KR102362443B1 - A blue colored photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

The blue photosensitive resin composition according to the present invention includes an alkali-soluble resin; blue colorant; and scattering particles comprising a metal oxide having an average particle diameter of 30 to 500 nm, wherein the alkali-soluble resin comprises a cardo-based binder resin including at least one repeating unit of Formulas 1 and 2.
The blue photosensitive resin composition according to the present invention can suppress residues generated on a substrate, and has advantages in sensitivity, pattern stability, diffusion rate, and the like.

Description

Blue photosensitive resin composition, color filter and image display device manufactured using the same

The present invention relates to a blue photosensitive resin composition comprising scattering particles, an alkali-soluble resin and a blue colorant, and a color filter and an image display device manufactured using the same.

A color filter is a thin film-type optical component that extracts three colors of red, green, and blue from white light and makes it possible in fine pixel units, and the size of one pixel is tens to hundreds of micrometers. These color filters include a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between each pixel, and a plurality of colors (typically red (R), green (G) and The pixel units in which the three primary colors of blue (B) are arranged in a predetermined order have a structure in which they are sequentially stacked.

Recently, as one of the methods of realizing a color filter, a pigment dispersion method using a pigment-dispersed photosensitive resin is applied. Efficiency is lowered, and color reproduction is deteriorated due to the characteristics of the pigment included in the color filter.

In particular, as color filters are used in various fields including various image display devices, performance such as excellent high brightness and high contrast ratio as well as excellent pattern characteristics as well as high color gamut are required. In order to solve this problem, quantum dots are used A method for manufacturing a color filter using a self-luminous photosensitive resin composition comprising

Korean Patent Application Laid-Open No. 2013-0000506 relates to a display device, comprising: a plurality of wavelength conversion particles for converting a wavelength of light; and a color conversion unit including a plurality of color filter particles absorbing light of a predetermined wavelength band from the light.

However, in the case of a color filter including quantum dots, the performance of the color filter may be somewhat deteriorated as the efficiency of the quantum dots, particularly, the efficiency of the blue quantum dots decreases, and in the case of the blue quantum dots, the overall manufacturing cost increases because they are expensive. .

Therefore, there is a demand for the development of a photosensitive resin composition capable of preventing a decrease in the efficiency of the blue pixel, lowering the manufacturing cost, and suppressing the occurrence of residues on the substrate when using the conventional photosensitive resin composition.

Republic of Korea Patent Publication No. 2013-0000506 (2013.01.03.)

An object of the present invention is to provide a blue photosensitive resin composition capable of preventing a decrease in efficiency of a blue pixel, lowering a manufacturing cost, and suppressing generation of a residue on a substrate.

Another object of the present invention is to provide a color filter and an image display device including a blue pixel layer manufactured by using the above-described blue photosensitive resin composition. Specifically, an object of the present invention is to provide a color filter and an image display device having excellent image quality, viewing angle, durability, reliability, and the like.

The blue photosensitive resin composition according to the present invention for achieving the above object is an alkali-soluble resin; blue colorant; and scattering particles comprising a metal oxide having an average particle diameter of 30 to 500 nm, wherein the alkali-soluble resin comprises a cardo-based binder resin comprising at least one repeating unit of Formula 1 and Formula 2 below. do.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

,

,

,

또는

이고,P is each independently

,

,

,

or

ego,

A is O, S, N, Si or Se,

R and R' are each independently hydrogen, a hydroxyl group, a thiol group, an amino group, a nitro group or a halogen atom,

Ar1 is each independently a C6 to C15 aryl group,

Y is an acid anhydride residue,

Z is an acid dianhydride residue,

a and b are each independently an integer of 1 to 6,

n and m are each an integer from 0 to 30,

provided that n and m are not 0 at the same time.

In addition, the present invention provides a color filter made of the above-described blue photosensitive resin composition and an image display device including the same.

The blue photosensitive resin composition of the present invention can provide excellent color reproduction characteristics and light efficiency, and has the advantage of suppressing the generation of residues on the substrate.

In addition, the color filter made of the blue photosensitive resin composition of the present invention and the image display device including the same can secure high-quality image quality, excellent viewing angle, high durability, and reliability, and have the advantage of reducing the manufacturing cost and improving the residue. have.

Hereinafter, the present invention will be described in more detail.

In the present invention, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

In the present invention, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated.

<Blue photosensitive resin composition>

One aspect of the present invention, alkali-soluble resin; blue colorant; and scattering particles comprising a metal oxide having an average particle diameter of 30 to 500 nm, wherein the alkali-soluble resin includes a cardo-based binder resin including at least one repeating unit of Formula 1 and Formula 2 below. Blue photosensitive resin to the composition.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

,

,

,

또는

이고,P is each independently

,

,

,

or

ego,

A is O, S, N, Si or Se,

R and R' are each independently hydrogen, a hydroxyl group, a thiol group, an amino group, a nitro group or a halogen atom,

Ar1 is each independently a C6 to C15 aryl group,

Y is an acid anhydride residue,

Z is an acid dianhydride residue,

a and b are each independently an integer of 1 to 6,

n and m are each independently an integer from 0 to 30,

provided that n and m are not 0 at the same time.

Alkali-soluble resin

The blue photosensitive resin composition of the present invention includes a cardo-based binder resin including at least one repeating unit of Formula 1 and Formula 2 below.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

,

,

,

또는

이고,P is each independently

,

,

,

or

ego,

A is O, S, N, Si or Se,

R and R' are each independently hydrogen, a hydroxyl group, a thiol group, an amino group, a nitro group or a halogen atom,

Ar1 is each independently a C6 to C15 aryl group,

Y is an acid anhydride residue,

Z is an acid dianhydride residue,

a and b are each independently an integer of 1 to 6,

n and m are each independently an integer from 0 to 30,

provided that n and m are not 0 at the same time.

The halogen atom is F, Cl, Br or I.

The aryl group may be a C6 to C15 monocyclic aryl group or a polycyclic aryl group. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group, and the like, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

Y in Formula 1 is a residue of the acid anhydride, and the acid anhydride capable of introducing the residue Y is not particularly limited, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydroanhydride Hydrophthalic acid, methylene anhydride, methylenetetrahydrophthalic acid, chlororenic anhydride, methyltetrahydrophthalic anhydride, etc. are mentioned.

Z in Formula 2 is a residue of acid dianhydride, and the acid dianhydride compound capable of introducing the residue Z is not particularly limited, for example, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic acid and dianhydride, bitenyl ether tetracarboxylic dianhydride, cyclohexylic acid dianhydride, and cyclobutylic acid dianhydride.

