Negative resist composition, color filter and display device

Abstract

To provide a negative resist composition useful for manufacturing a color filter that has high transmittance of light having a wavelength of 440 nm.SOLUTION: A negative resist composition of the invention includes a coloring agent and a resin. The coloring agent includes xanthene dye. An optical spectrum of a cured film formed from the negative resist composition satisfies the following condition 1. [Condition 1] A maximum absorption wavelength is present in a wavelength range of 500-580 nm. When transmittance in the wavelength is 5%, transmittance in a wavelength of 440 nm is 80% or more, and transmittance in a wavelength 620 nm is 80% or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a negative resist composition. [Background technology]

[0002] Coloring compositions are used in the production of color filters used in liquid crystal displays, etc. Known examples of such coloring compositions include coloring compositions containing quinacridone pigments (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-109487 Summary of the Invention [Problem to be solved by the invention]

[0004] It has been known that magenta can be obtained by mixing blue and red. However, conventional magenta color filters have insufficient transmittance for light with a wavelength of 440 nm. An object of the present invention is to provide a negative resist composition useful for producing a color filter with high transmittance for light with a wavelength of 440 nm. [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] A negative resist composition comprising a colorant and a resin, the colorant comprises a xanthene dye; A negative resist composition, wherein the optical spectrum of a cured film formed from the negative resist composition satisfies the following condition 1: [Condition 1] It has a maximum absorption wavelength in the wavelength range of 500 nm to 580 nm, and when the transmittance at this wavelength is taken as 5%, the transmittance at a wavelength of 440 nm is 80% or more, and the transmittance at a wavelength of 620 nm is 80% or more. [2] The negative resist composition according to [1], which has a transmittance of 90% or more at a wavelength of 620 nm. [3] The negative resist composition according to [1] or [2], wherein the xanthene dye is represented by formula (I).

[0006] [ka] [In formula (I), R 1 ~R 4 each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group is not -O-, -CO- or -NR 11 - may be replaced. R 5 -OH, -SO3 - , -SO3H, -SO3 - Z + , -CO2H, -CO2 - Z + , -CO2R 8 , -SO3R 8 , or -SO2NR 9 R 10 Represents. R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m represents an integer of 0 to 5. When m is 2 or more, a plurality of R 5 may be the same or different. a represents an integer of 0 or 1. X represents a halogen atom. Z + teeth, + N(R 11 )4, Na + , or K +represents the four R's 11 may be the same or different. R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. R 9 and R 10 each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group is -O-, -CO-, -NH-, or -NR 8 - may be replaced by R 9 and R 10 may be bonded to form a 3- to 10-membered heterocyclic ring together with the adjacent nitrogen atom. R 11 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.] [4] The negative resist composition according to [3], wherein the xanthene dye is represented by formula (Ia) and / or formula (Ib1).

[0007] [ka] [In formula (Ia), R a1 and R a4 are each independently a monovalent aromatic hydrocarbon group which may have two or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms. R a2 and R a3 are each independently a hydrogen atom, a methyl group, or an ethyl group. R 5 ~R 7 , m, a, and X have the same meanings as above.]

[0008] [ka] [In formula (Ib1), R b1 ~Rb4 each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent; R b1 ~R b4 At least one saturated hydrocarbon group or aromatic hydrocarbon group contained in 8 , -CO2H, -CO2R 8 , -SO3 - , -SO3H, -SO3 - Z + , -SR 8 , -SO2R 8 , -SO3R 8 , -SO2NR 9 R 10 , or -Si(OR 12 )(OR 13 )(OR 14 ) as a substituent, or R b1 ~R b4 At least one aromatic hydrocarbon group contained in the formula (I) has a monovalent saturated aliphatic hydrocarbon group having 3 or more carbon atoms and 1 to 4 as a substituent, R 12 , R 13 , and R 14 each independently represents a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom; R 5 ~R 10 , m, a, and X have the same meanings as above.] [5] The negative resist composition according to [4], wherein the xanthene dye is a combination of two or more kinds selected from those represented by formula (Ib1), or a combination of a dye represented by formula (Ib1) and a dye represented by formula (Ia). [6] The negative resist composition according to any one of [1] to [5], wherein the colorant is a dye alone, or a combination of a dye with a red pigment or a purple pigment. [7] The negative resist composition according to any one of [1] to [6], further comprising a polymerizable compound and a polymerization initiator. [8] The negative resist composition according to any one of [1] to [7], which is capable of forming a cured film having a thickness of 1.5 μm or less. [9] A color filter formed from the negative resist composition according to any one of [1] to [8].

[10] A display device comprising the color filter according to [9]. [Effects of the Invention]

[0009] The negative resist composition of the present invention can produce a color filter having high transmittance for light with a wavelength of 440 nm. DETAILED DESCRIPTION OF THE INVENTION

[0010] <Negative resist composition> The negative resist composition of the present invention is a negative resist composition comprising a colorant (A) and a resin (C), wherein the colorant (A) contains a xanthene dye, and the spectral spectrum of a cured film formed from the negative resist composition satisfies the following condition 1. [Condition 1] It has a maximum absorption wavelength in the wavelength range of 500 nm to 580 nm, and when the transmittance at this wavelength is taken as 5%, the transmittance at a wavelength of 440 nm is 80% or more, and the transmittance at a wavelength of 620 nm is 80% or more.

[0011] The above-described configuration allows for the production of a magenta color filter with high transmittance for light with a wavelength of 440 nm. A negative resist composition is a resist that has the property that the solubility of the exposed areas in a developer is reduced, so that the exposed areas remain after development. Furthermore, negative resist compositions are preferred because they tend to have a wider range of process conditions, from exposure to development, for finishing a pattern to the desired dimensional range, compared to positive resist compositions in which the solubility of the exposed areas in a developer is high.

[0012] The optical spectrum of the cured film can be obtained by preparing a cured film on a glass substrate under the following conditions and measuring the spectrum with a colorimeter such as OSP-SP-200 (manufactured by Olympus Corporation). [Cured film production method] A negative resist composition is applied to a 5 cm square glass substrate by spin coating, and then pre-baked at 100°C for 3 minutes to form a colored composition layer. After cooling, the resist is exposed to 60 mJ / cm 2 in an air atmosphere using an exposure machine. 2 The colored composition layer is irradiated with light at an exposure amount (based on 365 nm) of 1000 kJ / cm 2. Thereafter, post-baking is performed at 230° C. for 20 minutes.

[0013] To obtain the transmittance of the cured film, the film thickness of the cured film is adjusted so that the transmittance at the maximum absorption wavelength is 5%, and then the transmittance at a wavelength of 440 nm and the transmittance at a wavelength of 620 nm are measured. Alternatively, to obtain the transmittance of the cured film, the film thickness of the cured film may be adjusted as described above, but the transmittance at the maximum absorption wavelength, the transmittance at a wavelength of 440 nm, and the transmittance at a wavelength of 620 nm may be measured, and then the transmittance at a wavelength of 440 nm and the transmittance at a wavelength of 620 nm may be calculated so that the transmittance at the maximum absorption wavelength is 5%.

[0014] The transmittance at a wavelength of 440 nm is 80% or more, preferably 85% or more, more preferably 90% or more, and even more preferably 92% or more. On the other hand, the upper limit is not particularly limited, but may be 100% or less, or may be 99% or less.

[0015] The transmittance at a wavelength of 620 nm is 80% or more, preferably 90% or more, more preferably 93% or more, even more preferably 95% or more, and particularly preferably 97% or more. On the other hand, the upper limit is not particularly limited, but may be 100% or less.

[0016] Each component will be described in detail below. In this specification, the compounds exemplified as each component can be used alone or in combination unless otherwise specified.

[0017] <Colorant (A)> The colorant (A) contains a xanthene dye (A1). The content of the colorant (A) is preferably 5 to 60 mass%, more preferably 8 to 55 mass%, and even more preferably 10 to 50 mass%, relative to the solid content of the negative resist composition. When the content of the colorant is within the above range, the color density of the resulting color filter can be improved, and the composition can contain the necessary amount of resin and the like. Here, the solid content of the negative resist composition refers to the total amount of components excluding the solvent from the negative resist composition of the present invention. The solid content and the content of each component relative to the solid content can be measured using known analytical methods such as liquid chromatography or gas chromatography.

[0018] <Xanthene dyes (A1)> The xanthene dye (A1) is a dye containing a compound having a xanthene skeleton in the molecule. The xanthene dye (A1) is preferably a dye containing a compound represented by formula (I) (hereinafter, sometimes referred to as "compound (I)").

[0019] [ka] [In formula (I), R 1 ~R 4 each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group is not -O-, -CO- or -NR 11 - may be replaced. R 5 -OH, -SO3 - , -SO3H, -SO3 - Z + , -CO2H, -CO2 - Z + , -CO2R 8 , -SO3R 8 , or -SO2NR 9 R 10 Represents. R 6 and R 7each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m represents an integer of 0 to 5. When m is 2 or more, a plurality of R 5 may be the same or different. a represents an integer of 0 or 1. X represents a halogen atom. Z + teeth, + N(R 11 )4, Na + , or K + represents the four R's 11 may be the same or different. R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. R 9 and R 10 each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group is -O-, -CO-, -NH-, or -NR 8 - may be replaced by R 9 and R 10 may be bonded to form a 3- to 10-membered heterocyclic ring together with the adjacent nitrogen atom. R 11 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.]

[0020] Compound (I) may be a tautomer thereof. When compound (I) is used, the content of compound (I) in xanthene dye (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and most preferably 100% by mass.

[0021] R 1 ~R 4Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (I) include linear alkyl groups such as methyl, ethyl, propyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; and alicyclic saturated hydrocarbon groups having 2 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl. The number of carbon atoms in the saturated hydrocarbon group includes the number of carbon atoms in the substituent, if any. Examples of the substituent that the saturated hydrocarbon group may have include halogen atoms, -OH, -OR, and the like. 8 , -SO3 - , -SO3H, -SO3 - Z + , -CO2H, -CO2R 8 , -SR 8 , -SO2R 8 , -SO3R 8 , -SO2NR 9 R 10 , or -Si(OR 12 )(OR 13 )(OR 14 ) are listed. R 12 , R 13 , and R 14 each independently represents a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

[0022] R 1 ~R 4In the above formula, examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include monocyclic aromatic hydrocarbon groups such as a phenyl group, and polycyclic aromatic hydrocarbon groups such as a naphthyl group, anthryl group, phenanthryl group, biphenyl group, and terphenyl group. As the polycyclic aromatic hydrocarbon group, a non-condensed polycyclic aromatic hydrocarbon group such as a biphenyl group or a terphenyl group is preferred. Furthermore, it is preferred that the polycyclic aromatic hydrocarbon group does not have a substituent. Examples of the monovalent aromatic hydrocarbon group having a substituent include a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. When the aromatic hydrocarbon group has a substituent, the number of carbon atoms in the substituent is the number including the carbon atoms in the substituent. Examples of the substituent that the aromatic hydrocarbon group may have include a halogen atom, -R 8 , -OH, -OR 8 , -SO3 - , -SO3H, -SO3 - Z + , -CO2H, -CO2R 8 , -SR 8 , -SO2R 8 , -SO3R 8 , -SO2NR 9 R 10 , or -Si(OR 12 )(OR 13 )(OR 14 ) are listed.

[0023] R 8 ~R 11 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (I) include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl groups.

[0024] R 9 and R 10The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in the formula (I) may have a substituent, such as a hydroxy group or a halogen atom.

