Negative resist composition

Abstract

The present invention provides a negative resist composition for manufacturing a color filter having high transmittance of light having a wavelength of 440 nm. The negative resist composition of the present invention comprises a colorant containing a xanthene dye and a resin. The cured film formed from the negative resist composition satisfies the following condition 1. [Condition 1] The cured film has an absorption maximum in the wavelength range of 500 nm to 580 nm, and when the transmittance at the wavelength is set to 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.

Description

TECHNICAL FIELD

[0001] The present application relates to a negative resist composition. BACKGROUND

[0002] In order to manufacture a color filter used in a liquid crystal display device or the like, a coloring composition is used. As such a coloring composition, a coloring composition containing a quinacridone-based pigment is known (Patent Document 1).

[0003] PRIOR ART DOCUMENTS

[0004] PATENT DOCUMENTS

[0005] Patent Document 1: Japanese Patent Application Publication No. 2019-109487 SUMMARY

[0006] Hitherto, it has been known that magenta is obtained by mixing blue and red. However, in the conventional color filter of magenta, the transmittance of light having a wavelength of 440 nm is not sufficient. An object of the present application is to provide a negative resist composition for manufacturing a color filter having a high transmittance of light having a wavelength of 440 nm.

[0007] The present application comprises the following inventions.

[0008] [1] A negative resist composition characterized by containing a colorant and a resin,

[0009] The above colorant contains a xanthene dye,

[0010] The spectrophotometric spectrum of a cured film formed from the above negative resist composition satisfies the following condition 1.

[0011] [Condition 1]

[0012] In a wavelength range of 500 nm to 580 nm, there is an absorption maximum wavelength, and when the transmittance at this wavelength is set to 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.

[0013] [2] The negative resist composition according to [1], wherein the transmittance at a wavelength of 620 nm is 90% or more.

[0014] [3] The negative resist composition according to [1] or [2], wherein the xanthene dye is a compound represented by formula (I).

[0015]

[0016] [In formula (I), R 1 ~R 4each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which can have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which can have a substituent, -CH2- included in the saturated hydrocarbon group can be replaced with -O-, -CO-, or -NR 11 - substituted.

[0017] R 5 represents -OH, -SO3 - , -SO3H, -SO3 - Z + , -CO2H, -CO2 - Z + , -CO2R 8 , -SO3R 8 , or -SO2NR 9 R 10 .

[0018] R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0019] 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.

[0020] a represents an integer of 0 or 1.

[0021] X represents a halogen atom.

[0022] Z + represents + N(R 11 )4, Na + , or K + , 4 R 11 may be the same or different.

[0023] R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom included in the saturated hydrocarbon group can be replaced with a halogen atom.

[0024] R 9 and R 10 each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which can have a substituent, -CH2- included in the saturated hydrocarbon group can be replaced with -O-, -CO-, -NH-, or -NR 8 -substituted, R 9 and R 10 may be bonded and form a three- to ten-membered ring heterocycle together with the adjacent nitrogen atom.

[0025] R 11This refers to a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, or an aralkyl group with 7 to 10 carbon atoms.

[0026] [4] According to the negative resist composition of [3], wherein the zeolite dye is a compound represented by formula (Ia) and / or formula (Ib1).

[0027]

[0028] In formula (Ia),

[0029] R a1 and R a4 Each can be an independent monovalent aromatic hydrocarbon group having 1 to 4 monovalent saturated aliphatic hydrocarbon groups with no more than 2 carbon atoms.

[0030] R a2 and R a3 Each can be independently a hydrogen atom, a methyl group, or an ethyl group.

[0031] R 5 ~R 7 , m, a, and X represent the same meaning as above.

[0032]

[0033] In formula (Ib1), R b1 ~R b4 Each can independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents, or a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms that may have substituents.

[0034] R b1 ~R b4 The at least one saturated hydrocarbon group or aromatic hydrocarbon group contained herein has 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 ) as a substituent, or R b1 ~R b4 It contains at least one aromatic hydrocarbon group having three or more monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms as substituents.

[0035] R 12 , R 13 , and R 14 each independently represents a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group can be substituted with a halogen atom,

[0036] R 5 to R 10 , m, a, and X represent the same meanings as described above.

[0037] [5] The negative resist composition according to [4], wherein the xanthene dye is a combination of two or more selected from the compounds represented by the above formula (Ib1), or a combination of the compound represented by the above formula (Ib1) and the compound represented by the above formula (Ia).

[0038] [6] The negative resist composition according to any one of [1] to [5], wherein the colorant is only a dye, or is a combination of a dye and a red or purple pigment.

[0039] [7] The negative resist composition according to any one of [1] to [6], further comprising a polymerizable compound and a polymerization initiator.

[0040] [8] The negative resist composition according to any one of [1] to [7], capable of forming a cured film having a film thickness of 1.5 μm or less.

[0041] [9] A color filter formed from the negative resist composition according to any one of [1] to [8].

[0042]

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

[0043] A color filter having high transmittance of light having a wavelength of 440 nm is obtained from the negative resist composition of the present application. DETAILED DESCRIPTION

[0044] <NEGATIVE RESIST COMPOSITION>

[0045] The negative resist composition of the present application is a negative resist composition comprising a colorant (A) and a resin (C), the colorant (A) containing a xanthene dye, and the spectrophotometric spectrum of a cured film formed from the negative resist composition satisfies the following Condition 1.

[0046] [Condition 1]

[0047] The filter has a maximum absorption wavelength in the wavelength range of 500 nm to 580 nm, a transmittance of 5% at the maximum absorption wavelength, a transmittance of 80% or more at a wavelength of 440 nm, and a transmittance of 80% or more at a wavelength of 620 nm.

[0048] The filter has a high transmittance of light having a wavelength of 440 nm and a magenta color. The negative resist composition is a resist having a property that an exposed portion is left after development because of a decrease in solubility in a developer. The negative resist composition has a tendency that a range of process conditions from exposure to development for modifying a pattern to a desired size range is wider than that of a positive resist composition having a high solubility of an exposed portion in a developer, and thus is preferred.

[0049] The above-described spectral transmittance of the cured film can be obtained by producing a cured film on a glass substrate under the following conditions and measuring it with a colorimeter. As the colorimeter, OSP-SP-200 (manufactured by Olympus Corporation) can be given.

