TWI724045B - A blue photosensitive resin composition, blue color filter and display device comprising the same - Google Patents

Abstract

The present invention relates to a cyan photosensitive resin composition, a cyan color filter containing the same, and a display device. The cyan photosensitive resin composition includes a cyan colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. Excellent adhesion.

Description

Cyan photosensitive resin composition, cyan color filter and display device containing the same

Invention field

The present invention relates to a cyan photosensitive resin composition, a cyan color filter and a display device containing the same, and more specifically, to a cyan coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. A cyan photosensitive resin composition excellent in adhesiveness, a cyan color filter and a display device containing the same.

Background of the invention

As electronic display devices used in office automation equipment, portable small TVs, and video camera viewfinders, there are liquid crystal display (LCD), plasma display panel (PDP), and organic light-emitting diodes. Organic light emitting diode (OLED), etc., are actively engaged in technical research related to these.

The above-mentioned liquid crystal display device has the advantages of lighter weight, thinner, low price, low power consumption driving, and excellent bonding with integrated circuits, etc. The advantage is that the scope of its use in notebook personal computers, monitors, and TV images is expanding. Such a liquid crystal display device includes a lower substrate formed with a black matrix, color filters, and ITO pixel electrodes, an active circuit section composed of a liquid crystal layer, a thin film transistor, and a storage capacitor layer, and an upper substrate formed with ITO pixel electrodes. constitute.

The color filter is manufactured by coating a solid-state imaging element or a transparent substrate with fine areas colored with three or more colors. Such colored films are usually formed by a dyeing method, an electrodeposition method, a pigment dispersion method, etc., but recently, a pigment dispersion method having excellent heat resistance and durability has been used.

The pigment dispersion method is a method of forming a colored film through a series of processes of coating a photopolymerizable composition containing a colorant on a transparent substrate provided with a light-shielding layer (black matrix), exposure, development, and thermal curing. The pigment dispersion method has the advantages of being able to improve the heat resistance and durability, which are the most important properties of the color filter, and being able to maintain the thickness of the film uniformly.

The coloring photosensitive resin composition used in the manufacture of color filters using the pigment dispersion method generally consists of a binder resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives.

In recent years, high color reproduction of color filters is required, and as a result, the content of the coloring agent in the coloring photosensitive resin composition used in the production of the color filter is continuously increasing. In addition, in order to produce high-quality color filters with excellent visibility, there is a continuous demand for improvement in contrast.

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 in contrast due to the microparticulation of the pigment has also reached its limit. Thus, nowadays, researched In the method of using both a pigment and a dye as a coloring agent, if a color filter is manufactured using a colored photosensitive resin composition containing a dye, the sensitivity is insufficient, and there is a problem of peeling off the pattern formed during the development process using an alkali developer. In addition, when a color filter is manufactured from a colored photosensitive resin composition containing a dye, there are problems in that the compatibility of the dye is insufficient in the hard baking process, the dye is deposited on the surface, and the contrast is lowered.

Summary of the invention

The object of the present invention is to provide a cyan photosensitive resin composition that does not have a decrease in sensitivity due to the dye, and is excellent in adhesion, even though the dye is used in a minimum amount.

In addition, an object of the present invention is to provide a cyan photosensitive resin composition capable of displaying high transmittance and high contrast.

Furthermore, an object of the present invention is to provide a cyan color filter and a display device manufactured using the above-mentioned cyan photosensitive resin composition.

In order to achieve the above-mentioned object, the present invention provides a cyan photosensitive resin composition, which is a cyan photosensitive resin composition comprising a cyan colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and is characterized by The cyan coloring agent includes the dye of the following chemical formula 1, and the photopolymerization initiator includes the compound of the following chemical formula 2.

[Chemical formula 1]

The above R ₁ to R ₆ are each the same or different, and are hydrogen, a C 6-12 aryl group with or without a substituent, or a C 1-20 alkyl group. The above-mentioned C 1-20 alkyl group is Oxygen may be contained between the methylene groups, the hydrogen of the above-mentioned C1-20 alkyl group may be substituted by a halogen atom or an amine group, the above-mentioned R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may be respectively Combine each other to form a ring. The above R ₇ to R ₁₄ are the same or different, and are hydrogen, halogen atom, nitro, sulfonyl, hydroxyl, or C 1-8 alkyl, the above C 1-8 alkane The group may contain oxygen between the methylene groups, the above R ₁₅ is hydrogen, an alkyl group having 1 to 20 carbons, or an aryl group having 6 to 12 carbons with or without substituents, and the above X is oxygen, sulfur, Or an amine group, the above Y is a counter anion, and the above m is the oxidation number of Y.

[Chemical formula 2]

The above a and b are 0 or 1, when the above a is 1, the above b is 1, when the above a is 0, the above b is 0 or 1, (1) When the above a=0, b=0, the above R ₁₆ is hydrogen, a halogen atom, a nitro group, a sulfonyloxy group containing an alkyl group having 1 to 8 carbon atoms substituted or unsubstituted with a halogen atom, a phenylsulfonyloxy group containing or not containing a substituent, containing a halogen Atom-substituted or unsubstituted alkyl sulfonyl group with 1 to 8 carbon atoms, heterocyclic sulfonyl group with 7 to 20 carbon atoms with or without substituents, or carbon number with or without substituents Condensed cyclic sulfonyl group of 7-20, (2) In the case of a=0 and b=1 above, the above R ₁₆ is a phenyl group with or without substituents, and the number of carbons with or without substituents A 7-20 heterocyclic group, or a C7-20 condensed ring group with or without a substituent, (3) In the case of a=1 and b=1 above, the above R ₁₆ is a halogen atom containing The sulfonyloxy group of a substituted or unsubstituted alkyl group having 1 to 8 carbons, or a phenylsulfonyloxy group with or without a substituent, the above-mentioned R ₁₇ and R ₁₈ are the same or different, and are hydrogen, carbon An alkyl group of 1 to 22, an alkyl group of 1 to 10 carbons containing a halogen atom, an alkyl group of 1 to 15 carbons with an ether group or a thioether group at the end, a phenyl group with or without substituents, or A phenylalkyl group having 7 to 11 carbon atoms, the above R ₁₇ and R ₁₈ may form a ring, and the above R ₁₉ is the following chemical formula 3 or 4,

The above-mentioned R ₂₀ and R ₂₂ are the same or different, and are an alkyl group having 1 to 17 carbon atoms, an alkyl group having 2 to 5 carbon atoms containing a halogen atom, and an alkyl group having 2 to 7 carbon atoms having an ether group or thioether group at the end. Groups, phenyl groups with or without substituents, phenylalkyl groups with 7 to 11 carbons with or without substituents, phenoxyalkyl groups with 7 to 10 carbons with or without substituents, containing Or a heterocyclic group with 7 to 20 carbons without substituents, or a condensed ring group with 7 to 20 carbons with or without substituents, the above-mentioned R ₂₁ is an alkyl group with 1 to 17 carbons, containing halogen Alkyl groups with 1 to 7 carbon atoms, alkyl groups with 2 to 7 carbon atoms at the end of ether or thioether groups, aminoalkyl groups with 2 to 4 carbon atoms with or without substituents, containing or not A substituted phenyl group, a C7-11 phenylalkyl group with or without a substituent, an ether group or a thioether group at the end and a C7-10 phenylalkyl group with or without a substituent Group, a condensed ring group with 7 to 20 carbons with or without substituents, or a heterocyclic group with 7 to 20 carbons with or without substituents, the above-mentioned R ₂₃ is an alkyl group with 1 to 16 carbons , Alkyl groups with 1 to 6 carbon atoms containing halogen atoms, phenyl groups with or without substituents, phenylalkyl groups with 7 to 10 carbons with or without substituents, ether groups or thioether groups at the end In addition, a phenylalkyl group with 7 to 9 carbon atoms with or without substituents, a condensed ring group with 7 to 20 carbon atoms with or without substituents, or carbon 7-20 with or without substituents的heterocyclyl.

In addition, the present invention provides a cyan color filter manufactured using the above-mentioned cyan photosensitive resin composition.

Furthermore, the present invention provides a display device including the above-mentioned cyan color filter.

The cyan photosensitive resin composition of the present invention has an effect of excellent adhesion to the substrate, and no problem of pattern peeling occurs in the development process.

In addition, the cyan photosensitive resin composition of the present invention can exhibit the characteristics of high transmittance and high contrast even though the dye is used in a minimum amount.

Furthermore, the color filter and the display device manufactured using the cyan photosensitive resin composition of this invention have the effect of excellent color reproduction.

Detailed ways

The present invention will be described in more detail below.

The present invention relates to a cyan photosensitive resin composition, which is a cyan photosensitive resin composition containing a cyan colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and is characterized in that the cyan colorant contains The dye of the following chemical formula 1, and the photopolymerization initiator includes the compound of the following chemical formula 2.

