JP7392226B2 - Photosensitive coloring composition for blue color filter, color filter, solid-state image sensor and liquid crystal display device using the same - Google Patents

Description

The present invention relates to a photosensitive coloring composition for a blue color filter suitable for producing color filters used in liquid crystal display devices, solid-state imaging devices, and the like.

Solid-state imaging devices, such as C-MOS (Complementary Metal Oxide Semiconductor) and CCD (Charge Coupled Device), display an additive mixture of primary colors B (blue), G (green), and R (red) on their light receiving elements. Generally, color separation is performed by arranging color filters each having a filter segment. In recent years, the area per pixel has tended to become smaller due to the miniaturization and increase in the number of pixels of solid-state image sensors, and there is a strong demand for thinner color filters used in solid-state image sensors. Also,

Furthermore, even if the color filter is made thinner, the shape of the spectral wavelength is required to remain the same as before. In this case, it becomes necessary to increase the concentration of the colorant contained in the pixels of the color filter. For this purpose, it is necessary to increase the concentration of the colorant in the photosensitive coloring composition used to produce the color filter.

However, in order to increase the concentration of the colorant in the photosensitive coloring composition, it is necessary to reduce the amount of other components, which causes problems in the stability of the photosensitive coloring composition. Therefore, the challenge was to achieve both thinning and thinning.

Furthermore, as the concentration of the colorant contained in the photosensitive coloring composition increases, the solubility of the coating film in an alkaline developer tends to decrease significantly. There are problems that arise. In addition, with the high color reproduction of color filters, the pigments contained in colored radiation-sensitive compositions tend to become more and more finely divided, but in order to stably disperse finely divided pigments, dispersion with a high amine value is required. It is effective to use resin. However, when a dispersion resin with a high amine value is used, development itself with an alkaline developer becomes difficult.

In order to address the problems of high colorant concentration, developability, and residues on unexposed areas of the substrate or on the light-shielding layer during development, Patent Document 1 discloses that the colorant content is 30 to 60% by mass in the total nonvolatile matter. % of certain photopolymerizable monomers are disclosed. Patent Document 2 discloses a photoinitiator having a specific structure.

Japanese Patent Application Publication No. 2009-92839 Japanese Patent Application Publication No. 2009-134289

When applied to a highly concentrated coloring composition in which the blue pigment content of the radiation-sensitive composition disclosed in Patent Document 1 is 45% by mass based on the total non-volatile content, the adhesion of resist pattern dimensions is poor and pixels Chips were a problem.
With the colored curable composition using a specific initiator disclosed in Patent Document 2, the adhesion of the resist pattern can be ensured by increasing the exposure amount using a stepper exposure device, but there is a problem that a large amount of development residue remains. became. Therefore, in order to expose the resist pattern with a low exposure dose, it is necessary to increase the amount of initiator, making it difficult to simultaneously achieve thinning of the film.

The present invention provides a photosensitive coloring composition for a blue color filter, a color filter, which has excellent viscosity characteristics, dispersion stability, alkaline developability even in a thin film, and excellent pattern formation properties independent of exposure amount. The present invention also aims to provide a solid-state image sensor and a liquid crystal display device using the same.

The present invention is a photosensitive coloring composition for a blue color filter containing a colorant (A), a dispersion resin (B), an alkali-soluble resin (C), a photopolymerization initiator (D), and a polymerizable compound (E). The colorant (A) contains at least one organic pigment selected from the group consisting of a blue pigment (A1) and a purple pigment (A2), and the content of the colorant (A) is 45% by mass in the total nonvolatile matter. % to 70% by mass, the dispersion resin (B) contains a dispersion resin (B1) having an amine value of 70 mgKOH/g to 150 mgKOH/g, and the photopolymerization initiator (D) has the following general formula (1) and the general formula The present invention relates to a photosensitive coloring composition for a blue color filter, which contains at least one photopolymerization initiator selected from the group consisting of formula (2).

In general formula (1), R ₁ and R ₂ each independently represent an alkyl group having 4 or less carbon atoms. R ₃ is an alkyl group having 20 or less carbon atoms which may have a substituent, an alkoxy group having 20 or less carbon atoms which may have a substituent, or an aryl group having 20 or less carbon atoms which may have a substituent. represents a group, and adjacent substituents may be bonded to each other to form an aliphatic ring or an aromatic ring. _R4 is a nitro group, an alkyl group having 20 or less carbon atoms which may have a substituent, an alkoxy group having 20 or less carbon atoms which may have a substituent, or 20 carbon atoms which may have a substituent. It represents the following aryl group, and adjacent substituents may be bonded to each other to form an aliphatic ring or an aromatic ring.
In general formula (2), R ₅ to R ₇ each independently represent an alkyl group having 4 or less carbon atoms which may have a substituent.

According to the present invention, a photosensitive coloring composition for a blue color filter, which has excellent viscosity characteristics, dispersion stability, alkaline developability even in a thin film, and excellent pattern formation properties independent of exposure amount, A filter, a solid-state image sensor, and a liquid crystal display device using the same can be provided.

Define terms used in the present invention. When expressed as "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", unless otherwise specified, each , "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate" or "acrylamide and/or methacrylamide". "C.I." mentioned herein means color index (C.I.).

[Colorant (A)]
In the photosensitive coloring composition for a blue color filter of the present invention (hereinafter also referred to as coloring composition), the colorant (A) is at least one type selected from the group consisting of a blue pigment (A1) and a violet pigment (A2). It is characterized in that it contains an organic pigment, and the content of the colorant (A) is 45% by mass to 70% by mass based on the total nonvolatile matter. The colorant (A) may contain one or more types of only the blue pigment (A1), may contain the blue pigment (A1) and the purple pigment (A2), or may contain the purple pigment (A2) and the blue pigment. It may also contain pigments other than (A1).

(Blue pigment (A1))
The blue pigment (A1) is, for example, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33 , 35, 36, 56, 56:1, 60, 61, 61: 1, 62, 63, 64, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. . Among these, from the viewpoint of coloring power and pattern forming property, C.I. I. Pigment Blue 15:3, 15:4, and 15:6 are preferred.

(Purple pigment (A2))
The purple pigment is, for example, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. Among these, C.I., which is a dioxazine pigment, is preferred from the viewpoint of coloring power and pattern forming properties. I. Pigment Violet 23 is preferred.

The colorant (A) can be used alone or in combination of two or more.

From the viewpoint of thin film formation and developability, the content of the colorant (A) is preferably 45 to 70% by mass, more preferably 47 to 65% by mass, and more preferably 48 to 60% by mass, based on 100% by mass of the nonvolatile content of the coloring composition. Mass % is more preferred.

(Refining of organic pigments)
In the present invention, the organic pigment is preferably used in a finely divided form. The refinement method is not particularly limited, and, for example, any of wet grinding, dry grinding, and solution precipitation methods can be used. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle diameter of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. Note that from the viewpoint of dispersibility and coloring power, the average primary particle diameter is more preferably 10 to 70 nm.

Salt milling is a process in which a mixture of pigments, water-soluble inorganic salts, and water-soluble organic solvents is mechanically heated while being heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attriter, or sand mill. After kneading, water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for salt milling pigments, it is possible to obtain pigments with very fine primary particle diameters, narrow distribution widths, and sharp particle size distributions.

Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, sodium sulfate, etc., and sodium chloride (salt) is preferred from the viewpoint of cost. The amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by weight, more preferably 300 to 1,000 parts by weight, based on 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, a high boiling point solvent with a boiling point of 120° C. or higher is preferred from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

It is preferable to add a resin to the salt milling treatment from the viewpoint of coloring power and dispersion stability. The type of resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferably solid at room temperature, insoluble in water, and partially soluble in the above organic solvent. The amount of resin used is preferably 2 to 200 parts by weight per 100 parts by weight of the colorant (A).

It is preferable to add the dye derivative (A3) to the salt milling treatment from the viewpoint of dispersion stability and coloring power. The amount of the pigment derivative (A3) to be used is preferably 5 to 40 parts by weight based on 100 parts by weight of the organic pigment.

<Removal of metal>
When a coloring composition contains a large amount of a specific metal element as an impurity other than the constituent components of the pigment, dispersion stability over time is inhibited. Furthermore, heat resistance may be lowered or sensitivity may be lowered. In addition, color filters created using this may have foreign matter, which tends to cause a decrease in brightness as a result. It is preferable that the total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) contained in the photosensitive coloring composition is 500 mass ppm or less.

The total amount of the specific metal element is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less. Further, the lower limit of the total amount of the specific metal element is not particularly limited, but is preferably 1 ppm or more by mass, and more preferably 5 ppm or more by mass. Within the above range, it is possible to obtain a photosensitive coloring composition that can reduce costs, has excellent storage stability, and can form a color filter with less generation of foreign matter and less reduction in brightness.

The amount of each specific metal element contained in the photosensitive coloring composition is preferably 100 mass ppm or less, and more preferably 50 mass ppm or less.

In addition, metals such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co that make up pigments should be kept in small amounts as impurities that do not become constituents of pigments, and they can be treated in the same way as specific metal elements using the following method. It can be removed. Furthermore, since Mn, Cs, Ti, Co, Si, Pd, etc. may be mixed in from materials (eg, catalysts) used in the manufacturing process of various raw materials for the photosensitive coloring composition, they are removed as much as possible.

Methods for removing metals mixed in from the colorant (A) or equipment during the manufacturing process include JP-A No. 2010-83997, JP-A No. 2018-36521, JP-A No. 7-198928, and JP-A-8- Examples include the method of washing with water as described in JP-A No. 333521 and JP-A-2009-7432, and the method of removing magnetic foreign matter using a magnet as described in JP-A-2011-48736.

The content of the specific metal element can be measured by inductively coupled plasma emission spectroscopy (ICP).

<Dye derivative (A3)>
The photosensitive coloring composition of the present invention can contain a dye derivative. When the dye derivative is adsorbed onto the surface of the organic pigment, the surface of the organic pigment becomes polar and becomes more compatible with the dispersion resin, thereby further improving the dispersibility of the organic pigment. A dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Dye derivatives include, for example, compounds having acidic substituents such as sulfo groups, carboxy groups, or phosphoric acid groups, as well as amine salts thereof, sulfonamide groups, or basic substituents such as tertiary amino groups at the terminals. Examples include compounds having a neutral substituent such as a phenyl group or a phthalimide alkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, and benzoisomer pigments. Examples include indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

Diketopyrrolopyrrole dye derivatives are described in JP2001-220520A, WO2009/081930 pamphlet, WO2011/052617 pamphlet, WO2012/102399 pamphlet, JP2017-156397A, and phthalocyanine dye derivatives are described in JP 2007-226161, WO 2016/163351 pamphlet, JP 2017-165820, JP 5753266, anthraquinone dye derivatives are JP 63-264674, JP 09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325 pamphlet, quinacridone dye derivatives are disclosed in JP-A-48-54128, JP-A-03-9961. No. 2000-273383, dioxazine dye derivatives in JP2011-162662, thiazine indigo dye derivatives in JP2007-314785, and triazine dye derivatives in JP2007-314785. 61-246261, JP 11-199796, JP 2003-165922, JP 2003-168208, JP 2004-217842, JP 2007-314681, benzisoindole series The pigment derivative is disclosed in JP-A No. 2009-57478, and the quinophthalone-based pigment derivative is disclosed in JP-A-2003-167112, JP-A 2006-291194, JP-A 2008-31281, JP-A 2012-226110, Naphthol dye derivatives are disclosed in JP-A-2012-208329 and JP-A-2014-5439, azo-based dye derivatives are in JP-A-2001-172520 and JP-A-2012-172092, and acidic substituents are disclosed in JP-A-2012-172092. JP 2004-307854, the basic substituent is a dye derivative described in JP 2002-201377, JP 2003-171594, JP 2005-181383, JP 2005-213404. can be mentioned. In addition, in these documents, the dye derivative is sometimes described as a derivative, a dye derivative, a dispersant, a pigment dispersant, or simply a compound. A compound having a substituent such as a neutral group has the same meaning as a dye derivative.

