CN107793327A - Compounds, nucleocapsid dyestuff, Photosensitve resin composition and colored filter - Google Patents

Abstract

The present invention discloses a compound represented by Chemical Formula 1 and a core-shell dye, and also discloses a photosensitive resin composition comprising the compound represented by Chemical Formula 1 or the core-shell dye and the use of the photosensitive resin composition A manufactured color filter, the core-shell dye comprising: a core including the compound represented by Chemical Formula 1; and a shell surrounding the core. Color filters comprising the compounds or core-shell dyes of the invention have enhanced brightness and contrast. [chemical formula 1] In Chemical Formula 1, each substituent is the same as defined in the specification.

Description

Novel compound, core-shell dye, photosensitive resin composition and color filter

technical field

The present invention relates to a novel compound, a core-shell dye, a photosensitive resin composition comprising the novel compound or the core-shell dye, and a color filter manufactured using the photosensitive resin composition.

Background technique

Among various types of displays, liquid crystal display devices have the advantages of lightness, thinness, low cost, low operating power consumption, and high support for integrated circuits, and have been more widely used in laptop computers, monitors, and television screens . The liquid crystal display device includes a lower substrate and an upper substrate. A black matrix, a color filter, and an indium tin oxide pixel electrode are formed on the lower substrate, and a liquid crystal layer, a thin film transistor, and a capacitor layer are formed on the upper substrate. active circuit parts and indium tin oxide pixel electrodes. In the pixel area, each pixel is formed 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. A color filter is formed, and a black matrix layer is disposed on a transparent substrate in a predetermined pattern to form boundaries between pixels. A pigment dispersion method as one of various methods of forming a color filter, which provides a colored film by repeating a series of processes such as coating a photopolymerizable composition containing a colorant on a surface including a black matrix on a transparent substrate, expose the formed pattern, remove the unexposed parts with a solvent, and thermally cure it. A colored photosensitive resin composition for manufacturing a color filter according to a 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. Pigment dispersion methods are actively used in the manufacture of liquid crystal displays such as cell phones, laptops, monitors, and televisions. However, photosensitive resin compositions for color filters used in the pigment dispersion method have recently been required to improve performance and to have excellent pattern characteristics. Specifically, high color reproducibility and high brightness and high contrast characteristics are urgently required. An image sensor is a component used to capture images in a portable mobile phone camera or a digital still camera (DSC). Image sensors can be classified into charge-coupled device (CCD) image sensors and complementary metal oxide semiconductor (CMOS) image sensors depending on the manufacturing process and application methods. A color imaging device for a charge-coupled device image sensor or a complementary metal-oxide-semiconductor image sensor includes color filters, each of which has a filter color mixed with the primary colors red, green, and blue. piece segments, and the colors are separated. A recent color filter installed in a color imaging device has a pattern size of 2 μm or less, which is 1/100 to 1/200 of that of a conventional color filter pattern of a liquid crystal display. Therefore, increased resolution and reduced pattern residue are important factors in determining device performance. Color filters manufactured using conventional pigment-based photosensitive resin compositions have limitations in brightness and contrast due to the size of pigment particles. In addition, a color imaging device for an image sensor requires a smaller dispersed particle size to form a fine pattern. In order to meet the requirements, attempts have been made to prepare a photosensitive resin composition suitable for a dye that does not form particles by introducing the dye instead of a pigment, thereby realizing a color filter with improved brightness and contrast. However, dyes have poor durability such as light resistance and heat resistance, etc., relative to pigments, and thus brightness may be deteriorated.

Contents of the invention

Embodiments of the present invention provide a novel compound with enhanced brightness and contrast.

Another embodiment provides a core-shell dye comprising the novel compound.

Yet another embodiment provides a photosensitive resin composition comprising the novel compound or the core-shell dye.

Yet another embodiment provides a color filter manufactured using the photosensitive resin composition.

The embodiment of the present invention provides a compound represented by Chemical Formula 1.

[chemical formula 1]

In Chemical Formula 1,

R ¹ and R ² are independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl or substituted or unsubstituted C6 to C20 aryl, limited to ^The proviso is that R and R independently and must contain ^a functional group represented by Chemical Formula 1-1 and a chiral carbon, and

R ³ and R ⁴ are independently substituted or unsubstituted C1 to C20 alkyl or substituted or unsubstituted C6 to C20 aryl,

[chemical formula 1-1]

＊＊-OR ⁶

Wherein, in chemical formula 1-1,

R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group.

R ¹ and R ² may be independently represented by Chemical Formula 2-1 or Chemical Formula 2-2.

[chemical formula 2-1]

[chemical formula 2-2]

In Chemical Formula 2-1 and Chemical Formula 2-2,

L is a single bond, substituted or unsubstituted ^C1 to C10 alkylene or substituted or unsubstituted C3 to C10 cycloalkylene,

^L is substituted or unsubstituted C1 to C10 alkylene or substituted or unsubstituted C3 to C10 cycloalkylene, and

R ⁵ and R ⁶ are independently substituted or unsubstituted C1 to C20 alkyl.

R ⁶ may be C1 to C20 alkyl substituted with 'C1 to C10 alkyl or C6 to C20 aryl'.

R ⁶ may be represented by Chemical Formula 3.

[chemical formula 3]

In Chemical Formula 3,

R ⁷ and R ⁸ are independently substituted or unsubstituted C1 to C10 alkyl.

R ³ and R ⁴ may be independently C6 to C20 aryl substituted or unsubstituted by C1 to C10 alkyl.

The compound represented by Chemical Formula 1 may be one of the compounds represented by Chemical Formula 4 to Chemical Formula 10.

[chemical formula 4]

[chemical formula 5]

[chemical formula 6]

[chemical formula 7]

[chemical formula 8]

[chemical formula 9]

[chemical formula 10]

The compound represented by Chemical Formula 1 may have a maximum absorption wavelength (λ _max ) in 600nm to 700nm.

Another embodiment provides a core-shell dye including: a core including the compound represented by Chemical Formula 1; and a shell surrounding the core.

The shell may be represented by Chemical Formula 11 or Chemical Formula 12.

[chemical formula 11]

[chemical formula 12]

In chemical formula 11 and chemical formula 12,

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

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

The shell may be represented by Chemical Formula 11-1 or Chemical Formula 12-1.

[Chemical formula 11-1]

[Chemical formula 12-1]

The cage width (cage width) of described shell can be between to range.

The core may have a length of 1 nm to 3 nm.

The core may have a maximum absorption peak in a wavelength of 530 nm to 680 nm.

The core-shell dye may be selected from compounds represented by Chemical Formula 13 to Chemical Formula 26.

[chemical formula 13]

[chemical formula 14]

[chemical formula 15]

[chemical formula 16]

[chemical formula 17]

[chemical formula 18]

[chemical formula 19]

[chemical formula 20]

[chemical formula 21]

[chemical formula 22]

[chemical formula 23]

[chemical formula 24]

[chemical formula 25]

[chemical formula 26]

The core-shell dye may include the core and the shell in a molar ratio of 1:1.

