liquid crystal display panel is not particularly limited, and liquid crystal display panels of various modes used in the art, for example, TW (Twist-Nematic) mode, VA (Vertical Alignment) mode, IPS Liquid crystal panels of (In-Plane Swiching) mode can be used without limitation.

Next, the backlight unit 340 is to supply light to the liquid crystal display panel 310, the backlight unit 340 used in the art may be used without limitation. For example, the backlight unit may include a light source unit including at least one light source and a printed circuit board on which the light sources are mounted, and optical films for collecting or diffusing light of the light source unit. Film, diffusion film, diffusion plate, and the like).

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are only preferred examples of the present invention, and the present invention is not limited to the following Examples.

(Synthesis of dyes)

Synthesis Example 1 Synthesis of Dye represented by Chemical Formula 1-1

Scheme 1

5-Hydroxyindole (13.32g) was added to DMF (dimethylformamide) solvent (100ml) and NaH 60% in mineral oil (4.13g) was activated. After 2 hours, 18.40 g of 1-Iodobutane was added and reacted at 60 ° C. for 4 hours. Then NaH 60% in mineral oil (6.20g) was added, after 2 hours Iodomethane (21.8g) was added to react for 4 hours. Thereafter, ethyl acetate and ultrapure water (Di-water) are added, and the organic phase is distilled off by phase separation. After distillation, the intermediate A-1-1 was obtained by using Silica Column Chromatography.

Scheme 2

3,4-Dihydroxy-3-cyclobutene-1,2-dione (11.41g) and thionyl chloride (35.9g) are added to DMF and heated to 70 ° C and stirred for 4 hours. After removing DMF, methylene chloride (100ml) was added dropwise, followed by stirring with aluminum chloride (0.9mol). The intermediate A-1-1 is further added dropwise at 0 ° C, followed by stirring for 6 hours. The solvent was removed, extracted with ether, and recrystallized to obtain intermediate A-1.

The intermediate A-1 (100 mmol), N- (2-Cyanoethyl) -N-butylaniline (100 mmol) were added to toluene (300 mL) and butanol (300 mL) and refluxed to produce water produced by Dean-stark distillation apparatus. Remove it. After stirring for 12 hours, the reaction mixture was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following Chemical Formula 1-1.

[Formula 1-1]

(Maldi-tof MS: 483.60 m / z)

Synthesis Example 2 Synthesis of Dye represented by Chemical Formula 1-2

Scheme 3

N- (2-Cyanoethyl) -N- (2-hydroxyethyl) aniline (100mmol) and triethylamine (150mmol) are added to 100ml of chloroform solvent and cooled by stirring in an ice bath. After dropping Propionyl Chloride (150mmol) under cooling, stir for 2 hours at room temperature. After chloroform and Di-water input phase separated by organic phase distillation. After distillation, intermediate B-1 was obtained by using Silica Column Chromatography.

The intermediate A-1 (100 mmol) and the intermediate B-1 (100 mmol) were added to toluene (300 mL) and butanol (300 mL) and refluxed to remove the water produced by the Dean-stark distillation apparatus. After stirring for 12 hours, the reaction was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following formula 1-2.

[Formula 1-2]

(Maldi-tof MS: 527.61 m / z)

Synthesis Example 3: Synthesis of Dye represented by Chemical Formula 1-3

Add 3-Anilinopropionitrile (100mmol) and t-BuONa (150mmol) to 100 ml of toluene solvent and stir at room temperature. Then Pd (Acac) ₂ (0.5mmol) and (t-BuO) ₃ P (1mmol) was added and stirred for 30 minutes. 4-Bromo-m-xylene (100mmol) was added and stirred under heating for 4 hours under Reflux conditions. After distilling ethyl acetate and Di-water phase separated by distillation of the organic layer. After distillation, Intermediate C-1 was obtained by using Silica Column Chromatography.

Scheme 4

The intermediate A-1 (100 mmol) and the intermediate C-1 (100 mmol) were added to toluene (300 mL) and butanol (300 mL) and refluxed to remove water produced by Dean-stark distillation apparatus. After stirring for 12 hours, the reaction mixture was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by Chemical Formula 1-3.