The dye derivatives can be used alone or in combination of two or more types.

The amount of the dye derivative used is preferably 1 to 100 parts by weight, more preferably 3 to 70 parts by weight, and even more preferably 5 to 50 parts by weight, based on 100 parts by weight of the organic pigment.

When a pigment derivative is added to an organic pigment and subjected to micronization processing such as acid pasting, acid slurry, dry milling, salt milling, and solvent salt milling, the pigment derivative is adsorbed to the pigment surface and the pigment derivative is not added. The primary particles of the pigment can be made finer compared to the conventional method.

By adding a pigment derivative to an organic pigment and performing a dispersion process such as wet dispersion using two rolls, three rolls, or beads, the pigment derivative is adsorbed onto the pigment surface, making the pigment surface polar and creating a resin-type dispersant. Adsorption is promoted. This improves compatibility with other components, and improves the dispersion stability and viscosity stability over time of the photosensitive coloring composition.

[Dispersion resin (B)]
The colored composition of the present invention contains, as the dispersion resin (B), a dispersion resin (B1) in which at least one kind has an amine value of 70 mgKOH/g to 150 mgKOH/g.
The dispersion resin (B) in the present invention can be prepared by, for example, dispersing the colorant (A) in the dispersion resin (B) in advance to obtain a coloring composition that is a precursor of a photosensitive coloring composition, and then dispersing the colorant (A) in the dispersion resin (B). It can be distinguished from the alkali-soluble resin (C) by stirring and mixing the coloring composition and the alkali-soluble resin (C) to form a photosensitive coloring composition.

(Dispersed resin (B1))
The dispersion resin (B1) is a basic dispersion resin, and is preferably a copolymer obtained by radical polymerization of a monomer containing a basic group-containing monomer, for example. This dispersion resin has an affinity site containing a basic group that adsorbs to the pigment and stabilizes the dispersion.

The amine value of the basic dispersion resin (B1) used in the present invention is 70 to 150 mgKOH/g, more preferably 70 to 120 mgKOH/g.

In the present invention, the basic group is a functional group having a nitrogen atom. The basic dispersion resin (B1) is, for example, a nitrogen atom-containing graft copolymer, a side chain containing a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, pyridine, pyrimidine, pyrazine, etc. Examples include acrylic block copolymers, random copolymers, and urethane resins having nitrogen-containing heterocycles such as . Among these, block copolymers are more preferred.

In the present invention, from the viewpoint of dispersion stability, the basic group has at least one unit selected from the group represented by the following general formula (3), general formula (4), and general formula (5). is preferred.

In the general formula (3), _{R 1} to R ₃ each independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may have _a substituent; Two or more may be bonded to each other to form a cyclic structure. R ₄ represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y ⁻ represents a counter anion.
R ₁ to R ₃ in the general formula (3) are, for example, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an aralkyl group having 7 to 16 carbon atoms which may have a substituent. are more preferred, and methyl, ethyl, propyl, butyl, and benzyl groups are particularly preferred.

In general formula (4), R ₅ and R ₆ independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, and R ₅ and R ₆ may be combined with each other to form a cyclic structure. R ₄ represents a hydrogen atom or a methyl group, and X represents a divalent linking group.
R ₅ and R ₆ in the general formula (4) are, for example, more preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, and particularly a methyl group, an ethyl group, a propyl group, and a butyl group. preferable.

In the general formula (5), R ₇ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR ₁₂ , R ₁₂ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, and R ₈ , R ₉ , R ₁₀ and R ₁₁ each independently represent a methyl group, an ethyl group, or a phenyl group. R ₄ represents a hydrogen atom or a methyl group, and X represents a divalent linking group.
Examples of the alkyl group having 1 to 18 carbon atoms in R ₇ of the general formula (5) include linear, branched, and cyclic alkyl groups. Examples include methyl group, ethyl group, normal propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group and the like.
Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, and 2-naphthyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms include a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms. Examples include benzyl group, phenethyl group, α-methylbenzyl group, and 2-phenylpropan-2-yl group.
Examples of the acyl group include an alkanoyl group having 2 to 8 carbon atoms and an aroyl group. Examples include an acetyl group and a benzoyl group.
Among these, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an oxy radical group are particularly preferred, a hydrogen atom and a methyl group are more preferred, and a methyl group is even more preferred.

In general formulas (3), (4), and (5), the divalent linking group X is, for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, -CONH-R ₁₃ -, -COO -R ₁₄ - (wherein R ₁₃ and R ₁₄ are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), etc. It will be done. Among these, -COO-R ₁₄ - is preferred. Further, in the above formula (9), examples of the counter anion Y ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ⁻ and the like.

Examples of the quaternary ammonium base-containing monomer forming general formula (3) include (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, and (meth)acryloyloxyethyldimethylbenzylammonium chloride. , alkyl (meth)acrylate quaternary ammonium salts such as (meth)acryloyloxyethylmethylmorpholinoammonium chloride, (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminoethyltriethylammonium chloride, (meth)acryloylamino Examples include alkyl (meth)acryloylamide quaternary ammonium salts such as ethyldimethylbenzylammonium chloride, dimethyldiallylammonium methyl sulfate, trimethylvinylphenylammonium chloride, and the like.

The tertiary amine group-containing monomer forming general formula (4) is, for example, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylates having a tertiary amino group such as (meth)acrylate and N,N-diethylaminopropyl (meth)acrylate;
Tertiary compounds such as N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide (meth)acrylamides having an amino group;
etc.

Examples of the monomers forming general formula (5) include compounds represented by the following formulas (5-1) to (5-11).

In formulas (5-1) to (5-11), R ₄ represents hydrogen or a methyl group.

Among these, 2,2,6,6-tetramethylpiperidyl methacrylate (a compound in which R ₄ is a methyl group in the above formula (5-1)), 1,2,2,6,6-pentamethylpiperidyl methacrylate (Compounds in which R ₄ is a methyl group in the above formula (5-2)) are preferred, and 1,2,2,6,6-pentamethylpiperidyl methacrylate is particularly preferred.

Other monomers that can be copolymerized with the basic-containing monomer include:
For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth), tert-butyl (meth)acrylate, isoamyl (meth)acrylate , octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate , linear or branched alkyl (meth)acrylates such as isomyristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate;
Cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate;
(meth)acrylates having a heterocycle such as tetrahydrofurfuryl (meth)acrylate and 3-methyl-3-oxetanyl (meth)acrylate;
(Meth)acrylates having an aromatic ring such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate , diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, Triethylene glycol monoethyl ether (meth)acrylate, tripropylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polypropylene glycol monomethyl ether (meth)acrylate, polyethylene (Poly)alkylene glycol monoalkyl ether (meth)acrylates, such as glycol monolauryl ether (meth)acrylate, polyethylene glycol monostearyl ether (meth)acrylate, and octoxypolyethylene glycol-polypropylene glycol (meth)acrylate;
Phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paraacrylate Milphenoxyethylene glycol (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, and nonylphenoxypoly(ethylene glycol-propylene glycol) (meth)acrylate. ) (Poly)alkylene glycol (meth)acrylates having an aromatic ring such as acrylate;
Alkyloxy such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane (Meth)acrylates having a silyl group;
Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate; (meth)acryloxy-modified polydimethyl Siloxanes (silicone macromers);
N-substituted (meth)acrylamides such as (meth)acrylamide, dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, and acryloylmorpholine; Additionally, nitriles such as (meth)acrylonitrile and the like can be mentioned.
Also, styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acids such as vinyl acetate and vinyl propionate. Examples include vinyls.

Furthermore, a carboxyl group-containing monomer can also be used in combination. Examples of carboxyl group-containing monomers include (meth)acrylic acid, (meth)acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2-(meth)acryloyloxyethyl phthalate, and 2-(meth)acrylic acid dimer. ) Acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth)acrylate, and ω-carboxypolycaprolactone (meth) ) acrylate, etc.

Furthermore, amino group-containing monomers other than the units represented by general formulas (3), (4), and (5) may be used in combination without impairing the effects of the present invention.

The basic dispersion resin (B1) can be used by forming a salt with an acidic compound.
Examples of the acidic compound include phosphoric acid compounds and sulfonic acid compounds.

Examples of the phosphoric acid compound include monobutyl phosphoric acid, dibutyl phosphoric acid, methyl phosphoric acid, dibenzyl phosphoric acid, diphenyl phosphoric acid, phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, and the like.
Examples of the sulfonic acid compound include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethyl sulfate, monoethyl sulfate, mono-n-propyl sulfate, and the like. Note that a hydrate such as p-toluenesulfonic acid monohydrate may also be used.
Among these, phosphoric acid compounds are preferred from the viewpoint of suppressing foreign substances.

From the viewpoint of dispersion stability, the basic dispersion resin (B1) preferably has a weight average molecular weight of 1,000 to 100,000 in terms of polystyrene.

From the viewpoint of dispersion stability, the content of the basic dispersion resin (B1) is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the colorant (A).

The photosensitive coloring composition of the present invention contains, as the dispersion resin (B), one or more of a basic dispersion resin (B1), a phosphoric acid dispersion resin (B2), and a carboxylic acid dispersion resin (B3). Can be included.

(Phosphoric acid-based dispersion resin (B2))
The phosphoric acid-based dispersion resin (B2) is a resin having a phosphoric acid bond [(-O) ₃ P=O] in the molecule. A preferred example is, for example, a phosphoric acid-based dispersion resin shown in either (B2-1) or (B2-2) below.

[Phosphoric acid-based dispersion resin (B2-1)]
The phosphoric acid-based dispersion resin (B2-1) is a resin represented by the following general formula (6).
(HO-) _3-n -PO-(O-R ¹ ) _n General formula (6)
(In general formula (6), R ¹ represents a polyester residue having a number average molecular weight of 300 to 10,000, and n represents 1 or 2.)

The phosphoric acid-based dispersion resin represented by the general formula (6) has a large effect of suppressing re-aggregation of pigments after dispersion, so that a color filter with few foreign substances and excellent transparency can be produced.

The phosphoric acid-based dispersion resin represented by the general formula (6) can be prepared by, for example, performing ring-opening addition of a cyclic ester (first step) using a monoalcohol as an initiator, followed by phosphoric acid esterification (second step). It is preferable to manufacture by carrying out.

