TWI694307B - A blue colored photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

A blue photosensitive resin composition according to the present invention includes: an alkali-soluble resin; a blue colorant; and scattering particles including a metal oxide having an average particle diameter of 30 nm to 500 nm, wherein the alkali-soluble resin includes a cardo-based binder resin including at least one of repeating units represented by Formulae 1 to 3.

The blue colored photosensitive resin composition according to the present invention is capable of imparting excellent color reproduction properties and high light efficiency, eliminating the occurrence of pattern straightness and reverse tapering due to excellent heat flowability, resulting in excellent processability, eliminating the occurrence of image retention during panel operation, and high image quality due to an excellent anti-reflection effect, excellent heat resistance, excellent chemical resistance, high durability, and excellent reliability thereof may be realized.

Description

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

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

The color filter is a thin-film optical element that extracts three colors (ie, red, green, and blue) from white light to form fine pixel units, and the size of a single pixel is tens of microns to hundreds of microns. The color filters have a stacked structure in which black matrix layers and pixel units of multiple colors (usually three primary colors of red (R), green (G), and blue (B)) are sequentially arranged on a transparent substrate in a predetermined order Forming respective pixels, the black matrix layer is formed in a predetermined pattern to shield the boundary between the pixels from light.

Recently, as a method of manufacturing a color filter, a pigment dispersion method using a pigment dispersion type photosensitive resin has been applied, but part of the light is absorbed while the light emitted from the light source passes through the color filter Into the color filter, it leads to a decrease in light efficiency, and the color reproducibility is deteriorated due to the nature of the pigment contained in the color filter.

In particular, since color filters are used in various fields including various image display devices, etc., excellent pattern characteristics and performance such as high color reproducibility, high brightness, and high contrast are required. To solve these problems, a method of manufacturing a color filter using a self-luminous photosensitive resin composition containing sub-dots has been proposed.

Korean Patent Publication No. 2013-0000506 discloses a display device including a color conversion unit, the color conversion unit including: a plurality of wavelength conversion particles configured to convert the wavelength of light; A plurality of color filter particles of a wavelength beam.

However, in the case of a color filter including quantum dots, the efficiency of quantum dots, especially the efficiency of blue quantum dots, deteriorates, resulting in a slight decrease in the performance of the color filter. In addition, blue quantum dots are expensive, so the overall manufacturing cost increases, and inverted cones appear, and thus problems such as display defects occur.

Therefore, there is a need to develop a photosensitive resin composition that can prevent the reduction in the efficiency of blue pixels and can reduce the manufacturing cost.

[Related technical references]

[Patent Literature]

(Patent Document 1) Korean Patent Publication No. 2013-0000506 (January 3, 2013)

The technical object of the present invention is to provide a blue photosensitive resin composition that can prevent the reduction in the efficiency of blue pixels and can reduce the manufacturing cost.

Another technical object of the present invention is to provide a blue photosensitive resin composition, which has excellent thermal fluidity and can suppress the occurrence of flat patterns and inverted cones, and suppress outgassing ( outgassing).

Another technical object of the present invention is to provide a color filter and an image display device. The color filter and the image display device include a blue pixel layer formed using the blue photosensitive resin composition. Specifically, the present invention provides a color filter and an image display device that exhibit excellent image quality, excellent durability, excellent reliability, and the like.

To achieve the above object, the blue photosensitive resin composition according to the present invention includes: an alkali-soluble resin; a blue colorant; and scattering particles, including a metal oxide having an average particle diameter of 30 nm to 500 nm, wherein the The alkali-soluble resin includes a cardo-based binder resin containing at least one of the repeating units represented by the following Formula 1 to Formula 3:

[Form 3]

Y為酸酐殘基，Z為酸二酐殘基，R'為氫原子、乙基、苯基、-C₂H₄Cl、-C₂H₄OH、或-CH₂CH=CH₂，R1、R1'、R2、R2'、R3、R3'、R4、R4'、R5、R5'、R6、及R6'各自獨立為氫原子或甲基，R7、R7'、R8、及R8'各自獨立為直鏈或支鏈C₁至C₆伸烷基，其中該伸烷基可由酯鍵、C₆至C₁₄伸環烷基、及C₆至C₁₄伸芳基中的至少一者封端，R9、R9'、R10、R10'、R11、R11'、R12、及R12'各自獨立為氫原子、鹵素原子、或者直鏈或支鏈C₁至C₅烷基， m及n分別為滿足以下條件的整數：0

m

30以及0

n

30，但m與n不同時為0，以及其中，在式3中，R13與式1及式2中的X及X'之定義相同，R14為甲基丙烯酸酯基、乙烯基或丙烯酸酯基，R15為衍生自下式4所表示之單體的反應性殘基，r為1至20的整數，

However, in Formula 1 and Formula 2, X and X'are each independently a single bond, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-,

Y is an acid anhydride residue, Z is an acid dianhydride residue, R'is a hydrogen atom, ethyl, phenyl, -C ₂ H ₄ Cl, -C ₂ H ₄ OH, or -CH ₂ CH=CH ₂ , R1 , R1', R2, R2', R3, R3', R4, R4', R5, R5', R6, and R6' are each independently a hydrogen atom or a methyl group, R7, R7', R8, and R8' are independently Is a linear or branched C ₁ to C ₆ alkylene group, wherein the alkyl group can be terminated by at least one of an ester bond, C ₆ to C ₁₄ cycloalkyl group, and C ₆ to C ₁₄ aryl group , R9, R9', R10, R10', R11, R11', R12, and R12' are each independently a hydrogen atom, a halogen atom, or a linear or branched C ₁ to C ₅ alkyl group, m and n are respectively satisfied An integer with the following conditions: 0

m

30 and 0

n

30, but m and n are not 0 at the same time, and among them, in formula 3, R13 has the same definition as X and X'in formula 1 and formula 2, R14 is a methacrylate group, vinyl group or acrylate group , R15 is a reactive residue derived from the monomer represented by the following formula 4, r is an integer of 1 to 20,

However, in Formula 4, R16 and R17 are the same as or different from each other and are independently

The present invention also provides a color filter manufactured using the blue photosensitive resin composition and an image display device including the color filter.

The advantages of the blue photosensitive resin composition of the present invention are: it can give excellent color reproduction characteristics and light efficiency, will not form a pattern residue, due to good thermal fluidity, it suppresses the appearance of straight patterns and inverted cones, And to minimize the occurrence of outgassing.

In addition, the color filter manufactured using the blue photosensitive resin composition of the present invention and the image display device including the color filter have advantages in that high image quality can be ensured due to an excellent anti-reflection effect; Wide viewing angle, high durability and reliability; and can reduce manufacturing costs.

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

In the present invention, when an element is said to be "on" of another element, this includes not only the case where the element is in contact with another element, but also the presence of another element between the two elements Situation.

In the present invention, when a part is referred to as "including" an element, unless otherwise specified, this indicates that the part not only excludes other elements, but may also include other elements.

<Blue photosensitive resin composition>

An embodiment of the present invention provides a blue photosensitive resin composition including: an alkali-soluble resin; a blue colorant; and scattering particles, including an average particle diameter of 30 nm to 500 nm The metal oxide of rice, wherein the alkali-soluble resin includes a carbole-based binder resin containing at least one of the repeating units represented by Formula 1 to Formula 3 below:

Y為酸酐殘基，Z為酸二酐殘基，R'為氫原子、乙基、苯基、-C₂H₄Cl、-C₂H₄OH、或-CH₂CH=CH₂，R1、R1'、R2、R2'、R3、R3'、R4、R4'、R5、R5'、R6、及R6'各自獨 立為氫原子或甲基，R7、R7'、R8、及R8'各自獨立為直鏈或支鏈C₁至C₆伸烷基，其中該伸烷基可由酯鍵、C₆至C₁₄伸環烷基、及C₆至C₁₄伸芳基中的至少一者封端，R9、R9'、R10、R10'、R11、R11'、R12、及R12'各自獨立為氫原子、鹵素原子、或者直鏈或支鏈C₁至C₅烷基，m及n分別為滿足以下條件的整數：0

m

30及0

n

30，但m與n不同時為0，以及其中，在式3中，R13與式1及式2中的X及X'之定義相同，R14為甲基丙烯酸酯基、乙烯基或丙烯酸酯基，R15為衍生自由下式4所表示之單體的反應性殘基，r為1至20的整數，

However, in Formula 1 and Formula 2, X and X'are each independently a single bond, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-,

Y is an acid anhydride residue, Z is an acid dianhydride residue, R'is a hydrogen atom, ethyl, phenyl, -C ₂ H ₄ Cl, -C ₂ H ₄ OH, or -CH ₂ CH=CH ₂ , R1 , R1', R2, R2', R3, R3', R4, R4', R5, R5', R6, and R6' are each independently a hydrogen atom or a methyl group, R7, R7', R8, and R8' are independently Is a linear or branched C ₁ to C ₆ alkylene group, wherein the alkyl group can be terminated by at least one of an ester bond, C ₆ to C ₁₄ cycloalkyl group, and C ₆ to C ₁₄ aryl group , R9, R9', R10, R10', R11, R11', R12, and R12' are each independently a hydrogen atom, a halogen atom, or a linear or branched C ₁ to C ₅ alkyl group, m and n are respectively satisfied An integer with the following conditions: 0

m

30 and 0

n

30, but m and n are not 0 at the same time, and among them, in formula 3, R13 has the same definition as X and X'in formula 1 and formula 2, R14 is a methacrylate group, vinyl group or acrylate group , R15 is a reactive residue derived from the monomer represented by the following formula 4, r is an integer of 1 to 20,