[0050] [Method for producing a cured film]

[0051] A negative resist composition was applied to a 5 cm square glass substrate by a spin coating method, and a colored composition layer was formed by pre-baking at 100°C for 3 minutes. After cooling, the colored composition layer was subjected to light irradiation at an exposure amount of 60 mJ / cm2 (365 nm reference) in an air atmosphere using an exposure machine. Thereafter, post-baking was performed at 230°C for 20 minutes. 2 The transmittance of the cured film was measured at a wavelength of 440 nm and at a wavelength of 620 nm after adjusting the film thickness of the cured film so that the transmittance at the maximum absorption wavelength was 5%.

[0052] In measuring the transmittance of the cured film, the transmittance at a wavelength of 440 nm and the transmittance at a wavelength of 620 nm can be measured after adjusting the film thickness of the cured film so that the transmittance at the maximum absorption wavelength is 5%. Alternatively, the transmittance at a wavelength of 440 nm and the transmittance at a wavelength of 620 nm can be calculated from the transmittance at the maximum absorption wavelength after measuring the transmittance at the maximum absorption wavelength, the transmittance at a wavelength of 440 nm, and the transmittance at a wavelength of 620 nm without adjusting the film thickness of the cured film as described above.

[0053] The transmittance at a wavelength of 440 nm is preferably 85% or more, more preferably 90% or more, and further preferably 92% or more. On the other hand, the upper limit is not particularly limited, and can be 100% or less, or 99% or less.

[0054] The transmittance at a wavelength of 620 nm is preferably 80% or greater, more preferably 90% or greater, further preferably 93% or greater, particularly preferably 95% or greater, and even more preferably 97% or greater. On the other hand, the upper limit is not particularly limited and can be 100% or less.

[0055] Hereinafter, each component will be described in detail. Note that the compounds exemplified as each component in the present specification can be used alone or in combination with a plurality of kinds thereof, unless otherwise specified.

[0056] <Coloring agent (A)>

[0057] The coloring agent (A) contains a xanthene dye (Al). The content of the coloring agent (A) with respect to the solid components of the negative resist composition is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and further preferably 10 to 50% by mass. If the content of the coloring agent is within the above range, the color density when a color filter is produced can be improved, and the composition can contain a resin or the like in a desired amount. Here, the solid components of the negative resist composition refer to the total amount of components obtained by removing the solvent from the negative resist composition of the present application. The content of the solid components and each component with respect to the solid components can be measured, for example, using a known analysis means such as liquid chromatography or gas chromatography.

[0058] < Xanthene dye (Al) >

[0059] The xanthene dye (Al) is a dye containing a compound having a xanthene skeleton in the molecule. As the xanthene dye (Al), a dye containing a compound represented by formula (I) (hereinafter, sometimes referred to as "compound (I)") is preferable.

[0060]

[0061] [In formula (I), R 1 ~R 4 each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which can have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which can have a substituent, and -CH2- included in the saturated hydrocarbon group can be replaced with -O-, -CO-, or -NR 11 -substituted.

[0062] R 5 represents -OH, -SO3 - , -SO3H, -SO3 - Z + , -CO2H, -CO2 - Z + , -CO2R 8 , -SO3R 8 , or -SO2NR 9 R10 .

[0063] R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0064] 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.

[0065] a represents an integer of 0 or 1.

[0066] X represents a halogen atom.

[0067] Z + represents + N(R 11 )4, Na + , or K + , 4 R 11 may be the same or different.

[0068] R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group can be substituted with a halogen atom.

[0069] R 9 and R 10 each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which can have a substituent, and -CH2- contained in the saturated hydrocarbon group can be substituted with -O-, -CO-, -NH-, or -NR 8 R 9 and R 10 may be bonded and form a three- to ten-membered ring heterocycle together with the adjacent nitrogen atom.

[0070] 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.

[0071] The compound (I) can also be a tautomer thereof. When the compound (I) is used, the content of the compound (I) in the xanthene dye (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and most preferably 100% by mass.

[0072] R 1 to R 4straight-chain alkyl groups; isopropyl, isobutyl, isopentyl, neopentyl, 2- ethylhexyl and the like branched-chain alkyl groups; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and the like alicyclic saturated hydrocarbon groups having 2 to 20 carbon atoms. The number of carbon atoms of the saturated hydrocarbon group in the case where it has a substituent is the number including the carbon of the substituent. As the substituent which the saturated hydrocarbon group can have, there can be mentioned a halogen atom, -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 ). R 12 , R 13 and R 14 each independently represent a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group can be substituted with a halogen atom.

[0073] As the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms in R 1 to R 4 , there can be mentioned a monocyclic aromatic hydrocarbon group such as phenyl, and a polycyclic aromatic hydrocarbon group such as naphthyl, anthryl, phenanthryl, biphenyl, terphenyl and the like. As the polycyclic aromatic hydrocarbon group, a non-fused polycyclic aromatic hydrocarbon group such as biphenyl, terphenyl and the like is preferred. Further, the polycyclic aromatic hydrocarbon group preferably has no substituent. As the monovalent aromatic hydrocarbon group having a substituent, there can be mentioned tolyl, xylyl, mesityl, propylphenyl, butylphenyl and the like. The number of carbon atoms of the aromatic hydrocarbon group in the case where it has a substituent is the number including the carbon of the substituent. As the substituent which the aromatic hydrocarbon group can have, there can be mentioned a halogen atom, -R 8 , -OH, -OR 8 , -SO3 - , -SO3H, -SO3 - Z + , -CO2H, -CO2R 8 , -SR 8 , -SO2R 8 , -SO3R 8 , -SO2NR 9 R10 、or -Si(OR) 12 (OR) 13 (OR) 14 ).

[0074] As R 8 ~R 11 Monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms include, for example, straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and eicosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; and alicyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl.

[0075] R 9 and R 10 The monovalent saturated hydrocarbon group with 1 to 20 carbon atoms can have substituents. Examples of such substituents include hydroxyl groups and halogen atoms.

[0076] As R 12 ~R 14 The monovalent saturated hydrocarbon group with 1 to 4 carbon atoms in it includes, for example, straight-chain alkyl groups such as methyl, ethyl, propyl, and butyl; and alicyclic saturated hydrocarbon groups with 1 to 4 carbon atoms such as branched alkyl groups such as isopropyl and isobutyl.

[0077] Z + for + N(R 11 4. Na + or K + Preferred + N(R 11 4. + N(R 11 The four R's in )4 11 At least two of them are preferably monovalent saturated hydrocarbon groups with 5 to 20 carbon atoms. Additionally, the four R groups... 11 The total number of carbon atoms is preferably 20 to 80, more preferably 20 to 60. Compound (I) contains... + N(R 11 In case 4, if R 11 These groups enable the formation of a color filter with fewer foreign matter from the negative resist composition of the present invention containing compound (I).