Monoalcohol is a compound having one hydroxyl group in the molecule, and any of primary, secondary, and tertiary alcohols can be used. Monoalcohols include, for example, methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, t-butanol, pentanol, amyl alcohol, hexanol, heptanol, octanol, 2-ethylhexyl alcohol, nonanol, decanol, lauryl alcohol, myristyl alcohol. , cetyl alcohol, stearyl alcohol, oleyl alcohol, hexadecyl alcohol and the like. Among these, lauryl alcohol, N-hexanol, and hexadecyl alcohol are preferred.

In the first step, a polyester residue having a hydroxyl group at one end can be synthesized by ring-opening addition polymerization of ε-caprolactone, which is a cyclic ester, using a monoalcohol as an initiator. The addition reaction of ε-caprolactone can be carried out by a known method, for example, by charging a monoalcohol, ε-caprolactone, and a polymerization catalyst into a reactor connected to a dehydration tube and a condenser under a nitrogen stream. In addition, when using a monoalcohol with a low boiling point, the reaction can be carried out under pressure using an autoclave. In the reaction, no solvent or a suitable dehydrated solvent such as toluene or xylene can be used. After the reaction is complete, the solvent used in the reaction can be removed by distillation or other operations, or it can be used as is as part of the product.

The reaction temperature in the first step is preferably 120°C to 220°C, more preferably 160°C to 210°C. When the reaction is carried out at an appropriate temperature, the reactants can be efficiently obtained while suppressing side reactions.
The number of moles of ε-caprolactone added per mole of monoalcohol is preferably 1 to 50 moles, more preferably 3 to 20 moles. If the reaction is carried out at an appropriate ratio, a dispersed resin with an appropriate molecular weight can be obtained.

Examples of the polymerization catalyst include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodine, tetrabutylammonium iodine, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide. Quaternary ammonium salts such as tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodine, tetrabutylphosphonium iodine, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium In addition to quaternary phosphonium salts such as iodine, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodine, phosphorus compounds such as triphenylphosphine, and organic carbonates such as potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate. In addition to acid salts, alkali metal alcoholates such as sodium alcoholate and potassium alcoholate, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, and zinc compounds such as zinc chloride can be mentioned.

As the second step, a polyester residue having a hydroxyl group at one end is reacted with a phosphoric acid esterification agent such as phosphorus pentoxide, polyphosphoric acid, orthophosphoric acid, or phosphorus oxychloride, and the general formula ( A phosphoric acid-based dispersion resin represented by 6) can be obtained. Among these phosphoric acid esterification agents, one or more phosphoric acid selected from the group consisting of orthophosphoric acid, polyphosphoric acid, and phosphorus pentoxide is used because it does not produce by-products such as hydrochloric acid gas and does not require special equipment. Acid esterifying agents are preferred. Among these, polyphosphoric acid having a content of 116% by mass in terms of orthophosphoric acid is preferred.

The charging ratio of the phosphoric acid esterifying agent is preferably 0.5 to 1.5 as the molar ratio of the phosphorus atom in the phosphoric acid esterifying agent to the hydroxyl group of the polyester residue having a hydroxyl group at one end, and 1.0 to 1. .3 is more preferable, and 1.05 to 1.2 is more preferable. If the reaction is carried out at an appropriate ratio, a dispersed resin with few by-products can be obtained.

The reaction temperature in the second step is not particularly limited, but is preferably 40°C to 130°C, even more preferably 50°C to 110°C, and even more preferably 60°C to 100°C. When the reaction is carried out at an appropriate temperature, a dispersed resin with few unreacted substances and by-products can be obtained.

In the dispersion resin represented by the general formula (6), from the viewpoint of dispersibility, the molar ratio of the phosphoric ester with n=1 and the phosphoric ester with n=2 is preferably 100:0 to 100:30. preferable.

Further, in the dispersion resin represented by the general formula (6), it is preferable that R ¹ has a structure represented by the following general formula (6-1).
-(R ¹¹ -COO-) _m -R ¹² General formula (6-1)
(In general formula (6-1), R ¹¹ is a lactone residue, R ¹² is a monoalcohol residue, and m is an integer from 1 to 50.)
In the general formula (6-1), for example, it is preferable that R ¹ is a polycaprolactone residue because pigment dispersibility and dry solubility will be good. The number average molecular weight of the polycaprolactone residue is preferably 300 to 10,000.

[Phosphoric acid-based dispersion resin (B2-2)]
The phosphoric acid-based dispersion resin (B2-2) is a dispersion resin that is a copolymer of a phosphoric acid group-containing monomer and other monomers. This is a resin described in Publication No.-161737.

(Carboxylic acid-based dispersion resin (B3))
The carboxylic acid-based dispersion resin (B3) is a resin having dispersion ability and containing a carboxyl group (-COOH) in its molecule. A preferred example is a carboxylic acid-based dispersion resin represented by either (B3-1) or (B3-2) below.

[Carboxylic acid-based dispersion resin (B3-1)]
The carboxylic acid-based dispersion resin (B3-1) contains an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic dianhydrides and tricarboxylic anhydrides and a hydroxyl group in a hydroxyl group-containing compound. It is a resin containing a polyester portion having a carboxyl group, which is obtained by reacting, and a vinyl polymer portion, which is formed by radical polymerization of monomers.
First, the polyester portion will be explained. The polyester portion is a site where a plurality of ester groups derived from the reaction between an acid anhydride group and a hydroxyl group are present.

Examples of the tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 3,5,6 -Tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyclohexene-1 , 2-dicarboxylic dianhydride, aliphatic tetracarboxylic dianhydride such as bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyro Mellitic acid dianhydride, ethylene glycol dianhydride trimellitic acid ester, propylene glycol dianhydride trimellitic acid ester, butylene glycol dianhydride trimellitic acid ester, 3,3',4,4'-benzophenonetetracarboxylic dianhydride , 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4' -Tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'- Perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenyl phthalate) acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4 '-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1- Examples include aromatic tetracarboxylic dianhydrides such as naphthalenesuccinic dianhydride. Among these, aromatic tetracarboxylic dianhydrides are preferred from the viewpoint of adsorption to pigments.

The tetracarboxylic dianhydride is not limited to the above-mentioned exemplified compounds, and may have any structure as long as it has two acid anhydride groups. These may be used alone or in combination. Tetracarboxylic dianhydride forms a dispersion resin having two carboxyl groups per unit of tetracarboxylic dianhydride through reaction with a hydroxyl group-containing compound, so from the viewpoint of pigment adsorption, the dispersion of the present invention is It is preferable as a constituent element of resin.

Examples of the tricarboxylic anhydride include aliphatic tricarboxylic anhydride and aromatic tricarboxylic anhydride.

Aliphatic tricarboxylic acid anhydrides include, for example, 3-carboxymethylglutaric anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid-1 , 2-anhydride, 1,3,4-cyclopentanetricarboxylic anhydride, and the like.

Aromatic tricarboxylic acids include, for example, benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic acid Anhydrides (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride etc.), 3,4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenyl ethertricarboxylic anhydride, 3,4,4'-biphenyltricarboxylic anhydride, 2,3,2'- Examples include biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, and 3,4,4'-biphenylsulfonetricarboxylic anhydride. Among these, aromatic tricarboxylic acid anhydrides are preferred from the viewpoint of adsorption to pigments.

The molar ratio of the acid anhydride group in one or more acid anhydrides selected from tetracarboxylic anhydride and tricarboxylic acid anhydride to the hydroxyl group in the hydroxyl group-containing compound is acid anhydride group/hydroxyl group = 0.5 to 1.5 is preferred. When the reaction is carried out at an appropriate ratio, it is easy to obtain a dispersed resin with good dispersibility.

Among monools and polyols, the hydroxyl group-containing compound is preferably a polyol such as a diol having a plurality of hydroxyl groups. The hydroxyl group in the polyol functions as a bonding point with the vinyl polymer moiety.
Examples of the polyol that serves as a bonding point with the vinyl polymer portion include at least one hydroxyl group-containing compound selected from the group of compounds having two hydroxyl groups and one thiol group in the molecule and vinyl polymers containing a hydroxyl group at one end. . For example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin or 1-thioglycerol), 2-mercapto-1, 2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl -2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

The carboxylic acid-based dispersion resin (B3-1) is more preferably the following carboxylic acid-based dispersion resin (B3-1-1) or (B3-1-2).

≪Carboxylic acid-based dispersion resin (B3-1-1)≫
The vinyl polymer moiety of the carboxylic acid-based dispersion resin (B3-1-1) contains at least one thermally crosslinkable group-containing monomer selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, and a blocked isocyanate group. It is a dispersion resin containing monomeric units and carboxyl group-containing monomeric units.

(i-1) [Hydroxy group-containing monomer]
The hydroxyl group-containing monomer is a (meth)acrylate monomer having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4) - hydroxyalkyl (meth)acrylates such as hydroxybutyl (meth)acrylate and cyclohexanedimethanol mono(meth)acrylate, and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate;
(Meth)acrylamide monomers having a hydroxyl group, such as N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth) ) N-(hydroxyalkyl)(meth)acrylamide such as acrylamide;
Vinyl ether monomers having a hydroxyl group, such as hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-(or 3-) hydroxypropyl vinyl ether, and 2-(or 3- or 4-) hydroxybutyl vinyl ether;
Allyl ether monomers having a hydroxyl group, such as hydroxyalkyl allyl ether such as 2-hydroxyethyl allyl ether, 2-(or 3-) hydroxypropyl allyl ether, and 2-(or 3- or 4-) hydroxybutyl allyl ether Ether is an example.

In addition, monomers obtained by adding alkylene oxide and/or lactone to the above-mentioned hydroxyalkyl (meth)acrylate, alkyl-α-hydroxyalkyl acrylate, N-(hydroxyalkyl)(meth)acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether The body is also preferable. The alkylene oxide is preferably, for example, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, or a combination system of two or more of these. When two or more types of alkylene oxides are used together, the bonding format may be either random or block. As the lactone, for example, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these are used. Both alkylene oxide and lactone may be added.

(i-2) [Oxetane group-containing monomer]
Examples of the oxetane group-containing monomer include (vinyloxyalkyl)alkyloxetane, (meth)acryloyloxyalkyloxetane, and [(meth)acryloyloxyalkyl]alkyloxetane. Among them, (3-ethyloxetan-3-yl)methyl methacrylate and the like are preferred. Examples of commercially available products include ETERNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate) (manufactured by Ube Industries, Ltd.).

(i-3) [t-butyl group-containing monomer]
Examples of the t-butyl group-containing monomer include t-butyl methacrylate and t-butyl acrylate.

(i-4) [Blocked isocyanate group-containing monomer]
Examples of the blocked isocyanate group-containing monomer include 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, etc. . Commercially available products include, for example, Karenz MOI-BM (2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate) (manufactured by Showa Denko), Karenz MOI-BP (2-[(3, Examples include 5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (manufactured by Showa Denko).

The content of the thermally crosslinkable group-containing monomer unit is preferably 5 to 90% by mass, more preferably 20 to 60% by mass in the total monomers. When it is 5% by mass or more, it becomes possible to obtain a colored composition with excellent resistance due to the crosslinking effect, and when it is 90% by mass or less, the stability of the composition is improved.

(ii) [Carboxyl group-containing monomer]
Examples of the carboxyl group-containing monomer include (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Among these, (meth)acrylic acid is preferred because it has good copolymerizability and is easily available.