However, in Formula 4, R16 and R17 are the same as or different from each other and are independently

Alkali soluble resin

The blue photosensitive resin composition of the present invention includes a carbole-based binder resin containing at least one of the repeating units represented by the following Formula 1 to Formula 3:

Y為酸酐殘基，Z為酸二酐殘基，R'為氫原子、乙基、苯基、-C₂H₄Cl、-C₂H₄OH、或-CH₂CH=CH₂，R1、R1'、R2、R2'、R3、R3'、R4、R4'、R5、R5'、R6、及R6'各自獨立為氫原子或甲基，R7、R7'、R8、及R8'各自獨立為直鏈或支鏈C₁至C₆伸烷基，其中該伸烷基可由酯鍵、C₆至C₁₄伸環烷基、及C₆至C₁₄伸芳基中的至少一者封端，R9、R9'、R10、R10'、R11、R11'、R12、及R12'各自獨立為氫原子、鹵素原子、或者直鏈或支鏈C₁至C₅烷基，m及n分別為滿足以下條件的整數：0

m

30及0

n

30，但m與n不同時為0，以及其中，在式3中，R13與式1及式2中的X及X'之定義相同，R14為甲基丙烯酸酯基、乙烯基或丙烯酸酯基，R15為衍生自由下式4所表示之單體的反應性殘基，r為1至20的整數，

However, in Formula 1 and Formula 2, X and X'are each independently a single bond, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-,

Y is an acid anhydride residue, Z is an acid dianhydride residue, R'is a hydrogen atom, ethyl, phenyl, -C ₂ H ₄ Cl, -C ₂ H ₄ OH, or -CH ₂ CH=CH ₂ , R1 , R1', R2, R2', R3, R3', R4, R4', R5, R5', R6, and R6' are each independently a hydrogen atom or a methyl group, R7, R7', R8, and R8' are independently Is a linear or branched C ₁ to C ₆ alkylene group, wherein the alkyl group can be terminated by at least one of an ester bond, C ₆ to C ₁₄ cycloalkyl group, and C ₆ to C ₁₄ aryl group , R9, R9', R10, R10', R11, R11', R12, and R12' are each independently a hydrogen atom, a halogen atom, or a linear or branched C ₁ to C ₅ alkyl group, m and n are respectively satisfied An integer with the following conditions: 0

m

30 and 0

n

30, but m and n are not 0 at the same time, and among them, in formula 3, R13 has the same definition as X and X'in formula 1 and formula 2, R14 is a methacrylate group, vinyl group or acrylate group , R15 is a reactive residue derived from the monomer represented by the following formula 4, r is an integer of 1 to 20,

However, in Formula 4, R16 and R17 are the same as or different from each other and are independently

Preferably, R7, R7', R8 and R8' are each independently a linear or branched C ₁ to C ₆ alkylene group, wherein the extendable alkyl group may be terminated by at least one of the following: ester bond, C ₆ to C ₁₄ cycloalkyl, and C ₆ to C ₁₄ aryl, preferably ethyl,

In this regard, since R15 in Formula 3 contains a reactive residue derived from the monomer represented by Formula 4, the degree of curing is increased, the surface hardness is enhanced, and excellent heat resistance, excellent chemical resistance, Excellent strength and excellent hardness to obtain color filters with excellent durability and excellent reliability.

In one embodiment of the present invention, the repeating unit represented by Formula 3 can be represented by any one of the following Formula 5 to Formula 9, but the present invention is not limited to this, and may satisfy the above conditions and be in the technical field Any repeating unit known in

[Form 5]

[Form 9]

Among them, in Formula 5 to Formula 9, R13 has the same definition as in Formula 3, R14 is a methacrylate group, a vinyl group or an acrylate group, and r is an integer from 1 to 20.

Preferably, the amount of the repeating units of formula 5 to formula 9 in the alkali-soluble resin of the present invention may be 3 mol% to 80 mol% relative to 100 mol% (total mols) of the alkali-soluble resin , More preferably 5 mol% to 70 mol%. When the amount of the repeating units of Formula 5 to Formula 9 is within the above range, the pattern will not peel off during development due to excellent sensitivity and excellent adhesion, and excellent solvent resistance is obtained.

When the self-luminous blue photosensitive resin composition according to the present invention includes a carbole-based binder resin containing at least one of the repeating units of Formula 1 to Formula 3, excellent inter-process reliability is obtained. In addition, due to the effect of quickly adjusting the development speed, there is no pattern residue; due to the excellent thermal fluidity, there is no pattern straightness and inverted cone, which reduces the display defects; because the outgassing is minimized, so during panel operation No image retention occurs; high image quality can be obtained due to excellent anti-reflection effect; excellent heat resistance, excellent chemical resistance, excellent durability, and excellent reliability can be obtained.

When the carbole-based binder resin according to the present invention includes all the repeating units of Formula 1 to Formula 3, the molar ratio of m to n (m/n) is not particularly limited, but may be, for example, 1/99 to 90/ 10, more preferably 5/95 to 80/20.

When the molar ratio (m/n) is within the above range, the carboxyl content of the binder resin is properly maintained, so the alkali resistance can be maintained at a high level, and the developer will not elute at the exposed portion and show It exhibits excellent alkali developability and therefore can form micro patterns.

Y in Formula 1 is an acid anhydride residue, and can be obtained by reacting a bisphenol epoxy acrylate compound with an acid anhydride compound, where the bisphenol epoxy acrylate compound is a synthetic intermediate product of a carbole-based binder resin. The acid anhydride compound capable of introducing the residue Y is not particularly limited, and examples thereof include, but are not limited to, maleic anhydride, succinic anhydride, itaconic acid, phthalic anhydride anhydride), tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-methyl-tetramethylphthalic anhydride, chlorendic anhydride, and methyltetrahydrophthalic anhydride Formic anhydride.

Z of formula 2 is an acid dianhydride residue, and can be obtained by reacting a bisphenol epoxy acrylate compound with an acid dianhydride compound, wherein the bisphenol epoxy acrylate compound is the carbole-based binder resin of the present invention Synthesis of intermediate products. The acid dianhydride compound capable of introducing the residue Z is not particularly limited, and examples thereof include, but are not limited to, aromatic polycarboxylic acid anhydrides, such as pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, Biphenyl tetracarboxylic dianhydride and biphenyl ether tetracarboxylic dianhydride; cyclohexanoic dianhydride; and cyclobutyric dianhydride.

In the present invention, the term "single bond" refers to a structure directly connected without other functional groups, and for example, refers to a structure directly connected to an oxyphenyl group in the absence of X and X'in Formula 1.

In addition, in the present invention, the term "acid dianhydride" refers to a compound containing two acid anhydride groups in the molecule.

In the present invention, the method of preparing the carbole-based binder resin is not particularly limited. For example, the carbole-based binder resin can be prepared by reacting a bisphenol compound with an epoxy compound to synthesize a bisphenol epoxy compound, and reacting a synthesized bisphenol epoxy compound with an acrylate compound to synthesize a bisphenol epoxy acrylate Compound, and then the bisphenol epoxy acrylate compound is reacted with acid anhydride, acid dianhydride, or a mixture thereof, but the present invention is not limited thereto.

The alkali-soluble resin may have an acid value of 20 mg KOH/g to 200 mg KOH/g, preferably 30 mg KOH/g to 150 mg KOH/g. When the acid value of the alkali-soluble resin is within the above range, the solubility of the alkali-soluble resin in the developing solution increases, so the non-exposed portion is easily dissolved and the sensitivity increases. Therefore, the pattern of the exposed portion is retained during development, thereby improving the film residue rate.

The term "acid value" as used herein refers to the amount (mg) of potassium hydroxide required to neutralize 1 gram of acrylic-based polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution.

In addition, the weight average molecular weight of the alkali-soluble resin based on polystyrene measured by gel permeation chromatography (GPC; using tetrahydrofuran as the eluent) (hereinafter referred to as "weight average molecular weight") can be 2,000 to 200,000 , Preferably 3,000 to 100,000. When the weight average molecular weight of the alkali-soluble resin is within the above range, the hardness of the coating film is enhanced, the film residual rate is high, the solubility of the non-exposed portion in the developing solution is excellent, and the resolution is increased.

The alkali-soluble resin may have a molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of 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, the developability is excellent.

In one embodiment of the present invention, the content of the carbole-based binder resin may be 1 part by weight to 50 parts by weight, preferably 5 parts by weight to 40 parts relative to 100 parts by weight of the blue photosensitive resin composition Parts by weight, and more preferably 5 parts by weight to 30 parts by weight.

When the amount of the carbole-based binder resin is within the above range, its solubility in the developing solution is sufficient, so it is not easy to produce development residue on the non-pixel unit of the substrate, and it is at the pixel unit of the exposed portion during development The film thickness is not easily reduced, so that non-pixel units can be deleted satisfactorily.