[0078] As -OR 8 Examples include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, 2-ethylhexoxy, and eicosyloxy.

[0079] As a CO2R 8For example, methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, t- butyloxycarbonyl, hexyloxycarbonyl, eicosyloxycarbonyl, and the like can be mentioned.

[0080] as -SR 8 For example, methylthio, ethylthio, butylthio, hexylthio, decylthio, eicosylthio, and the like can be mentioned.

[0081] as -SO2R 8 For example, methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, eicosylsulfonyl, and the like can be mentioned.

[0082] as -SO3R 8 For example, methoxysulfonyl, ethoxysulfonyl, propyloxysulfonyl, t- butyloxysulfonyl, hexyloxysulfonyl, eicosyloxysulfonyl, and the like can be mentioned.

[0083] as -SO2NR 9 R 10 For example, sulfamoyl; N-methylsulfamoyl, N-ethylsulfamoyl, N- propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N- sec-butylsulfamoyl, N-tert-butylsulfamoyl, N-pentylsulfamoyl, N-(l- ethylpropyl)sulfamoyl, N-(l,l-dimethylpropyl)sulfamoyl, N-(l,2- dimethylpropyl)sulfamoyl, N-(2,2-dimethylpropyl)sulfamoyl, N-(l- methylbutyl)sulfamoyl, N-(2-methylbutyl)sulfamoyl, N-(3-methylbutyl)sulfamoyl, N- cyclopentylsulfamoyl, N-hexylsulfamoyl, N-(l,3-dimethylbutyl)sulfamoyl, N-(3,3- dimethylbutyl)sulfamoyl, N-heptylsulfamoyl, N-(l-methylhexyl)sulfamoyl, N-(l,4- dimethylpentyl)sulfamoyl, N-octylsulfamoyl, N-(2-ethylhexyl)sulfamoyl, N-(l,5- dimethylhexyl)sulfamoyl, N-(l,l,2,2-tetramethylbutyl)sulfamoyl, and the like N- monosubstituted sulfamoyl; N,N-dimethylsulfamoyl, N,N-ethylmethylsulfamoyl, N,N- diethylsulfamoyl, N,N-propylmethylsulfamoyl, N,N-isopropylmethylsulfamoyl, N,N- tert-butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-bis(l-methylpropyl)sulfamoyl, N,N-heptylmethylsulfamoyl, and the like N,N-disubstituted sulfamoyl; and the like can be mentioned.

[0084] as -Si(OR 12 )(OR 13 )(OR 14, for example, trimethoxysilyl group, triethoxysilyl group, etc.

[0085] R 5 -CO2H, -CO2 - Z + -CO2R 8 -SO3 - -SO3 - Z + -SO3H, or SO2NHR 9 , more preferably SO3 - -SO3 - Z + -SO3H, or SO2NHR 9 .

[0086] m represents an integer of 0 to 5, preferably 1 to 4, more preferably 1 or 2, further preferably 1.

[0087] As the alkyl group having 1 to 6 carbon atoms in R 6 and R 7 , the alkyl group having 1 to 6 carbon atoms in the above-mentioned alkyl group is exemplified, preferably the alkyl group having 1 to 2 carbon atoms. R 6 and R 7 is more preferably a hydrogen atom.

[0088] As the aralkyl group having 7 to 10 carbon atoms in R 11 , benzyl group, phenylethyl group, phenylbutyl group, etc. are exemplified.

[0089] As the halogen atom in X, chlorine atom, fluorine atom, bromine atom, etc. are exemplified.

[0090] a represents an integer of 0 or 1, preferably 0.

[0091] As the compound (I), the compound represented by the formula (Ia) (hereinafter sometimes referred to as "compound (Ia)") can be preferably exemplified. The compound represented by the formula (Ia) can be used in combination with the compound (I) other than the compound (Ia) (hereinafter sometimes referred to as "compound (Ib)"), or the compound (Ia) can be used in combination with the compound (Ib). In addition, two or more kinds of the compound (Ia) can be used in combination.

[0092]

[0093] [In the formula (Ia),

[0094] R a1 and R a4 each independently is a monovalent aromatic hydrocarbon group which can have a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms in number of 2 or less.

[0095] R a2 and R a3 each independently is a hydrogen atom, a methyl group, or an ethyl group.

[0096] R 5 ~R 7 , m, a, and X represent the same meanings as described above.

[0097] As R a1 and R a4 , among the same groups as R 1 and R 4 , monovalent aromatic hydrocarbon groups having no substituent or monovalent aromatic hydrocarbon groups having a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms in number of 2 or less can be given. Among them, monovalent aromatic hydrocarbon groups having a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms in number of 2 or less are preferred.

[0098] As monovalent aromatic hydrocarbon groups having no substituent, monocyclic aromatic hydrocarbon groups such as a phenyl group, polycyclic aromatic hydrocarbon groups such as a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like can be given. As polycyclic aromatic hydrocarbon groups, non-fused polycyclic aromatic hydrocarbon groups such as a biphenyl group, a terphenyl group, and the like are preferred. As monovalent aromatic hydrocarbon groups having a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms in number of 2 or less, a tolyl group, a xylyl group, a mesityl group, a monopropylphenyl group, a dipropylphenyl group, a monobutylphenyl group, a dibutylphenyl group, and the like can be given. The number of carbon atoms of the aromatic hydrocarbon group is preferably 7 to 20, more preferably 7 to 16, further preferably 7 to 10, most preferably 8. The number of carbon atoms of the aromatic hydrocarbon group is the number including carbon of a substituent. The aromatic hydrocarbon group preferably has no substituent other than the saturated aliphatic hydrocarbon group.

[0099] The number of saturated aliphatic hydrocarbon groups bonded to the aromatic hydrocarbon group is preferably 1 to 2, more preferably 2. The saturated aliphatic hydrocarbon group is preferably bonded to an ortho position or a meta position with respect to the bonding site of the aromatic hydrocarbon group, more preferably to an ortho position. As the saturated aliphatic hydrocarbon group, saturated aliphatic hydrocarbon groups having no substituent can be given. The number of carbon atoms of the saturated aliphatic hydrocarbon group is preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, most preferably 1.

[0100] As R a2 and R a3 , a hydrogen atom, a methyl group, an ethyl group can be given, of which a hydrogen atom or a methyl group is preferred, a hydrogen atom is more preferred.

[0101] As compound (Ib), the preferred compound is one represented by formula (Ib1) (hereinafter sometimes referred to as "compound (Ib1)"). Compound formula (Ib1) is preferably used in combination with compound (Ia), but may also be used without compound (Ia). That is, the zeolite dye (A1) can be compound (Ia) and / or compound (Ib1), preferably compound (Ia), or compound (Ia) and compound (Ib1), more preferably compound (Ia).