(iii) [Other monomers]
Other monomers can be used in the vinyl polymer portion of the carboxylic acid-based dispersion resin (B3-1-1).
Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2- Alkyl (meth)acrylates such as ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate;
Aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate;
Heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate;
Alkoxypolyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate and ethoxypolyethylene glycol (meth)acrylate;
N-substituted (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, acryloylmorpholine, etc. Acrylamides;
Examples include amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate; and nitriles such as (meth)acrylonitrile.

Also included are styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate and vinyl propionate. .

≪Carboxylic acid-based dispersion resin (B3-1-2)≫
The carboxylic acid-based dispersion resin (B3-1-2) is a resin having a polymerizable unsaturated group in the vinyl polymer portion.
The method for producing the carboxylic acid-based dispersion resin (B3-1-2) includes, for example, the reaction of glycidyl methacrylate with a polymer having a hydroxyl group or a carboxyl group and a reactant, or the reaction of methacryloyloxyethyl isocyanate with a polymer having a hydroxyl group or a carboxyl group. Examples include things. Examples of the carboxylic acid-based dispersion resin (B3-1-2) include the dispersion resin described in JP-A-2011-157416.

[Carboxylic acid-based dispersion resin (B3-2)]
The carboxylic acid-based dispersion resin (B3-2) is a dispersion resin represented by the following general formula (7), and specifically is a dispersion resin described in JP-A No. 2007-140487.
(HOOC-) _m -R ² -(-COO-[-R ⁴ -COO-] _n -R ⁵ ) _tGeneral formula (7)
(In general formula (7), R ² is a tetravalent tetracarboxylic acid compound residue, R ⁵ is a monoalcohol residue, R ⁴ is a lactone residue, m is 2 or 3, and n is an integer from 1 to 50. , t represents (4-m).)

[Alkali-soluble resin (C)]
The coloring composition in the present invention contains an alkali-soluble resin (C) from the viewpoints of film-forming properties, coating film resistance, developability, and pattern-forming properties.

The alkali-soluble resin (C) is preferably a resin that has a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm when a film with a thickness of 2 μm is formed. Note that the transmittance is more preferably 95% or more. Classifying the alkali-soluble resin (C) according to its main curing method, thermoplastic resins and active energy ray-curable resins are preferable. It is preferable that the active energy ray-curable resin has a thermosetting functional group. Moreover, the alkali-soluble resin (C) can be used alone or in combination of two or more types.

The content of the alkali-soluble resin (C) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on 100 parts by mass of the colorant (A) from the viewpoint of film-forming properties and coating film resistance. preferable.

(Thermoplastic resin)
Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, Examples include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.
Examples of thermoplastic resins include resins having acidic groups such as carboxyl groups and sulfone groups. For example, an acrylic resin having an acidic group, an α-olefin/(anhydrous) maleic acid copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or an isobutylene/(anhydrous) maleic acid copolymer. Examples include copolymers. Among them, at least one resin selected from acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers, especially thermoplastic resins having acidic groups and/or hydroxyl groups, has good developability, heat resistance, and transparency. Since it is expensive, it is preferably used.

(Active energy ray curable resin)
From the viewpoint of coating film resistance, the alkali-soluble resin (C) is preferably an active energy ray-curable resin having a polymerizable unsaturated group. In particular, by using a resin into which polymerizable unsaturated groups have been introduced by methods (i) and (ii) shown below, the resin can be three-dimensionally crosslinked when exposed to active energy rays to form a coating film. This increases the crosslinking density and improves coating resistance.

(Method (i))
In method (i), for example, a monocarboxylic acid having a polymerizable unsaturated group is added to the side chain epoxy group of a copolymer obtained by copolymerizing an epoxy group-containing monomer and other monomers. There is a method in which a carboxyl group of a monomer is subjected to an addition reaction, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to introduce a polymerizable unsaturated group and a carboxyl group.

Epoxy group-containing monomers include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4- Epoxycyclohexyl (meth)acrylate is mentioned. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the monocarboxylic acid monomer in the next step.

Monocarboxylic acid monomers include, for example, (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid. Examples include monocarboxylic acids such as.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and these may be used alone or in combination of two or more. I don't mind. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to remove the remaining anhydride. It is also possible to hydrolyze the group. Further, when tetrahydrophthalic anhydride or maleic anhydride, which has a polymerizable unsaturated group, is used as the polybasic acid anhydride, the number of polymerizable unsaturated groups can be further increased.

As a method similar to method (i), for example, a part of the side chain carboxyl group of a copolymer obtained by copolymerizing a monocarboxylic acid monomer and one or more other monomers Another method is to carry out an addition reaction with an epoxy group-containing monomer to introduce a polymerizable unsaturated group and a carboxyl group.

(Method (ii))
In method (ii), a hydroxyl group-containing monomer is used, and the side chain hydroxyl group of a copolymer obtained by copolymerizing a monocarboxylic acid monomer or other monomers is used. There is a method in which the isocyanate group of an isocyanate group-containing monomer is reacted.

Hydroxyl group-containing monomers include, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, Examples include acrylates and hydroxyalkyl methacrylates such as cyclohexanedimethanol mono(meth)acrylate. In addition, polyether mono(meth)acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the above-mentioned hydroxyalkyl (meth)acrylate, polyγ-valerolactone, polyε-caprolactone, and/or Polyester mono(meth)acrylate to which poly-12-hydroxystearic acid or the like is added can also be used. From the viewpoint of suppressing coating film foreign matter, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferable, and from the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups. Among them, glycerol mono(meth)acrylate is more preferable.

Examples of the isocyanate group-containing monomer include 2-(meth)acryloyl ethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

The monomers constituting the alkali-soluble resin include the following. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate (meth)acrylates such as acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate;
Alternatively, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine, etc. Acrylamides, styrenes such as styrene or α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, fatty acid vinyls such as vinyl acetate, or vinyl propionate. etc.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4'-bismaleimidiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4- Phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimide N-substituted maleimides such as hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl Acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, PO-modified (meth)acrylate of nonylphenol, etc. can be mentioned.

Additionally, carboxyl group-containing monomers can be used. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

Additionally, hydroxyl group-containing monomers can be used. The hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, or cyclohexanedimethanol monomer. Examples include hydroxyalkyl (meth)acrylates such as (meth)acrylate. In addition, polyether mono(meth)acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the above hydroxyalkyl (meth)acrylate, (poly)γ-valerolactone, (poly)ε-caprolactone and/or (poly)ester mono(meth)acrylates to which (poly)12-hydroxystearic acid and the like are added.

Also included are phosphate group-containing monomers. The phosphoric acid ester group-containing monomer can be, for example, a monomer obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

The monomers used in the synthesis of the alkali-soluble resin (C) can be used alone or in combination of two or more.

As the alkali-soluble resin (C), an alkali-soluble resin having a polymerizable unsaturated group and an alkali-soluble resin not having a polymerizable unsaturated group can be used together in order to adjust the degree of hardening of the coating film.

The weight average molecular weight (Mw) of the alkali-soluble resin (C) is from 2,000 to 40,000, preferably from 3,000 to 300,00, and from 4,000 to 20 ,000 or less is more preferable. Moreover, the value of Mw/Mn is preferably 10 or less. A suitable weight average molecular weight (Mw) improves adhesion to the substrate and improves solubility in alkali development.

The acid value of the alkali-soluble resin (C) is preferably 50 or more and 200 or less (mgKOH/g), more preferably 70 or more and 180 or less, and even more preferably 100 or more and 150 or less, in order to impart alkaline development solubility. A moderate acid value improves alkaline development solubility, reduces residue, improves pattern linearity, and improves adhesion to the substrate.

The alkali-soluble resin (C) can be used alone or in combination of two or more types.

[Photopolymerization initiator (D)]
The photopolymerization initiator (D) includes a photopolymerization initiator (D) represented by general formula (1) or general formula (2).

In general formula (1), R ₁ and R ₂ each independently represent an alkyl group having 4 or less carbon atoms. R ₃ is an alkyl group having 20 or less carbon atoms which may have a substituent, an alkoxy group having 20 or less carbon atoms which may have a substituent, or an aryl group having 20 or less carbon atoms which may have a substituent. represents a group, and adjacent substituents may be bonded to each other to form an aliphatic ring or an aromatic ring. _R4 is a nitro group, an alkyl group having 20 or less carbon atoms which may have a substituent, an alkoxy group having 20 or less carbon atoms which may have a substituent, or 20 carbon atoms which may have a substituent. It represents the following aryl group, and adjacent substituents may be bonded to each other to form an aliphatic ring or an aromatic ring.
In the general formula (2), R ₅ to R ₇ each independently represent an alkyl group having 4 or less carbon atoms which may have a substituent.

Specific examples of the photopolymerization initiator (D) represented by general formula (1) or general formula (2) are shown below. Note that the present invention is not limited to these.

The symbols in the table represent Me: methyl group, Et: ethyl group, and Bu: butyl group, respectively.

Commercially available products include, for example, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (IRGACURE OXE 02), NCI- 831, NCI-930 (all manufactured by ADEKA), and TRONLY TR-PBG-304 (manufactured by Changzhou Strong New Materials).

The photopolymerization initiator (D) can be used alone or in combination of two or more types.

The content of the photopolymerization initiator (D) is preferably 1 to 20 parts by weight, more preferably 2 to 7 parts by weight, based on 100 parts by weight of the colorant (A) from the viewpoint of photocurability and developability. preferable. When contained in an appropriate amount, the adhesion between the substrate and the pattern is improved, and the brightness of post-baking is less likely to decrease.

[Polymerizable compound (E)]
The polymerizable compound (E) is a monomer or oligomer containing a polymerizable unsaturated group. Examples of the polymerizable compound (E) include acid group-containing monomers, urethane bond-containing monomers, and other monomers.

Examples of the acid group of the acid group-containing monomer include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.
Acid group-containing monomers include, for example, esterification products of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohol and (meth)acrylic acid, and dicarboxylic acids; ) Examples include esterified products with acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. , free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydroxyethyl acrylate, 2-hydroxy Examples include free carboxyl group-containing oligoesters with monohydroxy monoacrylates or monohydroxy monomethacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

(Urethane bond-containing monomer)
The urethane bond-containing monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with an alcohol, and then a (meth)acrylate having a hydroxyl group. Examples include polyfunctional urethane acrylates obtained by reaction.

(Meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. ) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate methacrylate , glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy(meth)acrylate, a hydroxyl group-containing polyol polyacrylate, and the like.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, ) acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxy Tetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid Acid EO modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methylol Various acrylic esters and methacrylic esters such as (meth)acrylic acid ester of melamine, epoxy (meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, penta Examples include erythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

Examples of commercially available products of the polymerizable compound (E) include Aronix M309, M321, M350, M315, M305, M450, M408, M400, M402, M510, and M520 manufactured by Toagosei.

The polymerizable compound (E) can be used alone or in combination of two or more types.

The content of the polymerizable compound (E) is preferably 1 to 50% by weight, more preferably 2 to 40% by weight based on 100 parts by weight of the nonvolatile content of the photosensitive coloring composition.
The average number of functional groups of the photopolymerizable monomer (E) is preferably 3 to 5, more preferably 3 to 4, and the photopolymerizable monomer having an average number of functional groups of 3 to 5 is fully photopolymerizable. It is most preferable that the content of the monomer is 50% by mass or more, and photocurability and developability are improved.