When the cardo-based binder resin according to the present invention is included in the blue photosensitive resin composition, the pattern stability of the exposed part is increased while the adhesion between the non-exposed part and the substrate is decreased, so that the residue is improved.

The cardo-based binder resin including at least one repeating unit of Formula 1 and Formula 2 may be prepared, for example, by the following method.

Synthesis by reacting any one of the compounds represented by the following Chemical Formulas 3 to 7 with an epoxy compound such as epichlorohydrin under a base catalyst or an acid catalyst, and then reacting with a compound such as thiophenol, 1-thionaphthalene, and 2-thionaphthalene By doing so, compounds of the following formulas 8 to 13 can be obtained.

Thereafter, a cardo-based binder resin including at least one repeating unit of Chemical Formulas 1 and 2 may be obtained by polymerizing the compounds represented by Chemical Formulas 8 to 13 and carboxylic acid dianhydride.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Formulas 3 to 7, A, R and R' are as defined in Formulas 1 and 2.

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

In Formulas 8 to 12, c is an integer of 1 to 6,

A, Ar1, R and R' are as defined in Formulas 1 and 2.

Specific examples of the carboxylic acid dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride , 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzo Phenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis( 3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3- Dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxylphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2 ,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2, tetracarboxylic dianhydride of an aromatic ring such as 2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 Alicyclic tetracarboxylic dianhydride, such as ,3,4-cyclopentanetetracarboxylic dianhydride and 1,2,3,4-cyclohexanetetracarboxylic dianhydride, and 3,3',4,4 '-diphenylsulfonetetracarboxylic dianhydride or the like.

The polymerization may be carried out at 100 to 130°C, or 110 to 120°C, for example, for 2 hours to 24 hours, or 4 hours to 12 hours.

The carboxylic acid dianhydride may be added, for example, in an amount of 5 to 40 parts by weight, 10 to 30 parts by weight, or 10 to 20 parts by weight based on 100 parts by weight of the monomer represented by Chemical Formulas 8 to 12.

The method for producing a cardo-based binder resin including at least one repeating unit of Formula 1 and Formula 2 may include, for example, reacting by adding an end-capping agent after the polymerization reaction is started. have.

The end-capping reaction may be performed, for example, at 100 to 130° C., or 110 to 120° C. for 30 minutes to 4 hours, or 1 hour to 3 hours.

The end-capping agent may be added, for example, in an amount of 2 to 10 parts by weight, 2 to 5 parts by weight, or 3 to 5 parts by weight based on 100 parts by weight of the monomer represented by Chemical Formulas 8 to 12.

The end capping agent is, for example, preferably aromatic carboxylic acid anhydride, and a specific example thereof is phthalic anhydride, and in this case, heat resistance, high transmittance, and high refractive index are excellent.

The alkali-soluble resin may have an acid value of 20 to 200 mgKOH/g, preferably 30 to 150 mgKOH/g. When it has an acid value within the above range, the solubility in the developer is improved, so that the non-exposed portion is easily dissolved and the sensitivity is increased, so that the pattern of the exposed portion remains at the time of development, as a result, the residue can be improved.

In the present invention, "acid value" is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be usually obtained by titration using an aqueous potassium hydroxide solution.

In addition, the polystyrene reduced weight average molecular weight (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; using tetrahydrofuran as the elution solvent) is 2,000 to 200,000, preferably 3,000 to 100,000. Alkali-soluble resins are preferred. When the molecular weight is in the above range, the hardness of the coating film is improved, so that the solubility of the non-exposed part in the developer is excellent and the resolution tends to be improved, which is preferable.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.5 to 6.0. When the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] satisfies the above range, it is preferable because developability is excellent.

In one embodiment of the present invention, the cardo-based binder resin is 1 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 5 to 30 parts by weight based on 100 parts by weight of the blue photosensitive resin composition. may be included.

When the cardo-based binder resin is included within the above range, the solubility in the developer is sufficient, so that it is difficult to generate a developing residue on the substrate of the non-pixel portion, and it is difficult to reduce the film of the pixel portion of the exposed portion during development. Since there is an advantage in which omission property tends to be good, it is preferable.

In another embodiment of the present invention, the alkali-soluble resin may further include an acrylic binder resin. When the alkali-soluble resin further includes the acrylic binder resin, the size of the minimum pattern that can be formed without loss of the pattern is small, so it is preferable to realize a high-resolution pattern and have advantageous pattern straightness. In addition, it is preferable because the phenomenon of generating residues on the substrate can be suppressed.

The acrylic binder resin may include, for example, a carboxyl group-containing monomer and a copolymer of the monomer and other copolymerizable monomers.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and unsaturated polycarboxylic acids having one or more carboxyl groups in molecules such as unsaturated tricarboxylic acids. can Here, as an unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, a crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, for example, succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxyethyl) ), monophthalic acid mono(2-acryloyloxyethyl), phthalic acid mono(2-methacryloyloxyethyl), and the like.

The unsaturated polyhydric carboxylic acid may be a mono (meth) acrylate of the dicarboxy polymer at both terminals, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. . These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively. Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methyl Toxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, p- aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2- Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxy Ethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol Methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopenta Dienyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy- unsaturated carboxylic acid esters such as 3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; 2-Aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl groups such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate acid aminoalkyl esters; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, and a vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; Maleimide, benzylmaleimide, N-phenylmaleimide. unsaturated imides such as N-cyclohexyl maleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; and a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. and macromonomers having These monomers can be used individually or in mixture of 2 or more types, respectively.

In particular, as other monomers copolymerizable with the carboxyl group-containing monomer, bulky monomers such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton are preferable because they tend to lower the relative dielectric constant. .

The acrylic binder resin may be included, for example, in an amount of 10 to 90 parts by weight, preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, based on 100 parts by weight of the total alkali-soluble resin, in which case a high-resolution pattern There are advantages to fairness such as implementation and pattern straightness.

The content of the alkali-soluble resin is usually in the range of 1 to 50 parts by weight, preferably 3 to 40 parts by weight, and even more preferably 5 to 30 parts by weight based on 100 parts by weight of the total blue photosensitive resin composition. When the content of the alkali-soluble resin satisfies the above range, the solubility in the developer is sufficient, so that it is difficult to generate a developing residue on the substrate in the non-pixel portion, and it is difficult to reduce the film in the pixel portion in the exposed portion during development. Since the omission property of a part tends to be favorable, it is preferable.

blue colorant

The blue photosensitive resin composition of the present invention contains a blue colorant. Since the blue photosensitive resin composition according to the present invention further contains a blue colorant, the light of the light source reflected by the scattering particles, which will be described later, is reflected back by external light such as sunlight, thereby realizing high-quality image quality. There is an advantage.

