JP2017161886A - Blue photosensitive resin composition, and blue color filter and display device comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a blue photosensitive resin composition, and a blue color filter and a display device comprising the same.SOLUTION: This invention relates to a blue photosensitive resin composition with excellent adhesion, comprising a blue colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent; and a blue color filter and a display device comprising the same.SELECTED DRAWING: None

Description

The present invention relates to a blue photosensitive resin composition, a blue color filter including the same, and a display device, and more specifically, includes a blue colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The present invention relates to a blue photosensitive resin composition having excellent adhesion, a blue color filter including the same, and a display device.

Electronic display devices used in office automation devices, portable small TVs, video camera viewfinders, etc. include liquid crystal display devices (LCDs), plasma display panels (PDPs), and organic light emitting diodes (PDPs). There is an organic light emitting diode (OLED) and the like, and technical research related to these is being actively promoted.

The liquid crystal display device has advantages such as weight reduction, thinning, low price, low power consumption driving, and excellent integrated circuit connectivity, and has a range of use for notebook computers, monitors, and television images. It has spread. Such a liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and an ITO pixel electrode are formed, an active circuit portion including a liquid crystal layer, a thin film transistor, and a storage capacitor layer, and an upper portion on which the ITO pixel electrode is formed. And a substrate.

The color filter is manufactured by coating a fine area colored with three or more colors on a solid imaging element or a transparent substrate. Such a colored thin film is usually formed by a dyeing method, an electrodeposition method, a pigment dispersion method, or the like, but recently, a pigment dispersion method having excellent heat resistance and durability is used.

In the pigment dispersion method, coloring is performed by repeating a series of processes of coating, exposing, developing, and thermally curing a photopolymerizable composition containing a colorant on a transparent substrate provided with a light shielding layer (black matrix). This is a method of forming a thin film. The pigment dispersion method can improve heat resistance and durability, which are the most important properties of the color filter, and has an advantage that the thickness of the film can be kept uniform.

The colored photosensitive resin composition used for the production of a color filter by the pigment dispersion method is generally composed of a binder resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives. Become.

In recent years, high color reproduction of a color filter is required, and as a result, the content of the colorant in the colored photosensitive resin composition used in the production of the color filter is continuously increased. Further, in order to produce a high-quality color filter with excellent visibility, there is a continuous demand for improvement in contrast ratio.

However, in the conventional pigment dispersion system, the content of the pigment in the colored photosensitive resin composition has reached its limit, and the improvement of the contrast ratio due to the atomization of the pigment has reached the limit. As a result, a method of simultaneously using a pigment and a dye as a colorant has been studied so far. However, when a color filter is produced using a colored photosensitive resin composition containing a dye, the sensitivity is insufficient, and alkali development is performed. There is a problem that the pattern formed during the developing process with the liquid is peeled off. In addition, when a color filter is produced with a colored photosensitive resin composition containing a dye, there is a problem that the compatibility of the dye is insufficient in the hard baking process, and the dye is deposited on the surface and the contrast ratio is lowered.

An object of this invention is to provide the blue photosensitive resin composition excellent in adhesiveness, without the fall of the sensitivity by dye, using a dye in the minimum amount.

Another object of the present invention is to provide a blue photosensitive resin composition that can exhibit high transmission and a high contrast ratio.

Furthermore, an object of this invention is to provide the blue color filter and display apparatus which were manufactured using the said blue photosensitive resin composition.

To achieve the above objective,
The present invention is a blue photosensitive resin composition comprising a blue colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The blue colorant includes a dye of Formula 1 below:
The photopolymerization initiator includes a compound represented by Formula 2 below, and provides a blue photosensitive resin composition.

R _{1 to} R ₆ are the same as or different from each other, and are hydrogen, an aryl group having 6 to 12 carbon atoms, which may or may not contain a substituent, or an alkyl group having 1 to 20 carbon atoms,
The alkyl group having 1 to 20 carbon atoms may contain oxygen between methylene groups,
The hydrogen of the alkyl group having 1 to 20 carbon atoms may be substituted with a halogen atom or an amino group,
R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may be bonded to each other to form a ring,
R _{7 to} R ₁₄ are the same or different and are each a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms,
The alkyl group having 1 to 8 carbon atoms may contain oxygen between methylene groups,
Wherein _{R 15} is hydrogen, an alkyl group or with or without substituent aryl group having 6 to 12 carbon atoms, having 1 to 20 carbon atoms,
X is an oxygen, sulfur, or amine group;
Y is a counter anion;
The m is the oxidation number of Y.

A and b are 0 or 1,
When a is 1, b is 1,
When a is 0, b is 0 or 1,
(1) When a = 0 and b = 0,
R ₁₆ is hydrogen, a halogen atom, a nitro group, a sulfonyloxy group containing a C1-C8 alkyl group that is substituted or not substituted with a halogen atom, a phenylsulfonyloxy group that contains or does not contain a substituent, A sulfonyl group containing an alkyl group having 1 to 8 carbon atoms, which is substituted or unsubstituted by a halogen atom, a heterocyclic sulfonyl group having 7 to 20 carbon atoms, which contains or does not contain a substituent, or contains a substituent A condensed cyclic sulfonyl group having 7 to 20 carbon atoms,
(2) When a = 0 and b = 1,
R ₁₆ is a phenyl group containing or not containing a substituent, a heterocyclic group having 7 to 20 carbon atoms containing or not containing a substituent, or a condensed ring group having 7 to 20 carbon atoms containing or not containing a substituent. Yes,
(3) When a = 1 and b = 1,
R ₁₆ is a sulfonyloxy group containing an alkyl group having 1 to 8 carbon atoms which is substituted or unsubstituted with a halogen atom, or a phenylsulfonyloxy group which contains or does not contain a substituent,
R ₁₇ and R ₁₈ are the same or different and each represents hydrogen, an alkyl group having 1 to 22 carbon atoms, an alkyl group having 1 to 10 carbon atoms including a halogen atom, or a terminal having an ether group or a thioether group having 1 to 1 carbon atoms. 15 alkyl groups, phenyl groups with or without substituents, or phenylalkyl groups having 7 to 11 carbon atoms,
R ₁₇ and R ₁₈ may form a ring,
R ₁₉ is the following Chemical Formula 3 or Chemical Formula 4,

R ₂₀ and R ₂₂ are the same or different and are each an alkyl group having 1 to 17 carbon atoms, an alkyl group having 2 to 5 carbon atoms including a halogen atom, and an end having an ether group or a thioether group having 2 to 7 carbon atoms. Alkyl group, phenyl group with or without substituent, phenylalkyl group with 7 to 11 carbon atoms with or without substituent, phenyloxyalkyl group with 7 to 10 carbon atoms with or without substituent, substituent A heterocyclic group having 7 to 20 carbon atoms or not containing or a condensed ring group having 7 to 20 carbon atoms containing or not containing a substituent,
R ₂₁ includes an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 7 carbon atoms including a halogen atom, an alkyl group having 2 to 7 carbon atoms having an ether group or a thioether end, and a substituent. No C2-C4 aminoalkyl group, phenyl group with or without substituent, phenylalkyl group with C7-11 with or without substituent, terminal is ether group or thioether group, and substituent is A phenylalkyl group having 7 to 10 carbon atoms, including or not containing, a condensed ring group having 7 to 20 carbon atoms including or not including a substituent, or a heterocyclic group having 7 to 20 carbon atoms including or not including a substituent. ,
R ₂₃ is an alkyl group having 1 to 16 carbon atoms, an alkyl group having 1 to 6 carbon atoms including a halogen atom, a phenyl group including or not including a substituent, and a 7 to 10 carbon atom including or not including a substituent. A phenylalkyl group, a phenylalkyl group having 7 to 9 carbon atoms which is an ether group or a thioether group at the end and which may or may not contain a substituent, a condensed ring group having 7 to 20 carbon atoms which may or may not contain a substituent, or a substituent It is a C7-C20 heterocyclic group containing or not containing.

Moreover, this invention provides the blue color filter manufactured with the said blue photosensitive resin composition.

Furthermore, the present invention provides a display device including the blue color filter.

The blue photosensitive resin composition of this invention is excellent in adhesiveness with a board | substrate, and there exists an effect which does not generate | occur | produce the problem that a pattern peels at a image development process.