(Thermosetting compound (F))
The colored composition of the present invention can further contain a thermosetting compound (F). By including a thermosetting compound, when producing a color filter, it reacts during firing of the filter segments and improves the crosslinking density of the coating film. This improves heat resistance, suppresses pigment aggregation during firing, and improves coloring power.

The thermosetting compound (F) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[Epoxy compound (F-1)]
Epoxy compounds include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted Polycondensates of dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), phenol and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones. (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol, biphenyl dimethanol) , α, α, α', α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.) , polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins Examples include epoxy resin.

Commercially available products include, for example, Epicote 807, Epicote 815, Epicote 825, Epicote 827, Epicote 828, Epicote 190P, Epicote 191P (the above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicote 1004, Epicote 1256 (the above are trade names). ; made by Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (product name; made by Mitsui Chemicals), EPPN-501H, 502H (product name; made by Nippon Kayaku Co., Ltd.), JER 1032H60 (product name; made by Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (product name; made by Japan Epoxy Resin Co., Ltd.), EPPN-201 (product name; made by Nippon Kayaku Co., Ltd.), JER152, JER154 (the above are product names; made by Japan Epoxy Resin Co., Ltd.), EOCN-102S, EOCN- 103S, EOCN-104S, EOCN-1020 (trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (trade names; manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211, 212, 252, 313 , 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721, (the above are product names; manufactured by Nagase ChemteX), TEPIC-L, TEPIC-H, TEPIC- S (manufactured by Nissan Chemical Industries, Ltd.) and the like.

The content of the epoxy compound is preferably 0.5 to 300 parts by weight, more preferably 1.0 to 50 parts by weight, based on 100 parts by weight of the colorant (A). When blended in an appropriate amount, coloring power and heat resistance will improve.

[Oxetane compound (F-2)]
The oxetane compound is a compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or more functional oxetane compounds.
Examples of monofunctional oxetane compounds include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxy) silyl)propoxy]methyl}oxetane, and the like.
Specific examples include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

Bifunctional oxetane compounds include, for example, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether- 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl) -5-oxanonan, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3 -ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3- ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol F (3-ethyl-3-oxetanyl) Methyl) ether and the like.
Specific examples include OXBP, OXTP manufactured by Ube Industries, and OXT-121 and OXT-221 manufactured by Toagosei.

Trifunctional or higher functional oxetane compounds include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3 -oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol hexa(3-ethyl- 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (e.g. , oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462, etc.) and a polymer obtained by radical polymerization of a (meth)acrylic monomer such as the above-mentioned OXE-30.

The content of the oxetane compound is usually 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts by weight of the nonvolatile content of the coloring composition. It is preferable that the content of the oxetane compound is within the above range because an excellent coating film with good water stain resistance and high chemical resistance can be obtained.

A melamine compound refers to a compound having a melamine ring structure. The melamine compound is preferably a methylol type or an ether type, and a melamine compound having an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more is more preferable. When an appropriate amount of a melamine compound is used, the coloring power is improved and the resistance to N-methylpyrrolidone is also improved.

Commercially available products include, for example, Nikarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS- 001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 ( (manufactured by Sanwa Chemical Co., Ltd.), Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 (manufactured by Nippon Cytec Industries), and the like.

Among these, Nicarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30 have an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more. , MW-22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.) Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nihon Cytec Industries Co., Ltd.) etc. are preferable in terms of increasing the crosslinking density.

The thermosetting compound (F) can be used alone or in combination of two or more types.

(hardening agent)
In order to assist the curing of the thermosetting compound (F), a curing agent (curing accelerator) can be used in combination with the colored composition of the present invention, if necessary. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. The curing agent is, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, -Methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4 -methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino- S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.).

The curing agents can be used alone or in combination of two or more types.

The content of the curing agent is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the thermosetting compound (F).

[Organic solvent (G)]
The colored composition of the present invention can contain an organic solvent (G).
Examples of the organic solvent (G) include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, and 1,3-butylene glycol diol. Acetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3- Ethyl ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4 -heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether , ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene Glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, Cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol , triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene Glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic Examples include acid esters. Among these, from the viewpoint of dispersibility of organic pigments and solubility of alkali-soluble resins, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. Alcohols such as glycol acetates, benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

The organic solvent (G) can be used alone or in combination of two or more.

From the viewpoint of coatability, the coloring composition of the present invention preferably has a viscosity at 25°C of less than 50 mPa·S, more preferably less than 15 mPa·S, and even more preferably 10 mPa·S or less. The viscosity can be adjusted by adding an organic solvent (P) or the like.

[Sensitizer (H)]
The photosensitive coloring composition of the present invention can contain a sensitizer (H).
Examples of the sensitizer (H) include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone. Derivatives, polymethine dyes such as anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrin derivatives Radin derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-alpha Siloxy ester, acyl oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'- Examples include tetra(t-butylperoxycarbonyl)benzophenone and 4,4'-bis(diethylamino)benzophenone.

Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred, and 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 1-chloro-4-propoxy Thioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethyl More preferred are carbazole, 3,6-dibenzoyl-N-ethylcarbazole, and the like.

The sensitizer (H) can be used alone or in combination of two or more.

Commercially available products include, for example, "KAYACURE DETX-S" (2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.), "CHEMARK DEABP" (4,4'-bis(diethylamino)benzophenone manufactured by Chemark Chemical Co., Ltd.), etc. .

From the viewpoint of photocurability and developability, the content of the sensitizer (H) is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator (F). .

[Thiol chain transfer agent (I)]
The photosensitive coloring composition can contain a thiol chain transfer agent (I). When a thiol-based chain transfer agent is used in combination with a photopolymerization initiator, thiyl radicals, which are less susceptible to polymerization inhibition by oxygen, are generated during radical polymerization after light irradiation, thereby improving the sensitivity of the photosensitive coloring composition.

The thiol-based chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). In addition, it is more preferable that the thiol-based chain transfer agent has 4 or more SH groups. As the number of functional groups increases, it becomes easier to photocure from the surface of the film to the deepest part.

Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropionate. , trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris trimercaptopropionate (2-Hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine Preferable examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

Thiol-based chain transfer agents can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 1 to 10% by weight, more preferably 2 to 8% by weight based on 100% by weight of nonvolatile content of the photosensitive coloring composition. When contained in an appropriate amount, photosensitivity and tapered shape are improved, and wrinkles are less likely to occur on the coating surface.

[Polymerization inhibitor (J)]
The photosensitive coloring composition can contain a polymerization inhibitor (J). This prevents exposure due to diffracted light from the mask during exposure in photolithography, making it easier to obtain a good pattern shape.
Examples of the polymerization inhibitor (J) include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-t-butylcatechol, 3-t-butylcatechol, Alkylcatechol compounds such as 4-t-butylcatechol and 3,5-di-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4 - Alkylresorcinol compounds such as propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butyl Hydroquinone, alkylhydroquinone compounds such as 2,5-di-t-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine Examples include phosphine oxide compounds such as oxide, phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite, pyrogallol, and phloroglucin.

The content of the polymerization inhibitor is preferably 0.01 to 0.4% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When contained in an appropriate amount, it becomes easier to obtain a good pattern shape.

[Ultraviolet absorber (K)]
The photosensitive coloring composition can contain an ultraviolet absorber (K). The ultraviolet absorber (K) is an organic compound having an ultraviolet absorption function, and includes benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds. Examples include compounds.

Examples of benzotriazole compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3 ,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'- Hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1, 1-dimethylethyl)-4-hydroxy, a mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) Phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3- (2H-benzotriazol2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol2-yl)-4-(1,1, 3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-( 2H-benzotriazol2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol2-yl)-6-t-butyl-4-methylphenol, 2-(3,5-di-t -amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4- Hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2) -yl)phenyl]propionate.

Commercially available products include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Japan, and ADEKA STAB LA-29, LA-31RG, LA-32, LA manufactured by ADEKA. -36, KEMISORB71, 73, 74, 79, 279 manufactured by ChemiPro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4, 6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxy Reaction product of phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester, 2,4-bis(2-hydroxy-4 -butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-( hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6- Examples include tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Commercially available products include KEMISORB 102 manufactured by ChemiPro Kasei, TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan, ADEKA STAB LA-46, LA-F70, and CYASORB UV-1164 manufactured by Sun Chemical. It will be done.

Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3, 2-hydroxy-4-n- Octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octade Examples include siloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Commercially available products include KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei, SEESORB 101 and 107 manufactured by Shipro Kasei, ADEKA STAB 1413 manufactured by ADEKA, UV-12 manufactured by Sun Chemical, and the like.

Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tertbutylphenyl salicylate.

The content of the ultraviolet absorber (K) is preferably 5 to 70% by mass out of the total 100% by mass of the photopolymerization initiator and the ultraviolet absorber. When contained in an appropriate amount, it becomes easier to obtain a good pattern shape. In addition, when a sensitizer (H) is included, the content of the photopolymerization initiator (F) includes the content of the sensitizer (H).

Further, the total content of the photopolymerization initiator (D) and the ultraviolet absorber (K) is preferably 1 to 20% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. By containing an appropriate amount, it is easy to achieve both adhesion to the substrate and resolution. In addition, when a sensitizer (H) is included, the content of the photopolymerization initiator (D) includes the content of the sensitizer (H).

[Antioxidant (L)]
The photosensitive coloring composition can contain an antioxidant (L). Antioxidants are the photopolymerization initiators and thermosetting compounds contained in the photosensitive coloring composition that prevent yellowing due to oxidation and reduce the transmittance of the coating through heat curing or the thermal process during ITO annealing. It can be suppressed. In particular, when the organic pigment concentration of the photosensitive coloring composition is high, the content of the photopolymerizable compound (E) decreases relatively, so if the amount of the photopolymerization initiator is increased or a thermosetting compound is added, the coating will be formed. tends to yellow. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and suppress a decrease in transmittance of the film.

Examples of antioxidants include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In this specification, the antioxidant is preferably a compound that does not contain a halogen atom.
Among these, hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred from the viewpoint of achieving both transmittance and sensitivity of the coating film.

The hindered phenolic antioxidant is, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H ,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2- t-butyl-5-methylphenol), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis [3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8 , 10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3 ,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2' -Methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis (dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[ 3-(3-Methyl-4-hydroxy-5-t-butylphenyl)propionic acid] ethylenebisoxybisethylene, 1,6-hexanediolbis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2'-thio- Bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl) - Examples include phenol.

Commercially available products include ADEKA STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330, KEMINOX101, 179, 76, 9425 manufactured by Chemipro, and BASF Japan. IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by Sun Chemical Co., Ltd., and CYANOX CY-1790, CY-2777 manufactured by Sun Chemical Company.

Examples of hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6 -tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6 -tetramethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate , 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine , poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl) ) imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3, Ester of 5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl) amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy) decanedioate) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyriperidyl)[[3,5-bis(1, 1dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4 -diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2, 2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6- Hexamethylene diamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc. Can be mentioned.