The blue colorant may specifically include a blue pigment, and the blue pigment may include a compound classified as a pigment in the color index (published by The Society of Dyers and Colorists), and more specifically, the following Pigments having the same color index (CI) number may be mentioned, but are not necessarily limited thereto.

In another embodiment of the present invention, the blue colorant is C.I. Pigment Blue 15:3, 15:4, 15:6, 16, 21, 28, 60, 64, 76, and at least one or more blue pigments selected from the group consisting of combinations thereof; may include.

Among them, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, Pigment Blue 15:6, C.I. It is preferable in terms of the effect of suppressing external light reflection and implementing high color reproducibility to include at least one selected from the group consisting of Pigment Blue 16.

In another embodiment of the present invention, the blue colorant may further include at least one selected from the group consisting of a dye and a purple pigment.

The purple pigment is not limited thereto, for example, C.I. Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38 and may be at least one selected from the group consisting of combinations thereof, among which C.I. It is preferable to use Pigment Violet 23 in terms of realizing high color reproducibility even with a small content of colorant.

The dye may include a compound classified as a dye in the color index (published by The Society of Dyers and Colorists) or a known blue or purple dye described in a dyeing note (color dye).

For example, C.I. As a solvent dye,

C.I. Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67 and 70; and

C.I. solvent violet 8, 9, 13, 14, 36, 37, 47 and 49; and the like.

Among them, C.I. Solvent Blue 35, 36, 44, 45 and 70; and C.I. It is preferable to include at least one selected from the group consisting of solvent violet 13.

Also, C.I. As an acid dye,

CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103 , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1 , 335 and 340; and

C.I. Acid Violet 6B, 7, 9, 17, 19 and 66, and the like.

Among them, C.I. Acid Blue 80 and 90; and C.I. It is preferable to include at least one selected from the group consisting of acid violet 66.

Also, C.I. As a direct dye,

CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293; and

C.I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104;

Also, C.I. As a modanto dye,

CI Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83 and 84;

C.I. modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58;

Each of the above dyes may be used alone or in combination of two or more.

In another embodiment of the present invention, the blue colorant is included in an amount of 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight based on 100 parts by weight of the total blue photosensitive resin composition. can

If the content of the blue colorant is less than the above range, it may be somewhat difficult to obtain the desired external light reflection suppression effect. Therefore, it is used appropriately within the above range.

scattering particles

The blue photosensitive resin composition according to the present invention includes scattering particles containing a metal oxide having an average particle diameter of 30 to 500 nm.

In another embodiment of the present invention, the metal oxide is Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, It may include one or more oxides selected from the group consisting of Ti, Sb, Sn, Zr, Nb, Ce, Ta, In, and combinations thereof.

In another embodiment of the present invention, the metal oxide is Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO -Al, Nb ₂ O ₃ , SnO, MgO and at least one selected from the group consisting of combinations thereof may be included, and if necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate may be used. .

The content of the scattering particles is limited in the average particle diameter and the total composition to maximize the emission intensity of the color filter.

In the present invention, the "average particle diameter" may be a number average particle diameter, for example, it can be obtained from an image observed by a field emission principal electron microscope (FE-SEM) or a transmission electron microscope (TEM). Specifically, it is possible to obtain a value obtained by extracting several samples from an observation image of FE-SEM or TEM, measuring the diameters of these samples, and arithmetic average.

The metal oxide may have an average particle diameter of 30 to 500 nm, preferably 30 to 300 nm. When the average particle diameter of the metal oxide satisfies the above range, the scattering effect is increased, so that even if the blue photosensitive resin composition including the scattering particles does not contain blue quantum dots, it is preferable because the blue light source can serve as a blue pixel. And, since it is possible to obtain a blue pattern layer surface of uniform quality by preventing the sinking phenomenon in the composition, it can be appropriately adjusted within the above range.

In another embodiment of the present invention, the scattering particles may be included in an amount of 0.1 to 50 parts by weight, preferably 5 to 30 parts by weight, more preferably based on 100 parts by weight of the blue photosensitive resin composition. It may be included in an amount of 10 to 20 parts by weight. When the scattering particles are included within the above range, there is an advantage in that it is possible to manufacture a color filter having an excellent light emission intensity. Specifically, when the scattering particles are included within the above range, it is possible to easily secure the desired luminescence intensity, and there is an advantage in that the stability of the composition can be suppressed.

In another embodiment of the present invention, the blue photosensitive resin composition is a photopolymerizable compound; photoinitiator; solvent; And it may further include one or more selected from the group consisting of additives.

photopolymerization compound

The photopolymerizable compound contained in the blue photosensitive resin composition of the present invention is a compound capable of polymerization by the action of light and a photopolymerization initiator described later, and includes monofunctional monomers, difunctional monomers, and other polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl p Rollidone etc. are mentioned.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like.

Specific examples of the other polyfunctional monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate etc. are mentioned. Among these, the polyfunctional monomer more than bifunctional is used preferably.

The photopolymerizable compound is used in an amount of 1 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the total blue photosensitive resin composition. When the said photopolymerizable compound satisfies the said range, since the intensity|strength and smoothness of a pixel part tend to become favorable, it is preferable.

light curing initiator

The photopolymerization initiator used in the present invention preferably contains an acetophenone-based compound.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-( 2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propane-1 -one oligomer etc. are mentioned, Preferably, 2-benzyl-2- dimethylamino-1-(4-morpholinophenyl)butan-1-one etc. are mentioned.

Moreover, it can be used combining photoinitiators other than the said acetophenone type. Examples of the photopolymerization initiator other than the acetophenone type include active radical generators, sensitizers, and acid generators that generate active radicals by irradiating light.

Examples of the active radical generator include a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, and a triazine-based compound. As said benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzo isobutyl ether, etc. are mentioned, for example. Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra (t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned. As the thioxanthone-based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro -4-propoxythioxanthone etc. are mentioned. Examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl). )-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5- Triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloro methyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino) -2-methylphenyl)ethenyl]-1,3,5-triazine,2,4-bis(trichloromethyl)-6-[2-(3,4 dimethoxyphenyl)ethenyl]-1,3, 5-triazine etc. are mentioned. Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2,-bis(o-chlorophenyl)-4,4', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like can be used.