The core-shell dye may be a green dye.

The core-shell dye may have a maximum absorption wavelength (λ _max ) in 600 nm to 700 nm.

Another embodiment provides a photosensitive resin composition comprising the compound or the core-shell dye.

The photosensitive resin composition may further include a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

The photosensitive resin composition may further include a pigment.

Based on the total amount of the photosensitive resin composition, the photosensitive resin composition may include 0.5wt% to 10wt% of the compound or the core-shell dye; 0.1wt% to 30wt% of the binder resin; 0.1 wt% to 30 wt% of the photopolymerizable monomer; 0.1 wt% to 5 wt% of the photopolymerization initiator; and the balance of the solvent.

The photosensitive resin composition may further include malonic acid, 3-amino-1,2-propanediol, a silane coupling agent containing vinyl or (meth)acryloyloxy, a leveling agent, a surfactant, a free based polymerization initiators or combinations thereof.

Another embodiment provides a color filter manufactured using the photosensitive resin composition.

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

Compounds or core-shell dyes according to the embodiments enable color filters with enhanced brightness and contrast.

Description of drawings

FIG. 1 is a view showing a cage width of a shell represented by Chemical Formula 11-1.

Detailed ways

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

In this specification, when no specific definition is provided otherwise, "substituted" means that at least one hydrogen atom of the compound is replaced by the following substituents: halogen atom (F, Cl, Br or I), hydroxyl, C1 to C20 alkane Oxygen, nitro, cyano, amine, imino, azido, amidino, hydrazino, hydrazino, carbonyl, carbamoyl, thiol group, ester, ether, carboxyl or its salt, sulfonic acid or its salt, phosphoric acid or its salt, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C30 aryl, C3 to C20 cycloalkyl, C3 to C20 Cycloalkenyl, C3 to C20 cycloalkynyl, C2 to C20 heterocycloalkyl, C2 to C20 heterocycloalkenyl, C2 to C20 heterocycloalkynyl, or combinations thereof.

In this specification, when no specific definition is provided otherwise, "heterocycloalkyl", "heterocycloalkenyl", "heterocycloalkynyl" and "heterocycloalkylene" refer to Cyclic compounds of cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkylene having at least one heteroatom in P.

In the present specification, "(meth)acrylate" refers to both "acrylate" and "methacrylate" when no specific definition is provided otherwise.

In this specification, when no definition is provided otherwise, "combining" means mixing or copolymerizing. In addition, "copolymerization" means block copolymerization to random copolymerization, and "copolymer" means block copolymer to random copolymer.

In the chemical formulas in this specification, unless a specific definition is provided otherwise, when a chemical bond is not drawn where it should be given, the hydrogen bond is at the said position.

In addition, in this specification, when no definition is provided otherwise, "*" means a chiral carbon. A chiral carbon indicates a central carbon with four different functional groups around the carbon, and the actual image of a compound with a chiral carbon does not overlap its mirror image.

In addition, unless a definition is otherwise provided in this specification, a chiral carbon includes one selected from the group consisting of R configuration, S configuration, racemic mixtures thereof, and combinations thereof.

In this specification, when no definition is provided otherwise, "*" indicates a point of attachment of the same or different atoms or chemical formulas.

Compounds according to Examples are represented by Chemical Formula 1.

[chemical formula 1]

In Chemical Formula 1,

R ¹ and R ² are independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl or substituted or unsubstituted C6 to C20 aryl, limited to ^The proviso is that R and R independently and must contain ^a functional group represented by Chemical Formula 1-1 and a chiral carbon, and

R ³ and R ⁴ are independently substituted or unsubstituted C1 to C20 alkyl or substituted or unsubstituted C6 to C20 aryl,

[chemical formula 1-1]

＊＊-OR ⁶

Wherein, in chemical formula 1-1,

R ⁶ is a substituted or unsubstituted C1 to C20 alkyl group.

The compound represented by Chemical Formula 1 has excellent green spectral characteristics and a high molar extinction coefficient and may be used as a green dye. However, the compound is insufficient in durability compared with a pigment, and thus may deteriorate brightness during a baking process performed after being formed into a color resist. The compound according to the embodiment necessarily includes a functional group represented by Chemical Formula 1-1 and a chiral carbon as one of the substituents bonded to the nitrogen atom, and thus the durability can be improved and thus achieve a high brightness and high contrast ratio. color filter.

In Chemical Formula 1, R ¹ and R ² may be independently represented by Chemical Formula 2-1 or Chemical Formula 2-2.

[chemical formula 2-1]

[chemical formula 2-2]

In Chemical Formula 2-1 and Chemical Formula 2-2,

L is a single bond, substituted or unsubstituted ^C1 to C10 alkylene or substituted or unsubstituted C3 to C10 cycloalkylene,

^L is substituted or unsubstituted C1 to C10 alkylene or substituted or unsubstituted C3 to C10 cycloalkylene, and

R ⁵ and R ⁶ are independently substituted or unsubstituted C1 to C20 alkyl.

In Chemical Formula 2-1 and Chemical Formula 2-2, R ⁶ may be C1 to C20 alkyl substituted with 'C1 to C10 alkyl or C6 to C20 aryl'.

In Chemical Formula 2-1 and Chemical Formula 2-2, L ¹ may be a single bond, substituted or unsubstituted C1 to C10 alkylene, and L ² may be an unsubstituted C3 to C10 cycloalkylene.

For example, R ⁶ may be represented by Chemical Formula 3.

[chemical formula 3]

In Chemical Formula 3,

R ⁷ and R ⁸ may be independently C6 to C20 aryl substituted or unsubstituted by C1 to C10 alkyl.

When R ⁶ is represented by Chemical Formula 3, the compound according to the embodiment has an alkoxy group containing a branched chain alkyl group as a substituent instead of an alkoxy group containing a non-branched chain alkyl group (unsubstituted alkyl group) as a substituent , and thus the brightness and contrast can be further improved.

R ³ and R ⁴ may be independently C6 to C20 aryl substituted or unsubstituted by C1 to C10 alkyl.

For example, R ³ and R ⁴ may be independently represented by Chemical Formula A, but not limited thereto.

[chemical formula A]

In formula A,

^R is substituted or unsubstituted C1 to C10 alkyl, and

n is an integer ranging from 1 to 5.

For example, in Formula A, n may be an integer of 1 or 2.

For example, in Formula A, ^R9 may be present at the ortho and/or para positions.

When the compound represented by Chemical Formula 1 is used in the photosensitive resin composition (for example, as a dye), the solubility in the solvent described later may be greater than or equal to 5, for example, ranging from 5 to 10. Solubility can be obtained by the amount (g) of the dye (compound) dissolved in 100 g of solvent. When the solubility of the compound (such as a dye) is within the range, the compound can ensure compatibility with other components in the photosensitive resin composition (ie, the binder resin, photopolymerizable monomer and Photopolymerization initiator) compatibility and coloring properties, and can prevent dye precipitation.