Commercially available products are ADEKA STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA- 402F, LA - 502 853 etc.

Examples of phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, and 2,2'-methylenebis(4,6 -di-t-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4' -Isopropylidene diphenyl diphosphite, diphenylmono(2-ethylhexyl) phosphite, diphenylisodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)- 4,4-biphenyldiphosphonite, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4 '-Isopropylidene diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite phyto, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethylbis(2,4-phosphite) -di-t-butyl-6-methylphenyl) and the like.

Commercially available products include ADEKA STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP, BASF Japan IRGAFOS168, and Clariant Chemicals Hostanox P-EPQ. It will be done.

Sulfur-based antioxidants include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3'- Ditridecyl thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o- Examples include cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, and the like.

Commercially available products include ADEKA STAB AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by ChemiPro Kasei.

The antioxidant (L) can be used alone or in combination of two or more kinds.

The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. Containing an appropriate amount improves transmittance, spectral characteristics, and sensitivity.

[Leveling agent (M)]
The photosensitive coloring composition can contain a leveling agent. This further improves the wettability to the substrate during film formation and the drying properties of the film. Examples of the leveling agent include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

The leveling agent (M) can be used alone or in combination of two or more types.

The content of the leveling agent (M) is preferably 0.001 to 2.0% by weight, more preferably 0.005 to 1.0% by weight based on 100% by weight of nonvolatile content of the photosensitive coloring composition. By falling within this range, the balance between coating properties, pattern adhesion, and transmittance of the photosensitive coloring composition is further improved.

[Storage stabilizer (N)]
The photosensitive coloring composition can contain a storage stabilizer to stabilize the viscosity of the composition over time. Storage stabilizers (N) include, for example, quaternary ammonium chloride such as benzyl trimethyl chloride and diethyl hydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl. Examples include organic phosphines and phosphites. The content of the storage stabilizer (N) is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the organic pigment (A).

[Adhesion improver (O)]
The photosensitive coloring composition can contain an adhesion improver. This further improves the adhesion between the coating and the base material. Furthermore, it becomes easier to form narrow patterns using photolithography. Examples of the adhesion improver include silane coupling agents.

Examples of the adhesion improver (O) include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxy. Silane, 3-methacryloxypropyltriethoxysilane, (meth)acrylic silanes such as 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyl Epoxysilanes such as dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3- Aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1, Aminosilanes such as hydrochloride of 3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3- Mercaptos such as mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, bis(triethoxysilylpropyl)tetrasulfide Examples include silane coupling agents such as sulfides such as silane and isocyanates such as 3-isocyanatepropyltriethoxysilane.

The content of the adhesion improver is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant (A). When contained in an appropriate amount, the photosensitivity of the photosensitive coloring composition will be improved, the adhesion of the film will be further improved, and the resolution of the pattern will also be further improved.

<Method for producing colored composition>
The method for producing the colored composition of the present invention includes mixing a colorant (A), a pigment derivative, a dispersion resin (B), and an alkali-soluble resin (C), using a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, It can be produced by dispersing using various dispersion means such as a vertical sand mill, an annular bead mill, or an attritor. When using two or more types of colorants (A), they can also be separately dispersed. Note that the colorant (A) and the pigment derivative can be subjected to a micronization treatment in advance and subjected to a dispersion treatment.

The average dispersed particle size (secondary particle size) of the blue pigment (A1) and the purple pigment (A2) in the colored composition of the present invention is preferably 30 to 200 nm, more preferably 40 to 200 nm. Within this range, a photosensitive coloring composition with high dispersion stability can be obtained.

The average dispersed particle size (secondary particle size) can be measured using, for example, Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd., which employs a dynamic light scattering method (FFT power spectrum method). For example, the shape may be non-spherical and D50 may be the average diameter. It is preferable to use the organic solvent used for dispersion as the diluting solvent for measurement, and to measure the sample treated with ultrasonic waves immediately after sample preparation, because results with less variation can be easily obtained.

<Method for producing photosensitive coloring composition>
The photosensitive colored composition of the present invention can be prepared by mixing the colored composition, the photopolymerization initiator (D), and the polymerizable compound (E).

The photosensitive coloring composition of the present invention can be produced into coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, filtration with a sintered filter or membrane filter, etc. It is preferable to remove particles and mixed dust. As described above, it is preferable that the colored composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

The content of the colorant (A) in the photosensitive coloring composition of the present invention is preferably 45 to 70% by weight, and 46 to 65% by weight based on 100% by weight of the total nonvolatile content, from the viewpoint of developability and thin film formation. More preferably, 48 to 60% by mass is particularly preferred.

From the viewpoint of coatability, the photosensitive coloring composition preferably has a viscosity at 25°C of less than 50 mPa·S, more preferably less than 15 mPa·S, and particularly preferably 10 mPa·S or less.

<Moisture content in photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, it is preferable that the content of water contained in the photosensitive coloring composition is 2% by mass or less.

With the above water content, the photosensitive coloring composition has excellent dispersion stability and sensitivity even after storage over time.

The content of water contained in the photosensitive coloring composition is preferably 1.8% by mass or less, more preferably 1.6% by mass or less, and as long as the water content is sufficiently small within this range, even after storage over time. Problems with dispersion stability and sensitivity are unlikely to occur.

The method for controlling the water content is not particularly limited, and any known method can be used. Examples include a method of producing a photosensitive coloring composition while blowing dry inert gas, and a method of adding molecular sieves to dehydrate the composition after production. Among these, a method of manufacturing while blowing dry inert gas is preferred.

The water content can be measured by a known method such as the Karl Fischer method.

<Toluene amount in photosensitive coloring composition>
The photosensitive coloring composition of the present invention can contain toluene. The content of toluene in the photosensitive coloring composition is preferably 0.1 to 10 ppm by mass. The upper limit of the content of toluene is preferably 9 mass ppm or less, more preferably 8 mass ppm or less, and even more preferably 7 mass ppm or less. The lower limit is preferably 0.2 mass ppm or more, more preferably 0.3 mass ppm or more, and even more preferably 0.4 mass ppm or more.

<Color filter>
The color filter of the present invention includes a base material and a blue color filter segment formed from a photosensitive coloring composition. Preferably, the color filter segment used in conjunction with the blue color filter segment has a red filter segment and a green filter segment.
Examples of the substrate include a transparent substrate and a reflective substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[Manufacturing method of color filter]
The color filter of the present invention comprises a step of coating the photosensitive coloring composition of the present invention on a substrate to form a colored layer, a step of exposing the colored layer to light through a mask in a pattern, and an unexposed portion. It can be obtained by a process of removing by development and forming a colored pattern.
Furthermore, if necessary, a step of drying the colored layer (pre-bake step) and a step of thermosetting the colored pattern (post-bake step) may be provided.

Hereinafter, the method for manufacturing a color filter of the present invention will be explained in detail.

(Step of forming a colored layer)
In the step of forming a colored layer, the photosensitive colored composition of the present invention is applied onto a substrate by spin coating, roll coating, slit coating, cast coating, or inkjet coating, and as necessary. Dry (pre-bake) at a temperature of 50 to 120°C for 10 to 120 seconds using an oven, hot plate, etc.
Examples of the substrate include a substrate in which an imaging device such as a CCD or CMOS is provided on a glass substrate or a silicon substrate. An undercoat layer may be provided on the substrate, if necessary.

(Process of exposing in a pattern)
In the exposure step, the colored layer is exposed to light in a specific pattern through a mask using an exposure device such as a stepper. A cured film is thereby obtained.
For example, ultraviolet rays such as g-line, h-line, and i-line are preferably used for exposure.

The thickness of the cured film is preferably 1.0 μm or less, more preferably 0.2 to 0.8 μm, and particularly preferably 0.2 to 0.6 μm.

(Development process)
By performing the alkaline development treatment, the colored layer in the unirradiated portion in the exposure step is eluted into the alkaline aqueous solution, leaving only the hardened portion.
Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include alkaline compounds such as pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the developer is preferably 0.001 to 10% by weight, more preferably 0.01 to 1% by weight.
The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When the alkali concentration is within the above range, pattern roughness and peeling can be more effectively suppressed and the remaining film rate can be further improved. Further, it is possible to further suppress a decrease in development speed and the generation of development residues.

The developing method includes, for example, a dip method, a spray method, a paddle method, etc., and the temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

Next, after drying, it is preferable to perform a heat treatment (post-bake) in order to sufficiently cure the cured film. The heating temperature for post-baking is preferably 100 to 300°C, more preferably 150 to 250°C. Further, the heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

The color filter of the present invention can be suitably used in solid-state imaging devices such as CCDs and CMOSs, and is particularly suitable for high-resolution CCDs and CMOSs having more than 1 million pixels. The color filter of the present invention can be used, for example, as a color filter disposed between the light receiving section of each pixel constituting a CCD or CMOS and a microlens for condensing light.

<Solid-state imaging device>
The solid-state image sensor of the present invention includes the color filter described above. The solid-state image sensor of the present invention has, for example, the following configuration.

A plurality of photodiodes constituting the light receiving area of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon are provided on the substrate, and a phototransfer electrode is provided on the photodiode and the transfer electrode. The device has a light-shielding film made of tungsten or the like with an opening only at the light-receiving part of the diode, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. This is a configuration in which the color filter of the present invention is provided on a protective film.
Furthermore, a configuration in which a light condensing means (for example, a microlens, etc., the same applies hereinafter) is provided on the device protective layer and below the color filter (on the side closer to the substrate), or a configuration in which the condensing means is provided on the color filter. etc. may be used.

The color filter of the present invention can be used not only for the solid-state image sensor but also for image display devices such as liquid crystal display devices and organic EL display devices. A liquid crystal display device equipped with the color filter of the present invention can display a high-quality image with good color tone and excellent display characteristics.

EXAMPLES Hereinafter, the present invention will be explained more specifically by showing Examples and Comparative Examples. However, the present invention is not limited to these. Note that "part" means "part by mass" and "%" means "% by mass."

Prior to Examples, each measurement method will be explained.

The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH/g), and (mgKOH/g) of the resin are as follows.

(Average molecular weight of dispersed resin and alkali-soluble resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the dispersed resin and the alkali-soluble resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the equipment, two separation columns were connected in series, and the packing material for both was "TSK-GEL SUPER HZM-N" connected in two series, and the oven temperature was 40℃. The measurement was performed at a flow rate of 0.35 ml/min using a tetrahydrofuran (THF) solution as an eluent. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent, and 20 microliters of the sample was injected. The molecular weight is a polystyrene equivalent value.

(Acid value of dispersed resin and alkali-soluble resin)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the dispersion resin and alkali-soluble resin solution, stir to dissolve uniformly, and use an automatic titration device (COM -555'' (manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mgKOH/g). Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the nonvolatile content concentration of the resin solution.

(Amine value of basic dispersion resin)
The amine value of the basic dispersion resin is the value obtained by converting the measured total (mgKOH/g) into nonvolatile content in accordance with the method of ASTM D 2074.

<Production example of colorant (A)>
(Fine phthalocyanine blue pigment (A1-1))
Phthalocyanine blue pigment C. I. 100 parts of Pigment Blue 15:6 ("Lionor Blue ES" manufactured by Toyo Color Co., Ltd.), 800 parts of crushed common salt, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 12 hours. did. This mixture was poured into 3,000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry. After repeated filtration and water washing to remove salt and solvent, the mixture was heated to about 70°C for 24 hours. It was dried to obtain 98 parts of blue finely divided pigment (A1).