[0025] R 12 ~R 14 Examples of the monovalent saturated hydrocarbon group having 1 to 4 carbon atoms in the formula (I) include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; and alicyclic saturated hydrocarbon groups having 1 to 4 carbon atoms such as branched alkyl groups such as an isopropyl group and an isobutyl group.

[0026] Z + teeth, + N(R 11 )4, Na + or K + and preferably + N(R 11 )4. + N(R 11 ) 4 R's in 4 11 Among the four R, it is preferable that at least two of them are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. 11 The total number of carbon atoms in compound (I) is preferably 20 to 80, and more preferably 20 to 60. + N(R 11 )4 exists, R 11 When is one of these groups, a color filter containing little foreign matter can be formed from the negative resist composition of the present invention containing compound (I).

[0027] -OR 8 Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and an icosyloxy group.

[0028] -CO2R 8 Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

[0029] -SR 8 Examples of the sulfanyl group include a methylsulfanyl group, an ethylsulfanyl group, and a butylsulfanyl group. Examples thereof include a sulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group. -SO2R 8 Examples of the sulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group. -SO3R 8 Examples of the sulfonyl group include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

[0030] -SO2NR 9 R 10 Examples include a sulfamoyl group; N-Methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-(1,1-dimethylpropyl)sulfamoyl group, N-(1,2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group N-1-substituted sulfamoyl groups such as a sulfamoyl group, an N-(3-methylbutyl)sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, an N-(1,3-dimethylbutyl)sulfamoyl group, an N-(3,3-dimethylbutyl)sulfamoyl group, an N-heptylsulfamoyl group, an N-(1-methylhexyl)sulfamoyl group, an N-(1,4-dimethylpentyl)sulfamoyl group, an N-octylsulfamoyl group, an N-(2-ethylhexyl)sulfamoyl group, an N-(1,5-dimethyl)hexylsulfamoyl group, and an N-(1,1,2,2-tetramethylbutyl)sulfamoyl group; Examples include N,N-disubstituted sulfamoyl groups such as N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group and N,N-heptylmethylsulfamoyl group.

[0031] -Si(OR 12 )(OR 13 )(OR 14 ) includes, for example, a trimethoxysilyl group, a triethoxysilyl group, and the like.

[0032] R 5 -CO2H, -CO2 - Z + , -CO2R8 , -SO3 - , -SO3 - Z + , -SO3H, or SO2NHR 9 is preferred, and SO3 - , -SO3 - Z + , -SO3H or SO2NHR 9 is more preferred.

[0033] m represents an integer of 0 to 5, preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0034] R 6 and R 7 As the alkyl group having 1 to 6 carbon atoms in R, among the alkyl groups listed above, those having 1 to 6 carbon atoms can be mentioned, and alkyl groups having 1 to 2 carbon atoms are preferred. 6 and R 7 is more preferably a hydrogen atom.

[0035] R 11 Examples of the aralkyl group having 7 to 10 carbon atoms in the formula include a benzyl group, a phenylethyl group, and a phenylbutyl group.

[0036] Examples of the halogen atom in X include a chlorine atom, a fluorine atom, and a bromine atom.

[0037] a represents an integer of 0 or 1, with 0 being preferred.

[0038] Preferred examples of compound (I) include a compound represented by formula (Ia) (hereinafter referred to as "compound (Ia)"). The compound represented by formula (Ia) may be used without being combined with any other compound of compound (I) other than compound (Ia) (hereinafter referred to as "compound (Ib)"), or compound (Ia) and compound (Ib) may be used in combination. Two or more types of compound (Ia) may be used in combination.

[0039] [ka] [In formula (Ia), R a1 and R a4 are each independently a monovalent aromatic hydrocarbon group which may have two or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms. R a2 and R a3 are each independently a hydrogen atom, a methyl group, or an ethyl group. R 5 ~R 7 , m, a, and X have the same meanings as above.]

[0040] R a1 and R a4 As for the above R 1 and R 4 Among the groups similar to those mentioned above, examples include monovalent aromatic hydrocarbon groups that have no substituents, and monovalent aromatic hydrocarbon groups that have two or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms. Of these, monovalent aromatic hydrocarbon groups that have two or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms are preferred.

[0041] Examples of unsubstituted monovalent aromatic hydrocarbon groups include monocyclic aromatic hydrocarbon groups such as phenyl groups, and polycyclic aromatic hydrocarbon groups such as naphthyl groups, anthryl groups, phenanthryl groups, biphenyl groups, and terphenyl groups. Preferred polycyclic aromatic hydrocarbon groups are non-condensed polycyclic aromatic hydrocarbon groups such as biphenyl groups and terphenyl groups. Examples of monovalent aromatic hydrocarbon groups containing 1 to 4 monovalent saturated aliphatic hydrocarbon groups with two or less carbon atoms include toluyl groups, xylyl groups, mesityl groups, monopropylphenyl groups, dipropylphenyl groups, monobutylphenyl groups, and dibutylphenyl groups. The number of carbon atoms in the aromatic hydrocarbon group is preferably 7 to 20, more preferably 7 to 16, even more preferably 7 to 10, and most preferably 8. The number of carbon atoms in the aromatic hydrocarbon group includes the number of carbon atoms in the substituents. It is preferred that the aromatic hydrocarbon group does not have any substituents other than the saturated aliphatic hydrocarbon group.

[0042] The number of saturated aliphatic hydrocarbon groups bonded to the aromatic hydrocarbon group is preferably 1 to 2, and more preferably 2. The saturated aliphatic hydrocarbon group is preferably bonded to the ortho- or meta-position relative to the bond of the aromatic hydrocarbon group, and more preferably to the ortho-position. Examples of the saturated aliphatic hydrocarbon group include saturated aliphatic hydrocarbon groups that do not have a substituent. The number of carbon atoms in the saturated aliphatic hydrocarbon group is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 to 2, and most preferably 1.

[0043] R a2 and R a3 Examples of the alkyl group include a hydrogen atom, a methyl group, and an ethyl group. Of these, a hydrogen atom or a methyl group is preferred, and a hydrogen atom is more preferred.

[0044] Compound (Ib) is preferably a compound represented by formula (Ib1) (hereinafter sometimes referred to as "compound (Ib1)"). Compound (Ib1) is preferably used in combination with compound (Ia), but may be used without being combined with compound (Ia). That is, xanthene dye (A1) may be compound (Ia) and / or compound (Ib1), preferably compound (Ia) or compound (Ia) and compound (Ib1), and more preferably compound (Ia).

[0045] [ka] [In formula (Ib1), R b1 ~R b4 each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent; R b1 ~R b4 At least one saturated hydrocarbon group or aromatic hydrocarbon group contained in 8 , -CO2H, -CO2R 8, -SO3 - , -SO3H, -SO3 - Z + , -SR 8 , -SO2R 8 , -SO3R 8 , -SO2NR 9 R 10 , or -Si(OR 12 )(OR 13 )(OR 14 ) as a substituent, or R b1 ~R b4 At least one aromatic hydrocarbon group contained in the formula (I) has a monovalent saturated aliphatic hydrocarbon group having 3 or more carbon atoms and 1 to 4 as a substituent, R 12 , R 13 , and R 14 each independently represents a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom; R 5 ~R 10 , m, a, and X have the same meanings as above.]

[0046] R b1 and R b4 As for the above R 1 and R 4 Examples of groups similar to those listed above include a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having three or more monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms as substituents. Of these, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having three or more monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms as substituents is preferred.

[0047] The number of carbon atoms in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, is preferably 1 to 10, more preferably 2 to 8, and even more preferably 2 to 7. The number of carbon atoms in the saturated aliphatic hydrocarbon group includes the number of carbon atoms in the substituent. Examples of the substituent include a halogen atom, -OH, -OR 8 , -CO2H, -CO2R 8 , -SO3 - , -SO3H, -SO3 - Z + , -SR 8 , -SO2R 8 , -SO3R 8 , -SO2NR 9 R 10 , or -Si(OR 12 )(OR 13 )(OR 14 ) is preferred, and —OH, —OR 8 , -CO2H, -CO2R 8 , -SO3 - , -SO3H, -SO3 - Z + , -SR 8 , -SO2R 8 , -SO3R 8 , or -Si(OR 12 )(OR 13 )(OR 14 ), and more preferably —OH, —OR 8 , -CO2H, -CO2R 8 , or -Si(OR 12 )(OR 13 )(OR 14 ), most preferably -Si(OR 12 )(OR 13 )(OR 14 The number of substituents is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 or 2, and most preferably 1, per saturated aliphatic hydrocarbon group.

[0048] The number of carbon atoms in the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have a substituent, is preferably 7 to 20, more preferably 7 to 16, even more preferably 7 to 12, still more preferably 7 to 10, particularly preferably 7 to 8, and most preferably 8. The number of carbon atoms in the aromatic hydrocarbon group includes the number of carbon atoms in the substituent. Examples of the substituent include a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, -OH, -OR 8 , -CO2H, -CO2R 8 , -SO3 - , -SO3H, -SO3 - Z + , -SR 8 , -SO2R 8 , -SO3R 8 , -SO2NR 9 R 10 , or -Si(OR 12 )(OR 13 )(OR 14 ) is preferred, and more preferred are monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms, -OH, -OR 8 , -CO2H, -CO2R 8 , -SO3 - , -SO3H, -SO3 - Z + , -SR 8 , -SO2R 8 , -SO3R 8 , or -SO2NR 9 R 10 More preferably, it is a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, -OR 8 , -SO3 - , -SO3H, -SO3 - Z + , -SR 8 , -SO2R 8 , -SO3R 8 , or -SO2NR 9 R 10 The number of substituents per aromatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, even more preferably 1 or 2, and most preferably 2. The substituents are preferably bonded to the ortho- and / or meta-positions, more preferably ortho-positions, relative to the bonds of the aromatic hydrocarbon group.

[0049] The number of carbon atoms in an aromatic hydrocarbon group having three or more monovalent saturated aliphatic hydrocarbon groups each having 1 to 4 carbon atoms as a substituent is preferably 9 to 20, more preferably 9 to 13, even more preferably 9 to 12, and most preferably 9. The number of carbon atoms in the aromatic hydrocarbon group includes the number of carbon atoms in the substituent. The aromatic hydrocarbon group preferably has no substituents other than the saturated aliphatic hydrocarbon group. The number of saturated aliphatic hydrocarbon groups per aromatic hydrocarbon group is preferably 3 to 5, more preferably 3 to 4, and most preferably 3. The saturated aliphatic hydrocarbon groups are preferably bonded at the ortho and / or para positions relative to the bond of the aromatic hydrocarbon group, and more preferably at the ortho and para positions. The number of carbon atoms in the monovalent saturated aliphatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, even more preferably 1 or 2, and most preferably 1.

[0050] R b2 and R b3 As for the above R 2 and R 3 Of the groups similar to those listed above, preferred are hydrogen atoms and monovalent saturated hydrocarbon groups of 1 to 20 carbon atoms which may have a substituent. Of these, monovalent saturated hydrocarbon groups of 1 to 20 carbon atoms which may have a substituent are more preferred, and monovalent saturated hydrocarbon groups of 1 to 20 carbon atoms which have a substituent are even more preferred.