[0102]

[0103] In formula (Ib1), R b1 ~R b4 Each can independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents, or a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms that may have substituents.

[0104] R b1 ~R b4 The at least one saturated hydrocarbon group or aromatic hydrocarbon group contained herein has 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 ) as a substituent, or R b1 ~R b4 It contains at least one aromatic hydrocarbon group having three or more monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms as substituents.

[0105] R 12 R 13 and R 14 Each of these groups independently represents a monovalent saturated hydrocarbon group with 1 to 4 carbon atoms, where the hydrogen atoms in the saturated hydrocarbon group can be replaced by halogen atoms.

[0106] R 5 ~R 10 , m, a, and X represent the same meaning as above.

[0107] As R b1 and R b4 In relation to the aforementioned R 1 and R4 Among the same groups, a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which can have a substituent, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which can have a substituent, or an aromatic hydrocarbon group having 3 or more monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms which can have a substituent can be mentioned as the substituent. Among these, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which can have a substituent, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which can have a substituent, or an aromatic hydrocarbon group having 3 or more monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms which can have a substituent is preferred.

[0108] The number of carbon atoms of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which can have a substituent is preferably 1 to 10, more preferably 2 to 8, and further preferably 2 to 7. The number of carbon atoms of the saturated aliphatic hydrocarbon group is the number including the carbon of the substituent. As the substituent, 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 more preferred, -OH, -OR 8 , -CO2H, -CO2R 8 , -SO3 - , -SO3H, -SO3 - Z + , -SR 8 , -SO2R 8 , -SO3R 8 , or -Si(OR 12 )(OR 13 )(OR 14 ) is further preferred, and -OH, -OR 8 , -CO2H, -CO2R 8 , or -Si(OR 12 )(OR 13 )(OR 14 ) is most preferred. The number of substituents is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, and most preferably 1 per 1 saturated aliphatic hydrocarbon group. 12 13 14 The number of substituents is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, and most preferably 1 per 1 saturated aliphatic hydrocarbon group.​​

[0109] The number of carbon atoms of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms optionally having a substituent is preferably 7 to 20, more preferably 7 to 16, further preferably 7 to 12, more further preferably 7 to 10, particularly preferably 7 to 8, most preferably 8. The number of carbon atoms of the aromatic hydrocarbon group is the number of carbon atoms including those of the substituent. As the substituent, a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, -OH, -OR 8 8 - - Z + 8 8 8 9 R 10 12 13 14 , more preferably a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, -OH, -OR 8 8 - - Z + 8 8 8 9 R 10 . Further preferably a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, -OR 8 - - Z + 8 8 8 9 R 10 . The number of substituents is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, most preferably 2 per 1 aromatic hydrocarbon group. The bonding site of the substituent to the aromatic hydrocarbon group is preferably ortho and / or meta, more preferably ortho.

[0110] ​​​​​​​​​​​​​​​​​​​​​​​The number of carbon atoms of the aromatic hydrocarbon group having one or more saturated aliphatic hydrocarbon groups having 3 or more carbon atoms and 1 to 4 carbon atoms as substituents is preferably 9 to 20, more preferably 9 to 13, further preferably 9 to 12, and most preferably 9. The number of carbon atoms of the aromatic hydrocarbon group is the number including carbon atoms of the substituents. The aromatic hydrocarbon group preferably has no substituents other than the saturated aliphatic hydrocarbon group. The number of saturated aliphatic hydrocarbon groups is preferably 3 to 5, more preferably 3 to 4, and most preferably 3 per one aromatic hydrocarbon group. The bonding site of the saturated aliphatic hydrocarbon group to the aromatic hydrocarbon group is preferably the ortho position and / or the para position, and more preferably the ortho position and the para position. The number of carbon atoms of the monovalent saturated aliphatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, and most preferably 1.

[0111] as R b2 and R b3 , among the same groups as R 2 and R 3 , a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which can have a substituent can be preferably selected. Among them, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which can have a substituent is more preferable, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which has a substituent is further preferable.

[0112] The number of carbon atoms of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which can have a substituent is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. The number of carbon atoms of the saturated aliphatic hydrocarbon group is the number including carbon atoms of the substituents. As the substituent, 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 ) can be preferably selected. More preferably, -OH, -OR 8 , -CO2H, -CO2R 8 , -SO3 - , -SO3H, -SO3 - Z + , -SR 8 , -SO2R 8 , -SO3R 8 , or -Si(OR12 13 14 , further 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, further preferably 1 to 2, most preferably 1 in each 1 saturated aliphatic hydrocarbon group.

[0113] As the compound (Ia), preferably the compounds No. 1 to 48 identified by formula (IaX) and Table 1.

[0114]

[0115] [Table 1]

[0116] No. [R ax1 ]]> [R ax2 ]]> [R ax3 ]]> [R ax4 ]]> No. [R ax1 ]]> [R ax2 ]]> [R ax3 ]]> [R ax4 ]]> 1 Ph H H Ph 25 BPh2 H H BPh2 2 Ph CH3 CH3 Ph 26 BPh2 CH3 CH3 BPh3 3 Ph CH3CH2 CH3CH2 Ph 27 BPh2 <![CDATA[CH3CH2]]> CH3CH2 BPh3 4 o-Tolyl H H o-Tolyl 28 BPh3 H H BPh3 5 o-Tolyl CH3 CH3 o-Tolyl 29 BPh3 CH3 CH3 BPh3 6 o-Tolyl CH3CH2 CH3CH2 o-Tolyl 30 BPh3 CH3CH2 CH3CH2 BPh3 7 m-Tolyl H H m-Tolyl 31 TPh2' H H 2,6-Xylyl 8 m-Tolyl CH3 CH3 m-Tolyl 32 TPh2' CH3 CH3 2,6-Xylyl 9 m-Tolyl CH3CH2 CH3CH2 m-Tolyl 33 TPh2' CH3CH2 CH3CH2 2,6-Xylyl 10 p-Tolyl H H p-Tolyl 34 TPh2' H H BPh2 11 p-Tolyl CH3 CH3 p-Tolyl 35 TPh2' CH3 CH3 BPh2 12 p-Tolyl CH3CH2 CH3CH2 p-Tolyl 36 TPh2' CH3CH2 CH3CH2 BPh2 13 2,6-Xylyl H H 2,6-Xylyl 37 TPh2' H H BPh3 14 2,6-Xylyl CH3 CH3 2,6-Xylyl 38 TPh2' CH3 CH3 BPh3 15 2,6-Xylyl <![CDATA[CH3CH2]]> CH3CH2 2,6-Xylyl 39 TPh2' CH3CH2 CH3CH2 BPh3 16 2,6-Xylyl H H Ph 40 TPh2' H H TPh2' 17 2,6-Xylyl CH3 CH3 Ph 41 TPh2' CH3 CH3 TPh2' 18 2,6-Xylyl CH3CH2 CH3CH2 Ph 42 TPh2' CH3CH2 CH3CH2 TPh2' 19 2,6-Xylyl H H BPh2 43 p-ButylPh H H p-ButylPh 20 2,6-Xylyl CH3 CH3 BPh2 44 p-ButylPh CH3 CH3 p-ButylPh 21 2,6-Xylyl ​ CH3CH2 BPh2 45 p-ButylPh CH3CH2 CH3CH2 p-ButylPh 22 2,6-Xylyl H H BPh3 46 m-ButylPh H H m-ButylPh 23 2,6-Xylyl CH3 CH3 BPh3 47 m-ButylPh CH3 CH3 m-ButylPh 24 2,6-Xylyl ​ CH3CH2 BPh3 48 m-ButylPh CH3CH2 CH3CH2 m-ButylPh