The acid generator includes, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfo nate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts, such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned. In addition, as an active radical generator, there are also compounds that generate an acid simultaneously with an active radical among the above compounds. For example, a triazine-based photopolymerization initiator is also used as an acid generator.

The content of the photoinitiator used in the blue photosensitive resin composition according to the present invention is usually 0.1 to 40 parts by weight, preferably 1 to 40 parts by weight, based on the total amount of the alkali-soluble resin and the photopolymerizable compound based on 100 parts by weight of the total solid content. 30 parts by weight. When it exists in said range, since the said blue photosensitive resin composition becomes highly sensitive, since there exists a tendency for the intensity|strength of the pixel part formed using this composition and the smoothness on the surface of this pixel part to become favorable, it is preferable. Furthermore, in this invention, a photoinitiation adjuvant can be used. The photopolymerization initiation aid may be used in combination with the photopolymerization initiator, and is a compound used to promote polymerization of a photopolymerizable compound whose polymerization is initiated by the photoinitiator. As said photoinitiation adjuvant, an amine compound, an alkoxyanthracene type compound, a thioxanthone type compound, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzphenone (common name, Michler's ketone), 4,4'-bis(diethyl Amino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, etc. are mentioned, Among these, 4,4'-bis (diethylamino) benzophenone is preferable. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. and the like. As the thioxanthone-based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxythioxanthone etc. are mentioned. Such a photoinitiator (D) does not interfere even if it uses individually or in combination of plurality. Moreover, a commercially available thing can be used as a photoinitiation adjuvant, As a commercially available photoinitiation adjuvant, the brand name "EAB-F" [manufacturer: Hodogaya Chemical Industry Co., Ltd.] etc. are mentioned, for example.

When using these photoinitiator adjuvants, the usage-amount is 10 mol or less normally per 1 mol of photoinitiator, Preferably 0.01-5 mol is preferable. When it exists in said range, since there exists a tendency for the sensitivity of the said blue photosensitive resin composition to become higher and productivity of the color filter formed using this composition tends to improve, it is preferable.

solvent

The solvent in particular contained in the blue photosensitive resin composition of this invention is not restrict|limited, Various organic solvents used in the field|area of the blue photosensitive resin composition can be used. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol Alkylene glycol alkyl ether acetates such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, methyl ethyl ketone, acetone , methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3-methoxy Esters, such as methyl propionate, Cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned. Among the above solvents, organic solvents having a boiling point of 100°C to 200°C in the above solvents are preferable from the viewpoint of applicability and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxy Esters, such as ethyl propionate and 3-methoxy methyl propionate, are mentioned, More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy ethyl propionate, 3- and methyl methoxypropionate. Each of the above solvents may be used alone or in combination of two or more.

Content of the said solvent in the blue photosensitive resin composition of this invention is 40-90 weight part normally with respect to the total 100 weight part of the said blue photosensitive resin composition containing it, Preferably it is 70-85 weight part. When the content of the solvent satisfies the above range, the coating property tends to be good when applied with an application device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), inkjet, etc. It is preferable because there is

additive

In the blue photosensitive resin composition of the present invention, if necessary, a filler, another high molecular compound, and a pigment dispersant. It is also possible to use additives, such as an adhesion promoter, antioxidant, a ultraviolet absorber, and aggregation inhibitor, in parallel.

Specific examples of the filler include glass, silica, alumina, and the like. Specific examples of the other high molecular compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. can As said pigment dispersant, commercially available surfactant can be used, For example, surfactant, such as silicone type, fluorine type, ester type, cationic type, anionic type, nonionic type, amphoteric type, etc. are mentioned. These may be used individually or in combination of 2 or more types, respectively. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, polyethylene glycol diesters, sorbitan fatty esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes , polyethyleneimines, etc. In addition, as trade names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (manufactured by Dainippon Ink Chemical Co., Ltd.), Flourad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, manufactured by Asahi Glass Co., Ltd.), brush SOLSPERSE (manufactured by Zeneca), EFKA (manufactured by EFKA Chemicals), PB 821 (manufactured by Ajinomoto), and the like. As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminoprotriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned. Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol. Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzothiazole and alkoxybenzophenone. Specific examples of the aggregation inhibitor include sodium polyacrylate.

The additives can be used by those skilled in the art by adding them in an appropriate amount within a range that does not impair the effects of the present invention.

The manufacturing method of the blue photosensitive resin composition is not limited thereto, but may be prepared, for example, through the following method.

The scattering particles are mixed with a solvent in advance and dispersed using a bead mill or the like until the average particle diameter becomes 30 to 500 nm. At this time, a dispersing agent may be additionally used as needed, and a part or all of a blue colorant and an alkali-soluble resin may be blended. To the obtained dispersion (hereinafter sometimes referred to as mill base), the remainder of the alkali-soluble resin, a photopolymerizable compound, a photoinitiator, other components used as necessary, and an additional solvent are further added to a predetermined concentration if necessary Thus, the desired blue photosensitive resin composition can be obtained. In this case, the blue colorant preferably has an average particle diameter of 0.2 μm or less through a bead mill or the like.

<Color filter and image display device>

Another aspect of the present invention relates to a self-luminous pixel-containing color filter including a blue pattern layer including a cured product of the above-described blue photosensitive resin composition.

In the present invention, the blue photosensitive resin composition may be a blue photosensitive resin composition for forming a blue pattern layer. In the present invention, the blue photosensitive resin composition does not contain quantum dots.

Since the color filter according to the present invention is made of the above-described blue photosensitive resin composition instead of blue quantum dots, it is possible to lower the manufacturing cost and has an advantage of having an excellent viewing angle.

The color filter includes a substrate and a blue pattern layer formed on the substrate.

The substrate may be a substrate of the color filter itself, or may be a portion in which a color filter is located in a display device, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The blue pattern layer is a layer comprising the blue photosensitive resin composition of the present invention, and may be a layer formed by applying the blue photosensitive resin composition and exposing, developing and thermosetting in a predetermined pattern, and the pattern layer is conventional in the art. It can be formed by performing a method known as

The color filter may further include at least one selected from the group consisting of a red pattern layer and a green pattern layer. In other words, the color filter according to the present invention may include a self-luminous pixel including the above-described blue pattern layer and further including at least one selected from the group consisting of a red pattern layer and a green pattern layer.

The red pattern layer or the green pattern layer may include quantum dots and scattering particles. Specifically, the color filter according to the present invention may include a red pattern layer including red quantum dots or a green pattern layer including green quantum dots, and the red pattern layer or green pattern layer may include scattering particles. The red pattern layer or the green pattern layer may emit red light or blue light, respectively, by a light source emitting blue light, which will be described later.