[0051] The number of carbon atoms in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The number of carbon atoms in the saturated aliphatic hydrocarbon group includes the number of carbon atoms in the substituent. Examples of the substituent include a halogen atom, -OH, -OR 8 , -CO2H, -CO2R 8 , -SO3 - , -SO3H, -SO3 - Z + , -SR 8 , -SO2R 8 , -SO3R 8, -SO2NR 9 R 10 , or -Si(OR 12 )(OR 13 )(OR 14 ) is preferably mentioned, and more preferably —OH, —OR 8 , -CO2H, -CO2R 8 , -SO3 - , -SO3H, -SO3 - Z + , -SR 8 , -SO2R 8 , -SO3R 8 , or -Si(OR 12 )(OR 13 )(OR 14 ), and more preferably —OH, —OR 8 , -CO2H, -CO2R 8 , or -Si(OR 12 )(OR 13 )(OR 14 ), most preferably -CO2H or -CO2R 8 The number of substituents is preferably 1 to 5, more preferably 1 to 3, even more preferably 1 or 2, and most preferably 1, per saturated aliphatic hydrocarbon group.

[0052] As the compound (Ia), compounds No. 1 to 48 specified by the formula (IaX) and Table 1 are preferred.

[0053] [ka]

[0054] [Table 1]

[0055] The symbols in the formulae represent the following groups (in the following, * represents a bond).

[0056] [ka]

[0057] As the compound (Ib1), compounds Nos. 49 to 74 specified in formula (Ibx) and Table 2, and compounds represented by formulae A3-1 to A3-8 are preferred.

[0058] [ka]

[0059] [Table 2]

[0060] The symbols in the formulae represent the following groups (in the following, * represents a bond).

[0061] [ka]

[0062] [ka]

[0063] The colorant (A) may be a dye alone or a combination of a dye and a pigment. Among these, the colorant (A) is preferably a dye alone or a combination of a dye and a red pigment or a purple pigment, more preferably a xanthene dye (A1) alone or a combination of a xanthene dye (A1) and a red pigment or a purple pigment, even more preferably a xanthene dye (A1) alone or a combination of a xanthene dye (A1) and a purple pigment, and even more preferably a xanthene dye (A1) alone.

[0064] The xanthene dye (A1) is preferably the compound (Ia) and / or the compound (Ib1), i.e., the xanthene dye (A1) is preferably either the compound (Ia) or the compound (Ib1), or a combination of the compound (Ia) and the compound (Ib1).

[0065] The xanthene dye (A1) is preferably a combination of two or more selected from the compound (Ib), or a combination of the compound (Ib) and the compound (Ia), and more preferably a combination of two or more selected from the compound (Ib1), or a combination of the compound (Ib1) and the compound (Ia).

[0066] The content of the xanthene dye (A1) is preferably 30 to 100 mass%, more preferably 60 to 100 mass%, even more preferably 80 to 100 mass%, and most preferably 100 mass%, based on the total amount of the colorant (A). When the colorant (A) contains a pigment or the like, the content of the xanthene dye (A1) may be 90 mass% or less, 80 mass% or less, or 70 mass% or less.

[0067] The content of compound (Ia) in the xanthene dye (A1) is preferably 30 to 100% by mass, more preferably 60 to 100% by mass, even more preferably 80 to 100% by mass, and most preferably 100% by mass. When colorant (A) contains compound (Ib) or the like, the content of compound (Ia) may be 80% by mass or less, 70% by mass or less, or 60% by mass or less.

[0068] The content of the compound (Ib) in the xanthene dye (A1) is preferably from 20 to 80% by mass, more preferably from 30 to 70% by mass, and even more preferably from 40 to 60% by mass.

[0069] The content of compound (Ib) relative to 100 parts by mass of compound (Ia) is preferably 20 to 150 parts by mass, more preferably 50 to 130 parts by mass, and even more preferably 80 to 110 parts by mass.

[0070] <Other dyes (A2)> The colorant (A) may further contain a dye other than the xanthene dye (A1) (sometimes referred to as "other dye (A2)"). The other dye (A2) is not particularly limited as long as it is a dye other than the xanthene dye (A1), and examples thereof include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. Examples of such dyes include compounds classified as dyes in the Color Index (published by The Society of Dyes and Colourists), i.e., compounds that have a hue other than CI pigments, and known dyes listed in Dyeing Notes (Shikisensha). In terms of chemical structure, examples of such dyes include azo dyes, anthraquinone dyes, cyanine dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. <Pigment (A3)> The colorant (A) may contain a pigment (A3). Examples of the pigment (A3) include organic pigments and inorganic pigments, and include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

[0071] Examples of organic pigments include red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; Blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; purple pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; Examples include green pigments such as CI Pigment Green 7, 36, and 58.

[0072] Among these, red pigments and purple pigments are preferred, purple pigments are more preferred, and CI Pigment Violet 19 is even more preferred.

[0073] Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts, and specific examples include oxides or composite metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony.

[0074] The pigment (A3) may be subjected, as necessary, to a rosin treatment, a surface treatment using a pigment derivative having an acidic or basic group introduced therein or a dispersant, a grafting treatment onto the pigment surface using a polymer compound, a microparticle treatment using a sulfuric acid microparticle treatment, a washing treatment using an organic solvent or water to remove impurities, a treatment to remove ionic impurities using an ion exchange method, etc. Furthermore, it is preferable that the pigment (A3) has a uniform particle size.

[0075] When the pigment (A3) is used, the content of the pigment (A3) is preferably 10 to 90 mass %, more preferably 20 to 80 mass %, and even more preferably 30 to 70 mass %, based on the total amount of the colorant (A).

[0076] <Solvent (B)> The negative resist composition may contain a solvent (B). The solvent (B) is not particularly limited, and a solvent commonly used in the relevant field can be used. For example, a solvent selected from ester solvents (solvents containing -COO- in the molecule but not -O-), ether solvents (solvents containing -O- in the molecule but not -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule but not -COO-), alcohol solvents (solvents containing OH in the molecule but not -O-, -CO-, or -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. can be used.

[0077] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, propylene glycol diacetate, and 1,3-butylene glycol diacetate.

[0078] Examples of ether solvents include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether; phenol ethers such as anisole, phenetole, and methylanisole; 3-methoxy-1-butanol, and 3-methoxy-3-methylbutanol.

[0079] Examples of the ether ester solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate; dipropylene glycol monomethyl ether acetate and other dipropylene glycol monomethyl ether acetates; Propylene glycol monoalkyl ether acetates; methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and the like.

[0080] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0081] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0082] Aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, and the like.

[0083] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0084] Of the above solvents, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and / or 4-hydroxy-4-methyl-2-pentanone are preferred.

[0085] In particular, a solvent containing an ether ester solvent is preferred. In this case, the content of the ether ester solvent is preferably 40% by mass or more and 100% by mass or less, and from the viewpoint of dispersion stability, more preferably 40% by mass or more and 99% by mass or less, based on the total amount of solvent (B). The lower limit of the content of the ether ester solvent is preferably 60% by mass, more preferably 70% by mass. The ether ester solvent is preferably at least one selected from the group consisting of ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, and diethylene glycol monoalkyl ether acetates, and more preferably propylene glycol monomethyl ether acetate. When the solvent (B) is a mixed solvent, the solvent to be combined with the ether ester solvent is preferably at least one selected from the group consisting of ether solvents and ketone solvents, and more preferably at least one selected from the group consisting of propylene glycol monomethyl ether and 4-hydroxy-4-methyl-2-pentanone. If the solvent (B) is such a solvent, it is possible to produce a high-brightness color filter from the negative resist composition prepared from the negative resist composition of the present invention, which is therefore preferable. The solvent (B) is preferably a solvent in which the solubility of the colorant (A) at 23°C is 5% by mass or less, more preferably a solvent in which the solubility of the colorant (A) at 23°C is 0.3 to 3% by mass. The solvent (B) in which the solubility of the xanthene dye (A1) is within the above range is particularly preferred.

[0086] <Resin (C)> The negative resist composition of the present invention contains a resin (C). The resin (C) is preferably an alkali-soluble resin. By including an alkali-soluble resin in the negative resist composition, the solubility of the unexposed areas in a developer is improved. In addition, alkali-soluble resins have excellent compatibility with dispersants having an amine group, which will be described later. Examples of the resin (C) include the following resins [K1] to [K6]. Resin [K1]: A copolymer of at least one member (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond; Resin [K2]: a copolymer of (a), (b), and a monomer (c) copolymerizable with (a) (but different from (a) and (b)) (hereinafter sometimes referred to as "(c)"); Resin [K3] copolymer of (a) and (c); Resin [K4]: A resin obtained by reacting a copolymer of (a) and (c) with (b); Resin [K5]: A resin obtained by reacting a copolymer of (b) and (c) with (a); Resin [K6] A resin obtained by reacting a copolymer of (b) and (c) with (a) and then reacting it with a carboxylic acid anhydride.

[0087] Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid; bicyclounsaturated compounds containing a carboxy group, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; Unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids, such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate; Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred from the viewpoint of copolymerization reactivity and solubility of the resulting resin in an alkaline aqueous solution.

[0088] (b) refers to, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group. In this specification, "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid. The terms "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

[0089] Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)").

[0090] Examples of (b1) include a monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon has been epoxidized, and a monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon has been epoxidized.

[0091] Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyl Examples of such styrene include 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, and 2,4,6-tris(glycidyloxymethyl)styrene.

[0092] Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., CELLOXIDE (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., CYCLOMER (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., CYCLOMER M100; manufactured by Daicel Corporation), compounds represented by formula (BI), and compounds represented by formula (BII).

[0093] [ka]

[0094] [In formula (BI) and formula (BII), R a and R b represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. X a and X b is a single bond, *-R c -, *-R c -O-, *-R c -S- or *-R c represents -NH-. R c represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond to O.]

[0095] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Examples of alkyl groups in which a hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group. R a and R b Preferred examples of the alkyl group include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferred examples include a hydrogen atom and a methyl group.

[0096] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. X a and X b is preferably a single bond, a methylene group, an ethylene group, *-CH2-O- and *-CH2CH2-O-, and more preferably a single bond, *-CH2CH2-O- (* represents a bond to O).

[0097] Examples of the compound represented by formula (BI) include compounds represented by formulas (BI-1) to (BI-15). Preferred examples include compounds represented by formula (BI-1), (BI-3), (BI-5), (BI-7), (BI-9), or (BI-11) to (BI-15). More preferred examples include compounds represented by formula (BI-1), (BI-7), (BI-9), or (BI-15).

[0098] [ka]

[0099] [ka]

[0100] Examples of the compound represented by formula (BII) include compounds represented by formulas (BII-1) to (BII-15). Preferred examples include compounds represented by formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9), or formulas (BII-11) to (BII-15). More preferred examples include compounds represented by formula (BII-1), formula (BII-7), formula (BII-9), or formula (BII-15).

[0101] [ka]

[0102] [ka]

[0103] The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone, or the compound represented by formula (BI) and the compound represented by formula (BII) may be used in combination. When these are used in combination, the content ratio of the compound represented by formula (BI) and the compound represented by formula (BII) is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20 on a molar basis.

[0104] As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferred. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, and the like.

[0105] As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferred. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0106] As (b), (b1) is preferable in that it can further increase the reliability of the heat resistance, chemical resistance, etc. of the obtained color filter. Furthermore, (b1-2) is more preferable in that it provides excellent storage stability of the negative resist composition.