The compound represented by Chemical Formula 1 may have excellent heat resistance. That is, the thermal decomposition temperature measured by a thermogravimetric analyzer (thermogravimetric analyzer, TGA) may be greater than or equal to 200°C, and the thermal decomposition temperature is, for example, 200°C to 300°C.

The compound represented by Chemical Formula 1 has three resonance structures as shown in the figure below, but in this specification, the compound represented by Chemical Formula 1 having one resonance structure is shown for convenience. In other words, the compound represented by Chemical Formula 1 may have any one of the three resonance structures.

[picture]

The compound represented by Chemical Formula 1 may have a maximum absorption wavelength (λ _max ) in the range of 600 nm to 700 nm (refer to cyclohexanone).

The compound represented by Chemical Formula 1 may be selected from compounds represented by Chemical Formula 4 to Chemical Formula 10.

[chemical formula 4]

[chemical formula 5]

[chemical formula 6]

[chemical formula 7]

[chemical formula 8]

[chemical formula 9]

[chemical formula 10]

A core-shell dye according to another embodiment has a structure consisting of a core and a shell surrounding the core. The core contains the compound represented by Chemical Formula 1. Specifically, the shell may be a macrocyclic compound, and the shell surrounds the compound represented by Chemical Formula 1 to form a coating.

In an embodiment, the compound represented by Chemical Formula 1 is surrounded by a shell corresponding to a giant ring compound, that is, the compound represented by Chemical Formula 1 exists inside the giant ring, and thereby the durability of the core-shell dye can be improved, and Color filters with high brightness and high contrast can be realized.

The compound represented by Chemical Formula 1 contained in the core or constituting the core may have a length of 1 nm to 3 nm, for example, 1.5 nm to 2 nm. When the length of the compound represented by Chemical Formula 1 is within the range, the core-shell dye may easily have a structure in which a shell surrounds a core. In other words, the length of the compound represented by Chemical Formula 1 is within the range, and thus the compound may have a structure in which a macrocyclic compound (ie, a shell) surrounds the compound represented by Chemical Formula 1. When a compound having a length outside the range is used, a shell-surrounding-core compound structure cannot be obtained, and durability cannot be improved.

The compound represented by Chemical Formula 1 included in the core or constituting the core may have a maximum absorption peak in a wavelength of 530 nm to 680 nm. A core-shell dye using the compound represented by Chemical Formula 1 having the spectral characteristics as a core is used, for example, as a green dye, and thereby a photosensitive resin composition for a color filter having high brightness and high contrast can be provided.

A shell surrounding a core including the compound represented by Chemical Formula 1 may be represented by Chemical Formula 11 or Chemical Formula 12.

[chemical formula 11]

[chemical formula 12]

In chemical formula 11 and chemical formula 12,

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

In Chemical Formula 11 or Chemical Formula 12, L ^a to L ^d may be independently substituted or unsubstituted C1 to C10 alkylene groups. In this case, a structure having increased solubility and a shell surrounding a core including the compound represented by Chemical Formula 1 is easily formed.

For example, the core-shell dye according to the embodiment includes a non-covalent bond, that is, a hydrogen bond between an oxygen atom of the compound represented by Chemical Formula 1 and a nitrogen atom of the shell represented by Chemical Formula 11 or Chemical Formula 12.

The shell may be represented by, for example, Chemical Formula 11-1 or Chemical Formula 12-1.

[Chemical formula 11-1]

[Chemical formula 12-1]

The cage width of the shell can be between to range, and the volume of the shell can be between to range. The cage width in the present invention refers to the internal distance of the shell, for example, in the shell represented by Chemical Formula 11-1 or Chemical Formula 12-1, refers to the distance between two different phenylene groups through which two methylene groups are connected. distance (see Figure 1). When the cage width of the shell is within the range, a core-shell dye having a structure surrounding a core including the compound represented by Chemical Formula 1 can be obtained, and thus when the core-shell dye is added to the photosensitive resin composition , a color filter with improved durability and high brightness can be realized.

The core-shell dye includes a core including the compound represented by Chemical Formula 1 and a shell at a molar ratio of 1:1. When the core and the shell exist within the molar ratio, a coating layer (shell) surrounding the core including the compound represented by Chemical Formula 1 may be well formed.

The core-shell dye may have a maximum absorption wavelength (λ _max ) in the range of 600nm to 700nm (cf. cyclohexanone).

For example, the core-shell dye may be represented by one selected from the compounds represented by Chemical Formula 13 to Chemical Formula 26, but not limited thereto.

[chemical formula 13]

[chemical formula 14]

[chemical formula 15]

[chemical formula 16]

[chemical formula 17]

[chemical formula 18]

[chemical formula 19]

[chemical formula 20]

[chemical formula 21]

[chemical formula 22]

[chemical formula 23]

[chemical formula 24]

[chemical formula 25]

[chemical formula 26]

Core-shell dyes can be used alone as green dyes and can also be mixed with auxiliary dyes.

Auxiliary dyes can be triarylmethane dyes, anthraquinone dyes, benzylidene dyes, cyanine dyes, phthalocyanine dyes, azaporphyrin dyes, indigo dyes, xanthene dyes, azo Department of dyes, etc.

Core-shell dyes can be mixed with pigments.

The pigments may be red pigments, green pigments, blue pigments, yellow pigments, black pigments, and the like.

Examples of the red pigment may be color index (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 89, and the like. Examples of green pigments may be C.I. Green Pigment 36, C.I. Green Pigment 7, C.I. Green Pigment 58, C.I. Green Pigment 59, C.I. Green Pigment 62, and the like. Examples of blue pigments may be copper phthalocyanine pigments such as C.I. Blue Pigment 15:6, C.I. Blue Pigment 15, C.I. Blue Pigment 15:1, C.I. Blue Pigment 15:2, C.I. Blue Pigment 15:3 , C.I. Blue Pigment 15:4, C.I. Blue Pigment 15:5, C.I. Blue Pigment 16, etc. Examples of yellow pigments may be isoindoline-based pigments such as C.I. Yellow Pigment 139; quinophthalone-based pigments such as C.I. Yellow Pigment 138; nickel complex pigments such as C.I. Yellow Pigment 150 and the like. Examples of black pigments may be aniline black, perylene black, titanium black, carbon black, and the like. The pigments may be used alone or as a mixture of two or more, but not limited thereto.

The pigment may be contained in the photosensitive resin composition for a color filter in the state of a pigment dispersion liquid. Pigment dispersion liquid can be composed of pigment and solvent, dispersant, dispersing resin and so on.

The solvent can be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc., and is preferably propylene glycol methyl ether acetate .

Dispersants aid in uniform dispersion of the pigment, and may include nonionic, anionic, or cationic dispersants. Specific examples can be polyalkylene glycol or its ester, polyoxyalkylene, polyol ester alkylene oxide addition product, alcohol alkylene oxide addition product, sulfonate, sulfonate, carboxylate, carboxylic acid Salt, alkylamide alkylene oxide addition product, alkylamine, and these dispersants may be used alone or as a mixture of two or more.

The dispersion resin may be an acrylic resin containing carboxyl groups, and improves the stability of the pigment dispersion and the pattern properties of the pixels.