In another embodiment of the present invention, the alkali-soluble resin may further include a carbole-based binder resin including at least one selected from repeating units represented by Formula 10 and Formula 11 below :

其中R19及R20各自獨立為氫、羥基、硫醇基、胺基、硝基或鹵素原子；Ar1為C₆至C₁₅芳基；Y'為酸酐殘基；Z'為酸二酐殘基；A為氧(O)、硫(S)、氮(N)、矽(Si)或硒(Se)；a及b各自獨立為1至6的整數；以及p及q各自獨立為0至30的整數，但p與q不同時為0。 Among them, in formula 10 and formula 11, P is independently

Wherein R19 and R20 are each independently hydrogen, hydroxyl, thiol, amine, nitro or halogen atom; Ar1 is C ₆ to C ₁₅ aryl; Y'is an acid anhydride residue; Z'is an acid dianhydride residue; A is oxygen (O), sulfur (S), nitrogen (N), silicon (Si), or selenium (Se); a and b are each independently an integer of 1 to 6; and p and q are each independently 0 to 30 Integer, but p and q are not 0 at the same time.

The halogen atom is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

基(chrysenyl)或茀基(fluorenyl)， 但本發明並不限於此。 The aryl group may be a C ₆ to C ₁₅ monocyclic aryl group or a polycyclic aryl group. The monocyclic aryl group may be phenyl, biphenyl, terphenyl, or stylbenyl, but the present invention is not limited thereto. The polycyclic aryl group can be naphthyl, anthracenyl, phenanthryl, pyrenyl, perylenyl,

Chrysenyl or fluorenyl, but the invention is not limited thereto.

Y′ of Formula 10 is an acid anhydride residue, and the acid anhydride capable of introducing the residue Y′ may be the same as described above for Y.

Z′ of Formula 11 is an acid dianhydride residue, and the acid dianhydride compound capable of introducing the residue Z′ is not particularly limited, and may be the same as described above for Z.

When the carbole-based binder resin according to the present invention is contained in the blue photosensitive resin composition, luminous intensity, diffusivity, and external light reflectance can be further enhanced.

When the alkali-soluble resin further includes a carbole-based binder resin containing at least one selected from the group consisting of repeating units of Formula 10 and Formula 11, the carbole-based binder is relative to 100 parts by weight of the alkali-soluble resin The content of the resin may be 1 part by weight to 50 parts by weight, preferably 5 parts by weight to 40 parts by weight, and more preferably 5 parts by weight to 30 parts by weight.

When the amount of the carbole-based binder resin that can be further included is within the above range, the luminous intensity, diffusivity, and external light reflectance can be further enhanced.

The carbole-based binder resin containing at least one selected from the group consisting of repeating units of Formula 10 and Formula 11 can be prepared using, for example, the following method.

In the presence of an alkali catalyst or an acid catalyst, any of the compounds represented by the following formula 12 to formula 16 can be reacted with an epoxy compound such as epichlorohydrin (epichlorohydrin), and then with, for example, thiophenol, 1 -One of the compounds represented by the following formula 17 to formula 21 is synthesized by reacting compounds such as 1-thionaphthalene or 2-naphthalenethione.

Subsequently, one of the compounds of Formula 17 to Formula 21 and carboxylic dianhydride can be polymerized to obtain a carbole-based binder resin containing at least one of the repeating units of Formula 10 and Formula 11.

[Form 12]

Among them, in Formula 12 to Formula 16, A, R19 and R20 have the same definitions as in Formula 10 and Formula 11.

[Form 17]

However, in Formula 17 to Formula 21, c is an integer of 1 to 6, and A, Ar1, R19, and R20 have the same definitions as in Formula 10 and Formula 11.

Specific examples of carboxylic dianhydrides include: aromatic tetracarboxylic dianhydrides, such as 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'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxy Phenyl)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-dicarboxyphenyl) benzene dianhydride, bis(3,4-dicarboxy Phenyl) ether dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl) stilbene dianhydride, 9,9-bis{4-( 3,4-dicarboxyphenoxy)phenyl) stilbene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4 ,9,10-Perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, etc.; alicyclic tetracarboxylic dianhydride, such as 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,3,4-cyclohexane tetracarboxylic dianhydride, etc.; 3,3' ,4,4'-diphenylbenzene tetracarboxylic dianhydride; and so on.

The polymerization reaction may be performed at a temperature of, for example, 100°C to 130°C or 110°C to 120°C for 2 hours to 24 hours or 4 hours to 12 hours.

The addition amount of carboxylic dianhydride may be, for example, 5 to 40 parts by weight, 10 to 30 parts by weight, or 10 parts by weight with respect to 100 parts by weight of the monomer represented by one of Formula 17 to Formula 21 above Parts to 20 parts by weight.

The method of preparing the carbole-based binder resin containing at least one of the repeating units of Formula 10 and Formula 11 may include, for example, adding an end-capping agent for the reaction after the initial polymerization reaction.

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

The addition amount of the end-capping agent may be, for example, 2 parts by weight to 10 parts by weight, 2 parts by weight to 5 parts by weight, or 3 parts by weight to 5 parts by weight with respect to 100 parts by weight of the monomer of one of Formula 17 to Formula 21 Copies.

The blocking agent may be, for example, aromatic carboxylic anhydride, especially phthalic anhydride and the like. In this case, excellent heat resistance and excellent transmission and refraction characteristics can be obtained.

The carbole-based binder resin containing at least one of the repeating units of Formula 10 and Formula 11 may have, for example, 1,000 g/mole (g/mol) to 100,000 g/mole, preferably 2,000 g/mole to 50,000 g /Mole and more preferably a weight average molecular weight of 3,000 g/mole to 10,000 g/mole. When the weight-average molecular weight is within the above range, excellent heat resistance is obtained, and the development rate of the photoresist and the development thereof by the developing solution are appropriate, so that a pattern can be formed satisfactorily.

The weight average molecular weight can be measured by gel permeation chromatography (GPC).

The carbole-based binder resin containing at least one of the repeating units of Formula 10 and Formula 11 may have a degree of dispersion of, for example, 1.0 to 5.0, preferably 1.5 to 4.0. When the degree of dispersion thereof is within the above range, excellent heat resistance is obtained, and the development rate of the photoresist and the development thereof by the developing solution are appropriate, so that a pattern can be formed satisfactorily.

The degree of dispersion of the base material can be measured by GPC measurement.

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 an acrylic binder resin, the size of the smallest pattern formed without losing the pattern is small, so a high-resolution pattern can be obtained, and it is preferable in terms of flatness of the pattern.

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

The carboxyl group-containing monomer may be, for example, unsaturated carboxylic acid, such as unsaturated monocarboxylic acid; or unsaturated polycarboxylic acid having one or more carboxyl groups in the molecule, such as unsaturated dicarboxylic acid, unsaturated tricarboxylic acid, etc. . In this regard, the unsaturated monocarboxylic acid may be, for example, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like. The unsaturated dicarboxylic acid may be, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like. The unsaturated polycarboxylic acid may be an anhydride, especially maleic anhydride, itaconic anhydride, citraconic anhydride and the like. In addition, the unsaturated polycarboxylic acid may be a mono(2-methacryloxyalkyl) ester of the above acid anhydride, for example, mono(2-propenyloxyethyl) succinate, succinic acid mono(2-methyl Acryloyloxyethyl) phthalate, phthalic acid mono(2-acryloyloxyethyl) ester, phthalic acid mono(2-methacryloyloxyethyl) ester, etc.

The unsaturated polycarboxylic acid may be a mono(meth)acrylate of a dicarboxy polymer having unsaturated polycarboxylic acid at both ends, such as ω-carboxy polycaprolactone monoacrylate, ω-carboxy polycaprolactone Monomethacrylate, etc. One of these carboxyl group-containing monomers or a mixture of two or more of these monomers can be used. Examples of other monomers copolymerizable with carboxyl group-containing monomers include, but are not limited to, aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, P-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and indene; unsaturated carboxylic acid esters, such as methyl acrylate, methyl methacrylate, ethyl acrylate , Ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, methyl Isobutyl acrylate, secondary butyl acrylate, secondary butyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid 2-hydroxypropyl ester, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-acrylate Hydroxybutyl ester, 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-methoxyethyl methacrylate, 2-phenoxyethyl acrylate Ester, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol Glycol methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, Isocamphenyl methacrylate, dicyclopentyl diacrylate, dicyclopentyl dimethacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate and glycerol monomethacrylate; unsaturated carboxylic acid aminoalkyl esters, Such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate , 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate Propyl ester, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acid glycidyl esters, such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid Vinyl esters, such as vinyl acetate, vinyl propionate , Vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloropropene Nitrile and vinylidene cyanide; unsaturated amides, such as acrylamide, methacrylamide, α-chloropropene amide, N-2-hydroxyethylacrylamide, N-2-hydroxy Ethylmethacrylamide; unsaturated amide imines, such as maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; fat Group conjugated dienes, such as 1,3-butadiene, isoprene, and chloroprene; and macromolecules with a single propenyl acetyl group or a single methacryl acetyl group at the end of the polymer molecular chain Monomers such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. These monomers may be used alone or a mixture of two or more of these monomers may be used.

In particular, as other monomers copolymerizable with carboxyl group-containing monomers, macromonomers such as monomers having a norbornyl backbone, monomers having an adamantane backbone, and monomers having a rosin backbone can be used Monomer, etc. This is because it has a tendency to lower the dielectric constant value.