[Formula 1-3]

(Maldi-tof MS: 531.64 m / z)

Synthesis Example 4 Synthesis of Dye represented by Chemical Formula 1-4

Add 3-Anilinopropionitrile (100mmol) and t-BuONa (150mmol) to 100 ml of toluene solvent and stir at room temperature. Then Pd (Acac) ₂ (0.5mmol) and (t-BuO) ₃ P (1mmol) was added and stirred for 30 minutes. 1-Bromo-2,4-difluorobenzene (100mmol) was added thereto, followed by heating and stirring for 4 hours under Reflux conditions. After distilling ethyl acetate and Di-water phase separated by distillation of the organic layer. After distillation, Intermediate D-1 was obtained by using Silica Column Chromatography.

Scheme 5

The intermediate A-1 (100 mmol) and the intermediate D-1 (100 mmol) were added to toluene (300 mL) and butanol (300 mL) and refluxed to remove the water produced by the Dean-stark distillation apparatus. After stirring for 12 hours, the reaction mixture was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following Chemical Formula 1-4.

[Formula 1-4]

(Maldi-tof MS: 539.57 m / z)

Synthesis Example 5 Synthesis of Dye represented by Chemical Formula 1-5

Scheme 6

5-Hydroxyindole (13.32g) is added to DMF solvent (100ml) and NaH 60% in mineral oil (4.13g) is activated. After 2 hours, 18.40 g of 1-Iodobutane was added and reacted at 60 ° C. for 4 hours. Then NaH 60% in mineral oil (6.20g) was added, after 2 hours Iodomethane (21.8g) was added to react for 4 hours. After distillation with ethyl acetate and di-water, the phases are separated, dehydrated with MgSO ₄ , and the filtered organic layer is distilled off. After distillation, the mixture was added to a chloroform solvent (100ml), and 150ml of triethylamine was added and cooled. Drop the Propionyl Chloride (150mmol) into the cooled reaction solution and stir for 2 hours at room temperature. After chloroform and Di-water was added to the phase separated by distillation of the organic layer. After distillation, the intermediate A-2-1 was obtained by using Silica Column Chromatography.

Scheme 7

3,4-Dihydroxy-3-cyclobutene-1,2-dione (11.41g) and thionyl chloride (35.9g) are added to DMF and heated to 70 ° C and stirred for 4 hours. Remove DMF, add methylene chloride (100ml) dropwise, add aluminum chloride (0.9mol) and stir. Thereafter, the intermediate A-2-1 was further added dropwise at 0 ° C, followed by stirring for 6 hours. After removing the solvent and extracted with ether and recrystallized to obtain the intermediate A-2.

The intermediate A-2 (100 mmol) and N- (2-Cyanoethyl) -N-butylaniline (100 mmol) were added to toluene (300 mL) and butanol (300 mL) and refluxed to produce water. Remove it. After stirring for 12 hours, the reaction was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following Chemical Formula 1-5.

[Formula 1-5]

(Maldi-tof MS: 525.64 m / z)

Synthesis Example 6 Synthesis of Dye represented by Chemical Formula 1-6

The intermediate A-2 (100 mmol) and intermediate B-1 (100 mmol) were added to toluene (300 mL) and butanol (300 mL), and the resulting water was refluxed to remove the resulting Dean-stark distillation apparatus. After stirring for 12 hours, the reaction mixture was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following Chemical Formula 1-6.

[Formula 1-6]

(Maldi-tof MS: 555.60 m / z)

Synthesis Example 7 Synthesis of Dye represented by Chemical Formula 1-7

The intermediate A-2 (100 mmol) and the intermediate C-1 (100 mmol) were added to toluene (300 mL) and butanol (300 mL) and refluxed to remove water produced by a Dean-stark distillation apparatus. After stirring for 12 hours, the reaction mixture was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following Chemical Formula 1-7.

[Formula 1-7]

(Maldi-tof MS: 573.68 m / z)

Synthesis Example 8 Synthesis of Dye represented by Chemical Formula 1-8

Intermediate A-2 (100 mmol) and Intermediate D-1 (100 mmol) were added to toluene (300 mL) and butanol (300 mL), and the resulting water was removed by Dean-stark distillation. After stirring for 12 hours, the reaction mixture was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following Chemical Formula 1-8.