When the core-shell dye is mixed with the pigment, the core-shell dye and the pigment may be mixed in a weight ratio of 1:9 to 9:1, specifically, in a weight ratio of 3:7 to 7:3. When the core-shell dye and the pigment are mixed within the weight ratio range, high brightness and contrast can be obtained while maintaining color characteristics.

According to another embodiment, there is provided a photosensitive resin composition including the compound represented by Chemical Formula 1 or a core-shell dye.

The photosensitive resin composition includes (A) a colorant (a compound represented by Chemical Formula 1 or a core-shell dye), (B) a binder resin, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, and ( E) Solvents.

Hereinafter, each component is specifically explained.

(A) Colorant

The colorant may include the compound represented by Chemical Formula 1 and/or the core-shell dye, and the compound represented by Chemical Formula 1 and/or the core-shell dye are as described above.

The colorant may further include a pigment in addition to the compound represented by Chemical Formula 1 and/or the core-shell dye, and the pigment is as described above.

The compound represented by Chemical Formula 1 and/or the core-shell dye may be included in an amount of 0.5 wt % to 10 wt % (for example, 0.5 wt % to 5 wt %) based on the total amount of the photosensitive resin composition for a color filter . When using the compound represented by Chemical Formula 1 and/or the core-shell dye within the range, high brightness and high contrast with desired color coordinates may be achieved.

(B) Binder resin

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

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group. Examples of the monomer include (meth)acrylic acid, maleic acid, itaconic acid, fumaric acid, or combinations thereof.

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

The second ethylenically unsaturated monomer can be an aromatic vinyl compound, such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl methyl ether, etc.; an unsaturated carboxylic acid ester compound, such as (methyl styrene Base) methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzene (meth) acrylate Methyl ester, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, etc.; unsaturated aminoalkyl carboxylate compounds, such as 2-aminoethyl (meth)acrylate, 2-aminoethyl (meth)acrylate Dimethylaminoethyl ester, etc.; vinyl carboxylate compounds, such as vinyl acetate, vinyl benzoate, etc.; unsaturated glycidyl carboxylate compounds, such as glycidyl (meth)acrylate, etc.; acrylonitrile Compounds such as (meth)acrylonitrile, etc.; unsaturated amide compounds, such as (meth)acrylamide, etc.; etc., and the second ethylenically unsaturated monomer may be used alone or as two or more used as a mixture.

Specific examples of the binder resin may be methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, methacrylic acid/benzyl methacrylate/methacrylic acid 2-hydroxyethyl acrylate copolymer, methacrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, etc., but not limited thereto. These binder resins may be used alone or as a mixture of two or more.

The binder resin may have a weight average molecular weight of 3,000 g/mol to 150,000 g/mol (eg, 5,000 g/mol to 50,000 g/mol and eg, 20,000 g/mol to 30,000 g/mol). When the weight average molecular weight of the binder resin is within the range, the close contact property with the substrate and the physicochemical properties are improved, and the viscosity is appropriate.

The acid value of the binder resin may be 15 mgKOH/g to 60 mgKOH/g (eg, 20 mgKOH/g to 50 mgKOH/g). When the acid value of the binder resin is within the range, excellent pixel resolution can be obtained.

The binder resin may be included in an amount of 0.1 wt % to 30 wt % (eg, 5 wt % to 20 wt %) based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, developability may be improved, and excellent surface smoothness may be improved due to improved crosslinking during manufacture of a color filter.

(C) Photopolymerizable monomer

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

The photopolymerizable monomer can cause sufficient polymerization during exposure during pattern formation due to the ethylenically unsaturated double bond, and form a pattern having excellent heat resistance, light resistance, and chemical resistance.

Specific examples of the photopolymerizable monomer may be ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ) acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate Acrylates, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol mono Methyl ether (meth)acrylate, trimethylolpropane tri(meth)acrylate, tri(meth)acryloyloxy ethyl phosphate, novolak epoxy (meth)acrylate, etc.

Commercially available examples of photopolymerizable monomers may be as follows. Monofunctional (meth)acrylates may include Aronix (Toagosei Chemistry Industry Co., Ltd.); KAYARAD (Nippon Kayaku Co.,Ltd.); (Osaka Organic Chemical Ind., Ltd.), etc. Examples of difunctional (meth)acrylates may include Aronix (East Asia Chemical Co., Ltd.), Kayarad (KAYARAD) (Nippon Kayaku Co., Ltd.), V-335 (Osaka Organic Chemical Co., Ltd.), etc. Examples of trifunctional (meth)acrylates may include Aronix (East Asia Chemical Co., Ltd.), Kayarad (KAYARAD) (Nippon Kayaku Co., Ltd.), (Osaka Organic Chemical Co., Ltd.), etc. These photopolymerizable monomers may be used alone or as a mixture of two or more.

Photopolymerizable monomers can be treated with anhydrides to improve developability.

The photopolymerizable monomer may be included in an amount of 0.1 wt % to 30 wt % (eg, 5 wt % to 20 wt %) based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is contained within the range, pattern characteristics and developability during manufacture of a color filter may be improved.

(D) Photopolymerization initiator

The photopolymerization initiator may be 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 the like.

Examples of acetophenone-based compounds can be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone (2-hydroxy- 2-methylpropinophenone), p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2 -Methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinyl Phenyl)-butan-1-one, etc.

Examples of benzophenone-based compounds may be benzophenone, benzoyl benzoate, benzoyl methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzphenone Ketone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.

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

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 triazine compounds can 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) base)-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 Azine, 2-(naphthoyl 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthoyl 1-yl)-4,6-bis( Trichloromethyl)-s-triazine, 2-4-trichloromethyl (piperonyl)-6-triazine, 2-4-trichloromethyl (4'-methoxystyryl)-6 - Triazines etc.

Examples of oxime compounds can be 2-(o-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(o-acetyloxime)-1- [9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone and the like.

The photopolymerization initiator may further include 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 compounds.

The photopolymerization initiator may be included in an amount of 0.1 wt % to 5 wt % (eg, 1 wt % to 3 wt %) based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the range, the composition can sufficiently undergo photopolymerization when exposed during a pattern forming process for producing a color filter to achieve excellent sensitivity and improve transmission Rate.