[0107] Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0] 2,6 ]decan-8-yl(meth)acrylate (commonly known in the art as "dicyclopentanyl(meth)acrylate" and sometimes as "tricyclodecyl(meth)acrylate"), tricyclo[5.2.1.0 2,6 (meth)acrylic acid esters such as ]decen-8-yl (meth)acrylate (commonly known as "dicyclopentenyl (meth)acrylate" in the technical field), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate; hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene Bicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept -2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene bicyclounsaturated compounds such as ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide; Examples include styrene-based monomers such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene; nitrile-based monomers such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinylidene chloride; amide-based monomers such as acrylamide and methacrylamide; vinyl acetate; and diene-based monomers such as 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, and the like are preferred from the viewpoints of copolymerization reactivity and heat resistance.

[0108] In the resin [K1], the ratio of the structural units derived from each of these is as follows: Structural units derived from (a): 2 to 60 mol% Structural units derived from (b): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol% Structural units derived from (b): 50 to 90 mol% It is more preferable that: When the ratio of the structural units of the resin [K1] is within the above range, the storage stability of the negative resist composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter tend to be excellent.

[0109] Resin [K1] can be produced, for example, by the method described in the literature "Experimental Methods of Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and by reference to the references described in said literature.

[0110] Specifically, a method can be exemplified in which predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and the atmosphere is deoxygenated, for example by replacing oxygen with nitrogen, followed by heating and keeping the temperature while stirring. The polymerization initiator, solvent, and the like used here are not particularly limited, and those commonly used in the relevant field can be used. For example, polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). Solvents that dissolve the respective monomers can be used, and examples of the solvents include those described below as the solvent (B) of the negative resist composition of the present invention.

[0111] The resulting copolymer may be used as a solution after the reaction as is, or may be a concentrated or diluted solution, or may be extracted as a solid (powder) by methods such as reprecipitation. In particular, by using a solvent contained in the negative resist composition of the present invention as the solvent during polymerization, the solution after the reaction can be used as is to prepare the negative resist composition of the present invention, thereby simplifying the production process for the negative resist composition of the present invention.

[0112] In the resin [K2], the ratio of the structural units derived from each of these is as follows: Structural units derived from (a): 2 to 45 mol% Structural units derived from (b): 2 to 95 mol% Structural units derived from (c): 1 to 65 mol% It is preferred that Structural units derived from (a): 5 to 40 mol% Structural units derived from (b): 5 to 80 mol% Structural units derived from (c): 5 to 60 mol% It is more preferable that: When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the negative resist composition and the developability when forming a colored pattern tend to be excellent, and the solvent resistance, heat resistance, and mechanical strength of the obtained color filter tend to be excellent.

[0113] Resin [K2] can be produced, for example, in the same manner as described above for producing resin [K1].

[0114] In the resin [K3], the ratio of the structural units derived from each of these is as follows: Structural units derived from (a): 2 to 60 mol% Structural units derived from (c): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol% Structural units derived from (c): 50 to 90 mol% It is more preferable that: Resin [K3] can be produced, for example, in the same manner as described above for producing resin [K1].

[0115] Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and then adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic acid anhydride contained in (a). First, a copolymer of (a) and (c) is produced in the same manner as described for the production of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that described for resin [K3].

[0116] Next, a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms contained in (b). Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and (b) a reaction catalyst (e.g., tris(dimethylaminomethyl)phenol, etc.) for the reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether, a polymerization inhibitor (e.g., hydroquinone, etc.), etc. are placed in the flask, and the reaction is carried out, for example, at 60 to 130°C for 1 to 10 hours, thereby producing the resin [K4]. The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By using this range, the storage stability of the negative resist composition, the developability during pattern formation, and the balance of the solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern tend to be favorable. Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) used in resin [K4], and (b1-1) is even more preferred. The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total of (a), (b), and (c).The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total of (a), (b), and (c). The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc. As with the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc.

[0117] Resin [K5] is obtained in the first step by the same method as in the production of resin [K1] described above, to obtain a copolymer of (b) and (c). As in the above, the obtained copolymer may be used as a solution after the reaction as is, a concentrated or diluted solution, or a solid (powder) obtained by a method such as reprecipitation. The ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer are as follows: Structural units derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b): 10 to 90 mol% Structural units derived from (c): 10 to 90 mol% It is more preferable that:

[0118] Furthermore, under the same conditions as in the production method of resin [K4], resin [K5] can be obtained by reacting the cyclic ether derived from (b) contained in the copolymer of (b) and (c) with the carboxylic acid or carboxylic anhydride contained in (a). The amount of (a) used to react with the copolymer is preferably 5 to 80 moles per 100 moles of (b). Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) used in resin [K5], and (b1-1) is more preferred.

[0119] Resin [K6] is a resin obtained by further reacting resin [K5] with a carboxylic acid anhydride. A hydroxy group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride is reacted with a carboxylic acid anhydride. Examples of carboxylic acid anhydrides include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (himic anhydride), etc. The amount of carboxylic acid anhydride used is preferably 0.5 to 1 mole per mole of (a).

[0120] Specific examples of the resin (C) include 3,4-epoxycyclohexylmethyl (meth)acrylate / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl acrylate / (meth)acrylic acid copolymer and other resins [K1]; glycidyl (Meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decyl acrylate / (meth)acrylic acid / N -Cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl acrylate / (meth)acrylic acid / styrene monomer copolymer, 3-methyl Resins such as 3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer [K2]; benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer, etc. [K3]; resins obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer Resins [K4] such as a resin obtained by adding glycidyl (meth)acrylate to a styrene copolymer; resins [K5] such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid, a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate with (meth)acrylic acid; and resins [K6] such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid and then reacting the resulting copolymer with tetrahydrophthalic anhydride. Among these, resin (C) is preferably resin [K1] and / or resin [K2].

[0121] The polystyrene-equivalent weight average molecular weight of resin (C) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. The molecular weight distribution of resin (C) [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1 to 6, and more preferably 1.2 to 4.

[0122] The acid value of the resin (C) is preferably 50 to 170 mgKOH / g, more preferably 60 to 150 mgKOH / g, and even more preferably 70 to 135 mgKOH / g. The acid value is measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

[0123] <Dispersant (D)> The negative resist composition of the present invention preferably further comprises a dispersant (D). The dispersant (D) is not particularly limited as long as it has an amine group and an amine value of 0 to 55 mgKOH / g (preferably 2 to 40 mgKOH / g) and is usable for dispersing a colorant, and examples thereof include polymer dispersants.

[0124] Examples of the polymer dispersant include acrylic dispersants and urethane dispersants.

[0125] Examples of the acrylic dispersant include acrylic block copolymers. As the acrylic block copolymer, it is preferable to use a block copolymer having a colorant adsorption block that contains a basic group as a colorant adsorption group (also called a dye adsorption group), a colorant adsorption block that further contains an acid group as a colorant adsorption group, and a block that does not contain a colorant adsorption group.

[0126] As the colorant adsorption group, a colorant adsorption block that further contains an acid group in addition to a colorant adsorption block that contains a basic group can be formed by using a monomer having a basic group together with a monomer having an acidic group.

[0127] The monomer having a basic group is a monomer having a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium group, Specific examples include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylacrylamide, diethylacrylamide, dimethylaminopropyl methacrylamide, acryloylmorpholine, vinylimidazole, 2-vinylpyridine, a monomer having an amino group and a caprolactone skeleton, a reaction product of a monomer having a glycidyl group such as glycidyl (meth)acrylate with a compound having one secondary amino group in the molecule, and a reaction product of a (meth)acryloylalkyl isocyanate compound with 4-(2-aminomethyl)-pyridine, 4-(2-aminoethyl)-pyridine, 4-(2-hydroxyethyl)pyridine, 1-(2-aminoethyl)-piperazine, 2-amino-6-methoxybenzothiazole, 1-(2-hydroxyethylimidazole), N,N-diallylmelamine, or N,N-dimethyl-1,3-propanediamine.

[0128] The monomer having an acidic group is a monomer having a carboxy group, a sulfonic acid group, or a phosphoric acid group. Specific examples of the monomer having a carboxy group include unsaturated monocarboxylic acid compounds such as acrylic acid, methacrylic acid, and crotonic acid, unsaturated dicarboxylic acid compounds such as maleic acid, fumaric acid, and itaconic acid, and half esters thereof; monomers having a sulfonic acid group include 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, and styrenesulfonic acid; and monomers having a phosphoric acid group include acid phosphonyl(meth)acrylate and acid phosphonylethyl(meth)acrylate.

[0129] Examples of components of the block that do not contain a colorant-adsorbing group include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and benzyl chloride, unsaturated carboxylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate, unsaturated carboxylic acid aryl alkyl esters such as benzyl (meth)acrylate, polycaprolactone-containing monomers, and polyalkylene glycol monoester-based monomers. The acrylic block copolymer can be obtained by living anionic polymerization or the like, and a conventionally known polymerization method can be used.

[0130] The acrylic block copolymer has an amine value of 0 to 55 mgKOH / g, preferably 0 to 50 mgKOH / g, and more preferably 2 to 40 mgKOH / g. The amine value refers to the amine value per gram of solid content of the acrylic block copolymer, measured by potentiometric titration using a 0.1 mol / L aqueous hydrochloric acid solution (for example, COMTITE (AUTOTITRATOR COM-900, BURET B-900, TITSTATION K-900), manufactured by Hiranuma Sangyo Co., Ltd.), and then converted into an equivalent amount of potassium hydroxide.

[0131] Commercially available examples of the acrylic block copolymer include "Disperbyk (registered trademark)-112 (amine value 36 mg KOH / g)", "Disperbyk (registered trademark)-2000 (amine value 4 mg KOH / g)", "Disperbyk (registered trademark)-2001 (amine value 29 mg KOH / g)", "Disperbyk (registered trademark)-2020 (amine value 38 mg KOH / g)", "Disperbyk (registered trademark)-2050 (amine value 30 mg KOH / g)", and "Disperbyk (registered trademark)-2070 (amine value 20 mg KOH / g)", all manufactured by BYK Japan.

[0132] The urethane dispersant can be obtained by reacting the isocyanate group of a polyisocyanate compound with a compound having a number average molecular weight of 300 to 10,000 and one or more hydroxy groups in the molecule, and a basic group-containing compound having a functional group reactive with the isocyanate group in the molecule. Methods for obtaining such urethane dispersants include those described in JP-A-60-166318.

[0133] Examples of the polyisocyanate compound constituting the urethane-based dispersant include isocyanate compounds having two or more isocyanate groups, such as aromatic diisocyanate compounds such as 2,4-tolylene diisocyanate, a dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, and 3,3'-dimethylbiphenyl-4,4'-diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, and the like. Examples of suitable polyisocyanates include aliphatic and alicyclic polyisocyanates such as isocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, and 1,3-(isocyanatomethylene)cyclohexane; polyisocyanates having isocyanuric groups based on the above diisocyanates (such as polyisocyanates having isocyanuric groups formed by trimerization of the above diisocyanates), polyisocyanates obtained by reacting polyols with diisocyanates, and polyisocyanates obtained by the biuret reaction of diisocyanate compounds. Among the above polyisocyanate compounds, preferred are polyisocyanates having isocyanuric groups based on diisocyanates such as tolylene diisocyanate and isophorone diisocyanate.

[0134] Examples of the compound having one or more hydroxy groups in the molecule that constitutes the urethane-based dispersant include polyether compounds and polyester compounds. Examples of the polyether compound include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol; alkylene glycols such as ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, and dipentaerythritol; and ethylene oxide-modified, propylene oxide-modified, butylene oxide-modified, and tetrahydrofuran-modified products of low-molecular-weight monools such as methanol and ethanol.