[Formula 1-8]

(Maldi-tof MS: 581.60 m / z)

Synthesis Example 9 Synthesis of Dye represented by Chemical Formula 1-9

Scheme 8

5-Cyanoindole (13.32g) is added to DMF solvent (100ml) and NaH 60% in mineral oil (4.13g) is activated. After 2 hours, 18.40 g of 1-Iodobutane was added and reacted at 60 ° C. for 4 hours. After distilling ethyl acetate and Di-water phase separated by distillation of the organic layer. After distillation, the intermediate A-3-1 was obtained by using Silica Column Chromatography.

Scheme 9

3,4-Dihydroxy-3-cyclobutene-1,2-dione (11.41g) and thionyl chloride (35.9g) are added to DMF and heated to 70 ° C and stirred for 4 hours. After removing DMF, methylene chloride (100ml) was added dropwise, followed by stirring with aluminum chloride (0.9mol). Thereafter, intermediate A-3-1 was further added dropwise at 0 ° C, followed by stirring for 6 hours. The solvent was removed, followed by extraction with ether and recrystallization to obtain intermediate A-3.

The intermediate A-3 (100 mmol), N- (2-Cyanoethyl) -N-butylaniline (100 mmol) were added to toluene (300 mL) and butanol (300 mL) and refluxed to produce water. Remove it. After stirring for 12 hours, the reaction was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following Chemical Formula 1-9.

[Formula 1-9]

(Maldi-tof MS: 478.60 m / z)

Synthesis Example 10 Synthesis of Dye represented by Chemical Formula 1-10

The intermediate A-3 (100 mmol) and intermediate B-1 (100 mmol) were added to toluene (300 mL) and butanol (300 mL), and the resulting water was refluxed to remove the resulting Dean-stark distillation apparatus. After stirring for 12 hours, the reaction mixture was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following Chemical Formula 1-10.

[Formula 1-10]

(Maldi-tof MS: 522.60 m / z)

Synthesis Example 11 Synthesis of Dye represented by Chemical Formula 1-11

The intermediate A-3 (100 mmol) and the intermediate C-1 (100 mmol) were added to toluene (300 mL) and butanol (300 mL) and refluxed to remove the water produced by the Dean-stark distillation apparatus. After stirring for 12 hours, the reaction mixture was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following Chemical Formula 1-11.

[Formula 1-11]

(Maldi-tof MS: 526.60 m / z)

Synthesis Example 12 Synthesis of Dye represented by Chemical Formula 1-12

The intermediate A-3 (100 mmol) and the intermediate D-1 (100 mmol) were added to toluene (300 mL) and butanol (300 mL) and refluxed to remove water produced by Dean-stark distillation. After stirring for 12 hours, the reaction mixture was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following Chemical Formula 1-8.

[Formula 1-12]

(Maldi-tof MS: 534.60 m / z)

Synthesis Example 13: Synthesis of Dye represented by Chemical Formula 1-13

Scheme 10

Add 5-Bromoindole (19.61g) to DMF solvent (100ml) and activate NaH 60% in mineral oil (4.13g). After 2 hours, 18.40 g of 1-Iodobutane was added and reacted at 60 ° C. for 4 hours. After distilling ethyl acetate and Di-water phase separated by distillation of the organic layer. After distillation, the intermediate A-4-1 was obtained by using Silica Column Chromatography.

Scheme 11

3,4-Dihydroxy-3-cyclobutene-1,2-dione (11.41g) and thionyl chloride (35.9g) were added to DMF and heated to 70 ° C and stirred for 4 hours. After removing DMF, methylene chloride (100ml) was added dropwise, followed by stirring with aluminum chloride (0.9mol). Thereafter, the intermediate A-4-1 was further added dropwise at 0 ° C, followed by stirring for 6 hours. The solvent was removed, followed by extraction with ether and recrystallization to obtain an intermediate A-4.

The intermediate A-4 (100 mmol) and N- (2-Cyanoethyl) -N-butylaniline (100 mmol) were added to toluene (300 mL) and butanol (300 mL) and refluxed to produce water. Remove it. After stirring for 12 hours, the reaction mixture was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following Chemical Formula 1-13.