(E) solvent

The solvent is not particularly limited, and specifically, for example, alcohols such as methanol, ethanol, etc.; ethers, such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran, etc.; glycol ethers, such as ethyl Glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, etc.; acetic acid cellosolve, such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, etc.; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether Diethylene glycol diethyl ether, etc.; propylene glycol alkyl ether acetate, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons, such as toluene, xylene, etc.; ketones, such as methyl Ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-acetone, methyl-n-butanone, methyl-n-pentanone, 2-heptanone, etc.; saturated Alkyl aliphatic monocarboxylates, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; alkyl lactates, such as methyl lactate, ethyl lactate, etc.; alkyl glycolates, such as methyl glycolate esters, ethyl glycolate, butyl glycolate, etc.; alkoxyalkyl acetates such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethyl Oxymethyl acetate, ethoxyethyl acetate, etc.; alkyl 3-hydroxypropionate, such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc.; 3-alkoxy Alkyl propionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; 2- Alkyl hydroxypropionate, such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc.; alkyl 2-alkoxypropionate, such as 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; alkyl 2-hydroxy-2-methylpropionate, For example, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, etc.; alkyl 2-alkoxy-2-methylpropionate, such as 2-methoxy -Methyl 2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate esters, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutyrate, etc.; or ketoesters, such as ethyl pyruvate, etc., and additionally N-methylformamide, N,N-dimethyl Formamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetyl Acetone, Isophorone, Caproic Acid, Caprylic Acid, 1-Octanol, 1-Nonanol, Benzyl Alcohol, Benzyl Acetate, Ethyl Benzoate, Diethyl Oxalate, Diethyl Maleate, Gamma - Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc., the solvents may be used alone or as a mixture of two or more.

In consideration of miscibility and reactivity, solvents are desirably ketones, such as cyclohexanone, etc.; glycol ethers, such as ethylene glycol monoethyl ether, etc.; glycol alkyl ether acetates, such as ethyl cellosolve acetate Esters, etc.; Esters, such as 2-hydroxyethyl propionate, etc.; Diethylene glycol, such as diethylene glycol monomethyl ether, etc.; Propylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol propylene glycol ether acetate etc.

Based on the total amount of the photosensitive resin composition, the solvent is used in a balance, specifically 20wt% to 90wt%. The photosensitive resin composition for a color filter has coating properties and can maintain excellent flatness of a film having a thickness of 3 μm or more.

(F) Other additives

The photosensitive resin composition may further include additives such as malonic acid; 3-amino-1,2-propanediol; silane-based coupling agents containing vinyl or (meth)acryloyloxy groups; leveling agents; fluorine-based surfactants agent; radical polymerization initiator, etc., to prevent stains or spots during coating, to adjust leveling, or to prevent pattern residue due to undeveloped.

In addition, the photosensitive resin composition may further include additives such as epoxy compounds to improve close contact properties with the substrate.

Examples of epoxy compounds may be phenol novolac epoxy compounds, tetramethylbiphenyl epoxy compounds, bisphenol A epoxy compounds, alicyclic epoxy compounds, or combinations thereof.

The amount of additives can be controlled according to the desired properties.

Another embodiment provides a color filter manufactured using the photosensitive resin composition. A method of manufacturing a color filter is as follows.

Using appropriate methods such as spin coating, slot coating, etc., a bare glass substrate or coated with a thickness of to A photosensitive resin composition for a color filter was coated on a glass substrate with SiN _x as a protective layer to have a thickness of 3.1 μm to 3.4 μm. After the coating, light is irradiated to form a pattern required for the color filter. After irradiation, the coated layer is treated with an alkaline developer and the non-irradiated areas of the coated layer can be dissolved to form a pattern for the image color filter. This process is repeated for the desired number of reds, greens, and blues to produce a color filter with the desired pattern.

In addition, the image pattern obtained by development is cured by heat treatment, actinic ray irradiation, and the like, resulting in improved crack resistance, solvent resistance, and the like.

Hereinafter, preferred examples of the present invention are explained. However, these examples should not be construed as limiting the scope of the invention in any sense.

(Preparation of unimolecular compounds)

(Synthesis Example 1: Synthesis of Intermediate A)

Aniline (10 mol), 4-bromotoluene (10 mol), Pd ₂ (dba) ₃ (0.1 mol) and Xphos (0.1 mol) were added to toluene, and the mixture was heated and stirred at 100° C. 24 hours. To this solution was added ethyl acetate, and the obtained mixture was washed twice with water to extract an organic layer. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain Intermediate A.

(Synthesis Example 2: Synthesis of Intermediate B-1)

Added 2,4-dimethyldiphenylamine (10mol), 1,2-epoxyhexane (12mol) and sodium hydride (12mol) to N,N-dimethylformamide, and at 90°C The mixture was heated and stirred for 24 hours. To this solution was added ethyl acetate, and the obtained mixture was washed twice with water to extract an organic layer. The extracted organic layer was distilled under reduced pressure and separated by column chromatography to obtain Intermediate B-1.

(Synthesis Example 3: Synthesis of Intermediate B-2)

Intermediate B-2 was synthesized in the same manner as in Synthesis Example 2 except that 1,2-epoxybutylene was used instead of 1,2-epoxyhexane.

(Synthesis Example 4: Synthesis of Intermediate B-3)

Intermediate B-3 was synthesized in the same manner as in Synthesis Example 2, except that Intermediate A was used instead of 2,4-dimethyldiphenylamine.

(Synthesis Example 5: Synthesis of Intermediate B-4)

Intermediate B-4 was synthesized in the same manner as in Synthesis Example 2 except that 1,2-epoxycyclohexane was used instead of 1,2-epoxyhexane.

(Synthesis Example 6: Synthesis of Intermediate C-1)

To N,N-dimethylformamide were added Intermediate B-1 (10 mmol), iodomethane (15 mmol) and sodium hydride (15 mmol), and the mixture was stirred at room temperature for 24 hours. To this solution was added ethyl acetate, and the obtained mixture was washed twice with water to extract an organic layer. The extracted organic layer was distilled under reduced pressure and separated by column chromatography to obtain Intermediate C-1.

(Synthesis Example 7: Synthesis of Intermediate C-2)

Intermediate C-2 was synthesized in the same manner as in Synthesis Example 6 except that 2-iodopropane was used instead of methyl iodide.

(Synthesis Example 8: Synthesis of Intermediate C-3)

Intermediate C-3 was synthesized in the same manner as in Synthesis Example 6 except that Intermediate B-2 was used instead of Intermediate B-1.

(Synthesis Example 9: Synthesis of Intermediate C-4)

Intermediate C-4 was synthesized in the same manner as in Synthesis Example 8 except that iodoethane was used instead of methyl iodide.

(Synthesis Example 10: Synthesis of Intermediate C-5)

Intermediate C-5 was synthesized in the same manner as in Synthesis Example 8 except that 2-iodopropane was used instead of methyl iodide.

(Synthesis Example 11: Synthesis of Intermediate C-6)

Intermediate C-6 was synthesized in the same manner as in Synthesis Example 6, except that Intermediate B-3 was used instead of Intermediate B-1.

(Synthesis Example 12: Synthesis of Intermediate C-7)

Intermediate C-7 was synthesized in the same manner as in Synthesis Example 6 except that Intermediate B-4 was used instead of Intermediate B-1.

(Synthesis Example 13: Synthesis of Compounds Represented by Chemical Formula 4)

Intermediate C-1 (60mmol) and 3,4-dihydroxy-3-cyclobutyne-1,2-dione (30mmol) were added to toluene (200mL) and butanol (200mL), and Dean - A Dean-stark still removes the water produced by refluxing the mixture. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain the compound represented by Chemical Formula 4.

(Synthesis Example 14: Synthesis of Compounds Represented by Chemical Formula 5)

The compound represented by Chemical Formula 5 was synthesized according to the same method as Synthesis Example 13 except that Intermediate C-2 was used instead of Intermediate C-1.