[0117] The symbols in the formulae represent the following groups (hereinafter, * represents a bonding site).

[0118]

[0119] As the compound (Ib1), preferably the compounds No. 49 to 74 identified by formula (Ibx) and Table 2, and the compounds represented by formulae A3-1 to A3-8.

[0120]

[0121] [Table 2]

[0122] No. [R bx1 ]]> [R bx2 ]]> [R bx3 ]]> [R bx4 ]]> 49 CH3 CH3 CH3 PrTMS 50 CH3CH2 CH3CH2 CH3 PrTMS 51 CH3CH2 CH3CH2 CH3CH2 PrTMS 52 Ph PrCOOH PrCOOH Ph 53 o-Tolyl PrCOOH PrCOOH o-Tolyl 54 m-Tolyl PrCOOH PrCOOH m-Tolyl 55 p-Tolyl PrCOOH PrCOOH p-Tolyl 56 2,6-Xylyl PrCOOH PrCOOH 2,6-Xylyl 57 MT1 H H MT1 58 MT1 CH3 CH3 MT1 59 MT1 CH3CH2 ​ MT1 60 MT2 H H MT2 61 MT2 CH3 CH3 MT2 62 MT2 CH3CH2 CH3CH2 MT2 63 MT3 H H MT3 64 MT3 CH3 CH3 MT3 65 MT3 CH3CH2 CH3CH2 MT3 66 2,4,6-Mesityl H H 2,4,6-Mesityl 67 2,4,6-Mesityl CH3 CH3 2,4,6-Mesityl 68 2,4,6-Mesityl CH3CH2 CH3CH2 2,4,6-Mesityl 69 2,6-Xylyl H H MPh1 70 2,6-Xylyl CH3 CH3 MPh1 71 2,6-Xylyl ​ CH3CH2 MPh1 72 2,6-Xylyl H H MPh2 73 2,6-Xylyl CH3 CH3 MPh2 74 2,6-Xylyl CH3CH2 CH3CH2 MPh2

[0123] The symbols in the formulae represent the following groups (hereinafter, * represents a bonding site).

[0124]

[0125] The colorant (A) can be only a dye, or a combination of a dye and a pigment. Among them, the colorant (A) is preferably only a dye, or a combination of a dye and a red pigment or a violet pigment, more preferably only a xanthene dye (A1), or a combination of a xanthene dye (A1) and a red pigment or a violet pigment, further preferably only a xanthene dye (A1), or a combination of a xanthene dye (A1) and a violet pigment, still further preferably only a xanthene dye (A1).

[0126] ​​The xanthene dye (A1) is preferably a compound (Ia) and / or a compound (Ib1). That is, the xanthene dye (A1) is preferably either of the compound (Ia) or the compound (Ib1), or a combination of the compound (Ia) and the compound (Ib1).

[0127] The xanthene dye (A1) is also preferably a combination of two or more selected from the group consisting of the compound (Ib), or a combination of the compound (Ib) and the compound (Ia). More preferably, it is a combination of two or more selected from the group consisting of the compound (Ib1), or a combination of the compound (Ib1) and the compound (Ia).

[0128] The content of the xanthene dye (A1) is preferably 30 to 100% by mass, more preferably 60 to 100% by mass, further preferably 80 to 100% by mass, and most preferably 100% by mass, relative to the total amount of the colorant (A). In the case where the colorant (A) contains a pigment or the like, the content of the xanthene dye (A1) can be 90% by mass or less, 80% by mass or less, or 70% by mass or less.

[0129] The content of the compound (Ia) in the xanthene dye (A1) is preferably 30 to 100% by mass, more preferably 60 to 100% by mass, further preferably 80 to 100% by mass, and most preferably 100% by mass. In the case where the colorant (A) contains a compound (Ib) or the like, the content of the compound (Ia) can be 80% by mass or less, 70% by mass or less, or 60% by mass or less.

[0130] The content of the compound (Ib) in the xanthene dye (A1) is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and further preferably 40 to 60% by mass.

[0131] The content of the compound (Ib) is preferably 20 to 150 parts by mass, more preferably 50 to 130 parts by mass, and further preferably 80 to 110 parts by mass, relative to 100 parts by mass of the compound (Ia).

[0132] <Other dye (A2)>

[0133] The colorant (A) can further contain a dye other than the xanthene dye (A1) (sometimes referred to as "other dye (A2)"). As the other dye (A2), there is no particular limitation as long as it is a dye other than the xanthene dye (A1), and dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, sulfonamide derivatives of acid dyes, and the like can be given, for example, and compounds classified as dyes, i.e., substances having a color tone other than C.I. pigments, in the Color Index (published by The Society of Dyers and Colourists), and well-known dyes described in the Dyeing Guide (Sanchin Co., Ltd.) can be given. In addition, depending on the chemical structure, azo dyes, anthraquinone dyes, cyanine dyes, phthalocyanine dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes, and the like can be given.

[0134]

[0135] The colorant (A) can contain a pigment (A3). As the pigment (A3), organic pigments and inorganic pigments can be given, and compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists), and the like can be given.

[0136] As the organic pigment, for example, red pigments such as C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, and the like; blue pigments such as C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, and the like; violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, and the like; green pigments such as C.I. Pigment Green 7, 36, 58, and the like, and the like can be given.