[0135] Examples of the polyester compound include alkylene glycols such as ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, and dipentaerythritol; ε-caprolactone-modified products, γ-butyrolactone-modified products, δ-valerolactone-modified products, and methylvalerolactone-modified products of low-molecular-weight monools such as methanol and ethanol; and esters of aliphatic dicarboxylic acids such as adipic acid and dimer acid with polyols such as neopentyl glycol and methylpentanediol. polyester polyols such as aromatic polyester polyols which are esters of aromatic dicarboxylic acids such as terephthalic acid with polyols such as neopentyl glycol; esters of polyvalent hydroxyl group compounds such as polycarbonate polyols, acrylic polyols, and polytetramethylene hexaglyceryl ether (tetrahydrofuran-modified hexaglycerin) with dicarboxylic acids such as fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, and maleic acid; and polyvalent hydroxyl group-containing compounds such as monoglycerides obtained by transesterification of polyvalent hydroxyl group-containing compounds such as glycerin with fatty acid esters. Among the above compounds having one or more hydroxyl groups in the molecule, ε-caprolactone adducts of alcohols are preferred.

[0136] The number average molecular weight of the compound having one or more hydroxy groups in the molecule is 300 to 10,000, and preferably 300 to 6000. The number average molecular weight and weight average molecular weight can be measured by column chromatography.

[0137] The basic group-containing compound having a functional group capable of reacting with an isocyanate group in the molecule constituting the urethane dispersant is not particularly limited, but is preferably at least one compound selected from the group consisting of polyols, polythiols, and amines having an N,N-disubstituted amino group or a heterocyclic nitrogen atom. These compounds may be any known or commonly used compounds in the technical field of dispersants. These compounds have a Zerewitinoff active hydrogen atom and at least one nitrogen-containing basic group. Examples of such compounds include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,4-butanediamine, 2-dimethylaminoethanol, 1-(2-aminoethyl)-piperazine, 2-(1-pyrrolidyl)-ethylamine, 4-amino-2-methoxypyrimidine, 4-(2-aminoethyl)-pyridine, 1-(2-hydroxyethyl)-piperazine, 4-(2-hydroxyethyl)-morpholine, 2-mercaptopyrimidine, 2-mercaptobenzimidazole, 2-amino-6-methoxybenzothiazole, N,N-diallyl-melamine, 3-amino-1,2,4-triazole, 1-(2-hydroxyethyl)-imidazole, 3-mercapto-1,2,4-triazole, etc. Among these, amines having a heterocyclic nitrogen atom are preferred.

[0138] The reaction for synthesizing the urethane dispersant is not particularly limited and can be carried out by a conventionally known method. The amine value of the urethane dispersant is also 0 to 55 mgKOH / g, preferably 5 to 40 mgKOH / g.

[0139] Commercially available urethane dispersants include Disperbyk-161 (amine value 11 mgKOH / g, manufactured by BYK), Disperbyk-162 (amine value 13 mgKOH / g, manufactured by BYK), Disperbyk-167 (amine value 13 mgKOH / g, manufactured by BYK), and Disperbyk-182 (amine value 13 mgKOH / g, manufactured by BYK).

[0140] The dispersant is preferably an acrylic dispersant.

[0141] The negative resist composition of the present invention preferably further contains a polymerizable compound (E) and a polymerization initiator (F), which allows the composition to exhibit curability during exposure and other processes.

[0142] <Polymerizable compound (E)> The polymerizable compound (E) is a compound that can be polymerized by an active radical generated from the polymerization initiator (F) described below, an acid, etc., and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and preferably includes (meth)acrylic acid ester compounds.

[0143] Among these, the polymerizable compound (E) is preferably a polymerizable compound having three or more (preferably 4 to 10, more preferably 5 to 8) ethylenically unsaturated bonds, and more preferably an ester of an alcohol having three or more (preferably 4 to 10, more preferably 5 to 8) OH groups (for example, pentaerythritol, its condensate, or a modified product thereof) with (meth)acrylic acid. Examples of such polymerizable compounds include pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanate, and the like. Examples of the acrylate include benzophenone, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate. Among these, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

[0144] The weight average molecular weight of the polymerizable compound (E) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.

[0145] The content of the polymerizable compound (E) is preferably 7 to 65 mass %, more preferably 13 to 60 mass %, and even more preferably 17 to 55 mass %, relative to the solid content of the negative resist composition. When the content of the polymerizable compound (E) is within the above range, sufficient curing occurs, the residual film rate upon development improves, and undercutting is less likely to occur in the colored pattern, resulting in good adhesion.

[0146] <Polymerization initiator (F)> The polymerization initiator (F) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization, and known polymerization initiators can be used.

[0147] The polymerization initiator (F) is preferably a compound that generates active radicals by the action of light, and more preferably an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an oxime compound, or a biimidazole compound.

[0148] The alkylphenone compound is a compound having a partial structure represented by formula (d2) or (d3). In these partial structures, the benzene ring may have a substituent. In the formula, * represents a bond.

[0149] [ka]

[0150] Examples of compounds having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, etc. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (all manufactured by BASF) may also be used. Examples of compounds having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal. In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2), and 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one are more preferred.

[0151] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2- (5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

[0152] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.

[0153] The oxime compound is a compound having a partial structure represented by formula (d1): Hereinafter, * represents a bond.

[0154] [ka]

[0155] Examples of the oxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[ Examples of suitable hydroxybenzoates include 9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure (registered trademark) OXE01 and OXE02 (both manufactured by BASF) and N-1919 (manufactured by ADEKA) may also be used. Among these, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine are preferred. When these oxime compounds are used, and the negative resist composition of the present invention is prepared as a blue negative resist composition, the brightness of the resulting color filter tends to be higher.

[0156] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), and imidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913). Preferred examples include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

[0157] Further examples of the polymerization initiator (F) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator aid (F1) (particularly amines) described below.

[0158] Examples of acid generators that generate acid when exposed to light include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate; nitrobenzyl tosylates; and benzoin tosylates.

[0159] The content of the polymerization initiator (F) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (C) (when the negative resist composition of the present invention contains a resin (C') described below, this also includes the resin (C')) and the polymerizable compound (E). When the content of the photopolymerization initiator is within the above range, sensitivity is increased, exposure time is shortened, and productivity is improved.

[0160] The negative resist composition of the present invention may further contain at least one member selected from the group consisting of a polymerization initiation aid (F1) and a leveling agent (G).

[0161] <Polymerization initiator aid (F1)> The negative resist composition of the present invention may further contain a polymerization initiation aid (F1). The polymerization initiation aid (F1) is a compound used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator, or a sensitizer, and is usually used in combination with the polymerization initiator (F).

[0162] Examples of the polymerization initiation aid (F1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0163] Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, among which 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.

[0164] Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

[0165] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0166] Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0167] When a polymerization initiation aid (F1) is used, the amount used is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of resin (C) (when resin (C') described below is contained, resin (C') is also included) and polymerizable compound (E) in the negative resist composition of the present invention. When the amount of polymerization initiation aid (F1) is within this range, patterns can be formed with even higher sensitivity, and pattern productivity tends to improve.

[0168] <Leveling Agent (G)> Examples of the leveling agent (G) include silicone surfactants, fluorine surfactants, and silicone surfactants containing fluorine atoms, which may have a polymerizable group in the side chain.

[0169] Examples of silicone surfactants include surfactants having a siloxane bond, such as Toray Silicone (trade name) DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and 8400 (manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan, LLC).

[0170] Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain, such as Fluorad (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, and SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Research Institute, Ltd.).

[0171] Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain, such as Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0172] The content of the leveling agent (G) relative to the total amount of the negative resist composition of the present invention is preferably 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, and more preferably 0.005% by mass or more and 0.05% by mass or less. When the content of the leveling agent (G) is within the above range, the flatness of the color filter can be improved.

[0173] <Other ingredients> The negative resist composition of the present invention may, as necessary, contain various additives known in the technical field (hereinafter referred to as "other components"), such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents.

[0174] <Method for producing a negative resist composition> A negative resist composition can be obtained, for example, by dispersing a colorant (A) and a resin (C) in a solvent (B) containing a dispersant (D) to obtain a colorant dispersion, and then mixing, as necessary, a polymerizable compound (E), a polymerization initiator (F), a leveling agent (G), etc.

[0175] Dispersion treatment refers to mixing particles of colorant (A), resin (C), etc. until they are dispersed. This dispersion treatment crushes the particles into small particles. The dispersed state refers to the state in which the particles are suspended in the solvent (B) in the mixed liquid.

[0176] The content of the colorant (A) in the colorant dispersion is preferably 2% by mass or more, more preferably 5% by mass or more, and is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total amount of the colorant dispersion.

[0177] The content of the solvent (B) is preferably 60% by mass or more, more preferably 75% by mass or more, and is preferably 93% by mass or less, more preferably 90% by mass or less, and most preferably 85% by mass or less, based on the total amount of the colorant dispersion.

[0178] When the colorant dispersion contains a resin (C), the content of the resin (C) is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 15% by mass or less, more preferably 7% by mass or less, based on the total amount of the colorant dispersion. When the content of the resin (C) is within the above range, the dispersion state tends to be stable.

[0179] The content of the dispersant (D) in the colorant dispersion is preferably 1% by mass or more, more preferably 2% by mass or less, and more preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total amount of the colorant dispersion. When the content of the dispersant (D) is within the above range, the dispersion state tends to be stable.

[0180] The temperature when dispersing the colorant (A) in the solvent (B) and when dispersing the mixture is preferably 120°C or lower, more preferably 70°C or lower. The lower limit of the temperature when dispersing is not particularly limited, but is usually 20°C. The dispersion time is preferably 0.5 hours or longer, more preferably 2 hours or longer, and is preferably 48 hours or shorter, more preferably 20 hours or shorter. Examples of devices used for dispersion include roll mills, high-speed stirrers, bead mills, ball mills, sand mills, paint conditioners, ultrasonic dispersers, and high-pressure dispersers. The obtained colorant dispersion is preferably filtered through a filter with a pore size of about 1.0 to 5.0 μm.

[0181] When the polymerizable compound (E) and the polymerization initiator (F) are added to the colorant dispersion, it is preferable to further add a resin ("resin (C')"). Examples of the resin (C') include the same as those of the resin (C). The resin (C') may be the same as the resin (C), or may be a different type. As the resin (C'), resin [K1], resin [K2], resin [K5], and resin [K6] are preferred, resin [K5] and resin [K6] are more preferred, and resin [K6] is even more preferred.

[0182] The total content of resin (C) and resin (C') is preferably 7 to 65 mass%, more preferably 10 to 60 mass%, even more preferably 13 to 60 mass%, and particularly preferably 13 to 55 mass%, based on the total amount of solids. When the resin content is within the above range, the resolution of the colored pattern and the residual film rate of the colored pattern tend to be improved.

[0183] When the polymerizable compound (E) and the polymerization initiator (F) are added to the colorant dispersion, it is preferable to further add a solvent (B').

[0184] Examples of the solvent (B') include the same as those for the solvent (B). From the viewpoints of coatability and drying property, it is preferably an organic solvent having a boiling point of 120°C or more and 180°C or less at 1 atm, more preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, etc., and even more preferably propylene glycol monomethyl ether acetate, ethyl lactate, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol ethyl methyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, etc.

[0185] The total content of solvent (B) and solvent (B') in the negative resist composition is preferably 40 to 95 mass%, and more preferably 45 to 92 mass%, relative to the total amount of the negative resist composition. In other words, the solids content of the negative resist composition is preferably 5 to 60 mass%, and more preferably 8 to 55 mass%. When the solvent content is within this range, good flatness is achieved during coating, and when a color filter is formed, the color density is sufficient, which tends to result in good display characteristics.