The scattering particles may include a metal oxide having an average particle diameter of 30 to 500 nm, and the content regarding the scattering particles and the metal oxide applies to the scattering particles and the metal oxide contained in the blue photosensitive resin composition according to the present invention. can do.

In the present invention, the shape, configuration, and content of quantum dots included in the red pattern layer or the green pattern layer are not limited, and quantum dots commonly used in the art may be applied.

The color filter including the substrate and the pattern layer as described above may further include a barrier rib formed between each pattern, and may further include a black matrix, but is not limited thereto.

Another aspect of the present invention, the above-described color filter; and a light source emitting blue light. In short, the image display device according to the present invention includes a color filter including a blue pattern layer including a cured product of the above-described blue photosensitive resin composition and a light source emitting blue light.

The color filter of the present invention can be applied to various image display devices, such as an electroluminescence display, a plasma display, and a field emission display, as well as a general liquid crystal display.

When the image display device includes the light source and the color filter including the blue pattern layer according to the present invention, there is an advantage in having excellent light emission intensity or viewing angle. In addition, since the blue pattern layer included in the color filter according to the present invention does not contain blue quantum dots, there is an advantage in that an image display device having a low manufacturing cost can be manufactured.

Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art. In addition, "%" and "part" indicating the content hereinafter are based on weight unless otherwise specified.

Synthesis example : Synthesis of alkali-soluble resin

Synthesis example 1: Acrylic resin

A flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube was prepared, and as a monomer dropping funnel, 74.8 g (0.20 mole) of benzylmaleimide, 43.2 g (0.30 mole) of acrylic acid, and 118.0 of vinyltoluene were prepared. g (0.50 mol), t-butylperoxy-2-ethylhexanoate 4g, propylene glycol monomethyl ether acetate (PGMEA) 40g, prepared by stirring and mixing, and as a chain transfer agent dropping tank, n-dodecanthiol 6g, PGMEA 24g was put and stirred and mixed was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring. Then, the monomer and the chain transfer agent were started dripping from the dropping lot. The dropping proceeds for 2 h while maintaining 90 ° C. After 1 h, the temperature is raised to 110 ° C. and maintained for 3 h. Then, a gas introduction tube is introduced to bubbling the oxygen/nitrogen = 5/95 (v/v) mixed gas. started Next, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% based on the carboxyl group of acrylic acid used in this reaction)], 2,2'-methylenebis(4-methyl-6-t-butylphenol ) 0.4 g and 0.8 g of triethylamine were put into the flask, and the reaction was continued at 110° C. for 8 hours to obtain Resin A having a solid content acid value of 70 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 16,000, and the molecular weight distribution (Mw/Mn) was 2.3.

Synthesis example 2: in the comparative example used cardio Synthesis of the compound of the binder resin (A-1)

Synthesis Example 2-1: 3',6'-dihydroxyspiro (fluorene-9,9-xantene) (3',6'-dihydroxyspiro (fluorene-9,9-xantene) 364.4 in a 3000ml three-necked round flask g and 0.4159 g of t-butylammonium bromide were mixed, 2359 g of epichlorohydrin was added, and the reaction was heated to 90° C. 3,6-dihydroxyspiro (fluorene-9,9-) analyzed by liquid chromatography xanthene) was completely consumed, it was cooled to 30° C., and a 50% aqueous NaOH solution (3 equivalents) was slowly added thereto. When epichlorohydrin was completely consumed by liquid chromatography analysis, the organic layer was extracted with dichloromethane and washed with water 3 times. After drying over magnesium sulfate, dichloromethane was distilled under reduced pressure, and recrystallized using a mixture ratio of dichloromethane and methanol of 50:50.

1 equivalent of the thus synthesized epoxy compound, 0.004 equivalents of t-butylammonium bromide, 0.001 equivalents of 2,6-diisobutylphenol, and 2.2 equivalents of acrylic acid were mixed, and then 24.89 g of propylene glycol monomethyl ether acetate solvent was added and mixed. The reaction solution was dissolved by heating at a temperature of 90 to 100°C while blowing air at a rate of 25 ml/min. In a state in which the reaction solution was cloudy, the temperature was heated to 120° C. to completely dissolve it. When the solution became transparent and the viscosity increased, the acid value was measured and stirred until the acid value became less than 1.0 mgKOH/g. It took 11 hours for the acid value to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound.

Synthesis Example 2-2: After adding and dissolving 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Synthesis Example 2-1, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethyl ammonium bromide were mixed, and the temperature was gradually raised. The reaction was carried out at 110 ~ 115 ℃ for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90° C. for 6 hours to polymerize the cardo-based binder resin. The disappearance of the anhydride was confirmed by the IR spectrum. Resin A-1 whose solid content acid value is 70 mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 4,530.

Synthesis example 3: cardio Binder resin (B- 1,B - 2) of synthesis of compounds

(1) Synthesis Example 3-1: 2,2'-((((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis Synthesis of (oxirane)(2,2'-((((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis(oxirane))

Add 42.5 g of 9,9-bispehnolfluorene, 220 ml of 2-(chloromethyl) oxirane and 100 mg of t-butylammonium bromide together After stirring at 90° C. until all of the reactants are consumed, the mixture is distilled under reduced pressure. After lowering the temperature again to 30 ℃, dichloromethane (dichloromethane) was injected, NaOH was slowly added. After confirming that the product was 96% or more by high performance liquid chromatography (HPLC), 5% HCl was added dropwise to terminate the reaction. After the reaction product was extracted and separated into layers, the organic layer was washed with water and washed to become neutral. The organic layer was dried over MgSO ₄ and concentrated by distillation under reduced pressure using a rotary evaporator. Dichloromethane was added to the concentrated product, and methanol was added while raising the temperature to 40° C. while stirring, followed by lowering the solution temperature and stirring. After filtering the resulting solid, vacuum drying was performed at room temperature to obtain 52.7 g (yield 94%) of a white solid powder.

(2) Synthesis Example 3-2: 3,3'-((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis((oxy))bis(1-phenylthio) Propan-2-ol)(3,3'-(((9H-Fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(1-(phenylthio)propan-2- ol)) (BTCP) synthesis

The compound of Synthesis Example 3-1 (1000 g), 524 g of thiophenol, and 617 g of ethanol were added and stirred. 328 g of triethylamine was slowly added dropwise to the reaction solution. After confirming that the starting material disappeared by high performance liquid chromatography (HPLC), the reaction was terminated. After completion of the reaction, ethanol was removed by distillation under reduced pressure. The organic material was dissolved in dichloromethane, washed with water, and then dichloromethane was removed by distillation under reduced pressure. After the concentrated organic material was dissolved in ethyl acetate, an ether solvent was added dropwise and stirred for 30 minutes. The compound was distilled under reduced pressure to obtain 945 g (yield 64%) of pale yellow oil.