[Formula 1-13]

(Maldi-tof MS: 532.50 m / z)

Synthesis Example 14 Synthesis of Dye represented by Chemical Formula 1-14

The intermediate A-4 (100 mmol) and intermediate B-1 (100 mmol) were added to toluene (300 mL) and butanol (300 mL) and refluxed to remove the water produced by the Dean-stark distillation apparatus. After stirring for 12 hours, the reaction mixture was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following Chemical Formula 1-14.

[Formula 1-14]

(Maldi-tof MS: 576.48 m / z)

Synthesis Example 15 Synthesis of Dye represented by Chemical Formula 1-15

Intermediate A-4 (100 mmol) and Intermediate C-1 (100 mmol) were added to toluene (300 mL) and butanol (300 mL), and the resulting water was removed by Dean-stark distillation. After stirring for 12 hours, the reaction mixture was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following Chemical Formula 1-15.

[Formula 1-15]

(Maldi-tof MS: 580.50 m / z)

Synthesis Example 16 Synthesis of Dye represented by Chemical Formula 1-16

Intermediate A-4 (100 mmol) and Intermediate D-1 (100 mmol) were added to toluene (300 mL) and butanol (300 mL), and the resulting water was removed by Dean-stark distillation. After stirring for 12 hours, the reaction mixture was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by the following Chemical Formula 1-16.

[Formula 1-16]

(Maldi-tof MS: 588.40 m / z)

Synthesis Example 17 Synthesis of Core-Shell Dye

After dissolving the compound represented by Chemical Formula 1-1 (5 mmol) in 600 mL chloroform solvent, Isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL chloroform, and simultaneously added dropwise at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Chemical Formula 1-1-1.

[Formula 1-1-1]

(Maldi-tof MS: 1016.19 m / z)

Synthesis Example 18 Synthesis of Core-Shell Dye

After dissolving the compound represented by Formula 1-1 (5 mmol) in 600 mL chloroform solvent, triethylamine (50 mmol) was added thereto. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) are dissolved in 60 mL chloroform and added dropwise at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Chemical Formula 1-1-2.

[Formula 1-1-2]

(Maldi-tof MS: 1018.17 m / z)

Synthesis Example 19 Synthesis of Core-Shell Dye

After dissolving the compound represented by Chemical Formula 1-2 (5 mmol) in 600 mL chloroform solvent, isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL chloroform, and simultaneously added dropwise at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Chemical Formula 1-2-1.

[Formula 1-2-1]

(Maldi-tof MS: 1060.20 m / z)

Synthesis Example 20 Synthesis of Core-Shell Dye

Compound (5 mmol) represented by Chemical Formula 1-2 was dissolved in 600 mL chloroform solvent, and triethylamine (50 mmol) was added thereto. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) are dissolved in 60 mL chloroform and added dropwise at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Chemical Formula 1-2-2.

[Formula 1-2-2]

(Maldi-tof MS: 1060.20 m / z)

Synthesis Example 21 Synthesis of Core-Shell Dye

After dissolving the compound represented by Formula 1-5 (5 mmol) in 600mL chloroform solvent, Isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) are dissolved in 60mL chloroform, and added dropwise at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Chemical Formula 1-5-1.

[Formula 1-5-1]

(Maldi-tof MS: 1058.20 m / z)

Synthesis Example 22 Synthesis of Core-Shell Dye

Compound (5 mmol) represented by Chemical Formula 1-5 was dissolved in 600 mL chloroform solvent, and triethylamine (50 mmol) was added thereto. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) are dissolved in 60 mL chloroform and added dropwise at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Chemical Formula 1-5-2.

[Formula 1-5-2]

(Maldi-tof MS: 1060.20 m / z)

Synthesis Example 23 Synthesis of Core-Shell Dye

After dissolving the compound represented by Chemical Formula 1-9 (5 mmol) in 600 mL chloroform solvent, Isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL chloroform, and simultaneously added dropwise at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Chemical Formula 1-9-1.

[Formula 1-9-1]

(Maldi-tof MS: 1011.20 m / z)

Synthesis Example 24 Synthesis of Core-Shell Dye

The compound represented by the formula (1-9) (5 mmol) is dissolved in 600 mL chloroform solvent, and triethylamine (50 mmol) is added thereto. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) are dissolved in 60 mL chloroform and added dropwise at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Chemical Formula 1-9-2.