The above R ₁ to R ₆ are each the same or different, and are hydrogen, a C 6-12 aryl group with or without a substituent, or a C 1-20 alkyl group. The above-mentioned C 1-20 alkyl group is Oxygen may be contained between the methylene groups, the hydrogen of the above-mentioned C1-20 alkyl group may be substituted by a halogen atom or an amine group, the above-mentioned R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may be respectively Combine each other to form a ring. The above R ₇ to R ₁₄ are the same or different, and are hydrogen, halogen atom, nitro, sulfonyl, hydroxyl, or C 1-8 alkyl, the above C 1-8 alkane The group may contain oxygen between the methylene groups, the above R ₁₅ is hydrogen, an alkyl group having 1 to 20 carbons, or an aryl group having 6 to 12 carbons with or without substituents, and the above X is oxygen, sulfur, Or an amine group, the above Y is a counter anion, and the above m is the oxidation number of Y.

The above a and b are 0 or 1, when the above a is 1, the above b is 1, when the above a is 0, the above b is 0 or 1, (1) When the above a=0, b=0, the above R ₁₆ is a hydrogen, a halogen atom, a nitro group, a sulfonyloxy group containing an alkyl group having 1 to 8 carbon atoms which may be substituted or unsubstituted by a halogen atom, a phenylsulfonyloxy group containing or not containing a substituent, a Sulfonyl groups of alkyl groups with 1 to 8 carbons substituted or unsubstituted by halogen atoms, heterocyclic sulfonyl groups with 7 to 20 carbons with or without substituents, or carbons with or without substituents Condensed cyclic sulfonyl group of 7 to 20, (2) In the case of a=0 and b=1, the R ₁₆ is a phenyl group with or without a substituent, and a carbon with or without a substituent A heterocyclic group of 7 to 20, or a condensed ring group of 7 to 20 carbons with or without substituents, (3) In the case of a=1 and b=1 above, R ₁₆ is a halogenated Atom-substituted or unsubstituted alkyl sulfonyloxy group with 1 to 8 carbon atoms, or phenylsulfonyloxy group with or without substituents, R ₁₇ and R ₁₈ are the same or different, and are hydrogen and carbon An alkyl group of 1 to 22, an alkyl group of 1 to 10 carbons containing a halogen atom, an alkyl group of 1 to 15 carbons with an ether group or a thioether group at the end, a phenyl group with or without substituents, or A phenylalkyl group having 7 to 11 carbon atoms, the above R ₁₇ and R ₁₈ may form a ring, and the above R ₁₉ is the following chemical formula 3 or 4,

The above-mentioned R ₂₀ and R ₂₂ are the same or different, and are an alkyl group having 1 to 17 carbon atoms, an alkyl group having 2 to 5 carbon atoms containing a halogen atom, and an alkyl group having 2 to 7 carbon atoms having an ether group or a thioether group at the end. Groups, phenyl groups with or without substituents, phenylalkyl groups with 7 to 11 carbons with or without substituents, phenoxyalkyl groups with 7 to 10 carbons with or without substituents, containing Or a heterocyclic group with 7 to 20 carbons without substituents, or a condensed ring group with 7 to 20 carbons with or without substituents, the above-mentioned R ₂₁ is an alkyl group with 1 to 17 carbons, containing halogen Alkyl groups with 1 to 7 carbon atoms, alkyl groups with 2 to 7 carbon atoms at the end of ether or thioether groups, aminoalkyl groups with 2 to 4 carbon atoms with or without substituents, containing or not A substituted phenyl group, a C7-11 phenylalkyl group with or without a substituent, an ether group or a thioether group at the end and a C7-10 phenylalkyl group with or without a substituent Group, a condensed ring group with 7 to 20 carbons with or without substituents, or a heterocyclic group with 7 to 20 carbons with or without substituents, the above-mentioned R ₂₃ is an alkyl group with 1 to 16 carbons , Alkyl groups with 1 to 6 carbon atoms containing halogen atoms, phenyl groups with or without substituents, phenylalkyl groups with 7 to 10 carbons with or without substituents, ether groups or thioether groups at the end In addition, a phenylalkyl group with 7 to 9 carbon atoms with or without substituents, a condensed ring group with 7 to 20 carbon atoms with or without substituents, or carbon 7-20 with or without substituents的heterocyclyl.

In the present invention, by including the dye of the aforementioned chemical formula 1 as a colorant and the compound of the aforementioned chemical formula 2 as a photopolymerization initiator, it is necessary to provide a cyan photosensitive resin composition having excellent adhesion to a substrate and excellent developability.

The following is a description of the cyan photosensitive resin composition of the present invention Each component is explained in detail.

(A) Cyan colorant

The cyan colorant as a component of the cyan photosensitive resin composition of the present invention contains the dye of the following chemical formula 1, and can additionally contain a cyan pigment.

(a1) Cyan dye

The above-mentioned cyan coloring agent includes a cyan dye of the following chemical formula 1.

The above R ₁ to R ₆ are each the same or different, and are hydrogen, a C 6-12 aryl group with or without a substituent, or a C 1-20 alkyl group. The above-mentioned C 1-20 alkyl group is Oxygen may be contained between the methylene groups, the hydrogen of the above-mentioned C 1-20 alkyl group may be substituted by a halogen atom or an amine group, and the above-mentioned R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may each be Combine each other to form a ring. The above R ₇ to R ₁₄ are each the same or different, and are hydrogen, halogen atom, nitro, sulfonyl, hydroxyl, or alkyl with 1 to 8 carbons, and the above alkane with 1 to 8 carbons The group may contain oxygen between the methylene groups, the above R ₁₅ is hydrogen, an alkyl group having 1 to 20 carbons, or an aryl group having 6 to 12 carbons with or without substituents, and the above X is oxygen, sulfur, Or an amine group, the above Y is a counter anion, and the above m is the oxidation number of Y.

The above-mentioned Y preferably contains one or more anions selected from boron, aluminum, sulfur, fluorine, tungsten, molybdenum, silicon, and phosphorus, and these anions can additionally contain oxygen.

^{[Y] m- of the} above chemical formula 1, preferably, may be selected from the group consisting of anion of heteropolyacid containing tungsten, anion of homopolyacid containing tungsten, anion of phosphotungstic acid, anion of silicotungstic acid, and tong One of the anions of tungstic acid.

(kegging)型鎢磷酸離子，可列舉出α-[PW₁₂O₄₀]^3-，作為

(Dawson)型鎢磷酸離子，可列舉出α-[P₂W₁₈O₆₂]^6-和β-[P₂W₁₈O₆₂]^6-，作為

型鎢矽酸離子，可列舉出α-[SiW₁₂O₄₀]^4-、β-[SiW₁₂O₄₀]^4-、γ-[SiW₁₂O₄₀]^4-等，此外，可列舉出[P₂W₁₇O₆₁]^10-、[P₂W₁₅O₅₆]^12-、[H₂P₂W₁₂O₄₈]^12-、[NaP₅W₃₀O₁₁₀]^14-、α-[SiW₉O₃₄]^10-、γ-[SiW₁₀O₃₆]^8-、α-[SiW₁₁O₃₉]^8-、β-[SiW₁₁O₃₉]^8-、[W₆O₁₉]^2-、[W₁₀O₃₂]^4-、和WO₄ ^2-等。 ^{[Y] m- of the} above chemical formula 1, more specifically, for example, as

(kegging) type tungstophosphate ion, including α-[PW ₁₂ O ₄₀ ] ^3- , as

(Dawson) type tungstophosphate ion, including α-[P ₂ W ₁₈ O ₆₂ ] ^6- and β-[P ₂ W ₁₈ O ₆₂ ] ^6- as

Type tungstosilicic acid ions include α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ-[SiW ₁₂ O ₄₀ ] ^4- and the like. In addition, [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- etc.

Furthermore, it is preferable that the said m is a natural number of 1-15.

In addition, the above-mentioned cyan colorant can additionally be selected from acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and their derivatives. In addition to the compound, azo-based, xanthene-based, and phthalocyanine-based acid dyes and their derivatives can also be selected. Among them, azo-based acid dyes and their derivatives are preferably selected and used. In addition, preferably, the above-mentioned cyan dye includes a compound classified as a dye in the color index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (Sei Dyers Company).

The above-mentioned dyes that can be additionally used, specifically, for example, CI solvent dyes include CI solvent blue 5, 35, 36, 37, 44, 45, 59, 67, and 70; and CI solvent violet 8, 9 , 13, 14, 36, 37, 47, and 49 etc.

Among them, it is preferable to include one or more selected from C.I. Solvent Blue 35, 36, 44, 45, and 70; and C.I. Solvent Violet 13.

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

Among them, it preferably contains selected from C.I. Acid Blue 80 and 90; And one or more of C.I. Acid Violet 66.

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

In addition, examples of CI mordant dyes include CI mordant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31 , 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, and 84; CI mordant violet 1, 2, 4, 5, 7, 14, 22, 24, 30 , 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, and 58, etc.