In addition, the blue photosensitive resin composition of the present invention can exhibit characteristics of high transmission and high contrast ratio while using a minimum amount of dye.

Furthermore, the color filter and display device manufactured with the blue photosensitive resin composition of the present invention have an excellent effect on color reproduction.

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

The present invention is a blue photosensitive resin composition comprising a blue colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The blue colorant includes a dye of Formula 1 below:
The photopolymerization initiator relates to a blue photosensitive resin composition comprising a compound represented by the following chemical formula 2:

R _{1 to} R ₆ are the same as or different from each other, and are hydrogen, an aryl group having 6 to 12 carbon atoms, which may or may not contain a substituent, or an alkyl group having 1 to 20 carbon atoms,
The alkyl group having 1 to 20 carbon atoms may contain oxygen between methylene groups,
The hydrogen of the alkyl group having 1 to 20 carbon atoms may be substituted with a halogen atom or an amino group,
R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may be bonded to each other to form a ring,
R _{7 to} R ₁₄ are the same or different and are each a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms,
The alkyl group having 1 to 8 carbon atoms may contain oxygen between methylene groups,
R ₁₅ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms which may or may not contain a substituent;
X is an oxygen, sulfur, or amine group;
Y is a counter anion;
The m is the oxidation number of Y.

A and b are 0 or 1,
When a is 1, b is 1,
When a is 0, b is 0 or 1,
(1) When a = 0 and b = 0,
R ₁₆ is hydrogen, a halogen atom, a nitro group, a sulfonyloxy group containing a C1-C8 alkyl group that is substituted or not substituted with a halogen atom, a phenylsulfonyloxy group that contains or does not contain a substituent, A sulfonyl group containing an alkyl group having 1 to 8 carbon atoms, which is substituted or unsubstituted by a halogen atom, a heterocyclic sulfonyl group having 7 to 20 carbon atoms, which contains or does not contain a substituent, or contains a substituent A condensed cyclic sulfonyl group having 7 to 20 carbon atoms,
(2) When a = 0 and b = 1,
R ₁₆ is a phenyl group containing or not containing a substituent, a heterocyclic group having 7 to 20 carbon atoms containing or not containing a substituent, or a condensed ring group having 7 to 20 carbon atoms containing or not containing a substituent. Yes,
(3) When a = 1 and b = 1,
R ₁₆ is a sulfonyloxy group containing an alkyl group having 1 to 8 carbon atoms which is substituted or unsubstituted with a halogen atom, or a phenylsulfonyloxy group which contains or does not contain a substituent,
R ₁₇ and R ₁₈ are the same or different and each represents hydrogen, an alkyl group having 1 to 22 carbon atoms, an alkyl group having 1 to 10 carbon atoms including a halogen atom, or a terminal having an ether group or a thioether group having 1 to 1 carbon atoms. 15 alkyl groups, phenyl groups with or without substituents, or phenylalkyl groups having 7 to 11 carbon atoms,
R ₁₇ and R ₁₈ may form a ring,
R ₁₉ is the following Chemical Formula 3 or Chemical Formula 4,

R ₂₀ and R ₂₂ are the same or different and are each an alkyl group having 1 to 17 carbon atoms, an alkyl group having 2 to 5 carbon atoms including a halogen atom, and an end having an ether group or a thioether group having 2 to 7 carbon atoms. Alkyl group, phenyl group with or without substituent, phenylalkyl group with 7 to 11 carbon atoms with or without substituent, phenyloxyalkyl group with 7 to 10 carbon atoms with or without substituent, substituent A heterocyclic group having 7 to 20 carbon atoms or not containing or a condensed ring group having 7 to 20 carbon atoms containing or not containing a substituent,
R ₂₁ includes an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 7 carbon atoms including a halogen atom, an alkyl group having 2 to 7 carbon atoms having an ether group or a thioether end, and a substituent. No C2-C4 aminoalkyl group, phenyl group with or without substituent, phenylalkyl group with C7-11 with or without substituent, terminal is ether group or thioether group, and substituent is A phenylalkyl group having 7 to 10 carbon atoms, including or not containing, a condensed ring group having 7 to 20 carbon atoms including or not including a substituent, or a heterocyclic group having 7 to 20 carbon atoms including or not including a substituent. ,
R ₂₃ is an alkyl group having 1 to 16 carbon atoms, an alkyl group having 1 to 6 carbon atoms including a halogen atom, a phenyl group including or not including a substituent, and a 7 to 10 carbon atom including or not including a substituent. A phenylalkyl group, a phenylalkyl group having 7 to 9 carbon atoms which is an ether group or a thioether group at the end and which may or may not contain a substituent, a condensed ring group having 7 to 20 carbon atoms which may or may not contain a substituent, or a substituent It is a C7-C20 heterocyclic group containing or not containing.

In the present invention, a blue photosensitive resin composition having excellent adhesion to a substrate and excellent developability is provided by including the dye of Chemical Formula 1 as a colorant and the compound of Chemical Formula 2 as a photopolymerization initiator. Tried.

Hereinafter, the blue photosensitive resin composition of the present invention will be described in detail for each component.

(A) Blue colorant The blue colorant which is one component of the blue photosensitive resin composition of the present invention contains a dye represented by the following chemical formula 1, and may further contain a blue pigment.

(A1) Blue dye The blue colorant contains a blue dye of the following chemical formula 1.

R _{1 to} R ₆ are the same as or different from each other, and are hydrogen, an aryl group having 6 to 12 carbon atoms, which may or may not contain a substituent, or an alkyl group having 1 to 20 carbon atoms,
The alkyl group having 1 to 20 carbon atoms may contain oxygen between methylene groups,
The hydrogen of the alkyl group having 1 to 20 carbon atoms may be substituted with a halogen atom or an amino group,
R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may be bonded to each other to form a ring,
R _{7 to} R ₁₄ are the same or different and are each a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms,
The alkyl group having 1 to 8 carbon atoms may contain oxygen between methylene groups,
R ₁₅ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms which may or may not contain a substituent;
X is an oxygen, sulfur, or amine group;
Y is a counter anion;
The m is the oxidation number of Y.

Said Y is preferably an anion comprising one or more selected from the group consisting of boron, aluminum, sulfur, fluorine, tungsten, molybdenum, silicon, and phosphorus, and these anions are additionally oxygen Can be included.

[Y] ^{m− in} Formula 1 is preferably an anion of a heteropolyacid containing tungsten, an anion of an isopolyacid containing tungsten, an anion of phosphotungstic acid, an anion of silicon tungstate, and isopolytungsten. It may be one selected from the group consisting of acid anions.

More specifically, [Y] ^{m− in the} chemical formula 1 is, for example, α- [PW ₁₂ O ₄₀ ] ³⁻ as a kegging type tungstophosphoric acid ion or Dawson type tungstophosphoric acid ion. α- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ and β- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , α- [SiW ₁₂ O ₄₀ ] ⁴⁻ , β- [SiW ₁₂ O ₄₀ as Keggin-type tungstosilicate ions _{^{] 4-, γ- [SiW 12 O}} 40] 4- , and the like, ^{_{other, [P 2 W 17 O 61}} ] 10-, [P 2 W 15 O 56] 12-, [H 2 P 2 W 12 _{^{O 48] 12-, [NaP 5}} W 30 O 110] 14-, α- [SiW 9 O 34] 10-, γ- [SiW 10 O 36] 8-, α- [SiW 11 O 39] 8-, β- [SiW ₁₁ O ₃₉ ] ⁸⁻ , [W ₆ O ₁₉ ] ²⁻ , [W ₁₀ O ₃₂ ] ⁴⁻ , and WO ₄ ²⁻ are included.

Furthermore, m is preferably a natural number of 1 to 15.

The blue colorant is additionally selected from acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acidic dyes and nitrogen-containing compounds, sulfonamides of acidic dyes, and derivatives thereof. In addition, azo, xanthene, and phthalocyanine acid dyes and their derivatives may be selected, and among them, azo acid dyes and their derivatives are selected. And preferably used. Preferably, the blue dye may be a compound classified as a dye in a color index (published by The Society of Dyers and Colorists), or a known dye described in a dye note (color dye company). .

Specific examples of the additionally usable dye include, for example,
C. I. As solvent dye,
C. I. Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67, and 70; and C.I. I. Solvent violet 8, 9, 13, 14, 36, 37, 47, 49, etc. are mentioned.