(3) Synthesis Example 3-3: Synthesis of cardo-based binder resin (B-1)

200 g of BTCP monomer dissolved in 50% PGMEA solvent was added and the temperature was raised to 115 °C. 31.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (3,3',4,4'-Biphenyltetracarboxylic dianhydride) was added dropwise at 115°C, and maintained at 115°C for 6 hours. stirred. After adding 7.35 g of phthalic anhydride and stirring for an additional 2 hours, the reaction was terminated. After cooling, a binder resin having a weight average molecular weight of 3,500 g/mol was obtained.

(4) Synthesis Example 3-4: Synthesis of cardo-based binder resin (B-2)

200 g of BTCP monomer dissolved in 50% PGMEA solvent was added and the temperature was raised to 115 °C. After 21.1 g of pyromellitic dianhydride was added dropwise at 115°C, the mixture was stirred while maintaining 115°C for 6 hours. After adding 7.35 g of phthalic anhydride and stirring for an additional 2 hours, the reaction was terminated. After cooling, a binder resin having a weight average molecular weight of 4,500 g/mol was obtained.

At this time, the weight average molecular weight (Mw) of the resin was measured using the GPC method under the following conditions.

Device: HLC-8120GPC (manufactured by Toso Co., Ltd.)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection)

Column temperature: 40℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml/min

Injection volume: 50 μl

Detector: RI

Measurement sample concentration: 0.6 wt% (solvent = tetrahydrofuran)

Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Example 1 to 22 comparative example 1 to 8: Preparation of photosensitive resin composition

According to the compositions of Tables 1 to 5, photosensitive resin compositions according to Examples and Comparative Examples were prepared.

Kinds average particle diameter product name manufacturer E-1 TiO ₂ 220 nm TR-88 Huntsmansa E-2 TiO ₂ 30 nm TTO-55(C) Ishihara E-3 TiO ₂ 130 nm PT-401L Ishihara E-4 TiO ₂ 210 nm CR-63 Ishihara E-5 TiO ₂ 500 nm R-960 DuPont E-6 TiO ₂ 900 nm R-902 DuPont E-7 Al ₂ O ₃ 50 nm 0.05㎛ Aluminapowder Allied E-8 Al ₂ O ₃ 300 nm 0.3㎛ Alumina Powder Allied E-9 Al ₂ O ₃ 1000 nm 1.0㎛ Alumina Powder Allied E-10 SiO ₂ 2000 nm SYLYSIA 220A Fuji Temple

Kinds product name manufacturer B-1 C.I. Pigment B15:6 Fastogen Blue EP-7S DIC B-2 C.I. Pigment B15:4 Fastogen Blue 5424 DIC B-3 C.I. Pigment B15:3 Heliogen Blue L 7072 D BASF B-4 C.I.Pigment B16 Pigment Blue 16 CPMA V-1 C.I.Pigment V23 Fastogen Super Violet 140V DIC

Example One 2 3 4 5 6 7 8 9 10 scattering particles E-1 0.5 5 10 15 20 10 10 10 10 10 E-2 - - - - - - - - - - E-3 - - - - - - - - - - E-4 - - - - - - - - - - E-5 - - - - - - - - - - E-6 - - - - - - - - - - E-7 - - - - - - - - - - E-8 - - - - - - - - - - E-9 - - - - - - - - - - E-10 - - - - - - - - - - blue colorant B-1 3 3 3 3 3 5 15 30 - - B-2 - - - - - - - - 3 - B-3 - - - - - - - - - 3 B-4 - - - - - - - - - - purple colorant V-1 - - - - - - - - - - Alkali-soluble resin Cardo resin (A-1) - - - - - - - - - - Cardo-based resin (B-1) 9.75 9.75 9.75 9.75 9.75 9.75 9.75 9.75 9.75 9.75 Cardo resin (B-2) - - - - - - - - - - Acrylic resin (A) - - - - - - - - - - Photopolymerizable compound ^{1 )} 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 Initiator ^{2 )} 2.29 2.29 2.29 2.29 2.29 2.29 2.29 2.29 2.29 2.29 solvent ^{3 )} 77.96 73.46 68.46 63.46 58.46 66.46 56.46 41.46 68.46 68.46

1) Photopolymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

2) Initiator (D): Irgaqure-907 (manufactured by BASF)

3) Solvent (E): propylene glycol monomethyl ether acetate

Example 11 12 13 14 15 16 17 18 19 20 21 22 scattering particles E-1 10 10 - - - - - - 10 10 10 10 E-2 - - 10 - - - - - - - - - E-3 - - - 10 - - - - - - - - E-4 - - - - 10 - - - - - - - E-5 - - - - - 10 - - - - - - E-6 - - - - - - - - - - - - E-7 - - - - - - 10 - - - - E-8 - - - - - - - 10 - - - - E-9 - - - - - - - - - - - - E-10 - - - - - - - - - - - - blue colorant B-1 - 2.7 3 3 3 3 3 3 3 3 3 3 B-2 - - - - - - - - - - - - B-3 - - - - - - - - - - - B-4 3 - - - - - - - - - - - purple colorant V-1 - 0.3 - - - - - - - - - - Alkali-soluble resin Cardo resin (A-1) - - - - - - - - - - 4.875 - Cardo-based resin (B-1) 9.75 9.75 9.75 9.75 9.75 9.75 9.75 9.75 - 4.875 4.875 4.875 Cardo resin (B-2) - - - - - - - - 9.75 4.875 - - Acrylic resin (A) - - - - - - - - - - - 4.875 Photopolymerizable compound ^{1 )} 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 Initiator ^{2 )} 2.29 2.29 2.29 2.29 2.29 2.29 2.29 2.29 2.29 2.29 2.29 2.29 solvent ^{3 )} 68.46 68.46 68.46 68.46 68.46 68.46 68.46 68.46 68.46 68.46 68.46 68.46

1) Photopolymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

2) Initiator (D): Irgaqure-907 (manufactured by BASF)