[0186] Methods for producing a colored pattern of a color filter from the negative resist composition of the present invention include photolithography, inkjet printing, and printing. Among these, photolithography is preferred. The photolithography is a method in which the negative resist composition is applied to a substrate, dried to form a composition layer, and then exposed and developed through a photomask. In the photolithography, a colored coating film, which is a cured product of the composition layer, can be formed by not using a photomask during exposure and / or not developing.

[0187] The film thickness of the color filter (cured film) is preferably 20 μm or less, more preferably 6 μm or less, even more preferably 3 μm or less, still more preferably 1.5 μm or less, particularly preferably 0.5 μm or less, and is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0188] The substrate may be a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or silica-coated soda lime glass; a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate; silicon; or a substrate having a thin film of aluminum, silver, or a silver / copper / palladium alloy formed thereon. A separate color filter layer, a resin layer, a transistor, a circuit, or the like may be formed on these substrates. Alternatively, a silicon substrate treated with HMDS may be used.

[0189] Formation of each color pixel by photolithography can be carried out using known or conventional equipment and conditions. For example, it can be produced as follows. First, a negative resist composition is applied to a substrate, and volatile components such as the solvent are removed by heat drying (pre-baking) and / or vacuum drying to obtain a smooth composition layer. Examples of application methods include spin coating, slit coating, and slit and spin coating. The temperature for heat drying is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When vacuum drying is carried out, it is preferably carried out under a pressure of 50 to 150 Pa at a temperature of 20 to 25°C. The film thickness of the composition layer is not particularly limited and may be appropriately selected depending on the film thickness of the desired color filter.

[0190] Next, the composition layer is exposed through a photomask to form a desired color pattern. The pattern on the photomask is not particularly limited, and a pattern appropriate for the intended application is used. The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light less than 350 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm may be selectively extracted using a bandpass filter that extracts these wavelength ranges. Specific examples include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps. It is preferable to use a reduction projection exposure device or proximity exposure device such as a mask aligner or stepper, as this allows for uniform irradiation of the entire exposure surface with parallel light and allows for accurate alignment of the photomask and substrate.

[0191] A colored pattern is formed on the substrate by bringing the exposed composition layer into contact with a developer and developing it. The unexposed portions of the composition layer are dissolved and removed by development. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. The developer may also contain a surfactant. The development method may be any of a puddle method, a dipping method, a spray method, or the like. Furthermore, the substrate may be tilted at any angle during development. After development, it is preferable to wash with water.

[0192] Furthermore, it is preferable to post-bake the obtained colored pattern. The post-bake temperature is preferably 80 to 250° C., more preferably 100 to 245° C. The post-bake time is preferably 1 to 120 minutes, more preferably 2 to 30 minutes.

[0193] The colored patterns and colored coating films thus obtained are useful as color filters, and the color filters are useful as color filters used in display devices (e.g., liquid crystal display devices, organic EL devices, etc.), electronic paper, solid-state imaging devices, etc. [Example]

[0194] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples, and can be practiced with appropriate modifications within the scope of the above and below-mentioned aims, all of which are within the technical scope of the present invention. In the examples, "%" and "parts" refer to mass % and mass parts unless otherwise specified. The structures of the compounds were identified by mass spectrometry (LC: Agilent 1200 model, MASS: Agilent LC / MSD model).

[0195] <Dye synthesis> [Synthesis Example 1] 50.0 parts of Pink Base (manufactured by Taiyo Fine Chemical Co., Ltd.) represented by formula (1), 300 parts of N-methylpyrrolidone (NMP) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 247.0 parts of methyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 120.3 parts of potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 80°C, and stirred for 4 hours. After cooling the reaction solution to room temperature, the methyl iodide was distilled off under reduced pressure, and 3300 parts of 1N hydrochloric acid was added to the resulting slurry. The resulting precipitate was collected as a residue by suction filtration, washed with 1000 parts of ion-exchanged water, and then dried to obtain 50.6 parts of the compound represented by formula (2). The yield was 97%.

[0196] [ka]

[0197] [ka] Identification of the compound represented by formula (2) (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 603.2 Exact Mass: 602.2

[0198] [Synthesis Example 2] 10.0 parts of the compound represented by formula (3), 20.0 parts of 2,4,6-trimethylaniline (Tokyo Chemical Industry Co., Ltd.), and 60 parts of NMP (Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 160°C, and stirred for 7 hours. After cooling the reaction solution to room temperature, 120 parts of 1N hydrochloric acid was added, and the resulting precipitate was collected as a residue by suction filtration, washed with 100 parts of ion-exchanged water, and then dried to obtain 12.4 parts of the compound represented by formula (4). The yield was 83%.

[0199] [ka]

[0200] Identification of the compound represented by formula (4)

[0201] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 603.8 Exact Mass: 602.2

[0202] [Synthesis Example 3] The compound represented by formula (5) was obtained in a yield of 78% by the same method as in Synthesis Example 2, except that 2,4,6-trimethylaniline was replaced with 5-methoxy-2-methylaniline.

[0203] Identification of the compound represented by formula (5)

[0204] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 607.2 Exact Mass: 606.2

[0205] [Synthesis Example 4] The compound represented by formula (6) was obtained in a yield of 31% by the same method as in Synthesis Example 2, except that 2,4,6-trimethylaniline was replaced with 6-methoxy-2-methylaniline.

[0206] Identification of the compound represented by formula (6)

[0207] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 607.2 Exact Mass: 606.2

[0208] [Synthesis Example 5] 2.0 parts of the compound represented by formula (7), 20.0 parts of N-methylpyrrolidone (NMP) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 16.4 parts of methyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 8.0 parts of potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 80 ° C, and stirred for 16 hours. After cooling the reaction solution to room temperature, the methyl iodide was distilled off under reduced pressure, and 220.0 parts of 1 N hydrochloric acid was added to the resulting slurry. The resulting precipitate was collected as a residue by suction filtration, washed with 40 parts of ion-exchanged water, and then dried to obtain 1.0 part of the compound represented by formula (8). The yield was 49%.

[0209] Identification of the compound represented by formula (7)

[0210] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 519.1 Exact Mass: 518.1

[0211] Identification of the compound represented by formula (8)

[0212] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 547.2 Exact Mass: 546.2

[0213] [Synthesis Example 6] 40.6 parts of the compound represented by formula (3) and 8 parts of diethylamine (Tokyo Chemical Industry Co., Ltd.) were mixed in the presence of 50 parts of 1-methyl-2-pyrrolidone under light-shielded conditions and stirred at 30°C for 3 hours. The resulting reaction solution was cooled to room temperature and then added to a mixture of 400 parts of water and 20 parts of 35% hydrochloric acid. The mixture was stirred at room temperature for 1 hour, resulting in the precipitation of crystals. The precipitated crystals were collected as a residue by suction filtration and then dried to obtain 44 parts of the compound represented by formula (I-1-A).

[0214] [ka]

[0215] Next, 44 parts of the compound represented by formula (I-1-A) and 21.4 parts of trimethoxy[3-(methylamino)propyl]silane (manufactured by Tokyo Chemical Industry Co., Ltd.) were heated at 100°C for 5 hours in the presence of 50 parts of 1-methyl-2-pyrrolidone. The resulting reaction solution was cooled to room temperature, filtered, washed with 100 parts of water, and the resulting crystals were dried to obtain 52 parts of the compound represented by formula (I-1).

[0216] Identification of the compound represented by formula (I-1)

[0217] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 599.2 Exact Mass: 598.2

[0218] [Synthesis Example 7] One part of Pink Base (manufactured by Taiyo Fine Chemical Co., Ltd.) represented by formula (1), 7 parts of N-methylpyrrolidone, 1.0 part of potassium carbonate, and 2.0 parts of ethyl 4-bromobutyrate were added and stirred at 100°C for 7.5 hours. After cooling, 20 parts of 2N hydrochloric acid were added to the resulting reaction solution, which was then extracted twice with 45 parts of chloroform. The combined chloroform layers were washed with saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the mixture was dried under reduced pressure at 60°C to obtain 4.1 parts of a crude compound represented by formula (A-6-IM1).

[0219] Identification of the compound represented by formula (A-6-IM1)

[0220] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 803.5 Exact Mass: 802.3

[0221] A flask equipped with a condenser and a stirrer was charged with 4.1 parts of the compound represented by formula (A-6-IM1), 9.8 parts of methanol, and 3.5 parts of an 8% aqueous sodium hydroxide solution, followed by stirring at room temperature for 6 hours. The resulting reaction solution was added to 30 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes, resulting in the precipitation of crystals. The precipitated crystals were filtered, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 60°C to obtain 1.0 part of compound (A-6-IM2).

[0222] Identification of the compound represented by formula (A-6-IM2)

[0223] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 747.5 Exact Mass: 746.3

[0224] [Synthesis Example 8] A flask equipped with a condenser and a stirrer was charged with 15 parts of the dye represented by formula A0-3 (manufactured by Taiyo Fine Chemical Co., Ltd.), 150 parts of chloroform, and 8.9 parts of N,N-dimethylformamide. While stirring and maintaining the temperature at 20°C or below, 10.9 parts of thionyl chloride was added dropwise. After the dropwise addition, the mixture was heated to 50°C and allowed to react at that temperature for 5 hours, after which it was cooled to 20°C. To the cooled reaction solution, a mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise while stirring and maintaining the temperature at 20°C or below. The mixture was then stirred and allowed to react for 5 hours at the same temperature. The resulting reaction mixture was then distilled off using a rotary evaporator, after which a small amount of methanol was added and the mixture was vigorously stirred. This mixture was added to a mixture of 375 parts of ion-exchanged water with stirring, resulting in the precipitation of crystals. The precipitated crystals were collected by filtration, washed thoroughly with ion-exchanged water, and dried at 60°C under reduced pressure to obtain 11.3 parts of dye A3 (a mixed dye of dyes A3-1 to A3-8).

[0225] [ka] (In formula (A3), R g , R h and R i are each independently a hydrogen atom, -SO3 - , -SO3H or -SO2NHRa. Ra represents 2-ethylhexyl.

[0226] [ka]

[0227] [Synthesis Example 9] The compound represented by formula (9) was obtained in a 90% yield by the same method as in Synthesis Example 2, except that 2,4,6-trimethylaniline was replaced with O-toluidine.

[0228] Identification of the compound represented by formula (9)

[0229] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 575.2 Exact Mass: 574.2

[0230] [Synthesis Example 10] 4.00 parts of the compound represented by formula (3), 10.0 parts of 2-aminobiphenyl (Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 9 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1N hydrochloric acid were added, and the resulting precipitate was collected as a residue by suction filtration and further washed with 96.0 parts of 1N hydrochloric acid. 267 parts of acetone and 267 parts of methanol were added to the resulting residue, heated to 50°C, and stirred for 1 hour. The precipitate was collected as a residue by suction filtration. The resulting residue was dried to obtain 4.67 parts of the compound represented by formula (11). The yield was 71%.

[0231] Identification of the compound represented by formula (11)

[0232] [ka] (Mass spectrometry) Ionization mode = MALDI-TOF + : m / z= [M+H] + 671.1 Exact Mass: 670.2

[0233] [Synthesis Example 11] 4.00 parts of the compound represented by formula (3), 10.0 parts of 3-aminobiphenyl (Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 9 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1N hydrochloric acid were added, and the resulting precipitate was collected as a residue by suction filtration and further washed with 96.0 parts of 1N hydrochloric acid. 300 parts of acetone and 300 parts of methanol were added to the resulting residue, heated to 50°C, and stirred for 1 hour. The precipitate was collected as a residue by suction filtration. The resulting residue was dried to obtain 5.13 parts of the compound represented by formula (12). The yield was 78%.