Especially, C.I. I. Solvent Blue 35, 36, 44, 45, and 70; and C.I. I. It is preferable that 1 or more types selected from the group which consists of solvent violet 13 are included.

In addition, C.I. I. As an acid dye,
C. I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, and 340; and C.I. I. Acid Violet 6B, 7, 9, 17, 19, and 66 are included.

Especially, C.I. I. Acid Blue 80 and 90; and C.I. I. It is preferable to include one or more selected from the group consisting of Acid Violet 66.

Furthermore, C.I. I. As a direct dye
C. I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190,192,193,194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, and 293 And C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, and the like.

In addition, C.I. I. As a modern dye,
C. I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 44, 48, 49, 53, 61, 74, 77, 83, and 84;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 and the like.

The blue dyes can be used alone or in combination of two or more.

The blue dye is contained in an amount of 0.5 to 80% by weight, preferably 0.5 to 60% by weight, and more preferably 1 to 50% by weight based on the total weight of the blue colorant. When the blue colorant content in the blue colorant is 0.5 to 80% by weight, it is possible to prevent the problem of lowering the reliability of the dye eluting with an organic solvent after pattern formation, and the sensitivity is high. Become.

(A2) Blue pigment As the blue pigment, an organic pigment or an inorganic pigment generally used in this field can be used. The blue pigment is optionally treated with a resin, a surface treatment using a pigment derivative having an acidic group or a basic group introduced, a pigment surface graft treatment with a polymer compound, a sulfuric acid atomization method, etc. A pulverization treatment by an organic solvent, a cleaning treatment with an organic solvent or water for removing impurities, or an ionic impurity removal treatment by an ion exchange method or the like may be performed.

As the organic pigment, various pigments used in printing inks, inkjet inks and the like can be used. Specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolone pigments, Examples thereof include indoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthronetron pigments, indanthrone pigments, flavantron pigments, pyranthrone pigments, diketopyrrolopyrrole pigments.

Further, as the inorganic pigment, metal compounds such as metal oxides and metal complex salts can be used. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, Examples thereof include antimony, carbon black, organic black pigments, titanium black, and metal oxides or composite metal oxides such as pigments that are mixed with red, green, and blue to exhibit black.

In particular, examples of the organic pigment and the inorganic pigment include compounds classified as pigments in the color index (published by The Society of Dyers and Colorists), and more specifically, the following color index ( CI)) pigments are mentioned, but not necessarily limited thereto.

Specifically, the blue pigment is, for example,
C. I. Pigment violet 1, 14, 19, 23, 29, 32, 33, 36, 37, and 38; and C.I. I. Pigment blue 15: 3, 15: 4, 15: 6, 21, 28, 60, 64, and 76.

Especially, C.I. I. Pigment violet 23, C.I. I. It is preferable that 1 or more types selected from the group which consists of pigment blue 15: 3 and pigment blue 15: 6 are included.

When the pigment is additionally used with the dye of Formula 1, it is contained in an amount of 20 to 90% by weight, preferably 30 to 70% by weight, based on the total weight of the blue colorant. When the pigment is contained in an amount of 20 to 90% by weight, the viscosity is low, the storage stability is excellent, the dispersion efficiency is increased, and the contrast ratio can be increased.

The pigment is preferably a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the pigment particle size include a method of dispersing by adding a pigment dispersant (a3). The pigment is uniformly dispersed in a solution by the above method. A pigment dispersion can be obtained.

(A3) Pigment dispersant The pigment dispersant is added to disaggregate and maintain the stability of the pigment. Specific examples of the pigment dispersant include cationic, anionic, nonionic, and amphoteric. These include surfactants such as polyesters, polyesters, and polyamines, and these can be used alone or in combination of two or more.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, or quaternary ammonium salts.

Specific examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and the like. And alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan Examples include fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Other examples include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines.

The pigment dispersant preferably contains an acrylate dispersant (hereinafter referred to as an acrylate dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Examples of commercially available acrylate dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150. The acrylate dispersants may be used alone or in combination of two or more. Can be used as a mixture.

In addition to the acrylate-based dispersant, other resin-type pigment dispersants may be used as the pigment dispersant. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, in particular, polycarboxylic acid esters represented by polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, and polycarboxylic acid (partial). ) Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids and their modified products, or free ( free) Oily dispersants such as amides or salts thereof formed by the reaction of polyesters with carboxyl groups and poly (lower alkyleneimines); (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- ( (Meth) acrylate ester copolymer, styrene-ma Ynoic acid copolymers, polyvinyl alcohol or water-soluble resin or a water-soluble polymeric compounds such as polyvinyl pyrrolidone; polyesters; modified polyacrylate; addition products of ethylene oxide / propylene oxide; and the like and phosphate esters.

As a commercial product of the pigment dispersant of the other resin type, as the cationic resin dispersant, for example, trade names of BYK (Big) Chemie: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162 , DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF Corporation trade names: EFKA-44, EFKA-46, EFKA-47, EFKA -48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406 EFKA-4510, EFKA-4800; trade names of Lubilzol: SOLPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; trade names of Kawaken Fine Chemicals: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto brand names: AJISPUR PB-821, Ajisper PB-822, Azisper PB-823; Kyoeisha Chemical brand names: FLORENE DOPA-17HF, FLOREN DOPA-15BHF, FLOREN DOPA -33, florene DOPA-44 and the like.

In addition to the acrylate-based dispersant, other resin-type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylate-based dispersant.

The pigment dispersant is contained in an amount of 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content in the pigment. If the content of the pigment dispersant exceeds 60 parts by weight, the viscosity increases, and if it is less than 5 parts by weight, it may be difficult to atomize the pigment or cause problems such as gelation after dispersion.

Moreover, content of the said blue coloring agent is 5-60 weight% with respect to solid content total weight in a blue photosensitive resin composition, Preferably it contains 10-45 weight%. When the blue colorant is contained in the amount of 5 to 60% by weight, the color density of the pixel is sufficient when a thin film is formed, the omission of non-pixel portions is not lowered during development, and a residue is hardly generated. .

In the present invention, the solid content weight in the blue photosensitive resin composition means the total weight of the remaining components excluding the solvent of the blue photosensitive resin composition.

(B) Alkali-soluble resin The alkali-soluble resin which is one component of the blue photosensitive resin composition of the present invention is produced by copolymerizing an ethylenically unsaturated monomer (b1) containing a carboxyl group as an essential component.

Specific examples of the ethylenically unsaturated monomer (b1) containing a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; Anhydrides of dicarboxylic acids; mono (meth) acrylates of polymers containing a carboxyl group and a hydroxyl group at both ends such as ω-carboxypolycaprolactone mono (meth) acrylate; and the like, and acrylic acid and methacrylic acid are preferred.

In addition, a hydroxyl group can be added to the alkali-soluble resin in order to ensure additional developability.

The method for imparting the hydroxyl group includes (1) a method of copolymerizing and producing an ethylenically unsaturated monomer containing a carboxyl group and an ethylenically unsaturated monomer containing a hydroxyl group, and (2) carboxyl. A method of additionally reacting a copolymer of a glycidyl group with a copolymer of an ethylenically unsaturated monomer containing a group, and (3) an ethylenically unsaturated monomer containing a carboxyl group and a hydroxyl group. Examples thereof include a method in which a copolymer containing an ethylenically unsaturated monomer is additionally reacted with a compound containing a glycidyl group.

Specific examples of the ethylenically unsaturated monomer containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3- There are phenoxypropyl (meth) acrylate and N-hydroxyethyl acrylamide, among which 2-hydroxyethyl (meth) acrylate is preferable, and the ethylenically unsaturated monomer containing the hydroxyl group is a combination of two or more. Can be used.

Specific examples of the compound containing a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl. Ether, benzyl glycidyl ether, glycidyl 4-t-butylbenzoate, glycidyl stearate, aryl glycidyl ether, and glycidyl methacrylate, preferably butyl glycidyl ether, aryl glycidyl ether, and glycidyl methacrylate are The compound containing a glycidyl group can be used in combination of two or more.