The above-mentioned cyan dyes can be used individually or in combination of two or more kinds.

In addition, the cyan dye contains 0.5 to 80% by weight, preferably 0.5 to 60% by weight, and more preferably 1 to 50% by weight with respect to the total weight of the cyan coloring agent. Regarding the content of the cyan dye in the above cyan colorant In other words, if it contains the above 0.5 to 80% by weight, after pattern formation, the problem of reduced reliability of dye elution due to organic solvents can be prevented, and the sensitivity can be improved.

(a2) Cyan pigment

As the above-mentioned cyan pigment, organic pigments or inorganic pigments generally used in this field can be used. In addition, for the above-mentioned cyan pigments, if necessary, resin treatment, surface treatment using pigment derivatives introduced with acidic groups or basic groups, etc., grafting treatment of the surface of the pigment using polymer compounds, etc., and the use of sulfuric acid A micronization treatment such as a micronization method, a cleaning treatment using an organic solvent, water, etc. for removing impurities, or a removal treatment of ionic impurities such as an ion exchange method, and the like.

Various pigments used in printing inks, inkjet inks, etc. can be used as the above-mentioned organic pigments. Specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, and isoindolinones can be used. Pigments, isoindoline pigments, perylene pigments, perylene pigments, dioxazine pigments, anthraquinone pigments, dianthraquinone pigments, anthrapyrimidine pigments, anthrone pigments, indanthrone pigments, flavone pigments, anthracene Ketone pigments, diketopyrrolopyrrole pigments, etc.

In addition, as the above-mentioned inorganic pigments, metal compounds such as metal oxides and metal complex salts can be used. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, Metal oxides or composite metal oxides, such as organic black pigments, titanium black, and pigments that mix red, green, and cyan to give black.

In particular, as the above-mentioned organic pigments and inorganic pigments, there are Specifically, the compounds classified as pigments in the Excellent Index (published by The Society of Dyers and Colourists) can be cited. More specifically, the following color index (C.I.) pigments can be cited, but they are not necessarily limited to these.

Cyan pigments, specifically, for example, CI Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, and 38; and CI Pigment Blue 15:3, 15:4, 15:6, 21, 28, 60, 64, and 76, etc.

Among them, it is preferable to contain one or more selected from C.I. Pigment Violet 23, C.I. Pigment Blue 15:3, and Pigment Blue 15:6.

When the above-mentioned pigment is additionally used with the dye of the above-mentioned chemical formula 1, the above-mentioned pigment is contained in an amount of 20 to 90% by weight, preferably 30 to 70% by weight, relative to the total weight of the cyan colorant. If 20 to 90% by weight of the above-mentioned pigment is contained, the viscosity is low, the storage stability is excellent, the dispersion efficiency is improved, and the contrast can be improved.

It is preferable to use a pigment dispersion liquid in which the particle diameter of the pigment is uniformly dispersed for the above-mentioned pigment. As an example of a method for uniformly dispersing the particle size of the pigment, a method of containing the pigment dispersant (a3) and performing a dispersion treatment, etc. can be cited. By the above method, a state in which the pigment is uniformly dispersed in a solution can be obtained. Pigment dispersion.

(a3) Pigment dispersant

The above-mentioned pigment dispersant is added in order to maintain the deagglomeration and stability of the pigment. As a specific example of the pigment dispersant, cationic Surfactants such as progeny, anionic, nonionic, amphoteric, polyester, polyamine, etc. can be used individually or in combination of two or more.

As a specific example of the said cationic surfactant, amine salts, such as stearylamine hydrochloride and lauryl trimethyl ammonium chloride, or a quaternary ammonium salt, etc. are mentioned.

Specific examples of the anionic surfactants include higher alcohol sulfates such as sodium lauryl sulfate and sodium oleyl sulfate, and alkyl sulfuric acids such as sodium lauryl sulfate and ammonium lauryl sulfate. Salts, sodium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate and other alkyl aryl sulfonates.

As specific examples of the above-mentioned nonionic surfactants, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, ethylene oxide/ Propylene oxide block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene sorbitan fatty acid ester Oxyethylene alkylamine and so on.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified Polyurethanes, polyethyleneimines, etc.

In addition, the pigment dispersant preferably contains an acrylic dispersant containing butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA) (hereinafter referred to as acrylate Department of dispersant). Commercial products of the above-mentioned acrylic dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150. The above-mentioned acrylic dispersants can be used alone or in combination. Use a mixture of more than one species.

In addition to the acrylate-based dispersant, other resin-based pigment dispersants can also be used for the above-mentioned pigment dispersants. As the above-mentioned other resin-type pigment dispersants, known resin-type pigment dispersants, especially polycarboxylates represented by polyurethanes and polyacrylates, unsaturated polyamides, and polycarboxylates can be cited. Acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyamino amide phosphates, hydroxyl-containing polycarboxylic acids Esters and their modified products, or oily dispersants such as amides or their salts formed by the reaction of polyesters with free carboxyl groups and poly(lower alkyleneimines); Water-soluble resins such as meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone, or water-soluble Polymer compounds; polyesters; modified polyacrylates; ethylene oxide/propylene oxide addition products; and phosphate esters, etc.

)化學公司的商品名：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 公司的商品名：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；Lubirzol公司的商品名：SOLSPERS-24000、SOLSPERS-32550、NBZ-4204/10；川研精細化學株式會社的商品名：

(HINOACT)T-6000、

T-7000、

T-8000；味之素株式會社的商品名：

(AJISPUR)PB-821、

PB-822、

PB-823；共榮社化學株式會社的商品名：

(FLORENE)DOPA-17HF、

DOPA-15BHF、

DOPA-33、

DOPA-44等。 As a commercially available product of the above-mentioned other resin type pigment dispersant, as the cationic resin dispersant, for example, BYK (

) Trade names of chemical companies: 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's 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 Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; products of Kawaken Fine Chemical Co., Ltd. name:

(HINOACT) T-6000,

T-7000,

T-8000; Trade name of Ajinomoto Co., Ltd.:

(AJISPUR)PB-821,

PB-822,

PB-823; Trade name of Kyoeisha Chemical Co., Ltd.:

(FLORENE)DOPA-17HF,

DOPA-15BHF,

DOPA-33,

DOPA-44 and so on.

In addition to the acrylate-based dispersant described above, other resin-based pigment dispersants can be used individually or in combination of two or more, and can be used in combination with an acrylate-based dispersant.

The pigment dispersant is contained in 5 to 60 parts by weight, preferably 15 to 50 parts by weight, relative to 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 will increase. If the content is less than 5 parts by weight, it may be difficult to micronize the pigment or cause problems such as gelation after dispersion.

In addition, with respect to the total weight of the solid content in the cyan photosensitive resin composition, the cyan coloring agent is contained at 5 to 60% by weight, preferably 10 to 45% by weight. Containing the above 5~60% by weight of the above cyan dye In the case of the toner, when the thin film is formed, the color density of the pixel is sufficient, the peeling property of the non-pixel portion during development is not reduced, and it is difficult to generate residue.

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

(B) Alkali-soluble resin

The alkali-soluble resin which is a component of the cyan photosensitive resin composition of this invention is manufactured by copolymerizing the ethylenic unsaturated monomer (b1) containing a carboxyl group as an essential component.

The above-mentioned ethylenically unsaturated monomer (b1) containing a carboxyl group, as specific examples, 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; ω-carboxy polycaprolactone mono(meth)acrylates, etc., mono(meth)acrylates of polymers containing carboxyl groups and hydroxyl groups at both ends, etc., preferably acrylic acid and methacrylic acid.

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

As a method for imparting the above-mentioned hydroxyl group, (1) a method of copolymerizing an ethylenically unsaturated monomer containing a carboxyl group and an ethylenically unsaturated monomer containing a hydroxyl group to produce, and (2) making a glycidyl group-containing The compound is additionally reacted with a copolymer of a carboxyl-containing ethylenically unsaturated monomer to produce a method, and (3) a compound having a glycidyl group is additionally combined with a carboxyl-containing ethylenic unsaturated monomer and a hydroxyl-containing ethylenic It is a method for producing a copolymer of unsaturated monomers, etc.

As specific examples of the above-mentioned hydroxyl-containing ethylenically unsaturated monomers, there are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, ( 2-hydroxy-3-phenoxypropyl meth)acrylate, N-hydroxyethyl acrylamide, etc., among which 2-hydroxyethyl (meth)acrylate is preferred, the above-mentioned ethylenically unsaturated monomers containing hydroxyl groups Two or more types can be used in combination.

As specific examples of the above-mentioned glycidyl group-containing compound, there are butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, Glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, 4-tert-butyl glycidyl benzoate, hard Glycidyl fatty acid, aryl glycidyl ether, and glycidyl methacrylate, etc. Preferably, butyl glycidyl ether, aryl glycidyl ether, and glycidyl methacrylate can be cited, The above-mentioned glycidyl group-containing compound can be used in combination of two or more kinds.