(Fine phthalocyanine blue pigment (A1-2))
Phthalocyanine blue pigment C. I. 90 parts of Pigment Blue 15:6 (Toyo Color Co., Ltd. "Lionol Blue ES"), 10 parts of the pigment derivative (A3-1) represented by chemical formula (8), 800 parts of ground common salt, and 100 parts of diethylene glycol. The mixture was placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 12 hours. This mixture was poured into 3000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then heated to 80°C for 24 hours. It was dried to obtain 98 parts of blue finely divided pigment (A1).

(Finely divided dioxazine-based purple pigment (A2))
Dioxazine-based purple pigment C. I. 120 parts of Pigment Violet 23 ("Fast Violet RL" manufactured by Clariant), 1600 parts of ground common salt, and 100 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90° C. for 18 hours. This mixture was poured into 5000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry. After repeated filtration and water washing to remove salt and solvent, the mixture was heated to about 70°C for 24 hours. It was dried to obtain 118 parts of a purple finely divided pigment (A2).

(Dye derivative (A3))
A3-1:
Chemical formula (8)

A3-2: Solsperse 5000 (manufactured by Lubrizol: phthalocyanine acidic dye derivative)

<Method for producing basic dispersant (B1)>
(Basic dispersion resin (B1-1) solution)
50 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged into a reaction apparatus equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C while flowing nitrogen. The mixture was stirred for 1 hour, and the atmosphere in the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride and 133 parts of methoxypropyl acetate as a catalyst were charged, and the temperature was raised to 110°C under a nitrogen stream to form the first block (B polymerization of block) was started. After 4 hours of polymerization, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile content. Next, 61 parts of methoxypropyl acetate, 20 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of benzyl chloride salt of dimethylaminoethyl methacrylate were charged into this reactor, and the mixture was heated at 110°C in a nitrogen atmosphere. The reaction was continued by stirring while maintaining the . Two hours after adding dimethylaminoethyl methacrylate, the polymerization solution was sampled to measure the solid content, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of non-volatile content, and the reaction was completed. Polymerization was stopped by cooling the solution to room temperature. As a result of GPC measurement, the polymer Mw was 12000, the molecular weight distribution Mw/Mn was 1.2, and the reaction conversion rate was 98.5%. In this way, a basic dispersion resin (B1-1) having an amine value per solid content of 71.4 mgKOH/g was obtained. After cooling to room temperature, approximately 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. Glycol monomethyl ether acetate (PGMAc) was added to prepare an acrylic block copolymer (B1-1) solution.

(Production of basic dispersion resin (B1-2 to B1-7) solution)
Synthesis was carried out in the same manner as in (B1-1) except that the raw materials and amounts listed in Table 2 were used to obtain solutions of basic dispersion resins (B1-2) to (B1-7).

The amine value and weight average molecular weight of each basic dispersion resin were as shown in Table 2.

MMA; methyl methacrylate nBA; n-butyl acrylate HEMA; hydroxyethyl methacrylate DM; dimethylaminoethyl methacrylate DMAPMA; N,N-dimethylaminoethyl (meth)acrylamide LA-82; 1,2,2,6,6-pentamethyl Piperidyl methacrylate DE; diethylaminoethyl methacrylate DMC; benzyl chloride salt of DM DMAPMAC; benzyl chloride salt of DMAPMA LA-82C; benzyl chloride salt of LA-82C DEC; benzyl chloride salt of DE

<Production example of phosphoric acid-based dispersion resin (B2)>
(Phosphoric acid-based dispersion resin (B2-1) solution)
A reaction vessel equipped with a nitrogen gas inlet tube, a condenser, and a stirrer was charged with 186 g of lauryl alcohol, 571 g of ε-caprolactone monomer, and 0.6 g of tetrabutyl titanate, and after purging with nitrogen gas, the mixture was heated and stirred at 120° C. for 3 hours. . Disappearance of caprolactone monomer was confirmed using an RI detector of GPC (gel permeation chromatography) using tetrahydrofuran as an eluent. After cooling to below 40°C, the mixture was mixed with 84.5 g of polyphosphoric acid having an orthophosphoric acid equivalent content of 116%, and the temperature was gradually raised to 80°C for 6 hours with stirring. A phosphoric acid resin type dispersant (B2-1) with an abundance ratio of n=1 and 2 of 100:12 was obtained. By adjusting the nonvolatile content with PGMAc, a phosphoric acid-based dispersion resin (B2-1) solution with a nonvolatile content of 30% and an acid value per nonvolatile content of 166 mgKOH/g was obtained.

(Phosphoric acid-based dispersion resin (B2-2) solution)
A separable 4-necked flask was equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer, and 1,500 parts of cyclohexanone was charged therein, the temperature was raised to 80°C, and the inside of the reaction vessel was replaced with nitrogen. parts, n-butyl methacrylate 210 parts, 2-hydroxyethyl methacrylate 90 parts, methacrylic acid 60 parts, paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd. "Aronix M-110") 120 parts, acid phosphoxyethyl methacrylate 6 parts A mixed solution of 30 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain a phosphoric acid-based dispersion resin (B2-2) solution with a nonvolatile content of 30% and a weight average molecular weight of 24,000.

<Production example of carboxylic acid-based dispersion resin (B3)>
(Carboxylic acid-based dispersion resin (B3-1) solution)
10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc were charged into a reaction vessel equipped with a gas inlet tube, temperature, condenser, and stirrer, and the mixture was purged with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50°C, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a reaction was carried out for 7 hours while adding a solution of 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of PGMAc. It was confirmed by non-volatile content measurement that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 100°C for 7 hours. . After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the reaction was terminated, and the mixture was diluted with PGMAc so that the non-volatile content was 30% by measuring the non-volatile content, and the acid value was 70 mgKOH/g. A solution of a carboxylic acid-based dispersion resin (B3-1) having a weight average molecular weight of 8,500 was obtained.

(Carboxylic acid-based dispersion resin (B3-2) solution)
62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin(IV) oxide as a catalyst were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, and nitrogen gas was added. After replacing the mixture with , it was heated and stirred at 120° C. for 4 hours. After confirming that 98% of the reaction had occurred by measuring non-volatile content, 73.3 parts of pyromellitic anhydride was added, and the mixture was reacted at 120° C. for 2 hours. After measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. A carboxylic acid-based dispersion resin (B3-2) solution with a nonvolatile content of 30% was obtained by adjusting with PGMAc. The acid value of the obtained carboxylic acid-based dispersion resin (B3-2) was 49 mgKOH/g.

(Carboxylic acid-based dispersion resin (B3-1-1) solution)
3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of PGMAc, and 0.1 part of dimethylbenzylamine were placed in a reaction tank equipped with a gas introduction tube, condenser, stirring blade, and thermometer. I prepared it. After purging with nitrogen gas, the inside of the reaction vessel was heated to 120°C and reacted for 4 hours, and then at 80°C for 2 hours. Furthermore, 30 parts of tertiary butyl acrylate, 20 parts of ETERNACOLL OXMA ((3-ethyloxetan-3-yl) methyl methacrylate, manufactured by Ube Industries, Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of PGMAc were charged into a reaction vessel. While maintaining the inside at 80°C, 0.2 part of 2,2'-azobisisobutyronitrile was added in 15 portions every 30 minutes. One hour after the final addition, non-volatile content was measured and it was confirmed that 95% of the monomers had reacted. A carboxylic acid-based dispersion resin (B3-1-1) with an acid value of 51 mgKOH/g per non-volatile content and a weight average molecular weight (Mw) of 24,000 was diluted with PGMAc so that the non-volatile content was 30% as determined by non-volatile content measurement. A solution was obtained.

(Carboxylic acid-based dispersion resin (B3-1-2) solution)
108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, and the mixture was heated with nitrogen gas. After the substitution, the mixture was reacted at 120° C. for 5 hours (first step). Acid value measurement confirmed that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of nonvolatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, and 200 parts of methyl acrylate. 1 part, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, the inside of the reaction vessel was heated to 80°C, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours. (Second step). It was confirmed by non-volatile content measurement that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were charged, and 2270 cm based on the isocyanate group was measured by IR. The reaction was continued until the disappearance of ^{the -1} peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and adjusted with PGMAc to obtain a carboxylic acid-based dispersion resin (B3-1-2) solution with a nonvolatile content of 30%. The obtained carboxylic acid-based dispersion resin (C2-1-2) had an acid value of 68 mgKOH/g, an unsaturated double bond equivalent of 1,593, and a weight average molecular weight of 13,000.

<Production example of alkali-soluble resin (C)>

(Preparation of alkali-soluble resin solution (C-1))
196 parts of cyclohexanone was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, and the temperature was raised to 80°C. After purging the inside of the reaction vessel with nitrogen, the mixture was added dropwise. From the tube, 44.9 parts of n-butyl methacrylate, 15.6 parts of 2-hydroxyethyl methacrylate, 14.5 parts of methacrylic acid, 25 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), A mixture of 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content.Propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Ether acetate was added to obtain an alkali-soluble resin solution (C-1). The weight average molecular weight (Mw) was 26,000.

(Preparation of alkali-soluble resin solution (C-2))
207 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, the temperature was raised to 80°C, the inside of the reaction vessel was replaced with nitrogen, and then added dropwise. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain a copolymer resin solution. Next, the entire amount of the obtained copolymer solution was stirred while stopping the nitrogen gas supply and injecting dry air for 1 hour, and then cooled to room temperature. A mixture of 6.5 parts of MOI), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. An alkali-soluble resin solution (C-2) was prepared. The weight average molecular weight (Mw) was 18,000.

(Production of alkali-soluble resin (C-3 to C-6) solution)
Synthesis was carried out in the same manner as in (C-1) except that the raw materials and amounts listed in Table 3 were used to obtain solutions of basic dispersion resins (C-3) to (C-6).

The acid value and weight average molecular weight of each alkali-soluble resin were as shown in Table 3.

nBA: n-butyl methacrylate HEMA: 2-hydroxyethyl methacrylate M110: Paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.)
MOI; 2-methacryloyloxyethyl isocyanate MMA: Methyl methacrylate BzMA; Benzyl methacrylate MAA; Methacrylic acid

<Manufacture of colored composition>
(Colored composition (PB-1))
After stirring and mixing the following raw materials so that they were uniform, they were dispersed for 3 hours using an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) using zirconia beads with a diameter of 0.5 mm, and then the pore size was 1. The mixture was filtered through a 0 μm filter to prepare a colored composition (PB-1). The organic solvent (G-1) is PGMAc.
Finely divided phthalocyanine blue pigment (A1-1): 13.5 parts by mass Pigment derivative (A3-2): 1.5 parts by mass Basic dispersion resin (B1-1) solution: 10.0 parts by mass Organic solvent (G -1): 75.0 parts by mass

(Coloring composition (PB-2 to 26))
Colored compositions (PB-2 to PB-26) were prepared in the same manner as colored composition (PB-1) except that the material type and mass were changed as shown in Table 4.
I got it.