Further, during the production of the alkali-soluble resin, the unsaturated monomer copolymerizable with the ethylenically unsaturated monomer containing a carboxyl group may be an aromatic vinyl compound, an N-substituted maleimide compound, an alicyclic (meta ) Acrylates, hydroxyethyl (meth) acrylates, aryl (meth) acrylates, and unsaturated oxetane compounds, but are not limited thereto.

Specific examples of the aromatic vinyl compound include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, and o-vinylbenzyl methyl ether. M-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like.

Specific examples of the N-substituted maleimide compound include N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, and Np. -Hydroxyphenylmaleimide, N-o-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np- And methoxyphenylmaleimide.

Specifically, the alicyclic (meth) acrylates include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl ( Alkyl (meth) acrylates such as (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Methyl cyclohexyl (meth) acrylate, tricyclo [5.2.1.0.2.6] decan-8-yl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and the like. Can be mentioned.

Specifically, the hydroxyethyl (meth) acrylates are, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3- Examples include phenoxypropyl (meth) acrylate and N-hydroxyethyl acrylamide.

Specific examples of the aryl (meth) acrylates include phenyl (meth) acrylate and benzyl (meth) acrylate.

Specific examples of the unsaturated oxetane compound include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, and 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane. , 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like.

The unsaturated monomers can be used alone or in admixture of two or more.

The alkali-soluble resin preferably has an acid value of 30 to 150 mgKOH / g in order to ensure compatibility with the dye and storage stability of the blue photosensitive resin composition.

When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, the developing speed of the blue photosensitive resin composition is slow, and when it exceeds 150 mgKOH / g, the adhesion to the substrate is reduced and pattern short circuit is likely to occur. Problems with compatibility with the dye may occur, and the dye in the blue photosensitive resin composition may precipitate, storage stability may decrease, and viscosity may increase.

The alkali-soluble resin is contained in an amount of 10 to 80% by weight, preferably 10 to 70% by weight, based on the total weight of the blue photosensitive resin composition.

If the content of the alkali-soluble resin is from 10 to 80% by weight, the solubility in the developer is sufficient and the pattern can be easily formed. Good part omission.

(C) Photopolymerizable compound The photopolymerizable compound that is one of the blue photosensitive resin compositions of the present invention must be a compound that can be polymerized by the action of the photopolymerization initiator (D) described later.

As the photopolymerizable compound, a monofunctional monomer, a bifunctional monomer, or a polyfunctional monomer can be used, and a bifunctional monomer is preferably used, but is not limited thereto. It is not a thing.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl pyrrolidone. However, it is not limited to these.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Examples include, but are not limited to, bis (acryloyloxyethyl) ether of bisphenol A or 3-methylpentanediol di (meth) acrylate.

Specific examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth). Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, or dipentaerythritol hexa (meth) Examples include, but are not limited to, acrylates.

The photopolymerizable compound is contained in an amount of 5 to 50% by weight, preferably 7 to 50% by weight, based on the total weight of the blue photosensitive resin composition of the present invention. The photopolymerizable compound can improve the strength and reliability of the pixel portion in the range of 5 to 50% by weight.

(D) Photoinitiator The photoinitiator which is one of the blue photosensitive resin compositions of this invention contains the compound of following Chemical formula 2.

A and b are 0 or 1,
When a is 1, b is 1,
When a is 0, b is 0 or 1,
(1) When a = 0 and b = 0,
R ₁₆ is hydrogen, a halogen atom, a nitro group, a sulfonyloxy group containing a C1-C8 alkyl group that is substituted or not substituted with a halogen atom, a phenylsulfonyloxy group that contains or does not contain a substituent, A sulfonyl group containing an alkyl group having 1 to 8 carbon atoms, which is substituted or unsubstituted by a halogen atom, a heterocyclic sulfonyl group having 7 to 20 carbon atoms, which contains or does not contain a substituent, or contains a substituent A condensed cyclic sulfonyl group having 7 to 20 carbon atoms,
(2) When a = 0 and b = 1,
R ₁₆ is a phenyl group containing or not containing a substituent, a heterocyclic group having 7 to 20 carbon atoms containing or not containing a substituent, or a condensed ring group having 7 to 20 carbon atoms containing or not containing a substituent. Yes,
(3) When a = 1 and b = 1,
R ₁₆ is a sulfonyloxy group containing an alkyl group having 1 to 8 carbon atoms which is substituted or unsubstituted with a halogen atom, or a phenylsulfonyloxy group which contains or does not contain a substituent,
R ₁₇ and R ₁₈ are the same or different and each represents hydrogen, an alkyl group having 1 to 22 carbon atoms, an alkyl group having 1 to 10 carbon atoms including a halogen atom, or a terminal having an ether group or a thioether group having 1 to 1 carbon atoms. 15 alkyl groups, phenyl groups with or without substituents, or phenylalkyl groups having 7 to 11 carbon atoms,
R ₁₇ and R ₁₈ may form a ring,
R ₁₉ is the following Chemical Formula 3 or Chemical Formula 4,

R ₂₀ and R ₂₂ are the same or different and are each an alkyl group having 1 to 17 carbon atoms, an alkyl group having 2 to 5 carbon atoms including a halogen atom, and an end having an ether group or a thioether group having 2 to 7 carbon atoms. Alkyl group, phenyl group with or without substituent, phenylalkyl group with 7 to 11 carbon atoms with or without substituent, phenyloxyalkyl group with 7 to 10 carbon atoms with or without substituent, substituent A heterocyclic group having 7 to 20 carbon atoms or not containing or a condensed ring group having 7 to 20 carbon atoms containing or not containing a substituent,
R ₂₁ includes an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 7 carbon atoms including a halogen atom, an alkyl group having 2 to 7 carbon atoms having an ether group or a thioether end, and a substituent. No C2-C4 aminoalkyl group, phenyl group with or without substituent, phenylalkyl group with C7-11 with or without substituent, terminal is ether group or thioether group, and substituent is A phenylalkyl group having 7 to 10 carbon atoms, including or not containing, a condensed ring group having 7 to 20 carbon atoms including or not including a substituent, or a heterocyclic group having 7 to 20 carbon atoms including or not including a substituent. ,
R ₂₃ is an alkyl group having 1 to 16 carbon atoms, an alkyl group having 1 to 6 carbon atoms including a halogen atom, a phenyl group including or not including a substituent, and a 7 to 10 carbon atom including or not including a substituent. A phenylalkyl group, a phenylalkyl group having 7 to 9 carbon atoms which is an ether group or a thioether group at the end and which may or may not contain a substituent, a condensed ring group having 7 to 20 carbon atoms which may or may not contain a substituent, or a substituent It is a C7-C20 heterocyclic group containing or not containing.

R ₂₀ and R ₂₂ are preferably methyl groups.

The compound of Formula 2 prevents the sensitivity and transmittance from being lowered by the dye, and allows the blue photosensitive resin composition of the present invention containing the dye as a colorant to effectively exhibit photopolymerization characteristics.

Examples of the compound of Chemical Formula 2 include UPI-03 and UPI-22 as commercially available products.

The compound of Chemical Formula 2 is contained in an amount of 10 to 100% by weight, preferably 20 to 100% by weight, based on the total weight of the photopolymerization initiator.

When the compound of Formula 2 is contained in an amount of less than 10% by weight, the decrease in sensitivity due to the dye cannot be overcome, and a pattern short circuit is likely to occur during the development process.

In addition to the compound of Chemical Formula 2, the photopolymerization initiator may additionally include an acetophenone compound, a benzophenone compound, a triazine compound, from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, and the like. It is preferable to use one or more compounds selected from the group consisting of biimidazole compounds and thioxanthone compounds.

Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and 2- (4- Methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like. .

Specific examples of the benzophenone compounds include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specifically, the triazine compound is, 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-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -(4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5- Triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-me Ruphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like It is done.

Specifically, the biimidazole compound includes, for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2, 3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole, and imidazole compounds in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted with a carboalkoxy group. Of these, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole are preferably used.

Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

The photopolymerization initiator is contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total solid content in the blue photosensitive resin composition of the present invention.

When the photopolymerization initiator is contained in an amount of 0.1 to 40% by weight, the sensitivity of the blue photosensitive resin composition is increased, the exposure time is shortened, the productivity is improved, and a high resolution can be maintained. Further, the strength of the pixel portion and the smoothness on the surface of the pixel portion are improved.