The content of the acrylic binder resin relative to 100 parts by weight of the alkali-soluble resin may be, for example, 10 to 90 parts by weight, preferably 20 to 80 parts by weight, and more preferably 30 to 70 parts by weight . When the amount of the acrylic binder resin is within the above range, it is preferable in terms of workability such as formation of a high-resolution pattern and flatness of the pattern.

The amount of the alkali-soluble resin is usually 1 part by weight to 50 parts by weight, preferably 3 parts by weight to 40 parts by weight, and more preferably 5 parts by weight relative to 100 parts (total) of the blue photosensitive resin composition. 30 parts by weight. When the amount of the alkali-soluble resin is within the above range, its solubility in the developing solution is sufficient, so it is not easy to produce development residue on the non-pixel unit of the substrate, and the film at the pixel unit of the exposed portion during development The thickness is not easy to reduce, so non-pixel units can be deleted satisfactorily.

Blue colorant

The blue photosensitive resin composition of the present invention includes a blue colorant. Since the blue photosensitive resin composition according to the present invention further includes a blue colorant, it is possible to prevent the light from the light source reflected by the scattering particles (described later) from being reflected again by external light such as sunlight, and thus can be obtained High-quality images.

The blue colorant may specifically include a blue pigment, and the blue pigment may be a compound specifically classified as a pigment in the color index (published by the Society of Dyers and Colourists), and more specifically It is a pigment having the following color index (CI) number, but the invention is not limited thereto.

In another embodiment of the present invention, the blue colorant may include one selected from CI Pigment Blue 15:3, 15:4, 15:6, 16, 21, 28, 60, 64, and 76, and its Combined blue pigment.

Among them, in terms of external light reflection suppression effect and high color reproducibility, a group selected from CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, and CI Pigment Blue 16 may be used At least one of them.

In another embodiment of the present invention, the blue colorant may further include one or more selected from the group consisting of dyes and purple pigments.

The purple pigment may be, but is not limited to, one selected from the group consisting of, for example, C.I. Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, and 38, and combinations thereof. Among them, C.I. Pigment Violet 23 can be used in terms of achieving high color reproducibility and achieving reliability even when the colorant content is low.

Dyes may include those classified as dyes in the color index (published by the Association of Dyeing, Finishing, and Colorists) or conventional blue or purple dyes described in Dyeing Note (Color Dyeing Co.) Compound.

Examples of CI solvent dyes include but are not limited to CI Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67, and 70; and CI Solvent Violet 8, 9, 13, 14, 36, 37, 47, and 49.

Among them, the C.I. solvent dye preferably includes at least one selected from the group consisting of: C.I. Solvent Blue 35, 36, 44, 45, 70; and C.I. Solvent Violet 13.

In addition, examples of CI acid dyes include but are not limited to 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 CI Acid Violet 6B, 7, 9, 17, 19, and 66.

Among them, the C.I. acid dye preferably includes at least one selected from the group consisting of C.I. Acid Blue 80 and 90; and C.I. Acid Violet 66.

In addition, examples of CI direct dyes include but are not limited to 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 CI Direct Violet 47, 52, 54, 59, 60, 65 , 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, and 104.

In addition, examples of CI mordant dyes include but are not limited to CI mordant 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; and CI mordant violet 1, 2, 4, 5, 7, 14, 22, 24 , 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, and 58.

The above dyes may be used alone or a combination of two or more of these dyes may be used.

In another embodiment of the present invention, the content of the blue colorant may be 0.1 parts by weight to 50 parts by weight, preferably 0.5 parts by weight relative to 100 parts by weight (total) of the blue photosensitive resin composition To 30 parts by weight, and more preferably 1 to 20 parts by weight.

When the amount of blue colorant is less than the above range, it may be difficult to ensure the desired external light reflection suppression effect, while on the other hand, when the amount of blue colorant is more than the above range, the luminous intensity may be slightly deteriorated, and the composition The viscosity and stability of the substance may be reduced, so it is appropriate to use the blue colorant within the above range.

Scattering particles

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

In another embodiment of the present invention, the metal oxide may include an oxide selected from oxides of the following metals: lithium (Li), beryllium (Be), boron (B), sodium (Na), magnesium ( Mg), aluminum (Al), silicon (Si), potassium (K), calcium (Ca), scandium (Sc), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel ( Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), rubidium (Rb), strontium (Sr), yttrium (Y), molybdenum (Mo), cesium (Cs), barium ( Ba), lanthanum (La), hafnium (Hf), tungsten (W), thallium (Tl), lead (Pb), cerium (Ce), gallium (Pr), neodymium (Nd), yttrium (Pm), samarium ( Sm), europium (Eu), lanthanum (Gd), ytterbium (Tb), dysprosium (Dy), 鈥 (Ho), erbium (Er), squalene (Tm), ytterbium (Yb), titanium (Ti), antimony (Sm) Sb), tin (Sn), zirconium (Zr), niobium (Nb), tantalum (Ta), indium (In), and combinations thereof.

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

In order to maximize the luminous intensity of the color filter, the average particle size of the scattering particles and the amount in the entire composition are limited.

The term "average particle diameter" used herein may mean an average particle diameter, and may be obtained from an image observed by, for example, a field emission scanning electron microscope (FE-SEM) or a transmission electron microscope (TEM). Specifically, several samples can be collected from FE-SEM or TEM observation images, the diameters of these samples can be measured, and the measured values can be averaged.

The metal oxide may have an average particle size of 30 nm to 500 nm, preferably 30 nm to 300 nm. When the average particle diameter of the metal oxide is within the above range, the scattering effect can be enhanced. Therefore, although the blue photosensitive resin composition containing scattering particles does not contain blue quantum dots, the scattering particles can be used as blue by a blue light source Color pixels, and can prevent the precipitation of scattering particles in the composition, thereby obtaining a blue pattern layer surface with uniform quality. Therefore, the average particle diameter of the metal oxide can be appropriately adjusted within the above range.

In another embodiment of the present invention, the content of the scattering particles may be 0.1 to 50 parts by weight, preferably 5 to 30 parts by weight relative to 100 parts by weight (total) of the blue photosensitive resin composition Parts by weight, and more preferably from 10 parts by weight to 20 parts by weight. When the amount of scattering particles is within the above range, a color filter having excellent luminous intensity can be manufactured. In particular, when the amount of scattering particles is within the above range, the desired luminous intensity can be easily secured, and the decrease in the stability of the composition can be suppressed.

In another embodiment of the present invention, the blue photosensitive resin composition may further include at least one selected from the group consisting of: a photopolymerizable compound; a photopolymerization initiator; a solvent; and an additive.

Photopolymerizable compound

The photopolymerizable compound included in the blue photosensitive resin composition of the present invention may be a compound that is polymerizable in response to light and under the action of a photopolymerization initiator (described later), such as a monofunctional monomer, a bifunctional Functional monomers, other multifunctional monomers, etc.

Specific examples of monofunctional monomers include but are not limited to nonylphenylcarbitol acrylate (nonylphenylcarbitol acrylate), 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2 -Hydroxyethyl acrylate and N-vinyl pyrrolidone.

Specific examples of bifunctional monomers include, but are not limited to 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tri Ethylene glycol di(meth)acrylate, bis(acryloxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate.

Specific examples of other multifunctional monomers include, but are not limited to, trimethylolpropane tri(meth)acrylate, neopentylerythritoltri(meth)acrylate, neopentyltetraritoltri(meth)acrylate Meth) acrylate, dipentaerythritol penta (meth) acrylate and di neopentaerythritol hexa (meth) acrylate. Among them, polyfunctional monomers having two or more functional groups are preferably used.

The content of the photopolymerizable compound may be 1 to 30 parts by weight, preferably 5 to 20 parts by weight relative to 100 parts by weight (total) of the blue photosensitive resin composition. When the amount of the photopolymerizable compound is within the above range, the pixel unit may have good strength or smoothness.

Photopolymerization initiator

The photopolymerization initiator used in the present invention may include an acetophenone-based compound.

The acetophenone-based compound may be, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyl dimethyl ketal, 2-hydroxy-1-[ 4-(2-hydroxyethoxy)phenyl]-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)- 2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) butane-1-one, 2-hydroxy-2- Oligomer of methyl[4-(1-methylvinyl)phenyl]propane-1-one, etc. Preferably 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane-1-one and the like are used.

In addition, photopolymerization initiators other than acetophenone-based compounds may be used in combination. In addition to the acetophenone-based compound, the photopolymerization initiator may include an active radical generator that generates active radicals by light irradiation, a sensitizer, an acid generator, and the like.

The active radical generator may be, for example, a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, a triazine-based compound, or the like. The benzoin-based compound may be, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like. The benzophenone-based compound may be benzophenone, methyl o-benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis (tertiary butyl peroxycarbonyl) benzophenone, 2,4,6-trimethyl benzophenone, etc. The thioxanthone-based compound may be, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro -4-Propoxy thioxanthone, etc. The triazine-based compound may be, for example, 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)vinyl]-1,3,5-triazine, 2 ,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6- [2-(4-Diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3 ,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc. The active radical generator may be, for example, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2,2-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone (10-butyl- 2-chloroacridone), 2-ethylanthraquinone (2-ethylanthraquinone), benzyl, 9,10-phenanthrenequinone (9,10-phenanthrenequinone), camphorquinone (camphorquinone), phenylmethylglyoxalate (phenyl methyl glyoxylate), titanocene compounds, etc.