In addition, in the production of the above-mentioned alkali-soluble resin, unsaturated monomers that can be copolymerized with carboxyl-containing ethylenically unsaturated monomers include aromatic vinyl compounds, N-substituted maleimide compounds, and alicyclic compounds. Group (meth)acrylates, hydroxyethyl (meth)acrylates, aryl (meth)acrylates, unsaturated oxetane compounds, etc., but are not limited to these.

Specific examples of the above-mentioned aromatic vinyl compounds include styrene, vinyl toluene, α-methylstyrene, p-chlorostyrene, O-Methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl Methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether, etc.

The above-mentioned N-substituted maleimide-based compounds, specifically, for example, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N -O-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide Amine, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methyl Oxyphenyl maleimide, and N-p-methoxyphenyl maleimide, etc.

The alicyclic (meth)acrylates, specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate Alkyl (meth)acrylates such as propyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, etc.; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.02.6]decane-8-yl (meth)acrylate Esters, 2-biscyclopentyloxyethyl (meth)acrylate, and isobornyl (meth)acrylate, etc.

The above-mentioned hydroxyethyl (meth)acrylates, specifically, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate , (Methyl) Propane 2-hydroxy-3-phenoxypropyl enoic acid, and N-hydroxyethyl acrylamide, etc.

Specific examples of the aryl (meth)acrylate esters include phenyl (meth)acrylate, benzyl (meth)acrylate, and the like.

The above-mentioned unsaturated oxetane compound, specifically, for example, 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)-3- Ethyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-phenyl Oxetane, 2-(methacryloxymethyl)oxetane, and 2-(methacryloxymethyl)-4-trifluoromethyloxetane, etc. .

The above-mentioned unsaturated monomers can be used individually or in combination of two or more kinds.

In addition, the alkali-soluble resin preferably has an acid value of 30 to 150 mgKOH/g in order to ensure compatibility with dyes and storage stability of the cyan photosensitive resin composition.

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

Moreover, 10 to 80 weight% of the said alkali-soluble resin is contained with respect to the total weight of the cyan photosensitive resin composition, Preferably it contains 10 to 70 weight%.

If the content of the alkali-soluble resin is 10 to 80% by weight, the solubility in the developer is sufficient, the pattern formation is easy, the film of the pixel part of the exposed part is prevented from being reduced during development, and the peeling property of the non-pixel part becomes good. .

(C) Photopolymerizable compound

The photopolymerizable compound as a component of the cyan photosensitive resin composition of the present invention must be a compound that is polymerizable 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 it is not limited thereto.

As specific examples of the above-mentioned monofunctional monomers, there are nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate Ester, or N-vinylpyrrolidone, etc., but it is not limited to these.

As specific examples of the above-mentioned bifunctional monomers, there are 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tri Glycol di(meth)acrylate, bis(acryloxyethyl) ether of bisphenol A, or 3-methylpentanediol di(meth)acrylate, etc., but it is not limited to these.

As specific examples of the above-mentioned multifunctional monomers, there are trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tris (Meth) acrylate, 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)acrylate Esters etc. are not limited to these.

With respect to the total weight of the cyan photosensitive resin composition of this invention, 5-50 weight% of the said photopolymerizable compound is contained, Preferably it contains 7-50 weight%. When the photopolymerizable compound is in the range of 5 to 50% by weight, the strength and reliability of the pixel portion can be improved.

(D) Photopolymerization initiator

The photopolymerization initiator as a component of the cyan photosensitive resin composition of the present invention includes a compound of the following Chemical Formula 2.

The above a and b are 0 or 1, when the above a is 1, the above b is 1, when the above a is 0, the above b is 0 or 1, (1) When the above a=0, b=0, the above R ₁₆ is hydrogen, a halogen atom, a nitro group, a sulfonyloxy group containing a C1-C8 alkyl group substituted or unsubstituted by a halogen atom, a phenylsulfonyloxy group containing or not containing a substituent, containing a halogen atom Atom-substituted or unsubstituted alkyl sulfonyl group with 1 to 8 carbon atoms, heterocyclic sulfonyl group with 7 to 20 carbon atoms with or without substituents, or carbon 7 with or without substituents ~20 condensed cyclic sulfonyl group, (2) in the case of a=0 and b=1, the above R ₁₆ is a phenyl group with or without a substituent, and the carbon number with or without a substituent is 7 ~20 heterocyclic group, or a condensed ring group having 7 to 20 carbon atoms with or without substituents, (3) In the case of a=1 and b=1 above, the above R ₁₆ means that it is substituted by a halogen atom Or an unsubstituted sulfonyloxy group of an alkyl group having 1 to 8 carbons, or a phenylsulfonyloxy group with or without a substituent, the above-mentioned R ₁₇ and R ₁₈ are the same or different, and are hydrogen, and the carbon number is 1 ~22 alkyl groups, alkyl groups with 1 to 10 carbons containing halogen atoms, alkyl groups with 1 to 15 carbons at the end of ether or thioether groups, phenyl groups with or without substituents, or carbon numbers The phenylalkyl group of 7-11, the above R ₁₇ and R ₁₈ may form a ring, and the above R ₁₉ is the following chemical formula 3 or chemical formula 4,

[Chemical formula 4]

The above-mentioned R ₂₀ and R ₂₂ are the same or different, and are an alkyl group having 1 to 17 carbon atoms, an alkyl group having 2 to 5 carbon atoms containing a halogen atom, and an alkyl group having 2 to 7 carbon atoms having an ether group or a thioether group at the end. Groups, phenyl groups with or without substituents, phenylalkyl groups with 7 to 11 carbons with or without substituents, phenoxyalkyl groups with 7 to 10 carbons with or without substituents, containing Or a heterocyclic group with 7 to 20 carbons without substituents, or a condensed ring group with 7 to 20 carbons with or without substituents, the above-mentioned R ₂₁ is an alkyl group with 1 to 17 carbons, containing halogen Alkyl groups with 1 to 7 carbon atoms, alkyl groups with 2 to 7 carbon atoms at the end of ether or thioether groups, aminoalkyl groups with 2 to 4 carbon atoms with or without substituents, containing or not A substituted phenyl group, a C7-11 phenylalkyl group with or without a substituent, an ether group or a thioether group at the end and a C7-10 phenylalkyl group with or without a substituent Group, a condensed ring group with 7 to 20 carbons with or without substituents, or a heterocyclic group with 7 to 20 carbons with or without substituents, the above-mentioned R ₂₃ is an alkyl group with 1 to 16 carbons , Alkyl groups with 1 to 6 carbon atoms containing halogen atoms, phenyl groups with or without substituents, phenylalkyl groups with 7 to 10 carbons with or without substituents, ether groups or thioether groups at the end In addition, a phenylalkyl group with 7 to 9 carbon atoms with or without substituents, a condensed ring group with 7 to 20 carbon atoms with or without substituents, or carbon 7-20 with or without substituents的heterocyclyl.

The above-mentioned R ₂₀ and R _{22 are} preferably methyl groups.

The compound of the above-mentioned chemical formula 2 prevents the decrease in sensitivity and transmittance caused by the dye, and enables the cyan photosensitive resin composition of the present invention containing the dye as a colorant to effectively express photopolymerization characteristics.

As a commercially available product, the compound of the above chemical formula 2 includes UPI-03, UPI-22, and the like.

With respect to the total weight of the photopolymerization initiator, the compound of the above-mentioned chemical formula 2 is contained at 10 to 100% by weight, preferably 20 to 100% by weight.

If the compound of the above chemical 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 short-circuiting of the pattern is likely to occur in the development process.

In addition, in addition to the compound of Chemical Formula 2, the above-mentioned photopolymerization initiator is preferably selected from the group consisting of acetophenone compounds and benzophenone from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price. One or more compounds among triazine-based compounds, triazine-based compounds, biimidazole-based compounds, and thioxanthone-based compounds.

The above-mentioned acetophenone compounds, specifically, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzil dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4- (Methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2 -Hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one, and 2-(4-methylbenzyl)-2-(dimethylamino )-1-(4-morpholinophenyl)butan-1-one and the like.

The above-mentioned benzophenone-based compound specifically includes, for example, benzophenone, 0-benzophenone methyl benzoate, 4-phenylbenzophenone, and 4-benzophenone-4'- Methyl diphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone, etc.

Specific examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4- Bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan- 2-yl)vinyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl) Vinyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3, 5-triazine and so on.

The biimidazole compound, specifically, 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 4,4',5,5' phenyl groups are alkoxylated Carbonyl substituted imidazole compounds, etc. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) are preferably used )-4,4',5,5'-tetraphenylbiimidazole and 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1, 2'-Biimidazole.

The above-mentioned thioxanthone compounds, specifically, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4 -Propoxythioxanthone and the like.