3) Solvent (E): propylene glycol monomethyl ether acetate

comparative example One 2 3 4 5 6 7 8 scattering particles E-1 0.1 10 - - - - 10 10 E-2 - - - - - - - - E-3 - - - - - - - - E-4 - - - - - - - - E-5 - - - - - - - - E-6 - - 10 - - - - E-7 - - - - - - - - E-8 - - - - - - - - E-9 - - - 10 - - - - E-10 - - - - 10 10 - - blue colorant B-1 - 55 - - - - 3 3 B-2 - - 55 - - - - - B-3 - - - 55 - - - - B-4 - - - - 55 - - - purple colorant V-1 - - - - - 55 - - alkali-soluble resin Cardo-based resin (A-1) - 9.75 - - - - 9.75 - Cardo-based resin (B-1) 9.75 - 9.75 9.75 9.75 9.75 - - Cardo resin (B-2) - - - - - - - - Acrylic resin (A) - - - - - - - 9.75 photopolymerizable compound 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 Initiator ^{2 )} 2.29 2.29 2.29 2.29 2.29 2.29 2.29 2.29 solvent ^{3 )} 81.36 16.46 16.46 16.46 16.46 16.46 68.46 68.46

1) Photopolymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

2) Initiator (D): Irgaqure-907 (manufactured by BASF)

3) Solvent (E): propylene glycol monomethyl ether acetate

Manufacture of color filters

A color filter was prepared using the photosensitive resin composition prepared according to the above Examples and Comparative Examples. That is, each of the photosensitive resin compositions was applied on a glass substrate by spin coating, placed on a heating plate, and maintained at a temperature of 100° C. for 3 minutes to form a thin film.

Then, a test photomask having a transmission pattern of 20 mm x 20 mm square and a line/space pattern of 1 to 100 μm was placed on the thin film, and the distance from the test photomask was 100 μm, and ultraviolet rays were irradiated.

At this time, the ultraviolet light source was irradiated with light at an exposure dose (365 nm) of 200 mJ/cm ² in an atmospheric atmosphere using an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used.

The thin film irradiated with ultraviolet light was developed by immersing it in a developing solution of an aqueous KOH solution having a pH of 10.5 for 80 seconds. The glass plate coated with this thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150° C. for 10 minutes to prepare a color filter pattern. The film thickness of the color pattern prepared above was 5.0 μm.

Experimental example 1: Color filter development speed, sensitivity, pattern stability test

Development speed, sensitivity, and pattern stability were measured for the color filters prepared with the photosensitive resin compositions according to Examples and Comparative Examples. The evaluation criteria for each experiment are as follows. The measurement results are shown in Table 6.

Development speed (sec): The time it takes for the unexposed part to dissolve in the developer for the first time during development <Spray Developer HPMJ method>

Sensitivity: The degree to which a thin film without tearing of the sensitivity mask micropatterns (1 to 60) is formed (the lower the number, the better the sensitivity)

Pattern stability: the degree of error in the pattern after exposure of the pattern mask at a low exposure dose (20-100 mJ)

○: No error in pattern

△: When the error in the pattern is 1 or 2

×: 3 or more errors in the pattern

(○, △, × are the results of confirmation through an optical microscope of a three-dimensional surface shaper)

Experimental example 2: of color filter solvent resistance and heat resistance measurement

Evaluation of whether the color filter manufactured with the photosensitive resin composition according to the above Examples and Comparative Examples is stable to heat and solvents used in manufacturing color filters or liquid crystal display devices through heat resistance and solvent resistance measurement experiments did The measurement results are shown in Table 6.

Solvent resistance evaluation: The color filter prepared above is immersed in the solvent NMP (1-methyl-2-pyrrolidinone) for 30 minutes, and the color change before and after the evaluation is calculated for comparative evaluation. The equation used at this time is calculated by the following Equation (1), which represents the color change in a three-dimensional colorimetric system defined by L ^* , a ^* , b ^* .

Evaluation of heat resistance: After heating the color filter prepared by the above method in a heating oven at 230° C. for 2 hours, it was calculated by Equation (1) to measure the color change before and after heating.

Equation (1) ΔEab ^* = [(ΔL ^* ) ² + (Δa ^* ) ² +(Δb ^* ) ^{2 ] 1/2}

○: △Eab ^* = less than 1,

△: △Eab ^* = 1 to 3,

×: ΔEab ^* = greater than 3

Experimental example 3: Micro-pattern formation experiment

The size of the pattern obtained through a line/space pattern mask designed to be 100 μm among the color filters manufactured using the photosensitive resin according to the above Examples and Comparative Examples was measured using OM equipment (ECLIPSE LV100POL Nikon Corporation). . The measurement results are shown in Table 6.

If the difference between the design value of the line/space pattern mask and the measured value of the obtained fine pattern is 20 μm or more, it becomes difficult to implement the fine pixel, and if it has a negative value, it means a critical value that causes process defects.

Experimental example 4: residue Experiment

The color filter pattern prepared in Preparation Example was evaluated through an optical microscope. The evaluation evaluated the presence or absence of residues on the substrate, and the standards are as follows. The results are shown in Table 6 below.

○: no residue on the substrate

x: there is a residue on the board|substrate

development speed Sensitivity pattern stability fine pattern heat resistance solvent resistance residue Example 1 26 13 ○ 14 △ ○ ○ Example 2 25 12 ○ 13 ○ ○ ○ Example 3 25 10 ○ 11 ○ ○ ○ Example 4 25 8 ○ 10 ○ ○ ○ Example 5 24 7 ○ 8 ○ ○ ○ Example 6 20 8 ○ 9 ○ ○ ○ Example 7 16 6 ○ 8 ○ ○ ○ Example 8 10 4 ○ 8 ○ ○ ○ Example 9 24 10 ○ 10 ○ ○ ○ Example 10 25 9 ○ 11 ○ ○ ○ Example 11 24 9 ○ 10 ○ ○ ○ Example 12 23 9 ○ 10 ○ ○ ○ Example 13 24 10 ○ 11 ○ ○ ○ Example 14 21 8 ○ 10 ○ ○ ○ Example 15 22 10 ○ 11 ○ ○ ○ Example 16 24 10 ○ 11 ○ ○ ○ Example 17 25 9 ○ 9 ○ ○ ○ Example 18 24 10 ○ 10 ○ ○ ○ Example 19 24 11 ○ 10 ○ ○ ○ Example 20 24 12 ○ 9 ○ ○ ○ Example 21 21 13 ○ 13 ○ ○ △ Example 22 15 12 ○ 11 ○ ○ △ Comparative Example 1 23 15 △ 22 X ○ X Comparative Example 2 7 60 X -10 X X ○ Comparative Example 3 6 58 X -25 X X ○ Comparative Example 4 6 55 X -18 X X ○ Comparative Example 5 5 58 X -19 X X ○ Comparative Example 6 6 57 X -22 X X ○ Comparative Example 7 25 13 ○ 11 ○ ○ X Comparative Example 8 10 8 ○ 10 ○ ○ X

Accordingly, referring to Table 6, it was confirmed that fine patterns were well formed when the scattering particles of the metal oxide had an average particle diameter in the range of 30 to 500 nm. In addition, in the case of the comparative example, it was confirmed that it was difficult to form a fine pattern.