Examples of acid generators include, but are not limited to onium salts, such as 4-hydroxyphenyl dimethyl sulfonium p-toluenesulfonate (4-hydroxyphenyl dimethyl sulfonium p-toluenesulfonate), 4-hydroxyphenyl dimethyl sulfonium hexafluoroantimony Acid salt, 4-acetoxyphenyl dimethyl dimethyl benzoic acid p-toluene sulfonate, 4-acetoxy phenylmethyl benzyl benzoic hexafluoroantimonate, triphenyl acetal p-toluene sulfonate, Triphenylammonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate and diphenyliodonium hexafluoroantimonate; nitrobenzyl tosylates; and benzoin toluene Sulfonate. In addition, the compounds listed as active radical generators above include compounds that simultaneously generate active radicals and acids, and, for example, triazine-based photopolymerization initiators can also be used as acid generators.

The amount of the photopolymerization initiator used in the blue photosensitive resin composition according to the present invention is usually 0.1 to 40 parts by weight relative to the total amount of the alkali-soluble resin and the photopolymerizable compound, that is, 100 parts by weight of total solids. The part by weight is preferably 1 part by weight to 30 parts by weight. When the amount of the photopolymerization initiator is within the above range, the blue photosensitive resin composition is highly sensitive, and therefore the pixel unit formed using the composition can have good strength or good surface smoothness. In addition, in the present invention, a photopolymerization start aid may be used. In some cases, the photopolymerization initiation aid may be used in combination with the photopolymerization initiator, and is a compound for accelerating the polymerization of the polymerizable compound initiated by the photopolymerization initiator. As the photopolymerization start aid, an amine compound, an alkoxyanthracene compound, a thioxanthone compound, or the like can be used.

The amine-based compound may be, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylamine Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl p-toluidine, 4,4' -Bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'- Bis (ethylmethylamino) benzophenone and so on. Among them, 4,4'-bis(diethylamino)benzophenone is preferably used. The alkoxyanthracene-based compound may be, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9 , 10-diethoxyanthracene and so on. The thioxanthone-based compound may be, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro -4-Propoxy thioxanthone, etc. The photopolymerization initiators (D) may be used alone, or a combination of two or more of these compounds may be used. In addition, a commercially available photopolymerization start aid can be used, and for example, "EAB-F"® (manufactured by Hodogaya Kagaku Kogyo Kabushiki Kaisha) and the like.

When such a photopolymerization initiation aid is used, the amount may be generally 10 mol or less relative to 1 mol of the photopolymerization initiator, preferably 0.01 mol to 5 mol. When the amount of the photopolymerization initiation aid is within the above range, the blue photosensitive resin composition can have enhanced sensitivity, and the productivity of the color filter manufactured using the composition can be enhanced.

Solvent

The solvent contained in the blue photosensitive resin composition of the present invention is not particularly limited, and may be any organic solvent used in the field of blue photosensitive resin compositions. Specific examples of solvents may include but are not limited to 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 di Alkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetate, such as methylcellulose Methyl cellosolve acetate and ethylcellosolve acetate; alkyl glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetate, butyl methoxyacetate and pentyl methoxyacetate; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl Isobutyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; esters such as ethyl 3-ethoxypropionate and 3-methyl Methyloxypropionate; and cyclic esters such as γ-butyrolactone. Among the solvents listed above, in terms of coating properties and drying properties, organic solvents having a boiling point of 100°C to 200°C can be used. More preferably, alkanediol alkyl ether acetates, ketones, or esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. These solvents may be used alone or a mixture of two or more of these solvents may be used.

The amount of the solvent in the blue photosensitive resin composition of the present invention is usually 40 parts by weight to 90 parts by weight, preferably 70 parts by weight relative to 100 parts by weight (total) of the blue photosensitive resin composition including the solvent Up to 85 parts by weight. When the amount of the solvent is within the above range, use a coating machine such as a roll coater, a spin coater, a slit spin coater, a slit coater (referred to as a die coater in some cases), inkjet coating Machine isochronous can enhance the coating properties.

additive

The blue photosensitive resin composition of the present invention may further include additives such as fillers, other polymer compounds, pigment dispersants, tackifiers, antioxidants, ultraviolet (UV) absorbers, depolymerizing agents, and the like.

Specific examples of fillers include glass, silica, alumina, and the like. Specific examples of other polymer compounds include thermosetting resins such as epoxy resin, maleimide resin, etc.; and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylic acid Ester, polyester, polyurethane, etc. The pigment dispersant may be a commercially available surfactant, for example, silicon-based surfactant, fluorine-based surfactant, ester-based surfactant, cationic surfactant, anionic surfactant, nonionic surfactant, amphoteric surface Active agents, etc., and these materials may be used alone or a combination of two or more of these materials may be used. Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tris Grade amine modified polyurethane, polyethyleneimine, KP® (manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.), Polyflow® (Kyoeisha Chemical Co., Ltd.) Kyoeisha Kagaku Co., Ltd.), F-top® (Tochem Products), Megapak® (Dainippon Ink Kagaku Kogyo Co., Ltd.), Flourad® ( (Sumitomo 3M Co., Ltd.), Asahi Guard®, Surflon® (Asahi Glass Co., Ltd.), SOLSPERSE® (Zeneca) ), EFKA® (manufactured by EFKACHEMICALS), PB821® (manufactured by Ajinomoto Co., Ltd.), etc. The adhesion promoter may be, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3- Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidol Oxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. The antioxidant may particularly be 2,2′-thiobis(4-methyl-6-tertiary butylphenol), 2,6-ditertiary butyl-4-methylphenol and the like. The ultraviolet absorber may be 2-(3-tertiarybutyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, or the like. The depolymerizing agent may be sodium polyacrylate or the like.

Those skilled in the art can add additives in an appropriate amount within the scope of achieving the effects of the present invention.

The method of preparing the blue photosensitive resin composition can be performed using, for example, the following method, but is not limited thereto.

The scattering particles and the solvent are mixed and dispersed in the bead mill or the like in advance until the average particle diameter of the scattering particles reaches 30 nm to 500 nm. At this time, if necessary, a dispersant may be further used, and the blue colorant and part or all of the alkali-soluble resin may be mixed with it. The remaining portion of the alkali-soluble resin, the photopolymerizable compound, the photopolymerization initiator, other components used as needed, and additional solvents as needed may be further added to the obtained dispersion liquid (hereinafter referred to in some cases as The base material is ground) to a predetermined concentration, thereby obtaining a desired blue photosensitive resin composition. In this regard, the blue colorant can have an average particle diameter of about 0.2 micrometer or less through a bead mill or the like.

<Color filter and image display device>

Another embodiment of the present invention provides a color filter containing self-luminous pixels. The color filter includes a blue pattern layer containing a cured product of the 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 include quantum dots.

Since the above-mentioned blue photosensitive resin composition is used instead of using blue quantum dots to manufacture the color filter according to the present invention, the manufacturing cost can be reduced, and the color filter can have a wide viewing angle. In addition, the blue photosensitive resin composition according to the present invention has excellent thermal fluidity, and therefore, in the color filter and image display device using the same, pattern straightness and reverse taper do not occur during the manufacturing process No image retention during panel operation due to suppression of outgassing, high image quality due to excellent anti-reflection effect, excellent heat resistance, excellent chemical resistance, excellent durability and excellent reliability Sex.

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

The substrate may be the substrate of the color filter itself, or a part of the display device where the color filter is located, but it is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiO _x ), or a polymer substrate, and the polymer substrate may be made of polyether ash (PES), polycarbonate (PC), or the like.

The blue pattern layer is a layer including the blue photosensitive resin composition of the present invention, and may be a layer formed by applying a blue photosensitive resin composition, performing exposure, development and thermal curing in a predetermined pattern, and the pattern The layer can be formed using methods known in the art.

The color filter may further include at least one selected from the group consisting of a red pattern layer and a green pattern layer. For example, the color filter according to the present invention may include a self-luminous pixel including the above-mentioned 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 containing red quantum dots or a green pattern layer containing 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 transmit red light or blue light through a light source emitting blue light (to be described below), respectively.

The scattering particles may include metal oxides having an average particle diameter of 30 nm to 500 nm, and the scattering particles and the metal oxides may be the same as the scattering particles contained in the blue photosensitive resin composition powder according to the present invention above The same as described for metal oxides.

In the present invention, the type, structure, and amount of quantum dots included in the red pattern layer or the green pattern layer are not limited, and the quantum dots may be those commonly used in the art.

The color filter including the substrate and the pattern layer may further include barriers formed between the patterns, and may further include a black matrix, but the present invention is not limited thereto.

Another embodiment of the present invention provides an image display device including the above-mentioned color filter; and a light source configured to emit blue light. For example, the image display device according to the present invention includes a color filter including a blue pattern layer containing the cured product of the above blue photosensitive resin composition and a light source configured to emit blue light.

The color filter of the present invention can be applied to various image display devices, such as ordinary liquid crystal displays, electroluminescent displays, plasma displays, and field emission displays.