The photopolymerization initiator may additionally contain a photopolymerization initiation assistant (d1) in order to improve the sensitivity of the blue photosensitive resin composition of the present invention. When the blue photosensitive resin composition according to the present invention contains the photopolymerization initiation assistant (d1), the sensitivity can be further increased and the productivity can be improved.

As the photopolymerization initiation assistant, for example, one or more compounds selected from the group consisting of amine compounds and carboxylic acid compounds can be preferably used.

As the amine compound, an aromatic amine compound is preferably used. Specifically, for example, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, Ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethyl) Amino) benzophenone (common name: Michler's ketone), 4,4′-bis (diethylamino) benzophenone, and the like can be used.

As the carboxylic acid compound, aromatic heteroacetic acids are preferably used. Specifically, for example, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxy Examples include phenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The photopolymerization initiation assistant is contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total solid weight in the blue photosensitive resin composition.

When the photopolymerization initiation assistant is contained in an amount of 0.1 to 40% by weight, the sensitivity of the blue photosensitive resin composition is improved and the productivity of the color filter can be improved.

(E) Solvent As long as the solvent is effective for dissolving other components contained in the blue photosensitive resin composition, the solvent used in the normal blue photosensitive resin composition is not particularly limited. In particular, ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like are preferable.

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
And diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether.

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1- Butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate, 1,2-propylene glycol diacetate, ethylene Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol Examples thereof include diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, and propylene carbonate.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ-butyrolactone.

Examples of the amides include dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP).

The said solvent can be used individually or in mixture of 2 or more types, respectively.

The solvent is preferably an organic solvent having a boiling point of 100 ° C. to 200 ° C. in terms of coating properties and drying properties. For example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, Examples include butyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.

The solvent is contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the blue photosensitive resin composition. When the solvent is contained in the range of 60 to 90% by weight, it is applied when applied by a coater such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also called a die coater), and an ink jet. Good.

(F) Additive The additive can be selectively added as necessary. For example, an antioxidant, another polymer compound, a curing agent, a surfactant, an adhesion promoter, an ultraviolet absorber. , And one or more selected from the group consisting of anti-aggregation agents.

The antioxidant may include one or more selected from the group consisting of phenolic antioxidants and phosphorus antioxidants. In the case of phenolic antioxidants, the antioxidant is deteriorated in an oven at 150 ° C. for 200 hours or more. should not be done.

The phenolic antioxidant is preferably a hindered phenolic antioxidant. Specifically, for example, octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Octadecyl 3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate) (264 hours), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) ) Benzene (1,3,5-Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzene)) (240 hours), and pentaerythritol tetrakis (3,5-di) -Tert-butyl-4-hydroxyhydrocinnamate ) (Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)) and the like (960 hours).

Specific examples of the phosphorus antioxidant include triphenyl phosphate, isodecyl diphenyl phosphate, tris (2,4-di-tert-butylphenyl) phosphate (Tris (2)). 2,4-di-tert-butylphenyl) phosphate), 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (3,9-Bis) (Octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undekane), and 2,2'-methylenebis (4,6-di-tert-butyl-phenyl) 2-ethylhexyl phosphate (2,2'-methylenebis (4,6-di-tert-butyl-phenyl) -2-ethylhexyl phosphate) and the like.

The antioxidant is contained in an amount of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, based on 100 parts by weight of the photopolymerization initiator. When the antioxidant is contained in an amount of 1 to 100 parts by weight, it is possible to expect an increase in transmittance without a decrease in sensitivity of the blue photosensitive resin composition. When the antioxidant is contained in an amount of less than 1 part by weight, it is difficult to expect an increase in transmittance. On the other hand, when it exceeds 100 parts by weight, the reduction in sensitivity due to the dye cannot be overcome and the sensitivity is not increased. Short circuit pattern is likely to occur.

Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Etc.

The curing agent is used to enhance deep curing and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, and other aromatics. Epoxy resin, alicyclic epoxy resin, glycidyl ester resin, glycidylamine resin, or brominated derivatives of the epoxy resin, aliphatic resins other than the epoxy resin and brominated derivatives thereof, alicyclic or aromatic epoxy compounds Butadiene (co) polymer epoxidized product, isoprene (co) polymer epoxidized product, glycidyl (meth) acrylate (co) polymer, and triglycidyl isocyanurate.

In the curing agent, specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

The said hardening | curing agent can use together the hardening auxiliary compound which makes ring opening polymerization possible the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent.

Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. As the polyvalent carboxylic acid anhydride, a commercially available epoxy resin curing agent can be used. Examples of the commercially available products include ADEKA HARDNER EH-700 (manufactured by ADEKA INDUSTRY CO., LTD.), RIKACID HH (manufactured by Shin Nippon Rika Co., Ltd.) and MH-700 (manufactured by Nippon Nippon Rika Co., Ltd.). The exemplified curing agents can be used alone or in admixture of two or more.

The surfactant can be used to further improve the film formation of the blue photosensitive resin composition, and is a silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, amphoteric interface. An activator or the like is preferably used.

Examples of the commercially available silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Dow Corning Toray Silicone, Inc., and TSF-4440, TSF-4300, and TSF-4445 manufactured by GE Toshiba Silicone. , TSF-4446, TSF-4460, and TSF-4442.

Examples of the fluorosurfactant include Megapis F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink & Chemicals, Inc. as commercially available products.

Other commercially available products include KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (POLYFLOW) (Kyoeisha Chemical Co., Ltd.), FTOP (EFTOP) (Tochem Products), MegaFac (MEGAFAC) (Dainippon Ink Chemical Co., Ltd.), Florad (Sumitomo 3M), Asahi guard, Surflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) , EFKA (EFKA Chemicals), PB821 (Ajinomoto Co., Inc.), Disperbyk-series (BYK-chemi), and the like.

The exemplified surfactants can be used alone or in combination of two or more.

The kind of the adhesion promoter is not particularly limited, and specific examples of the adhesion promoter that can be used include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and N- (2-aminoethyl). ) -3-Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Propylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane Such as 3-isocyanate propyl trimethoxysilane and 3-isocyanate propyl triethoxysilane, and the like.

The exemplified adhesion promoters can be used alone or in combination of two or more. The adhesion promoter is usually contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total solid content in the blue photosensitive resin composition.

The type of the ultraviolet absorber is not particularly limited, and specific examples that can be used include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like. It is done.

The type of the anti-aggregation agent is not particularly limited, and specific examples that can be used include sodium polyacrylate.

The manufacturing method of the blue photosensitive resin composition of this invention is as follows.

A blue dye (a1) containing the above chemical formula 1, an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E) are added, and if necessary, an additive The blue photosensitive resin composition according to the present invention can be produced by further adding (F) to a predetermined concentration.

When a pigment is included as a blue colorant,
The blue pigment (a2) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. At this time, if necessary, a part or all of the pigment dispersant (a3) and the alkali-soluble resin (B) can be mixed with the solvent (E) to be dissolved or dispersed.

In the mixed colored product, the remainder of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and, if necessary, the additive (F) and the solvent (E) are added. The blue photosensitive resin composition according to the present invention can be produced by further adding to a predetermined concentration.

Moreover, this invention provides the blue color filter manufactured with the blue photosensitive resin composition, and a display apparatus provided with the same.

First, the blue photosensitive resin composition is applied on a substrate (usually glass) or a layer made of the solid content of the blue photosensitive resin composition previously formed, and then dried by heating to remove volatile components such as a solvent. Remove to obtain a smooth coating.

As the coating method, for example, spin coating, casting coating method, roll coating method, slit and spin coating, or slit coating method can be used. After application, heat drying (pre-baking) or drying after reduced pressure heats to volatilize volatile components such as a solvent. Here, heating temperature is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The coating thickness after heat drying is usually about 1 to 8 μm. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so that parallel light rays are uniformly irradiated on the entire exposure unit and accurate alignment between the mask and the substrate is performed. When the ultraviolet ray is irradiated, the portion irradiated with the ultraviolet ray is cured.

As the ultraviolet rays, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm) and the like can be used. The irradiation amount of ultraviolet rays can be appropriately selected as necessary, and is not limited in the present invention. When the cured coating film is brought into contact with a developing solution to dissolve the non-exposed portion and developed, a spacer having a target pattern shape can be obtained.