With respect to the total weight of the solid content in the cyan photosensitive resin composition of the present invention, the photopolymerization initiator is contained in an amount of 0.1 to 40% by weight, and preferably 1 to 30% by weight.

If the photopolymerization initiator is contained in an amount of 0.1 to 40% by weight, the cyan photosensitive resin composition is highly sensitive, the exposure time is shortened, productivity is improved, and high resolution can be maintained. In addition, the intensity of the pixel portion and the smoothness of the surface of the pixel portion become good.

In addition, the above-mentioned photopolymerization initiator can additionally contain a photopolymerization initiation assistant (d1) in order to increase the sensitivity of the cyan photosensitive resin composition of the present invention. When the cyan photosensitive resin composition according to the present invention contains the photopolymerization initiation auxiliary (d1), the sensitivity is further improved, 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 above-mentioned amine compound, aromatic amine compounds are preferably used. Specific examples include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, Ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylamino benzoate Ethyl, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler’s ketone) and 4,4'-bis(diethylamine) Benzyl Ketones and so on.

The above-mentioned carboxylic acid compounds are preferably aromatic heteroacetic acids. Specifically, for example, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, and methylethylphenylthioacetic acid can be cited. Acetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycerol Amino acid, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthyloxyacetic acid, etc.

With respect to the total weight of the solid content in the cyan photosensitive resin composition, the photopolymerization initiation auxiliary agent is contained in an amount of 0.1 to 40% by weight, and preferably 1 to 30% by weight.

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

(E) Solvent

As long as the above-mentioned solvent is effective for dissolving other components contained in the cyan photosensitive resin composition, solvents used in ordinary cyan photosensitive resin compositions can be used without particular limitation, and ethers, acetates, and aromatics are particularly preferred. Group hydrocarbons, ketones, alcohols, esters, or amines, etc.

Examples of the above-mentioned 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. ; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether and other diethylene glycol dialkyl Ethers and so on.

Examples of the above-mentioned acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, pentyl acetate, methyl lactate, ethyl lactate, and butyl lactate. Ester, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethyl acetate 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-butanediol 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 ethyl Acid esters, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, and propylene carbonate, etc.

As said aromatic hydrocarbons, benzene, toluene, xylene, mesitylene, etc. are mentioned, for example.

As said ketones, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc. are mentioned, for example.

As said alcohols, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, 4-hydroxy-4-methyl-2-pentanone, etc. are mentioned, for example.

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

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

The above-mentioned solvents can be used individually or in combination of two or more kinds.

The above-mentioned solvents preferably use organic solvents with a boiling point of 100°C to 200°C in terms of coating properties and drying properties. Examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, Ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate, etc.

With respect to the total weight of the cyan photosensitive resin composition, 60 to 90% by weight of the solvent is contained, and preferably 70 to 85% by weight. If the above-mentioned solvent is contained in the above-mentioned range of 60 to 90% by weight, roll coaters, spin coaters, slit and spin coaters, slit coaters (sometimes called die coaters), inkjets, etc. are used When the coating device is applied, the applicability becomes good.

(F) Additives

The above-mentioned additives can be selectively added as needed, and for example, can contain one or more selected from antioxidants, other polymer compounds, curing agents, surfactants, adhesion promoters, ultraviolet absorbers, and anti-aggregation agents.

The antioxidant may contain one or more selected from a phenol-based antioxidant and a phosphorus-based antioxidant. In the case of a phenol-based antioxidant, it does not deteriorate even in an oven at 150°C for 200 hours or more.

The above-mentioned phenol-based antioxidant is preferably a hindered phenol-based antioxidant. Specifically, for example, 3-(3,5-di-tert-butyl-4-hydroxybenzene) Base) 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-hydroxybenzyl) )benzene) (240 hours), and Pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (960 hours) etc.

The above-mentioned phosphorus antioxidants, specifically, for example, triphenyl phosphate, isodecyl diphenyl phosphate, tris(2,4-di-tert-butyl phosphate) ) Ester (Tris(2,4-di-tert-butylphenyl)phosphate), 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphine Spiro[5.5]undecane (3,9-Bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane), 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) etc.

The antioxidant is contained in an amount of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, with respect to 100 parts by weight of the photopolymerization initiator. If the antioxidant is contained in an amount of 1 to 100 parts by weight, the sensitivity of the cyan photosensitive resin composition does not decrease, and an increase in transmittance can be expected. If it contains less than 1 part by weight of the above antioxidant, it is difficult to expect an increase in transmittance, and if it exceeds 100 parts by weight, the sensitivity caused by dye cannot be overcome Decrease, the sensitivity cannot be increased, and short-circuiting of the pattern is likely to occur in the development process.

Specific examples of the above-mentioned other polymer compounds include curable resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, and polyfluoroalkyl acrylates. , Thermoplastic resins such as polyester and polyurethane.

The above-mentioned curing agent is used to improve deep curing and mechanical strength. Specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

Among the above curing agents, specific examples of epoxy compounds include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, Novolac type epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of the above epoxy resins, epoxy resins, and Aliphatic, alicyclic or aromatic epoxy compounds other than its brominated derivatives, butadiene (co)polymer epoxide, isoprene (co)polymer epoxide, (meth)acrylic acid Glycidyl ester (co)polymer, and triglycidyl isocyanurate, etc.

Among the above curing agents, specific examples of oxetane compounds include carbonate dioxetane, xylene dioxetane, adipate dioxetane, and p-benzene. Diformate dioxetane, and cyclohexane dicarboxylic acid dioxetane, etc.

The curing agent may be a curing auxiliary compound capable of ring-opening and polymerizing the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent.

EH-700(

工業(株)製造)、

HH(新日本理化(株)製造)和MH-700(新日本理化(株)製造)等。上述例示的固化剂可以單独使用或者将2种以上混合使用。 The curing auxiliary compound includes, for example, polycarboxylic acids, polycarboxylic anhydrides, acid generators, and the like. The above-mentioned polyvalent carboxylic acid anhydrides can use products marketed as epoxy resin curing agents. As the above-mentioned commercially available products, one can cite

EH-700(

Industrial Co., Ltd.),

HH (manufactured by New Japan Physical and Chemical Co., Ltd.) and MH-700 (manufactured by New Japan Physical and Chemical Co., Ltd.), etc. The curing agents exemplified above can be used alone or in combination of two or more kinds.

In order to further improve the film formation of the cyan photosensitive resin composition, the above-mentioned surfactants can be used, and it is preferable to use silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric surfactants, and the like.

The aforementioned organosilicon-based surfactants, for example, as commercially available products, include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Dow Corning Toray Organosilicon, and TSF-4440, TSF-4300, TSF- 4445, TSF-4446, TSF-4460 and TSF-4452 etc.

F-470、F-471、F-475、F-482和F-489等。 The above-mentioned fluorine-based surfactants are, for example, commercially available products from Dainippon Ink Chemical Industry Co., Ltd.

F-470, F-471, F-475, F-482 and F-489, etc.

(POLYFLOW)(共榮社化學(株))、

(EFTOP)(

社)、

(MEGAFAC)(大日本油墨化學工業(株))、

(Flourad)(住 友3M(株))、

(Asahi guard)、

(Surflon)(以上為旭硝子(株))、

(SOLSPERSE)(Lubrisol)、EFKA(EFKA化學公司)、PB 821(味之素(株))、Disperbyk系列(BYK-chemi)等。 In addition, other commercially available products that can be used include KP (Shin-Etsu Chemical Co., Ltd.),

(POLYFLOW) (Kyoeisha Chemical Co., Ltd.),

(EFTOP)(

Society),

(MEGAFAC) (Dainippon Ink Chemical Industry Co., Ltd.),

(Flourad) (Sumitomo 3M Co., Ltd.),

(Asahi guard),

(Surflon) (Above is Asahi Glass Co., Ltd.),

(SOLSPERSE) (Lubrisol), EFKA (EFKA Chemical Company), PB 821 (Ajinomoto Co., Ltd.), Disperbyk series (BYK-chemi), etc.

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

The type of the adhesion promoter is not particularly limited. Specific examples of the adhesion promoter that can be used include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris(2-methyl) (Oxyethoxy) silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3 ,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc.

The adhesion promoter exemplified above can be used alone or in combination of two or more kinds. With respect to the total weight of the solid content in the cyan photosensitive resin composition, the adhesion promoter is usually contained at 0.01 to 10% by weight, preferably 0.05 to 2% by weight.

The type of the above-mentioned ultraviolet absorber is not particularly limited. As a specific example that can be used, 2-(3-tert-butyl-2-hydroxyl 5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone and the like.

There is no particular limitation on the type of the above-mentioned anti-aggregation agent, and specific examples that can be used include sodium polyacrylate and the like.

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

The cyan dye (a1), alkali-soluble resin (B), photopolymerizable compound (C), photopolymerization initiator (D), and solvent (E) containing the above chemical formula 1 are added, and additives (F) are further added as needed so that When it becomes a predetermined density|concentration, the cyan photosensitive resin composition concerning this invention can be manufactured.