[Formula 1-9-2]

(Maldi-tof MS: 1013.20 m / z)

Synthesis Example 25 Synthesis of Core-Shell Dye

After dissolving the compound represented by Chemical Formula 1-13 (5 mmol) in 600 mL chloroform solvent, Isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL chloroform, and simultaneously added dropwise at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Chemical Formula 1-13-1.

[Formula 1-13-1]

(Maldi-tof MS: 1065.10 m / z)

Synthesis Example 26 Synthesis of Core-Shell Dye

After dissolving the compound represented by Chemical Formula 1-13 (5 mmol) in 600 mL chloroform solvent, triethylamine (50 mmol) was added thereto. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) are dissolved in 60 mL chloroform and added dropwise at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Chemical Formula 1-13-2.

[Formula 1-13-2]

(Maldi-tof MS: 1067.00 m / z)

(Synthesis of Adhesive Composition)

Example 1

78.583% by weight of acrylic binder resin (PL-8540; SAIDEN Chemical), 0.236% by weight of isocyanate-based curing agent (H-AL; Zirca ceramic), 0.145% by weight of aziridine-based curing agent (HDU-P25; manufacturer), release agent (MAC-2101) Soken) 0.028% by weight, antistatic agent (FC-4400L; 3M) 1.336% by weight, silane coupling agent (KBM-403; shinetsu) 0.024% by weight, pyrrole methine dye (Maximum absorption wavelength 493nm, FDB-007, Yamada chemical ) 0.1% by weight, phthalocyanine-based dyes (maximum absorption wavelength 754nm, FDN-001, Yamada chemical) 0.13% by weight, 0.1% by weight of the compound of Synthesis Example 17 (compound represented by the formula 1-1-1) and solvent (MEK) The residual amount (19.644 wt%) was mixed to prepare an adhesive composition for polarizing plate of Example 1. The pressure-sensitive adhesive composition including the pressure-sensitive adhesive film having a thickness of 20 μm was prepared by applying the prepared pressure-sensitive adhesive composition on a release film coated with a silicone release agent and drying at 90 ° C. for 5 minutes. The release film was peeled off from the adhesive sheet to obtain an adhesive film.

Example 2

A pressure-sensitive adhesive composition for a polarizing plate was manufactured in the same manner as in Example 1, except that the compound of Synthesis Example 18 (compound represented by Formula 1-1-2) was used instead of the compound of Synthesis Example 17.

Example 3

A pressure-sensitive adhesive composition for a polarizing plate was manufactured in the same manner as in Example 1, except that the compound of Synthesis Example 19 (compound represented by Formula 1-2-1) was used instead of the compound of Synthesis Example 17.

Example 4

A pressure-sensitive adhesive composition for a polarizing plate was manufactured in the same manner as in Example 1, except that the compound of Synthesis Example 20 (compound represented by Formula 1-2-2) was used instead of the compound of Synthesis Example 17.

Example 5

A pressure-sensitive adhesive composition for a polarizing plate was manufactured in the same manner as in Example 1, except that the compound of Synthesis Example 21 (compound represented by Formula 1-5-1) was used instead of the compound of Synthesis Example 17.

Example 6

A pressure-sensitive adhesive composition for a polarizing plate was manufactured in the same manner as in Example 1 except that the compound of Synthesis Example 22 (compound represented by Formula 1-5-2) was used instead of the compound of Synthesis Example 17.

Example 7

A pressure-sensitive adhesive composition for a polarizing plate was prepared in the same manner as in Example 1 except that the compound of Synthesis Example 23 (compound represented by Formula 1-9-1) was used instead of the compound of Synthesis Example 17.

Example 8

A pressure-sensitive adhesive composition for a polarizing plate was manufactured in the same manner as in Example 1, except that the compound of Synthesis Example 24 (compound represented by Formula 1-9-2) was used instead of the compound of Synthesis Example 17.

Example 9

A pressure-sensitive adhesive composition for a polarizing plate was prepared in the same manner as in Example 1 except that the compound of Synthesis Example 25 (compound represented by Formula 1-13-1) was used instead of the compound of Synthesis Example 17.