The developing method is not particularly limited to a liquid addition method, a dipping method, a spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound is not particularly limited to an inorganic or organic alkaline compound. Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate. Potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and ammonia.

Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Etc.

The inorganic or organic alkaline compounds can be used alone or in combination of two or more. The concentration of the alkaline compound in the developer is 0.01 to 10% by weight, preferably 0.03 to 5% by weight, based on the total weight of the developer.

As the surfactant in the developer, one or more selected from the group consisting of the above-described nonionic surfactants, anionic surfactants, and cationic surfactants can be used. The concentration of the surfactant in the developer is 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the developer. It is. After the development, it is washed with water and may be post-baked at 150 to 230 ° C. for 10 to 60 minutes as necessary.

Using the blue photosensitive resin composition of the present invention, a specific pattern can be formed on the substrate through the above steps.

Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments of the present invention can be modified into various different forms, and the scope of the present invention should not be construed as being limited to the embodiments described in detail below. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.

Synthesis Example 1 Synthesis of alkali-soluble resin An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 100 parts by weight of propylene glycol monomethyl ether acetate was added. Heated to 85 ° C. with stirring.

Next, in the flask, 19 parts by weight of methacrylic acid, 3,4-epoxytricyclo [5.2.1.02.6] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2 1.02.6] A mixture of decan-9-yl acrylate (molar ratio of 50:50) (trade name “E-DCPA”, manufactured by Daicel Corporation) in 171 parts by weight to 40 parts by weight of propylene glycol monomethyl ether acetate The dissolved solution was dropped over about 5 hours using a dropping pump.

A solution prepared by dissolving 26 parts by weight of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 120 parts by weight of propylene glycol monomethyl ether acetate was added over about 5 hours using another dropping pump. It was dripped in the flask. After dropping of the polymerization initiator is completed, the temperature is maintained at the same temperature for about 3 hours, and then cooled to room temperature, and an alkali-soluble resin having a solid content of 43.5% containing monomers of the following chemical formulas 5, 6 and 7 A solution was obtained.

The polystyrene-converted weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble resin were measured by the GPC measurement method under the following conditions.

Further, the ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight and number average molecular weight was defined as molecular weight distribution.

Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min Solid content concentration of test solution: 0.001 to 0.01% by weight
Injection volume: 50 μL
Detector: RI
Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The obtained alkali-soluble resin had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mgKOH / g.

<Synthesis of blue dye>
Synthesis Example 2
2-1.
This reaction was performed under a nitrogen atmosphere.

A flask equipped with a condenser and a stirrer was charged with 36.3 parts by weight of potassium thiocyanate and 160 parts by weight of acetone, and then stirred at room temperature for 30 minutes. Thereafter, 50 parts by weight of benzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise for 10 minutes.

After dropping, the mixture was stirred at room temperature for 2 hours, and the reaction mixture was ice-cooled, and 45.7 parts by weight of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 30 minutes.

Next, after cooling the reaction mixture with ice, 34.2 parts by weight of a 30% aqueous sodium hydroxide solution was added dropwise and stirred at room temperature for 30 minutes. Thereafter, 35.3 parts by weight of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours with heating under reflux.

Next, after allowing the reaction mixture to cool to room temperature, 120 parts by weight of tap water and 200 parts by weight of toluene were added to the reaction solution and stirred for 30 minutes. Then, it left still for 30 minutes and isolate | separated the reaction mixture into the organic layer and the water layer.

After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts by weight of 1N hydrochloric acid, 200 parts by weight of tap water, and 200 parts by weight of saturated saline in this order. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography, and the purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 52 parts by weight of the compound of the following chemical formula 8 (yield 50%).

2-2.
This reaction was performed under a nitrogen atmosphere.

In a flask equipped with a condenser and a stirrer, 9.3 parts by weight of the compound of Formula 8 prepared in Synthesis Example 2-1 and 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 After adding parts by weight and 20 parts by weight of toluene, 14.8 parts by weight of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours.

Next, the reaction mixture was cooled to room temperature and then diluted with 170 parts by weight of isopropanol. Thereafter, the diluted reaction solution was poured into 300 parts by weight of saturated saline, and then 100 parts by weight of toluene was added and stirred for 30 minutes. Stirring was stopped and the mixture was allowed to stand for 30 minutes to separate the reaction solution into an organic layer and an aqueous layer.

After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts by weight of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer.

The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. The blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 19.8 of the compound of the following chemical formula 9. Part by weight was obtained (yield 100%).

Mass spectrometric ionization mode of the compound of formula 9: ESI ⁺ : m / z = 601.3 [M-Cl] ⁺
Exact mass: 636.3

2-3.
This reaction was performed under a nitrogen atmosphere.

In a flask equipped with a condenser and a stirrer, 10 parts by weight of the compound of Formula 9 prepared in Synthesis Example 2-2, 4.5 parts by weight of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 100 parts by weight of N, N-dimethylformamide were added, followed by stirring at 50 to 60 ° C. for 3 hours.

Next, after cooling the reaction mixture to room temperature, it was added dropwise to 2000 parts by weight of tap water with stirring for 1 hour to obtain a dark blue suspension. The obtained suspension was filtered to obtain a blue-green solid. The blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.3 parts by weight of the compound of the following chemical formula 10 (yield 82%).

Dissolve 0.35 g of the compound of Formula 10 in chloroform to a volume of 250 cm ³ , of which 2 cm ³ is diluted with ion-exchanged water, and then the volume is 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm).

The compound of Chemical Formula 10 exhibited an absorbance of 2.9 at λmax = 628 nm.

Synthesis Example 3
3-1.
2 parts by weight of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 50 parts by weight of methanol. Thereafter, 15.41 parts by weight of 2,6-dihydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.09 parts by weight of boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and 8. Stir for 5 hours.

After cooling the mixed solution to room temperature, the precipitate was obtained by suction filtration and washed with 237 parts by weight of ion-exchanged water to obtain 10.9 parts by weight of a compound of the following chemical formula 11.

3-2.
This reaction was performed under a nitrogen atmosphere.

In a flask equipped with a condenser and a stirrer, 10 parts by weight of the compound of Formula 9 synthesized in Synthesis Example 2-2, 5.3 parts by weight of the compound of Formula 11 synthesized in Synthesis Example 3-1, and N, After adding 100 parts by weight of N-dimethylformamide, the mixture was stirred at 50 to 60 ° C. for 3 hours.

Next, after cooling the reaction mixture to room temperature, it was added dropwise to 2000 parts by weight of tap water with stirring for 1 hour to obtain a dark blue suspension. The suspension was filtered to obtain a blue-green solid, and the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 12 parts by weight of a compound of the following chemical formula 12 (yield 83%).

Dissolve 0.35 g of the compound of formula 12 in chloroform to a volume of 250 cm ³ , of which 2 cm ³ is diluted with ion-exchanged water, and then the volume is 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm).

The compound of the chemical formula 12 showed an absorbance of 2.6 at λmax = 628 nm.

Synthesis Example 4
This reaction was performed under a nitrogen atmosphere.

In a flask equipped with a condenser and a stirrer, 10 parts by weight of the compound of Formula 9 synthesized in Synthesis Example 2-2, 14.1 parts by weight of Tungstosilicic acid hydrate (manufactured by SIGMA-ALDRICH), and N, N -After adding 100 weight part of dimethylformamide, it stirred at 50-60 degreeC for 3 hours.

Next, after cooling the reaction mixture to room temperature, it was added dropwise to 2000 parts by weight of tap water with stirring for 1 hour to obtain a dark blue suspension. The suspension was filtered to obtain a blue-green solid, and the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 17.3 parts by weight of the compound of the following chemical formula 13 (yield 83%). .

Dissolve 0.35 g of the compound of Formula 13 in chloroform to a volume of 250 cm ³ , of which 2 cm ³ is diluted with ion-exchanged water, and then the volume is 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm).

The compound of Chemical Formula 13 showed an absorbance of 1.5 at λmax = 628 nm.

Synthesis Example 5
5-1.
This reaction was performed under a nitrogen atmosphere.

A flask equipped with a condenser and a stirrer was charged with 32.2 parts by weight of potassium thiocyanate and 160 parts by weight of acetone, and then stirred at room temperature for 30 minutes. Thereafter, 50 parts by weight of 2-fluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise for 10 minutes.