(Synthesis Example 15: Synthesis of Compounds Represented by Chemical Formula 6)

The compound represented by Chemical Formula 6 was synthesized according to the same method as Synthesis Example 13 except that Intermediate C-3 was used instead of Intermediate C-1.

(Synthesis Example 16: Synthesis of Compounds Represented by Chemical Formula 7)

The compound represented by Chemical Formula 7 was synthesized according to the same method as Synthesis Example 13 except that Intermediate C-4 was used instead of Intermediate C-1.

(Synthesis Example 17: Synthesis of Compounds Represented by Chemical Formula 8)

The compound represented by Chemical Formula 8 was synthesized according to the same method as Synthesis Example 13, except that Intermediate C-5 was used instead of Intermediate C-1.

(Synthesis Example 18: Synthesis of Compounds Represented by Chemical Formula 9)

The compound represented by Chemical Formula 9 was synthesized according to the same method as Synthesis Example 13 except that Intermediate C-6 was used instead of Intermediate C-1.

(Synthesis Example 19: Synthesis of Compound Represented by Chemical Formula 10)

The compound represented by Chemical Formula 10 was synthesized according to the same method as Synthesis Example 13, except that Intermediate C-7 was used instead of Intermediate C-1.

(Synthesis Example 20: Synthesis of a core-shell dye represented by Chemical Formula 13)

The compound represented by Chemical Formula 4 (5 mmol) was dissolved in 600 mL of chloroform solvent, and was added dropwise thereto at room temperature over 5 hours by dissolving isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) in 60 mL of chloroform. obtained solution. After 12 hours, the obtained mixture was distilled under reduced pressure and separated by column chromatography to obtain the compound represented by Chemical Formula 13.

Matrix-assisted laser desorption ionization-time of flight mass spectrometry (Matrix-assisted laser desorption ionization-time of flight mass spectrometry, Maldi-tof MS): 1232.64m/z

(Synthesis Example 21: Synthesis of a core-shell dye represented by Chemical Formula 14)

The compound represented by Chemical Formula 4 (5 mmol) was dissolved in 600 mL of chloroform solvent, and triethylamine (50 mmol) was added thereto. 2,6-Pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform, and the solutions were added thereto at room temperature over 5 hours. After 12 hours, the obtained mixture was distilled under reduced pressure and separated by column chromatography to obtain the compound represented by Chemical Formula 14.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 1234.63m/z

(Synthesis Example 22: Synthesis of a core-shell dye represented by Chemical Formula 15)

The compound represented by Chemical Formula 15 was synthesized according to the same method as Synthesis Example 20, except that the compound represented by Chemical Formula 5 was used instead of the compound represented by Chemical Formula 4.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 1288.70m/z

(Synthesis Example 23: Synthesis of a core-shell dye represented by Chemical Formula 16)

The compound represented by Chemical Formula 16 was synthesized according to the same method as Synthesis Example 21 except that the compound represented by Chemical Formula 5 was used instead of the compound represented by Chemical Formula 4.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 1290.69m/z

(Synthesis Example 24: Synthesis of a core-shell dye represented by Chemical Formula 17)

The compound represented by Chemical Formula 17 was synthesized according to the same method as Synthesis Example 20, except that the compound represented by Chemical Formula 6 was used instead of the compound represented by Chemical Formula 4.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 1176.57m/z

(Synthesis Example 25: Synthesis of a core-shell dye represented by Chemical Formula 18)

The compound represented by Chemical Formula 18 was synthesized according to the same method as Synthesis Example 21 except that the compound represented by Chemical Formula 6 was used instead of the compound represented by Chemical Formula 4.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 1178.56m/z

(Synthesis Example 26: Synthesis of a core-shell dye represented by Chemical Formula 19)

The compound represented by Chemical Formula 19 was synthesized according to the same method as Synthesis Example 20, except that the compound represented by Chemical Formula 7 was used instead of the compound represented by Chemical Formula 4.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 1204.60m/z

(Synthesis Example 27: Synthesis of Core-Shell Dye Represented by Chemical Formula 20)

The compound represented by Chemical Formula 20 was synthesized according to the same method as Synthesis Example 21, except that the compound represented by Chemical Formula 7 was used instead of the compound represented by Chemical Formula 4.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 1206.59m/z

(Synthesis Example 28: Synthesis of a core-shell dye represented by Chemical Formula 21)

The compound represented by Chemical Formula 21 was synthesized according to the same method as Synthesis Example 20, except that the compound represented by Chemical Formula 8 was used instead of the compound represented by Chemical Formula 4.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 1232.64m/z

(Synthesis Example 29: Synthesis of a core-shell dye represented by Chemical Formula 22)

The compound represented by Chemical Formula 22 was synthesized according to the same method as Synthesis Example 21 except that the compound represented by Chemical Formula 8 was used instead of the compound represented by Chemical Formula 4.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 1234.63m/z

(Synthesis Example 30: Synthesis of a core-shell dye represented by Chemical Formula 23)

The compound represented by Chemical Formula 23 was synthesized according to the same method as Synthesis Example 20, except that the compound represented by Chemical Formula 9 was used instead of the compound represented by Chemical Formula 4.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 1204.60m/z

(Synthesis Example 31: Synthesis of a core-shell dye represented by Chemical Formula 24)

The compound represented by Chemical Formula 24 was synthesized according to the same method as Synthesis Example 21, except that the compound represented by Chemical Formula 9 was used instead of the compound represented by Chemical Formula 4.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 1206.59m/z

(Synthesis Example 32: Synthesis of a core-shell dye represented by Chemical Formula 25)

The compound represented by Chemical Formula 25 was synthesized according to the same method as Synthesis Example 20, except that the compound represented by Chemical Formula 10 was used instead of the compound represented by Chemical Formula 4.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 1228.60m/z

(Synthesis Example 33: Synthesis of a core-shell dye represented by Chemical Formula 26)

The compound represented by Chemical Formula 26 was synthesized according to the same method as Synthesis Example 21, except that the compound represented by Chemical Formula 10 was used instead of the compound represented by Chemical Formula 4.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 1230.59m/z

(Comparative Synthesis Example 1: Synthesis of Compounds Represented by Chemical Formula X)

[chemical formula X]

The compound represented by Chemical Formula X was synthesized according to the same method as in Synthesis Example 13, except that Intermediate B-3 was used instead of Intermediate C-1.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 672.39m/z

(Comparative Synthesis Example 2: Synthesis of Compounds Represented by Chemical Formula Y)

[chemical formula Y]

Put 398mg squaraine and 2.23g 2-(3-(methyl(phenyl)amino)propylamino) ethyl acrylate in a 100mL 3-necked flask, add 40mL n-butanol and 20mL toluene therein, and at 120 The mixture was heated at reflux for 5 hours. A Dean-Stark trap set was used to remove water generated during the reaction and to facilitate the reaction. After the reaction was completed, the resultant therefrom was cooled, and then extracted with dichloromethane and processed by column chromatography, thereby synthesizing the compound represented by Chemical Formula Y in 60% yield.

Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry: 514.26m/z

(Comparative Synthesis Example 3: Synthesis of Core-Shell Dye)

Put 398mg squaraine and 2.23g 2-(3-(dibutylamino)phenoxy) ethyl acrylate in a 100mL 3-neck flask, add 40mL n-butanol and 20mL toluene to it, and at 120°C The obtained mixture was heated and refluxed for 5 hours. The water produced during the reaction was removed and the reaction was facilitated using a Dean-Stark separator set. After the reaction was completed, the resultant therefrom was cooled, and then extracted with dichloromethane and processed by column chromatography, thereby obtaining the compound represented by Chemical Formula Z-1 in 60% yield. Subsequently, 0.72 g (1 mmol) of the compound represented by the chemical formula Z-1 and 2.02 g (1 mmol) of the triacetyl β-cyclodextrin represented by the chemical formula Z-2 (Chemical Abstracts Service number (CAS#) 23739-88 -0, TCI Chemicals) was dissolved in 50 ml of dichloromethane, the solution was stirred at room temperature for about 12 hours, and the residue after complete solvent removal was dried under reduced pressure, About 2.7 g of core-shell dye was obtained in solid state. The core-shell dye has a structure in which the compound represented by Chemical Formula Z-2 surrounds the compound represented by Chemical Formula Z-1.

[Chemical formula Z-1]

[Chemical formula Z-2]

(Preparation of Photosensitive Resin Composition)

A photosensitive resin composition was prepared using the following components.

(A) Dye

(A-1) Monomolecular dye (represented by Chemical Formula 4) prepared in Synthesis Example 13

(A-2) Monomolecular dye (represented by Chemical Formula 5) prepared in Synthesis Example 14

(A-3) Monomolecular dye (represented by Chemical Formula 6) prepared in Synthesis Example 15

(A-4) Monomolecular dye (represented by Chemical Formula 7) prepared in Synthesis Example 16

(A-5) Monomolecular dye (represented by Chemical Formula 8) prepared in Synthesis Example 17

(A-6) Monomolecular dye (represented by Chemical Formula 9) prepared in Synthesis Example 18

(A-7) Monomolecular dye (represented by Chemical Formula 10) prepared in Synthesis Example 19

(A-8) Core-shell dye prepared in Synthesis Example 20 (represented by Chemical Formula 13)

(A-9) Core-shell dye prepared in Synthesis Example 21 (represented by Chemical Formula 14)

(A-10) Core-shell dye prepared in Synthesis Example 22 (represented by Chemical Formula 15)

(A-11) Core-shell dye prepared in Synthesis Example 23 (represented by Chemical Formula 16)

(A-12) The core-shell dye prepared in Synthesis Example 24 (represented by Chemical Formula 17)

(A-13) Core-shell dye prepared in Synthesis Example 25 (represented by Chemical Formula 18)

(A-14) Core-shell dye prepared in Synthesis Example 26 (represented by Chemical Formula 19)

(A-15) Core-shell dye prepared in Synthesis Example 27 (represented by Chemical Formula 20)

(A-16) Core-shell dye prepared in Synthesis Example 28 (represented by Chemical Formula 21)

(A-17) Core-shell dye prepared in Synthesis Example 29 (represented by Chemical Formula 22)

(A-18) The core-shell dye prepared in Synthesis Example 30 (represented by Chemical Formula 23)

(A-19) Core-shell dye (represented by Chemical Formula 24) prepared in Synthesis Example 31

(A-20) The core-shell dye prepared in Synthesis Example 32 (represented by Chemical Formula 25)

(A-21) The core-shell dye prepared in Synthesis Example 33 (represented by Chemical Formula 26)

(A-22) Monomolecular dye (represented by chemical formula X) prepared in Comparative Synthesis Example 1

(A-23) Monomolecular dye (represented by chemical formula Y) prepared in Comparative Synthesis Example 2

(A-24) core-shell dye prepared in Comparative Synthesis Example 3

(A') Pigment dispersion

(A'-1) C.I. Green Pigment 7

(A'-2) C.I. Green Pigment 58

(B) Binder resin

Methacrylic acid/benzyl methacrylate copolymer with a weight average molecular weight of 22,000 g/mol (blending weight ratio: 15wt%/85wt%)

(C) Photopolymerizable monomer

dipentaerythritol hexaacrylate

(D) Photopolymerization initiator

(D-1) 1,2-octanedione

(D-2) 2-Dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one

(E) solvent

(E-1) Cyclohexanone

(E-2) Propylene glycol methyl ether acetate

Example 1 to Example 21 and Comparative Example 1 to Comparative Example 5

A photosensitive resin composition was prepared by mixing each component of the compositions shown in Table 1 to Table 3 . Specifically, a photopolymerization initiator is dissolved in a solvent, the solution is stirred at room temperature for 2 hours, a dye (or pigment dispersion) is added thereto, the mixture is stirred for 30 minutes, and a binder is added thereto. resin and photopolymerizable monomer, and the resulting mixture was stirred at room temperature for 2 hours. The solution was filtered three times to remove impurities and prepare a photosensitive resin composition.

[Table 1]

(Unit: wt%)

[Table 2]

(Unit: wt%)

[table 3]

(Unit: wt%)

(Evaluate)

Evaluation 1: Brightness and Contrast

The photosensitive resin compositions according to Examples 1 to 21 and Comparative Examples 1 to 5 were coated to a thickness of 1 μm to 3 μm on a 1 mm thick degreased glass substrate, and dried on a hot plate at 90° C. for 2 minutes to Obtain the film. Subsequently, the film was exposed with a high-pressure mercury lamp having a dominant wavelength of 365 nm, and dried in a forced convection drying oven of an oven at 200° C. for 5 minutes. The brightness and contrast of the pixel layer were measured using a spectrophotometer (MCPD3000, Otsuka electronic Co., Ltd.), and the results are shown in Table 4.

[Table 4]

brightness contrast Example 1 65.5 14500 Example 2 65.7 14800 Example 3 65.5 14600 Example 4 65.3 14400 Example 5 65.8 14900 Example 6 65.3 14300 Example 7 65.5 14500 Example 8 67.5 14700 Example 9 67.6 14600 Example 10 67.9 15100 Example 11 67.8 15000 Example 12 67.3 14600 Example 13 67.2 14700 Example 14 67.5 14400 Example 15 67.4 14800 Example 16 67.8 15200 Example 17 67.9 15100 Example 18 67.6 14500 Example 19 67.5 14600 Example 20 67.4 14400 Example 21 67.3 14700 Comparative example 1 64.3 13200 Comparative example 2 64.5 13400 Comparative example 3 64.2 13100 Comparative example 4 62.1 12200 Comparative Example 5 63.5 12500

Referring to Table 4, compared with Comparative Examples 1 to 5 containing neither a single-molecule dye nor a core-shell dye, Examples 1 to 21 comprising a single-molecule dye or a core-shell dye according to an embodiment of the present invention Shows high brightness and high contrast. In addition, the compounds according to the examples exhibited much superior brightness and contrast when including a branched alkyl-substituted alkoxy group as a functional group than when not including the alkoxy group.