When a pigment is included as a cyan coloring agent, the cyan pigment (a2) and the solvent (E) are mixed and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, 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.

The remaining part (B) of the alkali-soluble resin, the photopolymerizable compound (C), the photopolymerization initiator (D) and the additives (F) and solvent (E) used as needed are further added to the above-mentioned mixed coloring material, so that it becomes With a predetermined concentration, the cyan photosensitive resin composition according to the present invention can be produced.

In addition, the present invention provides a cyan color filter manufactured from the cyan photosensitive resin composition and a display device having the same.

First, by applying the cyan photosensitive resin composition to After the substrate (usually glass) or the layer composed of the solid components of the cyan photosensitive resin composition formed earlier, it is heated and dried to remove volatile components such as the solvent and obtain a smooth coating film.

As the coating method, for example, spin coating, cast coating method, roll coating method, slit and spin coating, or slit coating method can be used. After coating, it is heated and dried (pre-baking), or dried under reduced pressure and then heated to volatilize volatile components such as the solvent. Among them, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C. The thickness of the coating film after heating and drying is usually about 1 to 8 μm. The coating film obtained in this way is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, the entire exposure part is uniformly irradiated with parallel light, and in order to perform accurate alignment of the mask and the substrate, it is preferable to use devices such as a mask aligner and a stepper. If ultraviolet rays are irradiated, the parts irradiated with ultraviolet rays are cured.

As the aforementioned 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 according to needs, and is not particularly limited in the present invention. By bringing the cured coating film into contact with a developing solution to dissolve the non-exposed part and perform development, a spacer having a target pattern shape can be obtained.

The above-mentioned development method is not particularly limited to a liquid addition method, a dipping method, a spray method, and the like. In addition, the substrate can be tilted at any angle during development. The above-mentioned developer is usually an aqueous solution containing a basic compound and a surfactant.

The above-mentioned basic compounds are not particularly limited to inorganic or Organic alkaline compounds. Examples of the above-mentioned inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, and silicic acid. Potassium, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and ammonia.

In addition, as organic basic compounds, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, Triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine, etc.

The said inorganic or organic basic compound can be used individually or in mixture of 2 or more types, respectively. The concentration of the alkaline compound in the developer is 0.01 to 10% by weight, preferably 0.03 to 5% by weight, relative to the total weight of the developer.

As the surfactant in the above-mentioned developer, one or more kinds selected from the above-mentioned 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 relative to the total weight of the developer, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight. After development, wash with water and, if necessary, perform post-baking at 150-230°C for 10-60 minutes.

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

Hereinafter, in order to specifically describe the present invention, a detailed description will be given with examples. However, the embodiments of the present invention can be modified into various In different forms, the scope of the present invention should not be construed as being limited to the examples detailed below. The embodiments of the present invention are provided in order to more fully explain the present invention to those of ordinary skill in the art.

Synthesis example 1. Synthesis of alkali-soluble resin

An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, replaced with a nitrogen atmosphere, charged with 100 parts by weight of propylene glycol monomethyl ether acetate, and heated to 85°C while stirring .

Next, in the above flask, 19 parts by weight of methacrylic acid and 3,4-epoxytricyclo[5.2.1.02.6]decane-8- acrylic acid were dropped in about 5 hours using a drop pump (pump). Base ester and acrylic acid 3,4-epoxy tricyclo [5.2.1.02.6] decane-9-yl ester mixture (50:50 mol ratio) (trade name "E-DCPA", Daicel Corporation Manufacturing) 171 parts by weight of a solution dissolved in 40 parts by weight of propylene glycol monomethyl ether acetate.

A separate drip pump was used to drop 26 parts by weight of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) into the flask for about 5 hours and dissolved in propylene glycol monomethyl ether ethyl. A solution of 120 parts by weight of acid ester. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature, and an alkali-soluble resin solution containing 43.5% of the solid content of the monomer of the following chemical formulas 5, 6 and 7 was obtained.

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

In addition, the ratio (Mw/Mn) of the weight average molecular weight in terms of polystyrene and the number average molecular weight (Mw/Mn) was taken as the molecular weight distribution.

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

Column: TSK-GELG2000HXL

Column temperature: 40℃

Solvent: THF

Flow rate: 1.0mL/min

Solid content concentration of the tested liquid: 0.001~0.01% by weight

Injection volume: 50μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The weight average molecular weight of the obtained alkali-soluble resin was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mgKOH/g.

<Synthesis of Cyan Dye>

Synthesis example 2.

2-1.

This reaction is carried out under a nitrogen atmosphere.

After putting 36.3 parts by weight of potassium thiocyanate and 160 parts by weight of acetone into a flask equipped with a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. Then, 50 parts by weight of benzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped over 10 minutes.

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

Next, after the reaction mixture was ice-cooled, 34.2 parts by weight of a 30% sodium hydroxide aqueous solution was dropped, and the mixture was stirred at normal temperature for 30 minutes. Then, 35.3 parts by weight of chloroacetic acid was dropped at room temperature. After the dripping, the mixture was stirred under heating and reflux for 7 hours.

Next, after the reaction mixture was allowed 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 30 minutes. Then, it was allowed to stand for 30 minutes to separate the reaction mixture into an organic layer and an aqueous layer.

After the above-mentioned water layer was discarded by a liquid separation operation, the organic layer was washed in the order of 200 parts by weight of 1N hydrochloric acid, 200 parts by weight of tap water, and 200 parts by weight of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dry organic layer. The obtained organic layer was removed by evaporating the solvent with an evaporator, and a pale yellow liquid was obtained. 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 is carried out under a nitrogen atmosphere.

Put 9.3 parts by weight of the compound of Chemical Formula 8 produced in the above Synthesis Example 2-1, 4,4'-bis(diethylamino)benzophenone (Tokyo Chemical Industry Co., Ltd.) into a flask with a cooling tube and a stirring device. Production) After 10 parts by weight and 20 parts by weight of toluene, 14.8 parts by weight of phosphorus oxychloride were added, and the mixture was stirred at 95-100°C for 3 hours.

Next, after the reaction mixture was cooled to normal temperature, it was diluted with 170 parts by weight of isopropanol. Then, after the diluted reaction solution was poured into 300 parts by weight of saturated brine, 100 parts by weight of toluene was added, and the mixture was stirred for 30 minutes. The 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 above-mentioned water layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts by weight of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dry organic layer.

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

Mass analysis of the compound of chemical formula 9

Ionization mode: ESI ⁺ : m/z=601.3[M-Cl] ⁺

Accurate quality: 636.3

2-3.

This reaction is carried out under a nitrogen atmosphere.

Into a flask with a cooling tube and a stirring device, 10 parts by weight of the compound of Chemical Formula 9 produced in Synthesis Example 2-2 and 4.5 parts by weight of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.) , And 100 parts by weight of N,N-dimethylformamide, and stirred at 50-60°C for 3 hours.

Next, after cooling the reaction mixture to room temperature, it was dropped into 2000 parts by weight of tap water while stirring for 1 hour to obtain a dark blue suspension. The suspension obtained above was filtered to obtain a cyan solid. The cyan solid was dried under reduced pressure at 60°C 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 the above chemical formula 10 in chloroform to make the volume 250cm ³ , ^{dilute 2cm 3 of it} with ion exchange water, make the volume 100cm ³ (concentration: 0.028g/L), use a spectrophotometer (quartz Cell, optical path length; 1cm) The absorption spectrum was measured.

The compound of the above Chemical Formula 10 showed an absorbance of 2.9 at λmax=628nm.

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. Then, 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 the mixture was stirred at 65°C for 8.5 hours.

After cooling the above-mentioned mixed liquid to room temperature, a 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 the compound of the following chemical formula 11.

3-2.

This reaction is carried out under a nitrogen atmosphere.

Into a flask equipped with a cooling tube and a stirring device, 10 parts by weight of the compound of Chemical Formula 9 synthesized in the above Synthesis Example 2-2, 5.3 parts by weight of the compound of Chemical Formula 11 synthesized in the above Synthesis Example 3-1, and N,N- After 100 parts by weight of dimethylformamide, the mixture was stirred at 50 to 60°C for 3 hours.

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

Dissolve 0.35 g of the compound of the above chemical formula 12 in chloroform to make the volume 250cm ³ , ^{dilute 2cm 3 of it} with ion exchange water, make the volume 100cm ³ (concentration: 0.028g/L), use a spectrophotometer (quartz Cell, optical path length; 1cm) The absorption spectrum was measured.

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

Synthesis example 4.

This reaction is carried out under a nitrogen atmosphere.

Into a flask equipped with a cooling pipe and a stirring device, 10 parts by weight of the compound of Chemical Formula 9 synthesized in the synthesis example 2-2, 14.1 parts by weight of tungstosilicic acid hydrate (manufactured by SIGMA-ALDRICH), and N,N- After 100 parts by weight of dimethylformamide, the mixture was stirred at 50 to 60°C for 3 hours.