When the image display device includes the color filter containing the blue pattern layer and the light source according to the present invention, the image display device has excellent luminous intensity or wide viewing angle. In addition, since the blue pattern layer included in the color filter according to the present invention does not include blue quantum dots, the image display device can be manufactured with low manufacturing cost.

Hereinafter, for specific explanation, the present specification will be described in more detail with reference to the following examples. However, these examples can be modified in many different forms, and the scope of this specification should not be construed as being limited by these examples. The examples of this specification are provided to explain this specification to those skilled in the art more comprehensively. In addition, unless specifically stated otherwise, the terms "%" and "parts" indicating contents in the following description are based on weight.

Synthesis example: Synthesis of alkali-soluble resin

Synthesis Example 1: Alkali-soluble resin

Prepare a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction tube. At the same time, as a monomer dropwise addition batch, add 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, 118.0 g (0.50 mol) of vinyl toluene, and 4 g of tertiary Butyl peroxy-2-ethylhexanoate and 40 grams of propylene glycol monomethyl ether acetate (PGMEA) and mix under stirring; and as a chain transfer agent, add the batch dropwise, add 6 grams of n-dodecanethiol And 24 grams of PGMEA and mix with stirring. Subsequently, 395 grams of PGMEA was introduced into the flask, the air atmosphere in the flask was replaced with a nitrogen atmosphere, and then the flask temperature was raised to 90°C while stirring. After that, the monomer and chain transfer agent began to drop from their respective dropping batches. The dropping process was maintained at a temperature of 90°C for 2 hours, then after 1 hour the temperature was raised to 110°C and held for 3 hours, then the gas introduction tube was introduced into the flask and the oxygen/nitrogen mixed gas was started (=5 /95 (volume/volume)) bubbling. Next, 28.4 g [(0.10 mol) (33 mol% relative to the carboxyl group of acrylic acid used in this reaction)] glycidyl methacrylate, 0.4 g of 2,2′-methylidene bis(4- Methyl-6-tertiary butylphenol) and 0.8 g of trimethylamine were placed in a flask and reacted at 110° C. for 8 hours to obtain resin A with a solid acid value of 70 mg KOH/g. The weight average molecular weight based on polystyrene measurement of resin A measured by GPC was 16,000, and the molecular weight distribution (Mw/Mn) was 2.3.

Synthetic Example 2: Synthesis of carbole-based binder resin (A-1)

(1) 138 g of 9,9-bis(4-glycidyloxyphenyl) stilbene (manufactured by Hear Chem) as a bisphenol epoxy compound, 54 g of 2-carboxyethyl acrylate, and 1.4 g of benzyl trioxide Ethyl ammonium chloride (made by Daejung Chemicals & Metals), 1 g of triphenylphosphine (made by Sigma-Aldrich), 128 g of propylene glycol methyl ethyl ethyl An acid ester (Daicel Chemical Corp.) and 0.5 g of hydroquinone were added to the reactor, the temperature of the reactor was increased to 120°C, and then maintained for 12 hours, thereby synthesizing the compound represented by the following formula 22.

(2) 60 g of the compound represented by formula 22, 11 g of biphenyltetracarboxylic dianhydride (Mitsubishi Gas Chemical Company, Inc.), 3 g of tetrahydrophthalic anhydride (Sigma) (Dridge Company), 20 grams of propylene glycol methyl ethyl acetate (Dacel Chemical Company) and 0.1 grams of N,N'-tetramethylammonium chlorite were placed in the reactor, and the reactor temperature was raised to 120°C And then held for 2 hours to synthesize the compound represented by the following formula 23. The resulting compound represented by Formula 23 had a weight average molecular weight of 5,400 g/mole.

[Form 22]

Synthesis Example 3: Synthesis of Carbodol-based binder resin (A-2)

(1) 138 g of 9,9-bis(4-glycidyloxyphenyl) stilbene (manufactured by Hear Chem) as a bisphenol epoxy compound, 54 g of mono-2-propenyloxyethyl succinate , 1.4 g of benzyltriethylammonium chloride (manufactured by Dazhong Chemicals and Metals Co., Ltd.), 1 g of triphenylphosphine (manufactured by Sigma-Aldrich), 128 g of propylene glycol methyl ethyl acetate (daicel Chemical Co., Ltd.) and 0.5 g of hydroquinone were added to the reactor, the reactor temperature was raised to 120° C., and then maintained for 12 hours, thereby synthesizing the compound represented by Formula 24 below.

(2) 60 g of the compound represented by Formula 24, 11 g of biphenyltetracarboxylic dianhydride (Mitsubishi Gas Chemical Company), 3 g of tetrahydrophthalic anhydride (Sigma Aldrich), and 20 g of propylene glycol methyl alcohol Ethyl ethyl acetate (Dacelu Chemical Co., Ltd.) and 0.1 g of N,N'-tetramethylammonium chlorite were added to the reactor, the reactor temperature was raised to 120°C, and then maintained for 2 hours to synthesize The compound represented by the following formula 25. The obtained compound represented by Formula 25 had a weight average molecular weight of 5,400 g/mol.

Synthesis Example 4: Preparation of Carbodol-based binder resin A-3

10 parts by weight of 2,2'-(4,4"-(9H-fu-9,9-diyl)bis(4,1-phenylene))bis(oxygen)bis(methylidene)bicyclo Oxyethane (2,2'-(4,4"-(9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy)bis(methylene)dioxirane), 30 parts by weight of acrylic acid And 10 parts by weight of propylene glycol monomethyl ether acetate was added to a 1000 ml flask equipped with a stirrer, thermometer and reflux condenser, and then the flask temperature was slowly raised to 100°C while stirring.

Subsequently, 0.3 parts by weight of tetramethylammonium chloride and 0.01 parts by weight of polymerization inhibitor were added to the resulting mixture and stirred while maintaining the temperature for 3 hours. When the reaction was completed, the temperature was slowly cooled to room temperature, and distilled water was added to the flask to cause precipitation. The resulting solution was filtered to obtain only a precipitate, and then the precipitate was washed with distilled water two to three times, and then dried.

Put 10 parts by weight of the resulting precipitate into a 1,000-ml flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction tube, and then add 3 parts by weight of tetramethylammonium chloride and 50 parts by weight of propylene glycol. Methyl ether acetate and 5 parts by weight of phthalic anhydride were added thereto, and then nitrogen substitution was performed.

After that, the reaction solution was stirred and the flask temperature was increased to 110°C, and then the reaction was allowed to proceed for 7 hours. After the reaction, 5 parts by weight of 5,5'-(perfluoropropane-2,2-diyl)dibenzo[de]isobenzopiperan-1,3-dione (5,5'- (perfluoropropane-2,2-diyl)dibenzo[de]isochromene-1,3-dione), further react for 6 hours. After purification, alkali-soluble resin A-3 with a solid acid value of 123 mg KOH/g was obtained, and the weight average molecular weight measured by GPC was 12,300.

Synthesis Example 5: Preparation of Carbodol-based binder resin A-4

10 parts by weight of 2,2'-(4,4"-(9H-fu-9,9-diyl)bis(4,1-phenylene))bis(oxygen)bis(methylidene)bicyclo Ethylene oxide, 30 parts by weight of acrylic acid, and 10 parts by weight of propylene glycol monomethyl ether acetate were added to a 1,000-ml flask equipped with a stirrer, thermometer, and reflux condenser, and then the flask temperature was slowly raised to 100°C while stirring.

Subsequently, 0.3 parts by weight of tetramethylammonium chloride and 0.01 parts by weight of polymerization inhibitor were added to the resulting mixture and stirred while maintaining the temperature for 3 hours. When the reaction was completed, the temperature was slowly cooled to room temperature, and distilled water was added to the flask to cause precipitation. The resulting solution was filtered to obtain only a precipitate, and then the precipitate was washed with distilled water two to three times, and then dried.

Put 10 parts by weight of the resulting precipitate into a 1,000-ml flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction tube, and then add 3 parts by weight of tetramethylammonium chloride and 50 parts by weight of propylene glycol. Methyl ether acetate and 5 parts by weight of phthalic anhydride were added thereto, and then nitrogen substitution was performed.

After that, the reaction solution was stirred and the flask temperature was raised to 110°C, and then the reaction was allowed to proceed for 7 hours. After the reaction, 5 parts by weight of 5,5'-(perfluoropropane-2,2-diyl)bis(hexahydroisobenzofuran-1,3-dione) was added thereto, and the reaction was further carried out for 6 hours. After purification, an alkali-soluble resin A-4 having a solid acid value of 130 mg KOH/g and a weight average molecular weight of 12,000 as measured by GPC was obtained.

Synthesis Example 6: Preparation of Carbodol-based alkali-soluble resin A-5

10 parts by weight of 2,2'-(4,4"-(9H-fu-9,9-diyl)bis(4,1-phenylene))bis(oxygen)bis(methylidene)bicyclo Ethylene oxide, 30 parts by weight of acrylic acid, and 10 parts by weight of propylene glycol monomethyl ether acetate were added to a 1,000-ml flask equipped with a stirrer, thermometer, and reflux condenser, and then the flask temperature was slowly raised to 100°C while stirring.