Assessment 2: Durability

The photosensitive resin compositions according to Examples 8 to 21 and Comparative Examples 1 to 5 were coated to a thickness of 1 μm to 3 μm on a 1 mm thick degreased glass substrate, respectively, and dried on a hot plate at 90° C. for 2 minutes to Obtain the film. The film was exposed with a high-pressure mercury lamp having a dominant wavelength of 365 nm and dried in an oven at 200° C. for 20 minutes, and the change in color coordinates was measured using a spectrophotometer (MCPD3000, Otsuka Electronics Co., Ltd.) and thus the durability was evaluated , and the results are shown in Table 5.

Durability Evaluation Benchmark

Good: the change in color coordinates is less than or equal to 0.005

Poor: the color coordinate change is greater than 0.005

[table 5]

Durability Example 8 good Example 9 good Example 10 good Example 11 good Example 12 good Example 13 good Example 14 good Example 15 good Example 16 good Example 17 good Example 18 good Example 19 good Example 20 good Example 21 good Comparative example 1 Difference Comparative example 2 Difference Comparative example 3 Difference Comparative example 4 good Comparative Example 5 good

Referring to Table 5, Compositions (Comparative Example 1 and Comparative Example 2) comprising a monomolecular dye different from the monomolecular dye according to the Examples and combinations comprising a core-shell dye different from the core-shell dyes according to the Examples Example 8 to Example 21 including the core-shell dye according to the Example showed excellent durability compared to the material (Comparative Example 3).

While the present invention has been described in connection with what are presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but on the contrary, the invention is intended to cover all aspects of the invention contained in the appended claims. Various modifications and equivalent configurations within the spirit and scope of the book. Therefore, the above-mentioned embodiments should be understood as exemplary rather than limiting the present invention in any way.

Claims (22)

1. a kind of compound, it is characterised in that represented by chemical formula 1：

[chemical formula 1]

Wherein, in chemical formula 1,

R¹And R²The C1 that is substituted or is unsubstituted independently is to C20 alkyl, the C3 for being substituted or being unsubstituted to C20 cycloalkanes Base or the C6 that is substituted or is unsubstituted to C20 aryl, its restrictive condition be R¹And R²Independently and it must include by chemical formula The functional group and chiral carbon that 1-1 is represented, and

R³And R⁴It is fragrant to C20 alkyl or the C6 for being substituted or being unsubstituted to C20 independently to be the C1 for being substituted or being unsubstituted Base,

[chemical formula 1-1]

*-O-R⁶

Wherein, in chemical formula 1-1,

R⁶For the C1 that is substituted or is unsubstituted to C20 alkyl.

2. compound according to claim 1, it is characterised in that R¹And R²Represented by chemical formula 2-1 or chemical formula 2-2：

[chemical formula 2-1]

[chemical formula 2-2]

*-L²-O-R⁶

Wherein, in chemical formula 2-1 and chemical formula 2-2,

L¹For singly-bound, the C1 for being substituted or being unsubstituted to C10 alkylidenes or the C3 for being substituted or being unsubstituted to C10 Asias ring Alkyl,

L²For the C1 that is substituted or is unsubstituted to the C10 alkylidenes or C3 for being substituted or being unsubstituted to C10 cycloalkylidenes, And

R⁵And R⁶The C1 that is substituted or is unsubstituted independently is to C20 alkyl.

3. compound according to claim 2, it is characterised in that R⁶To substitute through C1 to C10 alkyl or C6 to C20 aryl C1 to C20 alkyl.

4. compound according to claim 3, it is characterised in that R⁶Represented by chemical formula 3：

[chemical formula 3]

Wherein, in chemical formula 3,

R⁷And R⁸The C1 that is substituted or is unsubstituted independently is to C10 alkyl.

5. compound according to claim 1, it is characterised in that R³And R⁴Independently be through C1 to C10 alkyl substitute or not Through the alkyl-substituted C6 of C1 to C10 to C20 aryl.

6. compound according to claim 1, it is characterised in that the compound represented by chemical formula 1 is by chemistry One of compound that formula 4 represents to chemical formula 10：

[chemical formula 4]

[chemical formula 5]

[chemical formula 6]

[chemical formula 7]

[chemical formula 8]

[chemical formula 9]

[chemical formula 10]

7. compound according to claim 1, it is characterised in that the compound has maximum into 700nm in 600nm Absorbing wavelength.

A kind of 8. core-shell structure copolymer dyestuff, it is characterised in that including：

Core, include compound according to claim 1；And

Shell, around the core.

9. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the shell is represented by chemical formula 11 or chemical formula 12：

[chemical formula 11]

[chemical formula 12]

Wherein, in chemical formula 11 and chemical formula 12,

L^aTo L^dIt independently is singly-bound or the C1 that is substituted or is unsubstituted is to C10 alkylidenes.

10. core-shell structure copolymer dyestuff according to claim 9, it is characterised in that L^aTo L^dIt independently is and is substituted or is unsubstituted C1 to C10 alkylidenes.

11. core-shell structure copolymer dyestuff according to claim 9, it is characterised in that the shell is by chemical formula 11-1 or chemical formula 12-1 Represent：

[chemical formula 11-1]

[chemical formula 12-1]

12. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the shell hasExtremelyCage width.

13. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the core has 1nm to 3nm length.

14. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the core has in 530nm to 680nm wavelength There is maximum absorption band.

15. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the core-shell structure copolymer dyestuff be selected from by chemical formula 13 to The compound that chemical formula 26 represents：

[chemical formula 13]

[chemical formula 14]

[chemical formula 15]

[chemical formula 16]

[chemical formula 17]

[chemical formula 18]

[chemical formula 19]

[chemical formula 20]

[chemical formula 21]

[chemical formula 22]

[chemical formula 23]

[chemical formula 24]

[chemical formula 25]

[chemical formula 26]

16. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the core-shell structure copolymer dyestuff is with 1:1 mol ratio includes The core and the shell.

17. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the core-shell structure copolymer dyestuff is green colouring material.

18. core-shell structure copolymer dyestuff according to claim 8, it is characterised in that the core-shell structure copolymer dyestuff is in 600nm into 700nm With maximum absorption wavelength.

19. a kind of Photosensitve resin composition, it is characterised in that include

Compound according to claim 1 or core-shell structure copolymer dyestuff according to claim 8.

20. Photosensitve resin composition according to claim 19, it is characterised in that the Photosensitve resin composition is further Include adhesive resin, photopolymerizable monomer, Photoepolymerizationinitiater initiater and solvent.

21. Photosensitve resin composition according to claim 19, it is characterised in that the Photosensitve resin composition is further Include malonic acid, 3- amido-1,2-propanediols, silane system coupling agent, the levelling for including vinyl or (methyl) acryloxy Agent, surfactant, radical polymerization initiator or its combination.

22. a kind of colored filter, it is characterised in that made using Photosensitve resin composition according to claim 19 Make.