[0137] Among them, red pigments, violet pigments are preferred, and violet pigments are more preferred, and C.I. Pigment Violet 19 is further preferred.

[0138] As the inorganic pigment, metal compounds such as metal oxides, metal complexes can be given, and specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, or complex metal oxides can be given.

[0139] ​The pigment (A3) described above can be subjected to various treatments as needed, including rosin treatment, surface treatment using pigment derivatives with introduced acidic or basic groups, dispersants, grafting treatment of the pigment surface using polymer compounds, micronization treatment based on sulfuric acid micronization, cleaning treatment based on organic solvents or water to remove impurities, and removal treatment of ionic impurities based on ion exchange. Furthermore, the pigment (A3) is preferably of uniform particle size.

[0140] In addition, when using pigment (A3), the content of pigment (A3) relative to the total amount of colorant (A) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass.

[0141] <Solvent (B)>

[0142] The negative resist composition may contain a solvent (B). Solvent (B) is not particularly limited and may be any solvent commonly used in this field. For example, it may be selected from ester solvents (solvents containing -COO- and not -O-), ether solvents (solvents containing -O- and not -COO-), ether-ester solvents (solvents containing both -COO- and -O-), ketone solvents (solvents containing -CO- and not -COO-), alcohol solvents (solvents containing OH and not -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

[0143] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl 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-butanediol diacetate.

[0144] Examples of ether solvents include, for example, 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; tetrahydrofuran, tetrahydropyran, and 1,4-di(ethylene glycol monoethyl ether). alkyl ethers; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and the like; dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, and the like; phenyl ethers such as anisole, phenetol, methyl anisole, and the like; 3-methoxy-l-butanol, 3-methoxy-3-methylbutanol, and the like.

[0145] As the ether ester solvents, for example, monomethyl ether acetic acid esters of ethylene glycol such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and the like; monomethyl ether acetic acid esters of propylene glycol such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like; monoalkyl ether acetic acid esters of diethylene glycol such as diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like; monoalkyl ether acetic acid esters of dipropylene glycol such as dipropylene glycol monomethyl ether acetate, and the like; 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-methyl-2-methoxypropionate, ethyl 2-ethyl-2-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and the like can be given.

[0146] As the ketone solvents, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, and the like can be given.

[0147] As the alcohol solvents, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like can be given.

[0148] As the aromatic hydrocarbon solvents, benzene, toluene, xylene, mesitylene, and the like can be given.

[0149] As the amide solvents, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like can be given.

[0150] Among the above solvents, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and / or 4-hydroxy-4-methyl-2-pentanone is preferred.

[0151] A solvent containing an ether ester solvent is particularly preferred. In this case, the content of the ether ester solvent is preferably 40 to 100% by mass, and more preferably 40 to 99% by mass, relative to the total amount of the solvent (B) in terms of dispersion stability. The lower limit of the above content of the ether ester solvent is preferably 60% by mass, and more preferably 70% by mass.

[0152] 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.

[0153] When the solvent (B) is a mixed solvent, the solvent 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.

[0154] If the solvent (B) is such a solvent, a color filter with high brightness can be produced by the negative-type resist composition of the present application, and thus is preferred.

[0155] As the solvent (B), a solvent in which the solubility (23°C) of the colorant (A) is 5 mass% or less is preferred, and a solvent in which the solubility (23°C) of the colorant (A) is 0.3 to 3 mass% is more preferred. A solvent (B) in which the solubility of the xanthene dye (Al) is in the above range is particularly preferred.

[0156] <Resin (C)>

[0157] The negative-type resist composition of the present application contains a resin (C). As the resin (C), an alkali-soluble resin is preferred. By making the negative-type resist composition contain an alkali-soluble resin, the solubility of the unexposed portion in a developer is improved. In addition, the alkali-soluble resin has excellent compatibility with a dispersant having an amine group described later. As the resin (C), the following resins [Kl] to [K6] and the like can be given.

[0158] Resin [Kl]: a copolymer of at least one of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (a) (hereinafter, sometimes referred to as "(a)") and a monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "(b)");

[0159] Resin [K2]: a copolymer of (a) and (b) and a monomer (c) copolymerizable with (a) (wherein (c) is different from (a) and (b)) (hereinafter, sometimes referred to as "(c)");

[0160] Resin [K3]: a copolymer of (a) and (c);

[0161] Resin [K4]: a resin obtained by reacting (b) with a copolymer of (a) and (c);

[0162] Resin [K5]: a resin obtained by reacting (a) with a copolymer of (b) and (c);

[0163] Resin [K6]: a resin obtained by reacting the copolymer of (a) with (b) and (c) and further reacting a carboxylic anhydride.

[0164] As (a), specifically, for example, mention can be made of unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and the like;

[0165] 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, 1,4-cyclohexene dicarboxylic acid, and the like;

[0166] carboxyl-containing bicyclic unsaturated compounds 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, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, and the like;

[0167] unsaturated dicarboxylic 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, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, and the like;

[0168] unsaturated mono[(meth)acryloyloxyalkyl] esters of polycarboxylic acids having 2 or more valences such as succinic acid mono[2-(meth)acryloyloxyethyl] ester, phthalic acid mono[2-(meth)acryloyloxyethyl] ester, and the like;

[0169] unsaturated acrylic esters such as α-(hydroxymethyl)acrylic acid and the like containing a hydroxyl group and a carboxyl group in the same molecule.

[0170] Among them, from the viewpoint of copolymerizability and the solubility of the obtained resin in an aqueous alkali solution, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferred.

[0171] (b) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from a propylene oxide ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenic unsaturated bond. (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0172] It should be noted that in the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The same applies to "(meth)acryloyl group" and "(meth)acrylate" and the like.

[0173] As (b), for example, monomer (b1) having an oxiranyl group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "(b1)"), monomer (b2) having an oxetanyl group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "(b2)"), monomer (b3) having a tetrahydrofuryl group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "(b3)") and the like can be given.

[0174] As (b1), for example, monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon ring-epoxidized structure (hereinafter, sometimes referred to as "(b1-1)"), monomer (b1-2) having a cycloaliphatic unsaturated hydrocarbon ring-epoxidized structure (hereinafter, sometimes referred to as "(b1-2)") can be given.

[0175] As (b1-1), (meth)acrylic acid glycidyl ester, β-methyl (meth)acrylic acid glycidyl ester, β-ethyl (meth)acrylic acid glycidyl ester, 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(glycidyloxymethyl)styrene, 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, 2,4,6-tris(glycidyloxymethyl)styrene and the like can be given.