Next, after cooling the reaction mixture to room temperature, stir It was dripped into 2000 parts by weight of tap water while stirring for 1 hour to obtain a dark blue suspension. The suspension was filtered to obtain a cyan solid, and the cyan 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 the above chemical formula 13 in chloroform to make the volume 250cm ³ , ^{dilute 2cm 3 of it} with ion exchange water, make the volume 100cm ³ (concentration: 0.028g/L), use a spectrophotometer (quartz Cell, optical path length; 1cm) The absorption spectrum was measured.

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

Synthesis example 5.

5-1.

This reaction is carried out under a nitrogen atmosphere.

Put 32.2 parts by weight of potassium thiocyanate and 160 parts by weight of acetone into a flask equipped with a cooling tube and a stirring device, and then stir at room temperature. 30 minutes. Then, 50 parts by weight of 2-fluorobenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped for 10 minutes.

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

Next, after the reaction mixture was ice-cooled, 34.2 parts by weight of a 30% sodium hydroxide aqueous solution was dropped, and the mixture was stirred at normal temperature for 30 minutes. Then, 31.3 parts by weight of chloroacetic acid was dropped at normal temperature. After the dripping, the mixture was stirred under heating and reflux for 7 hours.

Next, after the reaction mixture was left to cool to normal temperature, 120 parts by weight of tap water and 200 parts by weight of toluene were added to the reaction solution, and the mixture was stirred for 30 minutes. Then, it was allowed to stand for 30 minutes, and the reaction mixture was separated into an organic layer and an aqueous layer.

After the above-mentioned water layer was discarded by a liquid separation operation, the organic layer was washed in the order of 200 parts by weight of 1N hydrochloric acid, 200 parts by weight of tap water, and 200 parts by weight of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dry organic layer. The obtained organic layer was evaporated and removed using 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 the compound of the following chemical formula 14 (yield 51%).

[Chemical formula 14]

5-2.

This reaction is carried out under a nitrogen atmosphere.

Into a flask with a cooling pipe and a stirring device, 9.9 parts by weight of the compound of the chemical formula 14 produced in the synthesis example 5-1, 4,4'-bis(diethylamino)benzophenone (Tokyo Kasei Co., Ltd. (Produced by the company) 10 parts by weight and 20 parts by weight of toluene, 14.8 parts by weight of phosphorus oxychloride were added, and the mixture was stirred at 95-100°C for 3 hours.

Next, after the reaction mixture was cooled to normal temperature, it was diluted with 170 parts by weight of isopropanol. Then, after pouring the diluted reaction solution into 300 parts by weight of saturated brine, 100 parts by weight of toluene was added, and the mixture was stirred for 30 minutes. The 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 above-mentioned water layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts by weight of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dry organic layer.

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

Mass analysis of the compound of chemical formula 15

Ionization mode: ESI ⁺ : m/z=619.3[M-Cl] ⁺

Accurate quality: 654.3

5-3.

This reaction is carried out under a nitrogen atmosphere.

Into a flask with a cooling tube and a stirring device, 10 parts by weight of the compound of Chemical Formula 15 produced in Synthesis Example 5-2 and 5.7 parts by weight of lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.) , And 30 parts by weight of N,N-dimethylformamide, and stirred at 40°C for 3 hours.

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

[Chemical formula 16]

Dissolve 0.35 g of the compound of the above chemical formula 16 in chloroform to make the volume 250cm ³ , ^{dilute 2cm 3 of it} with ion exchange water, make the volume 100cm ³ (concentration: 0.028g/L), use a spectrophotometer (quartz Cell, optical path length; 1cm) The absorption spectrum was measured.

The compound of the above Chemical Formula 16 showed an absorbance of 3.1 at λmax=630nm.

Synthesis example 6.

6-1.

This reaction is carried out under a nitrogen atmosphere.

After putting 33 parts by weight of potassium thiocyanate and 160 parts by weight of acetone into a flask equipped with a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. Then, 50 parts by weight of 2-methylbenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped for 10 minutes.

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

Next, after the reaction mixture was ice-cooled, 34.2 parts by weight of a 30% sodium hydroxide aqueous solution was dropped, and the mixture was stirred at normal temperature for 30 minutes. Of course Then, 32.1 parts by weight of chloroacetic acid was dropped at room temperature. After the dripping, the mixture was stirred under heating and reflux for 7 hours.

Next, after the reaction mixture was left to cool to normal temperature, 120 parts by weight of tap water and 200 parts by weight of toluene were added to the reaction solution, and the mixture was stirred for 30 minutes. Then, it was allowed to stand for 30 minutes, and the reaction mixture was separated into an organic layer and an aqueous layer.

After the water layer was discarded by a liquid separation operation, the organic layer was washed in the order of 200 parts by weight of 1N hydrochloric acid, 200 parts by weight of tap water, and 200 parts by weight of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dry organic layer. The obtained organic layer was evaporated and removed using 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 the compound of the following chemical formula 17 (yield 41%).

6-2.

This reaction is carried out under a nitrogen atmosphere.

9.7 parts by weight of the compound of the chemical formula 17 produced in the above synthesis example 6-1 was put into a flask with a cooling pipe and a stirring device, 4, After 10 parts by weight of 4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 20 parts by weight of toluene, 14.8 parts by weight of phosphorus oxychloride was added, and the mixture was stirred at 95-100°C 3 hours.

Next, after the reaction mixture was cooled to normal temperature, it was diluted with 170 parts by weight of isopropanol. Then, after pouring the diluted reaction solution into 300 parts by weight of saturated brine, 100 parts by weight of toluene was added, and the mixture was stirred for 30 minutes. The 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 above-mentioned water layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts by weight of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dry organic layer.

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

Mass analysis of the compound of chemical formula 18

Ionization mode: ESI ⁺ : m/z=615.4[M-Cl] ⁺

Accurate quality: 650.3

6-3.

This reaction is carried out under a nitrogen atmosphere.

Into a flask with a cooling tube and a stirring device, 10 parts by weight of the compound of Chemical Formula 18 produced in Synthesis Example 6-2, lithium bis(trifluoromethanesulfonyl)imide (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.7 parts by weight After 30 parts by weight and 30 parts by weight of N,N-dimethylformamide, the mixture was stirred at 40°C for 3 hours.

Next, after cooling the reaction mixture to room temperature, it was dropped into 500 parts by weight of tap water while stirring for 1 hour to obtain a dark blue suspension. The suspension obtained above was filtered to obtain a cyan solid. The cyan 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 the above chemical formula 19 in chloroform to make the volume 250cm ³ , ^{dilute 2cm 3 of it} with ion exchange water, make the volume 100cm ³ (concentration: 0.028g/L), use a spectrophotometer (quartz Cell, optical path length; 1cm) The absorption spectrum was measured.

The compound of the above Chemical Formula 13 showed an absorbance of 2.7 at λmax=627nm.

Production example 1. Production of pigment dispersion

CI Pigment Blue 15:6 12 parts by weight as a pigment, 4 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 44 parts by weight of propylene glycol methyl ether acetate as a solvent, and propylene glycol methyl ether 40 parts by weight were mixed and dispersed in a bead mill for 12 hours to produce a pigment dispersion liquid M1.

<Production of Cyan Photosensitive Resin Composition>

Examples 1 to 10, comparative examples 1 to 8.

The cyan photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 8 were produced according to the composition of Table 1 below.

Cyan colorant (A)

A-1: The compound of Chemical Formula 10 produced in Synthesis Example 2

A-2: The compound of Chemical Formula 12 produced in Synthesis Example 3

A-3: The compound of Chemical Formula 13 produced in Synthesis Example 4

A-4: The compound of Chemical Formula 16 produced in Synthesis Example 5

A-5: The compound of Chemical Formula 19 produced in Synthesis Example 6

M1: The pigment dispersion produced in Production Example 1

Alkali-soluble resin (B): Alkali-soluble resin produced in Synthesis Example 1

Photopolymerizable compound (C): KAYARAD DPHA (manufactured by Nippon Kayaku)

Photopolymerization initiator (D)

D-1: UPI-22 (manufactured by Daito Co., Ltd.)

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: Irganox1035 (manufactured by BASF)

Experimental example 1. Manufacture and characteristic evaluation of color filter

The cyan photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 8 were respectively coated on a 2-inch glass substrate (EAGLE XG) by spin coating, and then placed on a hot plate at a temperature of 100°C Maintained for 3 minutes, a thin film was formed. Then, a test photomask having a line/gap pattern of 1 to 100 μm was placed on the above-mentioned film so that the distance between the test photomask and the test photomask was 300 μm, and ultraviolet rays were irradiated. At this time, a high-pressure mercury lamp of 1 kW including all the g, h, and i lines was used to irradiate ultraviolet rays at an illuminance of ^{60 mJ/cm 2 without using a special optical filter.}

The film irradiated with the ultraviolet ray was immersed in a pH 10.5 aqueous KOH developing solution for 2 minutes to develop. Then, after washing the glass plate coated with the film with distilled water, it was dried by blowing nitrogen gas, and heated in a heating oven at 230° C. for 25 minutes to manufacture each color filter. The film thickness of the color filter manufactured above was 2.4 μm.