<Preparation of photosensitive coloring composition>

[Example 1]
(Photosensitive coloring composition (PR-1))
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (PR-1). The content of the colorant (A) is 50% by mass based on the total nonvolatile matter.
Coloring composition (PB-1): 30.65 parts by mass Coloring composition (PB-19): 10.01 parts by mass Alkali-soluble resin (C-1) solution: 7.19 parts by mass Photopolymerization initiator (D- 1): 0.75 parts by mass Photopolymerizable monomer (E-1): 1.28 parts by mass Epoxy compound (F-1): 0.02 parts by mass Oxetane compound (F-2): 0.02 parts by mass Part Sensitizer (H): 0.02 parts by mass Thiol chain transfer agent (I): 0.02 parts by mass Polymerization inhibitor (J): 0.02 parts by mass Ultraviolet absorber (K): 0.02 parts by mass Part antioxidant (L): 0.02 parts by mass Leveling agent (M): 0.67 parts by mass Storage stabilizer (N): 0.02 parts by mass Silane coupling agent (O): 0.02 parts by mass Organic Solvent (G): 49.27 parts by mass

[Examples 2 to 61, Comparative Examples 1 to 5]
(Photosensitive coloring compositions PR-2 to PR-66)
Photosensitive coloring compositions (PR-2 to PR-66) were produced in the same manner as in Example 1, except that the material types and masses were changed as shown in Table 5. The content of the colorant (A) is 50% by mass based on the total nonvolatile matter.
In addition, each raw material is as follows.

(Photopolymerization initiator (D))
(D-1) to (D-9) shown in specific examples of photopolymerization initiators,
(D-10) Irgacure OXE01 (manufactured by BASF Japan)
(D-11) TRONLY TR-PBG-345 (manufactured by Changzhou Strong New Materials Co., Ltd.)

(Polymerizable compound (E))
(E-1) Trimethylolpropane triacrylate
[Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(E-2) Dipentaerythritol penta and hexaacrylate
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
(E-3) Polybasic acidic acrylic oligomer
[Aronix M510 (manufactured by Toagosei Co., Ltd.)]
(E-4) Polybasic acidic acrylic oligomer
[Aronix M520 (manufactured by Toagosei Co., Ltd.)]
(E-5) Caprolactone-modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]

(Epoxy compound (F-1))
(F-1-1) 1,2- of 2,2'-bis(hydroxymethyl)-1-butanol
Epoxy-4-(2-oxiranyl)cyclohexane adduct
[EHPE-3150 (manufactured by Daicel)],
(F-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase ChemteX)],
(F-1-3) Triglycidyl isocyanurate The above (F-1-1) to (F-1-3) were mixed in equal amounts to form an epoxy compound (F-1).

(Oxetane compound (F-2))
3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane
[Aron oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

(Sensitizer (H))
(H-1) 2,4-diethylthioxanthone
[Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(H-2) 4,4'-bis(diethylamino)benzophenone
[CHEMARK DEABP (manufactured by Chemark Chemical)]
As described above, (H-1) and (H-2) were mixed in the same amount to prepare a sensitizer (H).

(Thiol chain transfer agent (I))
(I-1) Trimethylolethane tris (3-mercaptobutyrate)
[TEMB (manufactured by Showa Denko)]
(I-2) Trimethylolpropane tris (3-mercaptobutyrate)
[TPMB (manufactured by Showa Denko)]
(I-3) Pentaerythritol tetrakis (3-mercaptopropionate)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-4) Trimethylolpropane tris (3-mercaptopropionate)
[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate
[TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
The above (I-1) to (I-5) were mixed in the same amount to prepare a thiol chain transfer agent (I).

(Polymerization inhibitor (J))
(J-1) 3-methylcatechol (J-2) Methylhydroquinone (J-3) t-butylhydroquinone The above (J-1) to (J-3) were mixed in the same amount, and a polymerization inhibitor was added. (J).

(Ultraviolet absorber (K))
(K-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine
[TINUVIN400 (manufactured by BASF Japan)]
(K-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
[TINUVIN900 (manufactured by BASF Japan)]
The above (K-1) to (K-2) were mixed in the same amount to prepare an ultraviolet absorber (K).

(Antioxidant (L))
(L-1) Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (L-2) Dioctadecyl 3,3'-thiodipropanoate (L-3) Tris[2 ,4-di-(t)-butylphenyl]phosphine (L-4) bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (L-5) p-octylphenyl salicylate -1) to (L-5) were mixed in the same amount to prepare an antioxidant (L).

(Leveling agent (M))
(M-1) “BYK-330” manufactured by BYK Chemie
(M-2) DIC “Megafac F-551”
(M-3) "Emulgen 103" manufactured by Kao Corporation
A mixed solution in which 1 part of each of (M-1) to (M-3) were mixed and dissolved in 97 parts of PGMAc was used as a leveling agent (M).

(Storage stabilizer (N))
(N-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol (“BHT” manufactured by Honshu Chemical Industry Co., Ltd.)
(N-2) Triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.)
The above (N-1) to (N-2) were mixed in the same amount to prepare a storage stabilizer (N).

(Adhesion improver (O))
(O-1) 3-glycidoxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-2) 3-methacryloxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-3)N-2-(aminoethyl)-3-aminopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-4) 3-Mercaptopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
As described above, (O-1) to (O-4) were mixed in the same amount to prepare a silane coupling agent (O).

(Organic solvent (G))
(G-1) PGMAc 30 parts (G-2) Cyclohexanone 30 parts (G-3) Ethyl 3-ethoxypropionate 10 parts (G-4) Propylene glycol monomethyl ether 10 parts (G-5) Cyclohexanol acetate 10 parts (G-6) Dipropylene glycol methyl ether acetate 10 parts Above, (G-1) to (G-6) were mixed in the above mass parts, respectively, to prepare a solvent (G).

<Evaluation of photosensitive coloring composition>
The resulting photosensitive coloring compositions PR-1 to PR-66 were evaluated in terms of viscosity stability, alkali developability, pattern formation, and changes in exposure amount using the following methods. The evaluation results are shown in Table 6.

(Viscosity stability evaluation)
The initial viscosity on the next day after preparing the photosensitive coloring composition and the viscosity over time accelerated at 40°C for one week were measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.). The measurement was carried out at a temperature of 50 rpm. From this initial viscosity and the value of the viscosity over time, the rate of change in viscosity over time was calculated using the following formula, and the dispersion stability was evaluated. 3 or more can be used practically without any problem.
Formula: [Viscosity change rate over time] = | ([Initial viscosity] - [Viscosity over time]) / [Initial viscosity] | × 100
5: Rate of change less than 5% 4: Rate of change 5% or more, less than 10% 3: Rate of change 10% or more, less than 15% 2: Rate of change 15% or more, less than 20% 1: Rate of change 20% or more

(Alkali developability evaluation)
A flattening film resist solution (“HL-18s” manufactured by Nippon Steel Chemical Co., Ltd.) was applied onto a 6-inch silicon wafer by spin coating, heated on a hot plate at 100°C for 6 minutes, and then heated in an oven at 230°C for 1 hour. The coating film was cured by heating for a period of time to obtain a silicon wafer with a flat film.Next, a photosensitive coloring composition was spin-coated onto the flat film so that the film thickness after drying was 0.5 μm. method, pre-baked on a hot plate at 100°C for 1 minute, and used an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon) to form 1.0 μm square pixels at a wavelength of 365 nm. Pattern exposure was performed through a photomask at an exposure dose of 3000 J/ ^m2.The exposed coating film was paddle developed with an organic alkaline developer.After paddle development, it was washed with pure water in a spin shower for 20 seconds. The remaining water droplets on the wafer were blown off with high-pressure air, the substrate was air-dried, a square pixel pattern was formed, and the surface of the unexposed area washed away by development was examined using a scanning electron microscope (Hitachi High-Tech's "S"-3000N"), and the alkaline developability was determined based on the presence or absence of a residue. A value of 3 or higher can be used without any practical problems.
5: No residue after 1 minute development time 4: Slight residue visible after 1 minute development time 3: Slight residue observed after 1 minute development time 2: Residue observed after 1 minute development time 1: Development time 1 Severe residue can be seen within minutes

(Pattern formation)
Pattern exposure was performed at three levels of exposure dose: 1500 J/m ² , 3000 J/m ² , and 4500 J/m ² through a 1.0 μm square photomask. Next, a test substrate was formed using the same procedure as in the alkali developability test above, and the pattern pixels were observed using a scanning electron microscope ("S-3000N" manufactured by Hitachi High-Tech Corporation). 3 or more can be used practically without any problems.
5: There are no missing pixels among 50 pattern pixels 4: There are 1 or more missing pixels and less than 3 out of 50 pattern pixels 3: There are 3 or more missing pixels and less than 6 out of 50 pattern pixels 2: Pattern pixels 6 or more missing pixels out of 50 but less than 10 1: 10 or more missing pixels out of 50 pattern pixels

Claims (6)

Contains a colorant (A), a dispersion resin (B), an alkali-soluble resin (C), a photopolymerization initiator (D), and a polymerizable compound (E),
The colorant (A) contains an organic pigment of a blue pigment (A1) and a purple pigment (A2),
The content of the colorant (A) is 45% by mass to 70% by mass in the total nonvolatile matter,
The dispersion resin (B) contains a dispersion resin (B1) having an amine value of 70 mgKOH/g to 150 mgKOH/g,
The alkali-soluble resin (C) has an acid value of 95 mgKOH/g to 163 mgKOH/g , and a weight average molecular weight of 4,000 to 26,000 (excluding 12,000 or less),
A photosensitive colored composition for a blue color filter, characterized in that the photopolymerization initiator (D) contains at least one type of photopolymerization initiator selected from the group consisting of the following general formula (1) and general formula (2). A cured film of a blue color filter made of a material and having a film thickness of 0.2 to 1.0 μm .

In general formula (1), R ₁ and R ₂ each independently represent an alkyl group having 4 or less carbon atoms. R ₃ is an alkyl group having 20 or less carbon atoms which may have a substituent, an alkoxy group having 20 or less carbon atoms which may have a substituent, or an aryl group having 20 or less carbon atoms which may have a substituent. represents a group, and adjacent substituents may be bonded to each other to form an aliphatic ring or an aromatic ring. _R4 is a nitro group, an alkyl group having 20 or less carbon atoms which may have a substituent, an alkoxy group having 20 or less carbon atoms which may have a substituent, or 20 carbon atoms which may have a substituent. It represents the following aryl group, and adjacent substituents may be bonded to each other to form an aliphatic ring or an aromatic ring.
In the general formula (2), R ₅ to R ₇ each independently represent an alkyl group having 4 or less carbon atoms which may have a substituent. The cured film of a blue color filter according to claim 1, wherein the alkali-soluble resin (C) has an acid value of 100 mgKOH/g to 150 mgKOH/g. The blue color filter according to claim 1 or 2, wherein the polymerizable compound (E) contains 50% by mass or more of a polymerizable compound having an average functional group number of 3 to 4 based on the entire polymerizable compound (E). cured film. A color filter comprising a cured film of the blue color filter according to any one of claims 1 to 3 on a base material. A solid-state imaging device comprising the color filter according to claim 4. A liquid crystal display device comprising the color filter according to claim 4.