After dropping, the mixture was stirred at room temperature for 2 hours, and the reaction mixture was ice-cooled. Then, 40.5 parts by weight of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 30 minutes.

Next, after cooling the reaction mixture with ice, 34.2 parts by weight of a 30% aqueous sodium hydroxide solution was added dropwise and stirred at room temperature for 30 minutes. Thereafter, 31.3 parts by weight of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours with heating under reflux.

Next, after allowing the reaction mixture to cool to room temperature, 120 parts by weight of tap water and 200 parts by weight of toluene were added to the reaction solution and stirred for 30 minutes. Then, it left still for 30 minutes and isolate | separated the reaction mixture into the organic layer and the water layer.

After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts by weight of 1N hydrochloric acid, 200 parts by weight of tap water, and 200 parts by weight of saturated saline in this order. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography, and the purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 49.9 parts by weight of a compound of the following chemical formula 14 (yield: 51% ).

5-2.
This reaction was performed under a nitrogen atmosphere.

In a flask equipped with a condenser and a stirrer, 9.9 parts by weight of the compound of Formula 14 prepared in Synthesis Example 5-1 and 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 After adding parts by weight and 20 parts by weight of toluene, 14.8 parts by weight of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours.

Next, the reaction mixture was cooled to room temperature and then diluted with 170 parts by weight of isopropanol. Thereafter, the diluted reaction solution was poured into 300 parts by weight of saturated saline, and then 100 parts by weight of toluene was added and stirred for 30 minutes. Stirring was stopped and the mixture was allowed to stand for 30 minutes to separate the reaction solution into an organic layer and an aqueous layer.

After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts by weight of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer.

The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. The blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 19.8 of the compound of the following chemical formula 15. Part by weight was obtained (yield 85%).

Mass spectrometric ionization mode of the compound of formula 15: ESI ⁺ : m / z = 619.3 [M-Cl] ⁺
Exact mass: 654.3

5-3.
This reaction was performed under a nitrogen atmosphere.

In a flask equipped with a condenser and a stirrer, 10 parts by weight of the compound of Formula 15 prepared in Synthesis Example 5-2 and 5.7 parts by weight of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30 parts by weight of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours.

Next, after cooling the reaction mixture to room temperature, it was added dropwise to 500 parts by weight of tap water with stirring for 1 hour to obtain a dark blue suspension. The obtained suspension was filtered to obtain a blue-green solid. The blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.3 parts by weight of the compound of the following chemical formula 16 (yield 86%).

Dissolving 0.35 g of the compound of formula 16 in chloroform to a volume of 250 cm ³ , of which 2 cm ³ was diluted with ion-exchanged water and then the volume was set to 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm).

The compound of Formula 16 exhibited an absorbance of 3.1 at λmax = 630 nm.

Synthesis Example 6
6-1.
This reaction was performed under a nitrogen atmosphere.

A flask equipped with a condenser and a stirrer was charged with 33 parts by weight of potassium thiocyanate and 160 parts by weight of acetone, and then stirred at room temperature for 30 minutes. Thereafter, 50 parts by weight of 2-methylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise for 10 minutes.

After dropping, the mixture was stirred at room temperature for 2 hours, and the reaction mixture was ice-cooled, and 41.6 parts by weight of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 30 minutes.

Next, after cooling the reaction mixture with ice, 34.2 parts by weight of a 30% aqueous sodium hydroxide solution was added dropwise and stirred at room temperature for 30 minutes. Thereafter, 32.1 parts by weight of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours with heating under reflux.

Next, after allowing the reaction mixture to cool to room temperature, 120 parts by weight of tap water and 200 parts by weight of toluene were added to the reaction solution and stirred for 30 minutes. Then, it left still for 30 minutes and isolate | separated the reaction mixture into the organic layer and the water layer.

After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts by weight of 1N hydrochloric acid, 200 parts by weight of tap water, and 200 parts by weight of saturated saline in this order. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography, and the purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 40.5 parts by weight of a compound of the following chemical formula 17 (41% yield) ).

6-2.
This reaction was performed under a nitrogen atmosphere.

In a flask equipped with a condenser and a stirrer, 9.7 parts by weight of the compound of Formula 17 prepared in Synthesis Example 6-1 and 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 After adding parts by weight and 20 parts by weight of toluene, 14.8 parts by weight of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours.

Next, the reaction mixture was cooled to room temperature and then diluted with 170 parts by weight of isopropanol. Thereafter, the diluted reaction solution was poured into 300 parts by weight of saturated saline, and then 100 parts by weight of toluene was added and stirred for 30 minutes. Stirring was stopped and the mixture was allowed to stand for 30 minutes to separate the reaction solution into an organic layer and an aqueous layer.

After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts by weight of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer.

The obtained organic layer was removed by evaporating the solvent with an evaporator to obtain a blue-violet solid. The blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 15.1 of the compound represented by the following chemical formula 18. Part by weight was obtained (yield 75%).

Mass spectrometric ionization mode of the compound of formula 18: ESI ⁺ : m / z = 615.4 [M-Cl] ⁺
Exact mass: 650.3

6-3.
This reaction was performed under a nitrogen atmosphere.

In a flask equipped with a condenser and a stirrer, 10 parts by weight of the compound of Formula 18 prepared in Synthesis Example 6-2, 5.7 parts by weight of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30 parts by weight of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours.

Next, after cooling the reaction mixture to room temperature, it was added dropwise to 500 parts by weight of tap water with stirring for 1 hour to obtain a dark blue suspension. The obtained suspension was filtered to obtain a blue-green solid. The blue-green solid was dried at 60 ° C. under reduced pressure to obtain 13.2 parts by weight of the compound of the following chemical formula 19 (yield 96%).

Dissolve 0.35 g of the compound of formula 19 in chloroform to a volume of 250 cm ³ , of which 2 cm ³ is diluted with ion-exchanged water, and then the volume is 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm).

The compound of Chemical Formula 19 exhibited an absorbance of 2.7 at λmax = 627 nm.

Production Example 1 Production of pigment dispersions C.I. I. Pigment Blue 15: 6 12 parts by weight, DISPERBYK-2001 (manufactured by BYK) 4 parts by weight as a pigment dispersant, propylene glycol methyl ether acetate 44 parts by weight as a solvent, and propylene glycol methyl ether 40 parts by weight with a bead mill for 12 hours By mixing and dispersing, a pigment dispersion M1 was produced.

<Production of blue photosensitive resin composition>
Examples 1-10, Comparative Examples 1-8.
The blue photosensitive resin composition of Examples 1-10 and Comparative Examples 1-8 was manufactured with the composition of following Table 1.

Blue colorant (A)
A-1: Compound of Formula 10 prepared in Synthesis Example 2 A-2: Compound of Formula 12 prepared in Synthesis Example 3 A-3: Compound of Formula 13 prepared in Synthesis Example 4 A-4: In Synthesis Example 5 Compound A-5 of Formula 16 produced: Compound M of Formula 19 produced in Synthesis Example 6: Pigment dispersion prepared in Production Example 1 Alkali-soluble resin (B): Photopolymerizability of alkali-soluble resin produced in Synthesis Example 1 Compound (C): KAYARAD DPHA (Nippon Kayaku Manufacturing)
Photopolymerization initiator (D)
D-1: UPI-22 (manufactured by Daitosha)
D-2: OXE-01 (manufactured by BASF)
Solvent (E)
E-1: Propylene glycol monomethyl ether acetate E-2: Propylene glycol monomethyl ether additive (F)
Antioxidant: Irganox 1035 (manufactured by BASF)

Experimental Example 1 Production and characterization of color filter After applying the blue photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 8 on a 2-inch glass substrate (EAGLE XG) by spin coating, respectively. It was placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Thereafter, a test photomask having a line / space pattern of 1 to 100 μm was placed on the thin film, and an ultraviolet ray was irradiated at an interval of 300 μm from the test photomask. At this time, ultraviolet rays were irradiated at an illuminance of 60 mJ / cm ² using a 1 kW high-pressure mercury lamp including all g, h and i rays, and no special optical filter was used.

The thin film irradiated with ultraviolet rays was developed by immersing in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes. Thereafter, the glass plate coated with the thin film was washed with distilled water, then dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C. for 25 minutes to produce each color filter. The film thickness of the manufactured color filter was 2.4 μm.