1. Measurement of transmittance

The color filter was manufactured by the method described above, the color filter was manufactured without using a test photomask, and the transmittance was measured using a colorimeter (manufactured by Olympus Corporation, OSP-200). The results are shown in Table 2 below.

2. Measurement of adhesion

The pattern of the color filter manufactured as described above was observed with an optical microscope, and the degree of the small defect phenomenon on the pattern was evaluated. The results are shown in Table 2 below, and the evaluation criteria are as follows.

<Evaluation Criteria>

○: No small defects on the pattern

△: 1 to 3 small defects on the pattern

×: More than 4 small defects on the pattern

3. Determination of residual film rate

The cyan photosensitive resin compositions of the above Examples 1 to 10 and Comparative Examples 1 to 8 were respectively coated on a substrate using a spin coater, and then pre-baked at 100°C for 1 minute. After exposure at 365nm, the temperature was 230°C. The post-baking (postbake) was performed at °C for 20 minutes, the thickness ratio (%) of the resist film before and after the post-baking was measured, the evaluation results are shown below, and the results are shown in Table 2 below.

From the results of Table 2 above, Examples 1 to 10, which are the cyan photosensitive resin composition of the present invention, showed excellent results in transmittance, adhesion, and chemical resistance. More specifically, the cyan photosensitive resin composition of Examples 6 to 10 in which the cyan dye of Chemical Formula 1 and the cyan pigment were used as the cyan colorant and Example 1 in which only the cyan dye of Chemical Formula 1 was used as the cyan colorant Compared with the cyan photosensitive resin composition of ~5, the results showed excellent adhesion and chemical resistance.

In contrast, the cyan photosensitive resin compositions of Comparative Examples 1 to 5 that did not use the compound of the above-mentioned Chemical Formula 2 as the photopolymerization initiator had poor adhesion and residual film rate.

In addition, the cyan photosensitive resin composition of Comparative Example 6 in which the dye of the above chemical formula 1 was not used and the pigment was used showed slightly poor transmittance, adhesion, and residual film rate. The pigment was used and the dye of the above chemical formula 1 was not used. The cyan photosensitive resin composition of Comparative Example 7 with the photopolymerization initiator of the above Chemical Formula 2 showed poor adhesion and residual film rate.

The cyan photosensitive resin composition of Comparative Example 8 in which the dye of the above-mentioned chemical formula 1 was used, the pigment was not used, and the photopolymerization initiator of the above-mentioned chemical formula 2 was not used, showed poor adhesion and residual film rate.

Therefore, it can be confirmed that the cyan photosensitive resin composition of the present invention is excellent in transmittance, adhesion, and residual film rate, particularly excellent in adhesion, and there is no decrease in sensitivity due to dyes, and it can solve the problem of pattern peeling during the development process. problem.

Claims (6)

A cyan photosensitive resin composition comprising a cyan colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The cyan photosensitive resin composition is characterized by: With respect to the total weight of the solid content in the cyan photosensitive resin composition, it contains 5 to 60% by weight of cyan colorant, 10 to 80% by weight of alkali-soluble resin, 5 to 50% by weight of photopolymerizable compound, and 0.1% by weight of photopolymerization initiator. ~40% by weight, relative to the total weight of the cyan photosensitive resin composition, containing 60 to 90% by weight of the solvent, wherein the cyan photosensitive resin composition is used to improve the adhesion and to maintain the residual film rate 90% or more, the cyan colorant contains the dye of the following chemical formula 1, and the photopolymerization initiator contains the compound of the following chemical formula 2,

The above R ₁ to R ₆ are each the same or different, and are hydrogen, an aryl group having 6 to 12 carbons with or without a substituent, or an alkyl group having 1 to 20 carbons. The alkyl group having 1 to 20 carbons may be Oxygen is contained between the methylene groups, the hydrogen of the above-mentioned C1-20 alkyl group may be substituted by a halogen atom or an amine group, and the above-mentioned R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may be respectively Combine each other to form a ring. The above R ₇ to R ₁₄ are the same or different, and are hydrogen, halogen atom, nitro, sulfonyl, hydroxyl, or C 1-8 alkyl, the above C 1-8 alkane The group may contain oxygen between methylene groups, the above R ₁₅ is hydrogen, a C 1-20 alkyl group, or a C 6-12 aryl group with or without a substituent, and the above X is oxygen, sulfur, Or amine group, the above Y is a counter anion, the above m is the oxidation number of Y,

The above a and b are 0 or 1, when the above a is 1, the above b is 1, when the above a is 0, the above b is 0 or 1, (1) When the above a=0, b=0, the above R ₁₆ is a hydrogen, a halogen atom, a nitro group, a sulfonyloxy group containing an alkyl group having 1 to 8 carbon atoms which may be substituted or unsubstituted by a halogen atom, a phenylsulfonyloxy group containing or not containing a substituent, a Sulfonyl groups of alkyl groups with 1 to 8 carbons substituted or unsubstituted by halogen atoms, heterocyclic sulfonyl groups with 7 to 20 carbons with or without substituents, or carbons with or without substituents Condensed cyclic sulfonyl group of 7-20, (2) In the case of a=0 and b=1 above, R ₁₆ is a phenyl group with or without substituents, and a carbon with or without substituents A heterocyclic group of 7 to 20, or a condensed ring group of 7 to 20 carbons with or without substituents, (3) In the case of a=1 and b=1 above, R ₁₆ is a halogenated Atom-substituted or unsubstituted alkyl sulfonyloxy group with 1 to 8 carbon atoms, or phenylsulfonyloxy group with or without substituents, R ₁₇ and R ₁₈ are the same or different, and are hydrogen and carbon An alkyl group of 1 to 22, an alkyl group of 1 to 10 carbons containing a halogen atom, an alkyl group of 1 to 15 carbons with an ether group or a thioether group at the end, a phenyl group with or without substituents, or A phenylalkyl group having 7 to 11 carbon atoms, the above R ₁₇ and R ₁₈ may form a ring, and the above R ₁₉ is the following chemical formula 3 or 4,

The above-mentioned R ₂₀ and R ₂₂ are the same or different, and are an alkyl group having 1 to 17 carbon atoms, an alkyl group having 2 to 5 carbon atoms containing a halogen atom, and an alkyl group having 2 to 7 carbon atoms having an ether group or thioether group at the end. Groups, phenyl groups with or without substituents, phenylalkyl groups with 7 to 11 carbons with or without substituents, phenoxyalkyl groups with 7 to 10 carbons with or without substituents, containing Or a heterocyclic group with 7 to 20 carbons without substituents, or a condensed ring group with 7 to 20 carbons with or without substituents, the above-mentioned R ₂₁ is an alkyl group with 1 to 17 carbons, containing halogen Alkyl groups with 1 to 7 carbon atoms, alkyl groups with 2 to 7 carbon atoms at the end of ether or thioether groups, aminoalkyl groups with 2 to 4 carbon atoms with or without substituents, containing or not A substituted phenyl group, a C7-11 phenylalkyl group with or without a substituent, an ether group or a thioether group at the end and a C7-10 phenylalkyl group with or without a substituent Group, a condensed ring group with 7 to 20 carbons with or without substituents, or a heterocyclic group with 7 to 20 carbons with or without substituents, the above-mentioned R ₂₃ is an alkyl group with 1 to 16 carbons , Alkyl groups with 1 to 6 carbon atoms containing halogen atoms, phenyl groups with or without substituents, phenylalkyl groups with 7 to 10 carbons with or without substituents, ether groups or thioether groups at the end In addition, a phenylalkyl group with 7 to 9 carbon atoms with or without substituents, a condensed ring group with 7 to 20 carbon atoms with or without substituents, or carbon 7-20 with or without substituents的heterocyclyl. The cyan photosensitive resin composition of claim 1, wherein the cyan colorant additionally contains a pigment. The cyan photosensitive resin composition of claim 2, wherein the pigment contains one or more selected from C.I. Pigment Blue 15:6 and C.I. Pigment Violet 23. The cyan photosensitive resin composition of claim 1, wherein [Y] ^m- of the chemical formula 1 is selected from the group consisting of an anion of a heteropolyacid containing tungsten, an anion of a homopolyacid containing tungsten, an anion of phosphotungstic acid, One of the anion of silicotungstic acid and the anion of homopolytungstic acid. A cyan color filter produced by using the cyan photosensitive resin composition according to any one of claims 1 to 4. A display device including the cyan color filter as claimed in claim 5.