In addition, from the above evaluation results, it was confirmed that when the cardo binder of this example was used, the sensitivity, pattern stability, micropattern, reliability and residue improvement were very excellent compared to when the acrylic binder resin was applied alone or when the cardo binder containing an acrylic group was used.

Experimental example 5: Measurement of luminescence intensity

A portion formed in a 20 × 20 mm square pattern among the color filters manufactured using the photosensitive resin composition prepared according to the Examples and Comparative Examples through a 365 nm tube type 4 W UV irradiator (VL-4LC, VILBER LOURMAT) The light-converted region was measured, and in Examples and Comparative Examples, emission intensity in the 450 nm region was measured using a spectrum meter (Ocean Optics). The measurement results are shown in Table 7.

Experimental example 6: Measurement of the viewing angle

A variable angle photometer (GC-5000L, Nippon) was used to measure the light intensity according to the viewing angle under the light transmission condition on the part formed in a 20 × 20 mm square pattern among the color filters manufactured using the photosensitive resin composition prepared according to the above Examples and Comparative Examples. Denshoku), and the diffusion rate was calculated using Equation (2) below. The measurement results are shown in Table 7.

Equation (2)

Diffusion = (I70 + I20) / 2 × I5 × 100

I means the light intensity measured at the viewing angle.

Experimental example 7: Reflectance measurement

A spectrophotometer CM-3600A (Konica Minolta) was used to measure the light reflectance under light transmission conditions on a portion formed in a 20 × 20 mm square pattern among the color filters manufactured using the photosensitive resin composition prepared according to the Examples and Comparative Examples. was used, and the measurement results are shown in Table 7.

Luminescence intensity diffusion rate external light reflectance Example 1 26012 21.5 2.8 Example 2 29215 45.8 2.9 Example 3 30965 75.8 3 Example 4 31924 79.1 3.1 Example 5 32105 79.5 3.2 Example 6 31024 75.6 2.6 Example 7 30023 74.2 2.4 Example 8 30982 75.3 2 Example 9 31977 75.9 3 Example 10 31078 74.9 3.1 Example 11 30789 75.1 3.2 Example 12 30999 75.3 3.1 Example 13 31323 74.6 3 Example 14 30898 76.2 3.3 Example 15 30012 76.6 3.4 Example 16 29899 75.9 3.1 Example 17 29799 74.9 3 Example 18 31010 75.1 3.1 Example 19 30872 75.8 2.9 Example 20 31088 75.8 3 Example 21 31000 74.1 3.1 Example 22 28012 70.1 2.9 Comparative Example 1 10898 23.5 8 Comparative Example 2 8012 10.1 One Comparative Example 3 8235 5.9 0.8 Comparative Example 4 8111 6.4 1.2 Comparative Example 5 8216 4.5 1.1 Comparative Example 6 8320 4.4 One Comparative Example 7 30012 73.2 2.9 Comparative Example 8 18132 69 2.1

The higher the measured light emission intensity, the higher the light efficiency. Accordingly, referring to Table 7, it was confirmed that the luminescence intensity was improved in the case of Examples in which the scattering particles of the metal oxide had an average particle diameter in the range of 30 to 500 nm.

The higher the measured diffusion, the better the viewing angle. Accordingly, referring to Table 7, it was confirmed that the viewing angle was improved in Examples 1 to 22 compared to Comparative Examples 3 to 6, in which the scattering particles of the metal oxide had an average particle diameter of 30 to 500 nm. In addition, in the case of the comparative example, it was confirmed that the viewing angle was lowered.

The lower the measured reflectance, the better the effect of suppressing external light reflection, which means that it is advantageous for high-quality image quality. Accordingly, referring to Table 7, it was confirmed that the reflectance was excellent and the luminescence intensity was excellent in the case of Examples.

Claims (12)

alkali-soluble resin;
blue colorants including blue pigments; and
Including; scattering particles comprising a metal oxide having an average particle diameter of 30 to 500 nm;
The alkali-soluble resin includes a cardo-based binder resin including at least one repeating unit of Formula 1 and Formula 2 below,
A blue photosensitive resin composition that does not contain quantum dots:
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
P is each independently

,

,

,

or

ego,
R and R' are each independently hydrogen, a hydroxyl group, a thiol group, an amino group, a nitro group or a halogen atom,
Ar1 is each independently a C6 to C15 aryl group,
Y is an acid anhydride residue,
Z is an acid dianhydride residue,
A is O, S, N, Si or Se,
a and b are each independently an integer of 1 to 6,
n and m are each independently an integer from 0 to 30,
provided that n and m are not 0 at the same time. According to claim 1,
The metal oxide is Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, A blue photosensitive resin composition comprising at least one oxide selected from the group consisting of Ce, Ta, In, and combinations thereof. 3. The method of claim 2,
The metal oxide is Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , SnO, A blue photosensitive resin composition comprising at least one selected from the group consisting of MgO and combinations thereof. According to claim 1,
The alkali-soluble resin is a blue photosensitive resin composition further comprising an acrylic binder resin. According to claim 1,
The scattering particles are included in the blue photosensitive resin composition in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the total blue photosensitive resin composition. According to claim 1,
The cardo-based binder resin is included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the total blue photosensitive resin composition. According to claim 1,
The blue colorant includes at least one blue pigment selected from the group consisting of CI pigment blue 15:3, 15:4, 15:6, 16, 21, 28, 60, 64, 76, and combinations thereof; The blue photosensitive resin composition. 8. The method of claim 7,
The blue colorant is a blue photosensitive resin composition further comprising at least one selected from the group consisting of a dye and a purple pigment. According to claim 1,
The blue colorant is included in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the total blue photosensitive resin composition. According to claim 1,
photopolymerizable compounds; photoinitiator; solvent; And the blue photosensitive resin composition further comprising at least one selected from the group consisting of additives. A color filter containing a self-luminous pixel comprising a; a blue pattern layer comprising a cured product of the blue photosensitive resin composition according to any one of claims 1 to 10. The color filter according to claim 11; and a light source emitting blue light.