[0234] Identification of the compound represented by formula (12)

[0235] [ka] (Mass spectrometry) Ionization mode = MALDI-TOF + : m / z= [M+H] + 671.1 Exact Mass: 670.2

[0236] [Synthesis Example 12] 4.00 parts of the compound represented by formula (3), 8.84 parts of 4-tert-butylaniline (Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 170 ° C, and stirred for 9 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 N hydrochloric acid were added, and the resulting precipitate was collected as a residue by suction filtration and further washed with 96.0 parts of 1 N hydrochloric acid. To the resulting residue, 357 parts of acetone and 357 parts of methanol were added, heated to 50 ° C, and stirred for 1 hour. The precipitate was collected as a residue by suction filtration. The resulting residue was dried to obtain 5.59 parts of the compound represented by formula (13). The yield was 90%.

[0237] Identification of the compound represented by formula (13)

[0238] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 631.2 Exact Mass: 630.3

[0239] [Synthesis Example 13] 4.00 parts of the compound represented by formula (3), 10.0 parts of 3,5-di-tert-butylaniline (Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 170 ° C, and stirred for 9 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 N hydrochloric acid were added, and the resulting precipitate was collected as a residue by suction filtration and further washed with 96.0 parts of 1 N hydrochloric acid. 264 parts of acetone and 264 parts of methanol were added to the resulting residue, heated to 50 ° C, and stirred for 1 hour. The precipitate was collected as a residue by suction filtration. The resulting residue was dried to obtain 4.70 parts of the compound represented by formula (14). The yield was 64%.

[0240] Identification of the compound represented by formula (14)

[0241] [ka] (Mass spectrometry) Ionization mode = MALDI-TOF + : m / z=[M+H] + 743.5 Exact Mass: 742.4

[0242] [Synthesis Example 14] 2,6-Diphenylaniline was synthesized with reference to the literature (Chun Liu, Xiaoxiao Song, Qijian Ni, and Jieshan Qiu; ARKIVOC, 2012, 9, 62-75). Next, 4.00 parts of the compound represented by formula (3), 9.69 parts of 2,6-diphenylaniline, 2.69 parts of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.), and 24.0 parts of sulfolane (Tokyo Chemical Industry Co., Ltd.) were mixed at room temperature, heated to 250 °C, and stirred for 4 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 N hydrochloric acid was added. The resulting precipitate was collected as a residue by suction filtration and further washed sequentially with 24.0 parts of toluene, 18.0 parts of N,N-dimethylformamide, and 20.0 parts of N,N-dimethylformamide. The resulting residue was dried to obtain 5.18 parts of the compound represented by formula (15). The yield was 64%.

[0243] Identification of the compound represented by formula (15)

[0244] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 823.3 Exact Mass: 822.3

[0245] [Synthesis Example 15] 10.0 parts of the compound represented by formula (3), 16.5 parts of 2,6-dimethylaniline (Tokyo Chemical Industry Co., Ltd.), and 70.0 parts of N-methylpyrrolidone (Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 80°C, and stirred for 2 hours. After the reaction solution was cooled to room temperature, 140 parts of 1N hydrochloric acid was added, and the resulting precipitate was collected as a residue by suction filtration and further washed with 280 parts of 1N hydrochloric acid. The resulting residue was dried to obtain 9.06 parts of the compound represented by formula (16). The yield was 75%.

[0246] Identification of the compound represented by formula (16)

[0247] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 490.2 Exact Mass: 489.1

[0248] 4.00 parts of the compound represented by formula (16), 3.80 parts of aniline (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 24.0 parts of N-methylpyrrolidone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 3 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1N hydrochloric acid were added, and the resulting precipitate was collected as a residue by suction filtration and further washed with 96.0 parts of 1N hydrochloric acid and 36.8 parts of N,N-dimethylformamide. The resulting residue was dried to obtain 3.28 parts of the compound represented by formula (17). The yield was 74%.

[0249] Identification of the compound represented by formula (17)

[0250] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 547.2 Exact Mass: 546.2

[0251] [Synthesis Example 16] 4.00 parts of the compound represented by formula (16), 6.25 parts of 2,4-dimethoxyaniline (Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 3 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1N hydrochloric acid were added, and the resulting precipitate was collected as a residue by suction filtration and washed with 96.0 parts of 1N hydrochloric acid and 42.4 parts of N,N-dimethylformamide. The resulting residue was dried to obtain 2.88 parts of the compound represented by formula (18). The yield was 58%.

[0252] Identification of the compound represented by formula (18)

[0253] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 607.2 Exact Mass: 606.2

[0254] [Synthesis Example 17] 4.00 parts of the compound represented by formula (16), 5.03 parts of 4-methoxyaniline (Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 3 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1N hydrochloric acid were added, and the resulting precipitate was collected as a residue by suction filtration and washed with 96.0 parts of 1N hydrochloric acid and 41.9 parts of N,N-dimethylformamide. The resulting residue was dried to obtain 5.00 parts of the compound represented by formula (19). The yield was 69%.

[0255] Identification of the compound represented by formula (19)

[0256] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 577.3 Exact Mass: 576.2

[0257] [Synthesis Example 18] 4.00 parts of the compound represented by formula (16), 6.91 parts of 3-aminobiphenyl (Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 5 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1N hydrochloric acid were added, and the resulting precipitate was collected as a residue by suction filtration and further washed with 96.0 parts of 1N hydrochloric acid and 75.2 parts of N,N-dimethylformamide. The resulting residue was dried to obtain 3.79 parts of the compound represented by formula (20). The yield was 75%.

[0258] Identification of the compound represented by formula (20)

[0259] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 623.2 Exact Mass: 622.2

[0260] [Synthesis Example 19] 4.00 parts of the compound represented by formula (16), 6.91 parts of 2-aminobiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 3 hours. After the reaction solution was cooled to room temperature, 48.0 parts of 1N hydrochloric acid was added, and the resulting precipitate was collected as a residue by suction filtration and further washed with 96.0 parts of 1N hydrochloric acid and 44.8 parts of N,N-dimethylformamide. The resulting residue was dried to obtain 3.55 parts of the compound represented by formula (21). The yield was 70%.

[0261] Identification of the compound represented by formula (21)

[0262] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] +623.2 Exact Mass: 622.2

[0263] [Synthesis Example 20] 13.0 parts of the compound represented by formula (3), 39.3 parts of 2,6-diphenylaniline, and 78.0 parts of N-methylpyrrolidone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 85°C, and stirred for 5 hours. After the reaction solution was cooled to room temperature, 156 parts of 1N hydrochloric acid was added, and the resulting precipitate was collected as a residue by suction filtration and further washed with 312 parts of 1N hydrochloric acid. The resulting residue was dried to obtain 16.2 parts of the compound represented by formula (22). The yield was 82%.

[0264] Identification of the compound represented by formula (22)

[0265] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 614.5 Exact Mass: 613.1

[0266] 4.00 parts of the compound represented by formula (22), 3.95 parts of 2,6-xylidine (Fujifilm Wako Pure Chemical Industries, Ltd.), 1.78 parts of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.), and 24.0 parts of sulfolane (Tokyo Chemical Industry Co., Ltd.) were mixed at room temperature, heated to 250 °C, and stirred for 3 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 N hydrochloric acid were added, and the resulting precipitate was collected as a residue by suction filtration and further washed with 96.0 parts of 1 N hydrochloric acid and 69.5 parts of N,N-dimethylformamide. The resulting residue was dried to obtain 3.05 parts of the compound represented by formula (23). The yield was 67%.

[0267] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] +699.2 Exact Mass: 698.2

[0268] [Synthesis Example 21] 4.00 parts of the compound represented by formula (22), 5.51 parts of 3-aminobiphenyl (Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 6 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1N hydrochloric acid were added, and the resulting precipitate was collected as a residue by suction filtration and further washed with 96.0 parts of 1N hydrochloric acid and 28.5 parts of N,N-dimethylformamide. The resulting residue was dried to obtain 2.85 parts of the compound represented by formula (24). The yield was 59%.

[0269] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 747.2 Exact Mass: 746.2

[0270] [Synthesis Example 22] 4.00 parts of the compound represented by formula (22), 5.51 parts of 2-aminobiphenyl (Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 6 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1N hydrochloric acid were added, and the resulting precipitate was collected as a residue by suction filtration and further washed with 96.0 parts of 1N hydrochloric acid and 49.2 parts of N,N-dimethylformamide. The resulting residue was dried to obtain 2.88 parts of the compound represented by formula (25). The yield was 59%.

[0271] [ka] (Mass spectrometry) Ionization mode = ESI + : m / z= [M+H] + 747.2 Exact Mass: 746.2

[0272] <Resin synthesis> [Synthesis Example 23 Resin C-1] 276.8 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred and heated to 120°C while purging with nitrogen. Next, a monomer mixture consisting of 92.4 g of 2-ethylhexyl acrylate, 184.9 g of glycidyl methacrylate, and 12.3 g of dicyclopentanyl methacrylate, plus 35.3 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator), was added dropwise from the dropping funnel to the flask over 2 hours. After the dropwise addition was completed, the mixture was stirred for an additional 30 minutes at 120°C to carry out the copolymerization reaction, producing an addition copolymer. The flask was then purged with air, and 93.7 g of acrylic acid, 1.5 g of triphenylphosphine (catalyst), and 0.8 g of methoquinone (polymerization inhibitor) were added to the addition copolymer solution. The reaction was continued at 110°C for 10 hours. The epoxy groups derived from glycidyl methacrylate reacted with the acrylic acid, cleaving the epoxy groups and simultaneously introducing polymerizable unsaturated bonds into the polymer side chains. Next, 24.2 g of succinic anhydride was added to the reaction system, and the reaction was continued at 110°C for 1 hour. The hydroxyl groups generated by the cleavage of the epoxy groups reacted with the succinic anhydride, introducing carboxyl groups into the side chains, yielding a polymer. Finally, 383.3 g of propylene glycol monomethyl ether acetate was added to the reaction solution, yielding a polymer (Resin (C-1)) solution with a polymer solids content of 40%. The weight-average molecular weight Mw of the resulting copolymer (polymer; Resin (C-1)) was 6.3 x 10 3 The acid value calculated as solid content was 34 mg-KOH / g.

[0273] [Synthesis Example 24 Resin C-2] A flask equipped with a reflux condenser, a dropping funnel, and a stirrer was filled with an appropriate amount of nitrogen to create a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was added, followed by heating to 80°C with stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0] 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 A solution of 289 parts of a mixture of decan-9-yl acrylate (1:1 content) dissolved in 125 parts of propylene glycol monomethyl ether acetate was added dropwise using a dropping pump over approximately 5 hours. Meanwhile, a solution of 33 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over approximately 6 hours using another dropping pump. After the addition was completed, the mixture was maintained at the same temperature for 4 hours and then cooled to room temperature to obtain a polymer (resin (C-2)) solution with a polymer solids content of 35.1%. The weight-average molecular weight Mw of the resulting copolymer (polymer; resin (C-2)) was 9200, the polydispersity was 2.08, and the acid value calculated as solids was 77 mg-KOH / g. The resulting copolymer had the following structural units:

[0274] [ka]

[0275] (Preparation of Dispersion 1) 8 parts of CI Pigment Red 122, 3.0 parts of a dispersant (BYKLPN-6919 manufactured by BYK), 3.0 parts of the above resin (C-2) (solid content equivalent), 81 parts of propylene glycol monomethyl ether acetate, and 5 parts of diacetone alcohol were mixed, to which 300 parts of 0.4 mm zirconia beads were added, followed by shaking for 1 hour using a paint conditioner (LAU). The zirconia beads were then removed by filtration, yielding dispersion 1.