Subsequently, 0.3 parts by weight of tetramethylammonium chloride and 0.01 parts by weight of a polymerization inhibitor were added to the resulting mixture and stirred while maintaining the temperature for 3 hours. When the reaction was completed, the temperature was slowly cooled to room temperature, and distilled water was added to the flask to cause precipitation. The resulting solution was filtered to obtain only a precipitate, and then the precipitate was washed with distilled water two to three times, and then dried.

Put 10 parts by weight of the resulting precipitate into a 1000-ml flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, and then add 3 parts by weight of tetramethylammonium chloride and 50 parts by weight of propylene glycol mono Methyl ether acetate and 5 parts by weight of phthalic anhydride were added thereto, and then nitrogen substitution was performed.

After that, the reaction solution was stirred and the flask temperature was increased to 110°C, and then the reaction was allowed to proceed for 7 hours. After the reaction, 5 parts by weight of 4,4'-(hexafluoroisopropylidene) diphthalic acid was added thereto, and the reaction was further carried out for 6 hours. After purification, an alkali-soluble resin A-5 having a solid acid value of 120 mgKOH/g and a weight average molecular weight of 12,100 as measured by GPC was obtained.

Synthetic Example 7: Synthesis of carbole-based binder resin (B-1, B-2)

(1) Synthesis Example 7-1: 2,2'-(((((9H-fu-9,9-diyl)bis(4,1-phenylene))bis(oxygen))bis(methylene )) Synthesis of bis(ethylene oxide)

Add 42.5 g of 9,9-bisphenol stilbene and stir with 220 ml of 2-(chloromethyl)ethylene oxide and 100 mg of tertiary butyl ammonium bromide until all the reactants are consumed at 90°C, Then vacuum distillation. The temperature was cooled to 30°C, dichloromethane was added and NaOH was slowly added to the resulting product. High performance liquid chromatography (HPLC) confirmed that the resulting product was 96% or higher, and then 5% HCl was added dropwise to the resulting product to terminate the reaction. The reaction product was extracted, then separated into layers, and then the organic layer was washed with water and washed to neutralize. The organic layer was dried with MgSO ₄ , followed by vacuum distillation and concentration using a rotary evaporator. Dichloromethane was added to the concentrate, and the temperature was raised to 40°C while adding methanol while stirring, and then the temperature of the solution was lowered, followed by stirring. The resulting solid was filtered, and then vacuum dried at room temperature, thereby obtaining 52.7 g of white solid powder (yield: 94%).

(2) Synthesis Example 7-2: 3,3'-(((9H-fu-9,9-diyl)bis(4,1-phenylene))bis(oxygen))bis(1-(benzene Thio)propan-2-ol)(BTCP)

1,000 g of the compound of Synthesis Example 7-1, 524 g of thiophenol and 617 g of ethanol were added and stirred. 328 g of trimethylamine was slowly added dropwise to the reaction solution. After confirming the disappearance of the raw materials by HPLC, the reaction was terminated. After the reaction was completed, ethanol was removed by vacuum distillation. The organic substance was dissolved in dichloromethane, then washed with water, and then dichloromethane was removed by vacuum distillation. The concentrated organic matter was dissolved in ethyl acetate, and then ether solvent was added dropwise thereto, followed by stirring for 30 minutes. The obtained compound was vacuum distilled to obtain 945 g of light yellow oil (yield: 64%).

(3) Synthesis Example 7-3: Synthesis of carbole-based binder resin (B-1)

200 grams 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 was added dropwise thereto at 115°C, and then stirred for 6 hours while maintaining the temperature at 115°C. To the resulting mixture, 7.35 g of phthalic anhydride was added and further stirred for 2 hours, and then the reaction was terminated. After cooling, a binder resin with a weight average molecular weight of 3,500 g/mole was obtained.

(4) Synthesis Example 7-4: Synthesis of carbole-based binder resin (B-2)

200 grams of BTCP monomer dissolved in 50% PGMEA solvent was added and the temperature was raised to 115°C. 21.1 g of pyromellitic dianhydride was added dropwise thereto at 115°C, and then stirred for 6 hours while maintaining the temperature at 115°C. To the resulting mixture, 7.35 g of phthalic anhydride was added and further stirred for 2 hours, and then the reaction was terminated. After cooling, a binder resin with a weight average molecular weight of 4,500 g/mole was obtained.

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

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

Column: TSK-GELG4000HXL+TSK-GELG2000HXL (tandem)

Column temperature: 40℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml/min

Injection volume: 50 μl

Detector: RI

Determination of sample concentration: 0.6% by mass (solvent = tetrahydrofuran)

Standard materials for calibration: TSK standard polystyrene F-40, F-4, F-1, A-2500, A-500 (manufactured by DOSO Co., Ltd.)

The ratio of the obtained weight average molecular weight to the number average molecular weight is defined as the molecular weight distribution (Mw/Mn).

Example 1 to Example 49 and Comparative Example 1 to Comparative Example 5: Preparation of photosensitive resin composition

The photosensitive resin composition according to each Example and each comparative example was prepared according to the composition shown in Table 1 to Table 9 below (Table 1 shows scattering particles, Table 2 shows blue colorant and purple colorant, table 3 to Table 8 show the blue photosensitive resin composition according to each example, and Table 9 shows the components and amounts of the photosensitive resin composition according to each comparative example).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Manufacturing of color filters

A color filter was manufactured using each photosensitive resin composition prepared according to each example and each comparative example. That is, each photosensitive resin composition was applied on a glass substrate by spin coating, the resulting structure was placed on a hot plate, and held at a temperature of 100° C. for 3 minutes to form a thin film.

Subsequently, a test mask having a square transmission pattern of 20 mm (width)×20 mm (length) and a line/space pattern of 1 μm to 100 μm was positioned on the film, and then ultraviolet rays were irradiated 100 μm from the test mask.

At this time, as the ultraviolet light source, an ultra-high pressure mercury lamp (product name: USH-250D) manufactured by Ushio Denki Co., Ltd. was used at 200 mJ/cm2 (mJ/ cm ² ) (365 nanometers) of exposure intensity is irradiated with light, and no specific optical filter is used.

The film irradiated with ultraviolet light was immersed in a KOH aqueous solution (pH 10.5) as a developing solution for 80 seconds to perform development. The glass substrate coated with the thin film was washed with distilled water, dried with a stream of nitrogen, and heated in a heating furnace at 150° C. for 10 minutes, thereby manufacturing a color filter pattern. The manufactured color filter pattern has a film thickness of 5.0 microns.

Experimental Example 1: Testing the development rate, sensitivity and pattern stability of color filters

The development rate, sensitivity, and pattern stability of the color filter manufactured using the photosensitive resin composition of each Example and each comparative example were measured. The evaluation criteria for each test are as follows. The measurement results are shown in Table 7.

Development rate (seconds): the time required for the non-exposed portion to start to dissolve in the developer during development <spray developer HPMJ method>

Sensitivity: the degree to which a thin film (1 to 60) without peeling off the photomask is formed (the lower the number, the better the sensitivity)

Pattern stability: the degree of error of the pattern after the pattern mask is exposed at a low exposure intensity (20 mJ to 100 mJ)

○: No error in the pattern

△: One to two errors in the pattern

×: Three or more errors in the pattern

(○, △, × are the inspection results of the three-dimensional surface profile obtained through the optical microscope)

Experimental Example 2: Determination of solvent resistance and heat resistance of color filters

By measuring the heat resistance and solvent resistance of the color filters manufactured using the photosensitive resin compositions of the Examples and Comparative Examples, it is evaluated whether each color filter is useful for manufacturing color filters or liquid crystals The heat and solvent used in the display device are stable. The measurement results are shown in Table 7.

Solvent resistance evaluation: The manufactured color filter is immersed in 1-methyl-2-pyrrolidone (NMP) solvent, and the color change before and after the evaluation is calculated, and comparative evaluation is performed. At this time, the color change in the three-dimensional colorimeter system defined by L ^* , a ^*, and b ^{* is} calculated by Equation 1 below.

Evaluation of heat resistance: The color filter manufactured using the above method is heated in a heating furnace at 230° C. for 2 hours, and then the color change before and after heating is measured by using Equation 1 below to calculate.

[Equation 1] △Eab ^* =[(△L ^* ) ² +(△a ^* ) ² +(△b ^* ) ² ] ^1/2 ○: △Eab ^* = less than 1, △: △Eab ^* =1 To 3, ×: △Eab ^* = greater than 3

Experimental Example 3: Outgassing test

The outgas measurement of the color filter manufactured using the photosensitive resin composition of each Example and each comparative example was performed by the following method. Each photosensitive resin composition was applied on a glass substrate by spin coating, and then the resulting structure was placed on a hot plate and maintained at a temperature of 100° C. for 3 minutes to form a thin film. Subsequently, a photomask <pattern area: 3 cm×3 cm> was placed on the film, and then ultraviolet light was irradiated from the test mask 100 μm. At this time, a 1 kilowatt (kW) high-pressure mercury lamp containing all of g-line, h-line, and i-line was used as the ultraviolet light source, and light irradiation was performed at a light intensity of 100 mJ/cm 2 without using a specific optical filter. The film irradiated with ultraviolet light was immersed in a KOH aqueous solution (pH 10.5) as a developing solution for 2 minutes to perform development. The glass substrate coated with the thin film was washed with distilled water, dried with a stream of nitrogen, and heated in a heating furnace at 200°C for 30 minutes. The pattern form (film) of the resulting color filter has a thickness of 1 micrometer to 5 micrometers, more preferably about 2 micrometers to about 4 micrometers. The formed thin film substrate was pyrolyzed at 230°C for 30 minutes through Py-GC/FID to analyze the captured compound. The analysis criteria are as follows.