[0176] As (b1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Daicel Corp.), (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Corp.), (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester (for example, Cyclomer (registered trademark) M100; manufactured by Daicel Corp.), a compound represented by formula (BI) and a compound represented by formula (BII) and the like can be given.

[0177]

[0178] [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, in which a hydrogen atom included in the alkyl group can be substituted with a hydroxyl group.

[0179] X a and X b represents a single bond, -R c -, *-R c -O-, *-R c -S-, or *-R c -NH-.

[0180] R c represents an alkanediyl group having 1 to 6 carbon atoms.

[0181] * represents a bonding site to O.

[0182] As the alkyl group having 1 to 4 carbon atoms, there can be mentioned a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and the like.

[0183] As the alkyl group in which a hydrogen atom is substituted with a hydroxyl group, there can be mentioned 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, a 4-hydroxybutyl group, and the like.

[0184] As R a and R b , there can be preferably mentioned a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, and more preferably a hydrogen atom, a methyl group.

[0185] As the alkanediyl group, there can be mentioned 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, a hexane-1, 6-diyl group, and the like.

[0186] As X a and X b , there can be preferably mentioned a single bond, a methylene group, an ethylene group, *-CH2-O-, and *-CH2CH2-O- (* represents a bonding site to O), and more preferably a single bond, *-CH2CH2-O- (* represents a bonding site to O).

[0187] As the compound represented by formula (BI), there can be mentioned compounds represented by formulae (BI-1) to (BI-15), and the like. Compounds represented by formula (BI-1), (BI-3), (BI-5), (BI-7), (BI-9), or (BI-11) to (BI-15) can be preferably selected. Compounds represented by formula (BI-1), (BI-7), (BI-9), or (BI-15) can be more preferably selected.

[0188]

[0189]

[0190] As the compound represented by formula (BI), there can be mentioned compounds represented by formulae (BI-1) to (BI-15), and the like. Compounds represented by formula (BI-1), (BI-3), (BI-5), (BI-7), (BI-9), or (BI-11) to (BI-15) can be preferably selected. Compounds represented by formula (BI-1), (BI-7), (BI-9), or (BI-15) can be more preferably selected.

[0191]

[0192] The compound represented by formula (BI) and the compound represented by formula (BII) can be used alone, respectively, or the compound represented by formula (BI) and the compound represented by formula (BII) can be used in combination. When they are used in combination, the 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 further preferably 20:80 to 80:20, on a molar basis.

[0193] As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable. As (b2), there can be mentioned 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

[0194] As (b3), a monomer having a tetrahydrofurfuryl group and a (meth)acryloyloxy group is more preferable. As (b3), specifically, acrylic acid tetrahydrofurfuryl ester (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), methacrylic acid tetrahydrofurfuryl ester, and the like can be given.

[0195] As (b), (b1) is preferable in terms of being able to make the reliability of the obtained color filter, such as heat resistance, reagent resistance, and the like, higher. Further, (b1-2) is more preferable in terms of the storage stability of the negative resist composition being excellent.

[0196] As (c), for example, (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-butyl ester, (meth)acrylic acid sec-butyl ester, (meth)acrylic acid tert-butyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid dodecyl ester, (meth)acrylic acid lauryl ester, (meth)acrylic acid stearyl ester, (meth)acrylic acid cyclopentyl ester, (meth)acrylic acid cyclohexyl ester, (meth)acrylic acid 2-methylcyclohexyl ester, (meth)acrylic acid tricyclo[5.2.1.0 2,6 ]decane-8-yl ester (which is called as "(meth)acrylic acid dicyclopentyl ester" as a conventional name in the technical field. In addition, sometimes called as "(meth)acrylic acid tricyclodecyl ester"), (meth)acrylic acid tricyclo[5.2.1.0 2,6 ]decene-8-yl ester (which is called as "(meth)acrylic acid dicyclopentenyl ester" as a conventional name in the technical field), (meth)acrylic acid dicyclopentyloxyethyl ester, (meth)acrylic acid isobornyl ester, (meth)acrylic acid adamantyl ester, (meth)acrylic acid allyl ester, (meth)acrylic acid propargyl ester, (meth)acrylic acid phenyl ester, (meth)acrylic acid naphthyl ester, (meth)acrylic acid benzyl ester, and the like (meth)acrylate esters;

[0197] (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, and the like (meth)acrylate esters containing a hydroxyl group;

[0198] maleic acid diethyl ester, fumaric acid diethyl ester, itaconic acid diethyl ester, and the like dicarboxylic acid diesters;

[0199] bicyclic unsaturated compounds such as 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, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(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-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, and the like;

[0200] N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-succinimidyl-3-maleimide propionate, N-(9-acridinyl)maleimide, and the like carbonylimide derivatives;

[0201] styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like styrene-based monomers; acrylonitrile, methacrylonitrile, and the like nitrile-based monomers; vinyl chloride, vinylidene chloride, and the like halogenated ethylenes; acrylamide, methacrylamide, and the like amide-based monomers; vinyl acetate; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like diene-based monomers, and the like.

[0202] Among them, from the aspects of copolymerizability and heat resistance, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, and the like are preferred.

[0203] In the resin [Kl], the ratio of the structural units from each unit is preferably 2 to 60 mol% of the structural unit from (a) and 40 to 98 mol% of the structural unit from (b), and more preferably 10 to 50 mol% of the structural unit from (a) and 50 to 90 mol% of the structural unit from (b), among all the structural units constituting the resin [Kl].

[0204] When the ratio of the structural units of the resin [Kl] is within the above range, there is a tendency that the storage stability of the negative resist composition, the developing property at the time of forming a colored pattern, and the solvent resistance of the obtained color filter are excellent.

[0205] The resin [Kl] can be produced, for example, by using the method described in the literature "Experimental Method of Polymer Synthesis" (Nobuo Oki, issued by Shokabo Publishing Co., Inc., 1st edition, 1st printing, March 1, 1972) and the references described in the literature as a reference.

[0206] Specifically, a method in which a prescribed amount of (a) and (b), a polymerization initiator, and a solvent or the like are charged into a reaction vessel, a deoxidized atmosphere is prepared, for example, by replacing oxygen with nitrogen, and heating and keeping warm are performed while stirring can be mentioned. Note that the polymerization initiator and the solvent or the like used here are not particularly limited, and a polymerization initiator and a solvent generally used in the field can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and the like), organic peroxides (benzoyl peroxide, and the like) can be mentioned, and as the solvent, a solvent described later as the solvent (B) of the negative resist composition of the present application and the like can be mentioned as long as it is a solvent that dissolves each monomer.