[0276] (Preparation of Dispersion 2) Dispersion 2 was obtained in the same manner as Dispersion 1, except that CI Pigment Violet 19 was used instead of CI Pigment Red 122.

[0277] (Preparation of Dispersion 3) Dispersion 3 was obtained in the same manner as Dispersion 1, except that Pink Base manufactured by Taiyo Fine Chemical Co., Ltd. was used instead of CI Pigment Red 122.

[0278] (Preparation of Dispersion 4) Dispersion 4 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 1 was used instead of CI Pigment Red 122.

[0279] (Preparation of Dispersion 5) Dispersion 5 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 2 was used instead of CI Pigment Red 122.

[0280] (Preparation of Dispersion 6) Dispersion 6 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 3 was used instead of CI Pigment Red 122.

[0281] (Preparation of Dispersion 7) Dispersion 7 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 4 was used instead of CI Pigment Red 122.

[0282] (Preparation of Dispersion 8) Dispersion 8 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 5 was used instead of CI Pigment Red 122.

[0283] (Preparation of Dispersion 9) Dispersion 9 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 9 was used instead of CI Pigment Red 122.

[0284] (Preparation of Dispersion 10) Dispersion 10 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 10 was used instead of CI Pigment Red 122.

[0285] (Preparation of Dispersion 11) Dispersion 11 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 11 was used instead of CI Pigment Red 122.

[0286] (Preparation of Dispersion 12) Dispersion 12 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 12 was used instead of CI Pigment Red 122.

[0287] (Preparation of Dispersion 13) Dispersion 13 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 13 was used instead of CI Pigment Red 122.

[0288] (Preparation of Dispersion 14) Dispersion 14 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 14 was used instead of CI Pigment Red 122.

[0289] (Preparation of Dispersion 15) Dispersion 15 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 15 was used instead of CI Pigment Red 122.

[0290] (Preparation of Dispersion 16) Dispersion 16 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 16 was used instead of CI Pigment Red 122.

[0291] (Preparation of Dispersion 17) Dispersion 17 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 17 was used instead of CI Pigment Red 122.

[0292] (Preparation of Dispersion 18) Dispersion 18 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 18 was used instead of CI Pigment Red 122.

[0293] (Preparation of Dispersion 19) Dispersion 19 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 19 was used instead of CI Pigment Red 122.

[0294] (Preparation of Dispersion 20) Dispersion 20 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 20 was used instead of CI Pigment Red 122.

[0295] (Preparation of Dispersion 21) Dispersion 21 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 21 was used instead of CI Pigment Red 122.

[0296] (Preparation of Dispersion 22) Dispersion 22 was obtained in the same manner as Dispersion 1, except that the compound obtained in Synthesis Example 22 was used instead of CI Pigment Red 122.

[0297] [Examples 1 to 27, Comparative Examples 1 and 2] Dispersions 1 to 22, compounds (A-9) to (A-11) of Synthesis Examples 6 to 8, resins, polymerizable compounds, polymerization initiators, leveling agents, and solvents were mixed so as to obtain the final compositions shown in Tables 3 and 4 below, thereby obtaining negative resist compositions of Examples 1 to 27 and Comparative Examples 1 and 2.

[0298] [Table 3]

[0299] [Table 4]

[0300] In Tables 3 and 4, each component represents the following compound. Compound (A-9): Compound of Synthesis Example 6 Compound (A-10): Compound of Synthesis Example 7 Compound (A-11): Compound of Synthesis Example 8 Resin (C-1): Resin (C-1) (solid content) Polymerizable compound (E-1): Dipentaerythritol polyacrylate ("A9550" manufactured by Shin-Nakamura Chemical Co., Ltd.) Polymerization initiator (F-1): N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine (PBG-327; O-acyloxime compound; Changzhou Powerful New Electronic Materials Co., Ltd.) Leveling agent (G-1): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) Solvent (B-1): Diacetone alcohol (DAA) Solvent (B-2): Ethyl lactate (EL) Solvent (B-3): Propylene glycol monomethyl ether acetate (PGMA)

[0301] <Preparation of cured film> A negative resist composition was applied by spin coating onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated), and then prebaked at 100°C for 3 minutes to form a colored composition layer. After cooling, the resist was exposed to light at 60 mJ / cm2 in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). 2 The colored composition layer was irradiated with light at an exposure dose of 1000 nm (based on 365 nm). Thereafter, post-baking was performed in an oven at 230°C for 20 minutes to obtain a cured film. In preparing the cured film, the film thickness was adjusted so that the transmittance at the maximum absorption wavelength described below was 5%.

[0302] <Film thickness measurement> The thickness of the cured film obtained on the glass substrate was measured using a film thickness measuring device (DEKTAK3, manufactured by Nippon Shinku Gijutsu Co., Ltd.). The results are shown in Tables 5 and 6.

[0303] <Measurement of maximum absorption wavelength and transmittance> The resulting cured film on the glass substrate was subjected to spectral analysis using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). Specifically, the transmittance and maximum absorption wavelength at wavelengths of 400 to 700 nm were measured. The maximum absorption wavelength, the transmittance at the maximum absorption wavelength (T(λmax)), the transmittance at a wavelength of 440 nm (T(440nm)), and the transmittance at a wavelength of 620 nm (T(620nm)) are shown in Tables 5 and 6. Furthermore, the ratio (parts by mass) of each colorant contained in the cured film and the concentration (% by mass) of the colorant contained in the cured film are shown in Tables 5 and 6.

[0304] [Table 5]

[0305] [Table 6]

[0306] As shown in Tables 5 and 6, the negative resist compositions of Examples 1 to 27 contained the compound represented by formula (I) above, and the cured films obtained therefrom had a maximum absorption wavelength in the wavelength range of 500 nm to 580 nm, and when the transmittance at these wavelengths was taken as 5%, the transmittance at a wavelength of 440 nm was 80% or more, and the transmittance at a wavelength of 620 nm was 80% or more. On the other hand, the negative resist compositions of Comparative Examples 1 and 2 did not contain the compound represented by formula (I) above, and the cured films obtained therefrom had a transmittance at a wavelength of 440 nm of less than 80%. [Industrial Applicability]

[0307] The negative resist composition of the present invention can produce a color filter having high transmittance for light with a wavelength of 440 nm.

Claims

1. A negative resist composition comprising a colorant and a resin, the colorant comprises a xanthene dye; the xanthene dye is represented by formula (Ia) and / or formula (Ib1), 【Chemistry 1】 [In formula (Ia), R a1 and R a4 each independently represent a monovalent aromatic hydrocarbon group which may have two or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms. R a2 and R a3 are the same and each represent a hydrogen atom, a methyl group, or an ethyl group. R 5 represents —OH, —SO 3 − , —SO 3 H, —SO 3 − Z + , —CO 2 H, —CO 2 − Z + , —CO 2 R 8 , —SO 3 R 8 or —SO 2 NR 9 R 10 . R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m represents an integer of 0 to 5. When m is 2 or more, the multiple R 5 s may be the same or different. a represents an integer of 0 or 1; X represents a halogen atom. Z + represents + N(R 11 ) 4 , Na + or K + , and the four R 11 s may be the same or different. R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. R 9 and R 10 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the —CH 2 — contained in the saturated hydrocarbon group may be replaced by —O—, —CO—, —NH—, or —NR 8 —, and R 9 and R 10 may be bonded to form a 3- to 10-membered heterocycle together with the adjacent nitrogen atom. R 11 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.] 【Chemistry 2】 [In formula (Ib1), R b1 to R b4 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent; At least one saturated hydrocarbon group contained in R b1 to R b4 has a halogen atom, —OR 8 , —CO 2 R 8 , —SO 3 − , —SO 3 H, —SO 3 − Z + , —SR 8 , —SO 2 R 8 , —SO 3 R 8 , —SO 2 NR 9 R 10 , or —Si(OR 12 )(OR 13 )(OR 14 ) as a substituent, or at least one aromatic hydrocarbon group contained in R b1 to R b4 has a halogen atom, —OH, —OR 8 , —CO 2 H, —CO 2 R 8 , —SO 3 − , —SO 3 H, —SO 3 − Z + , —SR 8 , —SO 2 R 8 , —SO 3 R 8 , —SO 2 NR 9 R 10 , or —Si(OR 12 )(OR 13 )(OR 14 ) as a substituent. R 10 or —Si(OR 12 )(OR 13 )(OR 14 ) as a substituent, or at least one aromatic hydrocarbon group included in R b1 to R b4 has a monovalent saturated aliphatic hydrocarbon group having 3 or more carbon atoms and 1 to 4 as a substituent, R 12 , R 13 , and R 14 each independently represent a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. R 5 represents —OH, —SO 3 − , —SO 3 H, —SO 3 − Z + , —CO 2 H, —CO 2 − Z + , —CO 2 R 8 , —SO 3 R 8 or —SO 2 NR 9 R 10 . R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m represents an integer of 0 to 5. When m is 2 or more, the multiple R 5 s may be the same or different. a represents an integer of 0 or 1; X represents a halogen atom. Z + represents + N(R 11 ) 4 , Na + or K + , and the four R 11 s may be the same or different. R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. R 9 and R 10 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the —CH 2 — contained in the saturated hydrocarbon group may be replaced by —O—, —CO—, —NH—, or —NR 8 —, and R 9 and R 10 may be bonded to form a 3- to 10-membered heterocycle together with the adjacent nitrogen atom. R 11 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.] A negative resist composition, characterized in that the spectral spectrum of a cured film formed from the negative resist composition according to the following method for producing a cured film satisfies the following condition 1. [Condition 1] It has a maximum absorption wavelength in the wavelength range of 500 nm to 580 nm, and when the transmittance at this wavelength is taken as 5%, the transmittance at a wavelength of 440 nm is 80% or more, and the transmittance at a wavelength of 620 nm is 80% or more. [Method for producing cured film] A negative resist composition is applied to a 5 cm square glass substrate by spin coating, and then pre-baked at 100°C for 3 minutes to form a colored composition layer. After cooling, the resist is exposed to 60 mJ / cm2 in an air atmosphere using an exposure machine. 2 The colored composition layer is irradiated with light at an exposure amount (based on 365 nm) of 1000 kJ / cm 2. Thereafter, post-baking is performed at 230° C. for 20 minutes.

2. 2. The negative resist composition according to claim 1, wherein the transmittance at a wavelength of 620 nm is 90% or more.

3. 2. The negative resist composition according to claim 1, wherein the xanthene dye is a combination of two or more kinds selected from those represented by formula (Ib1), or a combination of one represented by formula (Ib1) and one represented by formula (Ia).

4. 4. The negative resist composition according to claim 1, wherein the colorant is a dye alone or a combination of a dye and a red or purple pigment.

5. 5. The negative resist composition according to claim 1, further comprising a polymerizable compound and a polymerization initiator.

6. 6. The negative resist composition according to claim 1, which is capable of forming a cured film having a thickness of 1.5 μm or less.

7. A color filter formed from the negative resist composition according to any one of claims 1 to 6.

8. A display device comprising the color filter according to claim 7.

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