1. Measurement of transmittance A color filter is manufactured by the above method, but a color filter is manufactured without using a test photomask, and the transmittance is measured using a chromaticity meter (manufactured by Olympus, OSP-200). The results are shown in Table 2 below.

2. Measurement of adhesion The pattern of the produced color filter was observed with an optical microscope, and the degree of peeling phenomenon was evaluated on the pattern and shown in Table 2 below. The evaluation criteria are as follows.
<Evaluation criteria>
○: No slap on the pattern △: 1 to 3 splats on the pattern ×: 4 or more splats on the pattern

3. Measurement of Remaining Film Ratio The blue photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 8 were applied on a substrate using a spin coater, and then prebaked at 100 ° C. for 1 minute, to 365 nm. After the exposure, the film was post-baked at 230 ° C. for 20 minutes, and the thickness ratio (%) before and after the post-baking of the resist film was measured. The evaluation results are as follows. It was shown in 2.

From the result of the said Table 2, Examples 1-10 which are the blue photosensitive resin compositions of this invention showed the result excellent in the transmittance | permeability, adhesiveness, and chemical resistance. More specifically, the blue photosensitive resin compositions of Examples 6 to 10 using the blue dye and blue pigment of Formula 1 as the blue colorant used only the blue dye of Formula 1 as the blue colorant. The result which was excellent in adhesiveness and chemical resistance than the blue photosensitive resin composition of Examples 1-5 was shown.

On the other hand, the blue photosensitive resin compositions of Comparative Examples 1 to 5 that did not use the compound of Chemical Formula 2 as a photopolymerization initiator had poor adhesion and residual film ratio.

In addition, the blue photosensitive resin composition of Comparative Example 6 using a pigment without using the dye of Chemical Formula 1 showed slightly poor results in transmittance, adhesion, and residual film rate. The blue photosensitive resin composition of Comparative Example 7 that did not use the dye 1 and the photopolymerization initiator of the chemical formula 2 showed poor adhesion and residual film ratio.

The blue photosensitive resin composition of Comparative Example 8 that uses the dye of Chemical Formula 1 but does not use a pigment and does not use the photopolymerization initiator of Chemical Formula 2 has poor adhesion and residual film ratio. Indicated.

Therefore, it can be confirmed that the blue photosensitive resin composition of the present invention is excellent in transmittance, adhesion, and residual film ratio, and particularly excellent in adhesion, without a decrease in sensitivity due to the dye, in the development step. The problem that the pattern is peeled off can be solved.

Claims (7)

A blue photosensitive resin composition comprising a blue colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The blue colorant includes a dye of Formula 1 below:
The blue photopolymerization initiator, wherein the photopolymerization initiator includes a compound represented by the following chemical formula 2.

(In the formula, R _{1 to} R ₆ are the same as or different from each other, and each represents hydrogen, an aryl group having 6 to 12 carbon atoms which may or may not contain a substituent, or an alkyl group having 1 to 20 carbon atoms;
The alkyl group having 1 to 20 carbon atoms may contain oxygen between methylene groups,
The hydrogen of the alkyl group having 1 to 20 carbon atoms may be substituted with a halogen atom or an amino group,
R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may be bonded to each other to form a ring,
R _{7 to} R ₁₄ are the same or different and are each a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms,
The alkyl group having 1 to 8 carbon atoms may contain oxygen between methylene groups,
R ₁₅ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms which may or may not contain a substituent;
X is an oxygen, sulfur, or amine group;
Y is a counter anion;
The m is the oxidation number of Y. )

(Wherein, a and b are 0 or 1,
When a is 1, b is 1,
When a is 0, b is 0 or 1,
(1) When a = 0 and b = 0,
R ₁₆ is hydrogen, a halogen atom, a nitro group, a sulfonyloxy group containing a C1-C8 alkyl group that is substituted or not substituted with a halogen atom, a phenylsulfonyloxy group that contains or does not contain a substituent, A sulfonyl group containing an alkyl group having 1 to 8 carbon atoms, which is substituted or unsubstituted by a halogen atom, a heterocyclic sulfonyl group having 7 to 20 carbon atoms, which contains or does not contain a substituent, or contains a substituent A condensed cyclic sulfonyl group having 7 to 20 carbon atoms,
(2) When a = 0 and b = 1,
R ₁₆ is a phenyl group containing or not containing a substituent, a heterocyclic group having 7 to 20 carbon atoms containing or not containing a substituent, or a condensed ring group having 7 to 20 carbon atoms containing or not containing a substituent. Yes,
(3) When a = 1 and b = 1,
R ₁₆ is a sulfonyloxy group containing an alkyl group having 1 to 8 carbon atoms which is substituted or unsubstituted with a halogen atom, or a phenylsulfonyloxy group which contains or does not contain a substituent,
R ₁₇ and R ₁₈ are the same or different and each represents hydrogen, an alkyl group having 1 to 22 carbon atoms, an alkyl group having 1 to 10 carbon atoms including a halogen atom, or a terminal having an ether group or a thioether group having 1 to 1 carbon atoms. 15 alkyl groups, phenyl groups with or without substituents, or phenylalkyl groups having 7 to 11 carbon atoms,
R ₁₇ and R ₁₈ may form a ring,
R ₁₉ is the following Chemical Formula 3 or Chemical Formula 4,

R ₂₀ and R ₂₂ are the same or different and are each an alkyl group having 1 to 17 carbon atoms, an alkyl group having 2 to 5 carbon atoms including a halogen atom, and an end having an ether group or a thioether group having 2 to 7 carbon atoms. Alkyl group, phenyl group with or without substituent, phenylalkyl group with 7 to 11 carbon atoms with or without substituent, phenyloxyalkyl group with 7 to 10 carbon atoms with or without substituent, substituent A heterocyclic group having 7 to 20 carbon atoms or not containing or a condensed ring group having 7 to 20 carbon atoms containing or not containing a substituent,
R ₂₁ includes an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 7 carbon atoms including a halogen atom, an alkyl group having 2 to 7 carbon atoms having an ether group or a thioether end, and a substituent. No C2-C4 aminoalkyl group, phenyl group with or without substituent, phenylalkyl group with C7-11 with or without substituent, terminal is ether group or thioether group, and substituent is A phenylalkyl group having 7 to 10 carbon atoms, including or not containing, a condensed ring group having 7 to 20 carbon atoms including or not including a substituent, or a heterocyclic group having 7 to 20 carbon atoms including or not including a substituent. ,
R ₂₃ is an alkyl group having 1 to 16 carbon atoms, an alkyl group having 1 to 6 carbon atoms including a halogen atom, a phenyl group including or not including a substituent, and a 7 to 10 carbon atom including or not including a substituent. A phenylalkyl group, a phenylalkyl group having 7 to 9 carbon atoms which is an ether group or a thioether group at the end and which may or may not contain a substituent, a condensed ring group having 7 to 20 carbon atoms which may or may not contain a substituent, or a substituent It is a C7-C20 heterocyclic group containing or not containing. ) The blue photosensitive resin composition according to claim 1, wherein the blue colorant additionally contains a pigment. The pigment is C.I. I. Pigment blue 15: 6 and C.I. I. The blue photosensitive resin composition according to claim 2, comprising at least one selected from the group consisting of CI pigment violet 23. [Y] ^{m− in} Formula 1 is an anion of a heteropolyacid containing tungsten, an anion of an isopolyacid containing tungsten, an anion of phosphotungstic acid, an anion of silicon tungstic acid, and an anion of isopolytungstic acid. The blue photosensitive resin composition according to claim 1, wherein the blue photosensitive resin composition is one selected from the group consisting of ions. 5 to 60% by weight of a blue colorant, 10 to 80% by weight of an alkali-soluble resin, 5 to 50% by weight of a photopolymerizable compound, and a photopolymerization initiator based on the total solid weight in the blue photosensitive resin composition 2. The blue photosensitive resin composition according to claim 1, comprising 0.1 to 40 wt% and containing 60 to 90 wt% of solvent with respect to the total weight of the blue photosensitive resin composition. The blue color filter manufactured with the blue photosensitive resin composition of any one of Claims 1-5. A display device comprising the blue color filter according to claim 6.