Example 10

A pressure-sensitive adhesive composition for a polarizing plate was prepared in the same manner as in Example 1 except that the compound of Synthesis Example 26 (compound represented by Formula 1-13-2) was used instead of the compound of Synthesis Example 17.

Comparative Example 1

A pressure-sensitive adhesive composition for a polarizing plate was prepared in the same manner as in Example 1, except that a commercially available tetraazapopyrine-based dye (maximum absorption wavelength: 594 nm, FGD-007, Yamada chemical) was used instead of the compound of Synthesis Example 1.

Evaluation: Measurement of Color Reproducibility of Adhesive Film

After applying the pressure-sensitive adhesive composition according to Examples 1 to 10 and Comparative Example 1 and dried for 4 minutes at 90 ℃, and aged for 24 hours at 23 ℃ and 55% relative humidity to prepare a pressure-sensitive adhesive film, this one panel (backlight On the contrary), color reproducibility was measured using a spectrophotometer (SR-3, Topcon), and the results are shown in Table 1 below.

(unit: %) Color reproduction rate (%) Example 1 111 Example 2 112 Example 3 113 Example 4 114 Example 5 111 Example 6 112 Example 7 111 Example 8 112 Example 9 112 Example 10 111 Comparative Example 1 109

As can be seen in Table 1, it can be seen that Examples 1 to 10 to which the compounds of Synthesis Examples 17 to 26 are applied, respectively, have better color reproducibility than Comparative Example 1.

As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to this, It can be variously modified and implemented in a claim, a detailed description of an invention, and the range of an accompanying drawing. Naturally, it belongs to the scope of the invention.

Claims (16)

(A) a dye comprising a compound represented by the following formula (1);
(B) resins;
(C) curing agent; And
(D) solvent
Pressure-sensitive adhesive composition comprising:
[Formula 1]

In Chemical Formula 1,
R ¹ to R ⁵ are each independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
R ⁶ is a halogen atom, cyano group, substituted or unsubstituted C1 to C20 alkoxy group or substituted or unsubstituted C1 to C20 alkylester group.
The method of claim 1,
Compound represented by Formula 1 is a pressure-sensitive adhesive composition represented by the following Formula 1A:
[Formula 1A]

In Chemical Formula 1A,
R ¹ to R ⁵ are each independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
R ⁶ is a halogen atom, cyano group, substituted or unsubstituted C1 to C20 alkoxy group or substituted or unsubstituted C1 to C20 alkylester group.
The method of claim 1,
At least one of the R ² and R ³ is a pressure-sensitive adhesive composition comprising a cyano group at the end.
The method of claim 1,
R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom or a cyano group.
The method of claim 1,
R ⁴ and R ⁵ are each independently a hydrogen atom pressure-sensitive adhesive composition.
The method of claim 1,
Compound represented by Formula 1 has a maximum absorption peak at a wavelength of 490nm to 600nm.
The method of claim 1,
Compound represented by Formula 1 is a pressure-sensitive adhesive composition represented by any one of the following formula 1-1 to formula 1-16.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

[Formula 1-15]

[Formula 1-16]

The method of claim 1,
The dye is a core-shell dye,
The core is represented by the formula (1),
The shell is an adhesive composition represented by the following formula (2) or (3):
[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,
L ^a to L ^d are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
The method of claim 8,
L ^a to L ^d are each independently a substituted or unsubstituted C1 to C10 alkylene group.
The method of claim 8,
The shell is a pressure-sensitive adhesive composition represented by the formula 2-1 or 3-1.
[Formula 2-1]

[Formula 3-1]

The method of claim 10,
Wherein the shell has a cage width of 6.5 kPa to 7.5 kPa.
The method of claim 8,
The core has a length of 1nm to 3nm pressure-sensitive adhesive composition.
The method of claim 1,
The pressure-sensitive adhesive composition further comprises a silane coupling agent, an antistatic agent, an ultraviolet absorber, a cationic initiator, a release agent or a combination thereof.
The adhesive film manufactured using the adhesive composition of any one of Claims 1-13.
The polarizing plate containing the adhesive film of Claim 14.
A display device comprising the polarizing plate of claim 15.

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