Outgassing measurement value: Set the value of Comparative Example 1 to 100%, and express the outgassing measurement value as a percentage based on the value of Comparative Example 1. The lower the value, the better the effect.

Experimental Example 4: Test micropattern formation

In the color filter manufactured using the photosensitive resin composition according to each example and each comparative example, a line/space pattern with a transmission design of 100 μm was measured using an OM device (ECLIPSE LV100POL manufactured by Nikon Corporation) The size of the pattern obtained by the mask. The measurement results are shown in Table 10 below.

When the difference between the design value of the line/space pattern mask and the measured value of the obtained micropattern is 20 micrometers or more, it is difficult to form a micro pixel, and a negative value indicates a critical value that causes the process to fail.

From the results shown in Table 10, it can be confirmed that compared with the case of each comparative example in which the average particle diameter of the metal oxide scattering particles exceeds the range of 30 nm to 500 nm, the case of each example is satisfactorily formed Micropattern. In addition, it was confirmed that in the case of the comparative example, it is difficult to form a micropattern.

In addition, according to the evaluation results, it was confirmed that when a carbole-based binder is introduced or a combination of a carbole-based binder and an acrylic-based binder is used, excellent sensitivity, pattern stability, and reliability are obtained, and the use of only acrylic-based Compared with the binder resin, the formation of micropatterns is more satisfactory.

Experimental Example 5: Angle measurement

Use an angular photometer (GC-5000L, manufactured by Nippon Denshoku) to measure the light intensity depending on the viewing angle when the light passes through the color filter and is formed into a square pattern of 20 mm × 20 mm. The filter was manufactured using the photosensitive resin composition according to each example and each comparative example, and the diffusivity was calculated using Equation 2 below. The measurement results are shown in Table 11 below.

[Equation 2] Diffusion rate=(I70+I20)/2×I5×100 I represents the luminous intensity measured under the viewing angle.

Experimental Example 6: Reflectance measurement

A spectrophotometer (CM-3600A manufactured by Konica Minolta) was used to measure the light reflectance when the light passed through the color filter formed into a square pattern of 20 mm × 20 mm, in which the color filter The sheet system was manufactured using the photosensitive resin composition according to each example and each comparative example, and the measurement results are shown in Table 11 below.

Experimental Example 7: Luminous intensity measurement

The color filter manufactured using the photosensitive resin composition of each example and each comparative example was formed into a 20 mm × 20 mm square pattern using a 365 nm tube type 4 watt ultraviolet light irradiator (VL-4LC, VILBER LOURMAT) Ultraviolet light was partially irradiated to measure the light-modified area, and for each of the cases of each example and each comparative example, a 450 nm area was measured using a spectrometer (manufactured by Ocean Optics) Luminous intensity. The measurement results are shown in Table 11 below.

Higher measured luminous intensity indicates higher light efficiency. From the results shown in Table 11, it can be confirmed that compared with the cases of Comparative Examples 3 to 5 in which the average particle diameter of the metal oxide scattering particles exceeds the range of 30 nm to 500 nm, Examples 1 to 49 The situation shows increased luminous intensity. In addition, it was confirmed that the cases of Comparative Examples 1 and 2 showed reduced light efficiency. It was confirmed that the cases of Comparative Examples 3 to 5 have lower luminous intensity than the cases of Examples 1 to 49.

The higher the measured diffusion rate, the wider the viewing angle. From the results shown in Table 11, it can be confirmed that the case of each example shows an enhanced viewing angle compared to the case of each comparative example.

The lower the measured reflectance, the better the external light reflection suppression effect, indicating better image quality. From the results shown in Table 11, it can be confirmed that the cases of the examples show excellent reflectance and excellent luminous intensity compared to the cases of the comparative examples.

Claims (13)

A blue photosensitive resin composition, comprising: an alkali-soluble resin; a blue colorant; and scattering particles, including a metal oxide having an average particle diameter of 30 nm to 500 nm, wherein the alkali-soluble resin includes A cardo-based binder resin of at least one of the repeating units represented by Formula 1 to Formula 3, and at least one selected from the group consisting of repeating units represented by Formula 10 and Formula 11 below Carbole-based binder resin:

However, in Formula 1 and Formula 2, X and X'are each independently a single bond, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-,

,

,

,

,

Y is an acid anhydride residue, Z is an acid dianhydride residue, R'is a hydrogen atom, ethyl, phenyl, -C ₂ H ₄ Cl, -C ₂ H ₄ OH, or -CH ₂ CH=CH ₂ , R1 , R1', R2, R2', R3, R3', R4, R4', R5, R5', R6, and R6' are each independently a hydrogen atom or a methyl group, R7, R7', R8, and R8' are independently It is a linear or branched C ₁ to C ₆ alkylene group, wherein the alkyl group is sealed with at least one of an ester bond, C ₆ to C ₁₄ cycloalkyl group, and C ₆ to C ₁₄ aryl group Terminal, R9, R9', R10, R10', R11, R11', R12, and R12' are each independently a hydrogen atom, a halogen atom, or a linear or branched C ₁ to C ₅ alkyl group, m and n are each independent It is an integer of 0 to 30, but m and n are not 0 at the same time. Among them, in Formula 3, R13 is the same as X and X'in Formula 1 and Formula 2, R14 is a methacrylate group, vinyl group Or acrylate group, R15 is a reactive residue derived from the monomer represented by the following formula 4, r is an integer of 1 to 20,

However, in Formula 4, R16 and R17 are the same as or different from each other and are independently

However, in Formula 10 and Formula 11, P is independently

,

,

R19 and R20 are each independently hydrogen, hydroxyl, thiol, amine, nitro, or halogen atom, Ar1 is a C ₆ to C ₁₅ aryl group, Y'is an acid anhydride residue, Z'is an acid dianhydride residue, A is oxygen (O), sulfur (S), nitrogen (N), silicon (Si), or selenium (Se), a and b are each independently an integer of 1 to 6, and p and q are each independently 0 to 30 Integer, but p and q are not 0 at the same time. The blue photosensitive resin composition according to claim 1, wherein the repeating unit represented by Formula 3 is represented by at least one of the following Formula 5 to Formula 9: [Formula 5]

[Form 9]

However, in Formula 5 to Formula 9, R13, R14 and r are the same as in Formula 3. The blue photosensitive resin composition according to claim 1, wherein the metal oxide includes an oxide selected from oxides of the following metals: lithium (Li), beryllium (Be), boron (B), sodium ( Na), magnesium (Mg), aluminum (Al), silicon (Si), potassium (K), calcium (Ca), scandium (Sc), vanadium (V), chromium (Cr), manganese (Mn), iron ( Fe), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), rubidium (Rb), strontium (Sr), yttrium (Y), molybdenum (Mo), cesium ( Cs), barium (Ba), lanthanum (La), hafnium (Hf), tungsten (W), thallium (Tl), lead (Pb), cerium (Ce), palladium (Pr), neodymium (Nd), yttrium (Cd) Pm), Samarium (Sm), Europium (Eu), Ethium (Gd), Ytterbium (Tb), Dysprosium (Dy), Y (Ho), Erbium (Er), Sham (Tm), Ytterbium (Yb), Titanium ( Ti), antimony (Sb), tin (Sn), zirconium (Zr), niobium (Nb), tantalum (Ta), indium (In), and combinations thereof. The blue photosensitive resin composition according to claim 3, wherein the metal oxide contains one selected from the following: 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 combinations thereof. The blue photosensitive resin composition according to claim 1, wherein the alkali-soluble resin further contains an acrylic binder resin. The blue photosensitive resin composition according to claim 1, wherein the content of the scattering particles is from 0.1 part by weight to 50 parts by weight with respect to 100 parts by weight (total) of the blue photosensitive resin composition. The blue photosensitive resin composition according to claim 1, wherein the content of the carbole-based binder resin is 1 part by weight to 50 parts by weight relative to 100 parts by weight (total) of the blue photosensitive resin composition Copies. The blue photosensitive resin composition according to claim 1, wherein the blue colorant contains a blue pigment selected from the group consisting of: CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15: 6, CI Pigment Blue 16, CI Pigment Blue 21, CI Pigment Blue 28, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Blue 76, and combinations thereof. The blue photosensitive resin composition according to claim 8, wherein the blue colorant further comprises at least one selected from the group consisting of dyes and purple pigments. The blue photosensitive resin composition according to claim 1, wherein the content of the blue colorant is 0.1 parts by weight to 50 parts by weight relative to 100 parts by weight (total) of the blue photosensitive resin composition . The blue photosensitive resin composition according to claim 1, further comprising at least one selected from the group consisting of: a photopolymerizable compound; a photopolymerization initiator; a solvent; and an additive. A self-luminous pixel-containing color filter comprising: a blue pattern layer containing the cured product of the blue photosensitive resin composition according to any one of claims 1 to 11. An image display device comprising: the color filter according to claim 12.; and a light source for emitting blue light.