[0207] Note that the obtained copolymer can be used directly as the solution after the reaction, can be used as a solution after concentration or dilution, and can be used as a substance taken out in a solid (powder) form by a method such as reprecipitation. In particular, by using the solvent contained in the negative resist composition of the present application as the solvent at the time of the polymerization, the solution after the reaction can be directly used for the production of the negative resist composition of the present application, and thus the manufacturing process of the negative resist composition of the present application can be simplified.

[0208] In the resin [K2], the ratio of the structural units from each unit is preferably 2 to 45 mol% of the structural unit from (a), 2 to 95 mol% of the structural unit from (b), and 1 to 65 mol% of the structural unit from (c), and more preferably 5 to 40 mol% of the structural unit from (a), 5 to 80 mol% of the structural unit from (b), and 5 to 60 mol% of the structural unit from (c), among all the structural units constituting the resin [K2].

[0209] When the ratio of the structural units of the resin [K2] is within the above range, there is a tendency that the storage stability of the negative resist composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the obtained color filter are excellent.

[0210] The resin [K2] can be produced, for example, in the same manner as described as the production method of the resin [K1].

[0211] In the resin [K3], the ratio of the structural units from each unit is preferably 2 to 60 mol% of the structural unit from (a) and 40 to 98 mol% of the structural unit from (c), and more preferably 10 to 50 mol% of the structural unit from (a) and 50 to 90 mol% of the structural unit from (c), in all the structural units constituting the resin [K3].

[0212] The resin [K3] can be produced, for example, in the same manner as described as the production method of the resin [K1].

[0213] The resin [K4] can be produced by adding the cyclic ether having 2 to 4 carbon atoms of (b) to the carboxylic acid and / or carboxylic anhydride of (a).

[0214] First, the copolymer of (a) and (c) is produced in the same manner as described as the production method of the resin [K1]. In this case, the ratio of the structural units from each unit is preferably the same as the ratio described in the resin [K3].

[0215] Next, the cyclic ether having 2 to 4 carbon atoms of (b) is reacted with a part of the carboxylic acid and / or carboxylic anhydride from (a) in the above copolymer.

[0216] After the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and a reaction catalyst (for example, tris(dimethylaminomethyl)phenol or the like) and a polymerization inhibitor (for example, hydroquinone or the like) of (b), carboxylic acid or carboxylic anhydride, and cyclic ether are put into the flask, and, for example, reacted at 60 to 130°C for 1 to 10 hours, whereby the resin [K4] can be produced.

[0217] The use amount of (b) is preferably 5 to 80 mol, and more preferably 10 to 75 mol, relative to 100 mol of (a). By being within this range, the balance of the storage stability of the negative resist composition, the developability when forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern can become good. From the viewpoint that the reactivity of the cyclic ether is high and unreacted (b) is unlikely to remain, (b1) is preferable, and (b1-1) is further preferable, as (b) used in the resin [K4].

[0218] The amount of the above-mentioned reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b), and (c). The amount of the above-mentioned polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b), and (c).

[0219] The feeding method, reaction temperature, and time, and other reaction conditions can be appropriately adjusted in consideration of the manufacturing equipment, heat generation amount based on polymerization, and the like. Note that the feeding method, reaction temperature, and time can be appropriately adjusted in consideration of the manufacturing equipment, heat generation amount based on polymerization, and the like, as with the polymerization conditions.

[0220] For the resin [K5], as the first stage, a copolymer of (b) and (c) is obtained in the same manner as in the production method of the above-mentioned resin [Kl]. As with the above-mentioned, for the obtained copolymer, the solution after the reaction can be used as it is, or a solution after concentration or dilution can be used, or a substance taken out in the form of a solid (powder) using a method such as reprecipitation can be used.

[0221] The ratio of the structural units from (b) and (c) relative to the total number of moles of all the structural units constituting the above-mentioned copolymer is preferably 5 to 95 mol% of the structural units from (b) and 5 to 95 mol% of the structural units from (c), respectively, and more preferably 10 to 90 mol% of the structural units from (b) and 10 to 90 mol% of the structural units from (c), respectively.

[0222] Further, the carboxylic acid or carboxylic anhydride possessed by (a) is reacted with the cyclic ether from (b) possessed by the copolymer of (b) and (c) under the same conditions as in the production method of the resin [K4], whereby the resin [K5] can be obtained.

[0223] The amount of (a) used in the reaction with the above-mentioned copolymer is preferably 5 to 80 moles relative to 100 moles of (b). From the viewpoint that the reactivity of the cyclic ether is high and unreacted (b) is unlikely to remain, (bl) is preferable, and (bl-1) is further preferable as (b) used in the resin [K5].

[0224] The resin [K6] is a resin obtained by further reacting a carboxylic anhydride with the resin [K5]. The carboxylic anhydride is reacted with the hydroxyl group generated by the reaction of the cyclic ether and the carboxylic acid or carboxylic anhydride.

[0225] As the carboxylic anhydride, 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 (nadic anhydride) and the like can be given. The amount of the carboxylic anhydride used is preferably 0.5 to 1 mole relative to 1 mole of the amount of (a) used.

[0226] As the resin (C), specifically, resin [Kl] such as (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester / (meth)acrylic acid copolymer, acrylic acid 3,4-epoxytricyclo[5.2.1.02'6]decyl ester / (meth)acrylic acid copolymer and the like; resin [K2] such as glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, acrylic acid 3,4-epoxytricyclo[5.2.1.02'6]decyl ester / (meth)acrylic acid / styrene copolymer, 3-methyl-3-(meth)acryloyloxymethyl oxetane / (meth)acrylic acid / styrene copolymer and the like; resin [K3] such as benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer and the like; resin [K4] such as a resin obtained by addition of glycidyl (meth)acrylate to benzyl (meth)acrylate / (meth)acrylic acid copolymer, a resin obtained by addition of glycidyl (meth)acrylate to tricyclodecanyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, a resin obtained by addition of glycidyl (meth)acrylate to tricyclodecanyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer and the like; resin [K5] such as a resin obtained by reaction of (meth)acrylic acid with a copolymer of tricyclodecanyl (meth)acrylate / glycidyl (meth)acrylate, a resin obtained by reaction of (meth)acrylic acid with a copolymer of tricyclodecanyl (meth)acrylate / styrene / glycidyl (meth)acrylate and the like; resin [K6] such as a resin obtained by further reaction of a resin obtained by reaction of (meth)acrylic acid with a copolymer of tricyclodecanyl (meth)acrylate / glycidyl (meth)acrylate with tetrahydrophthalic anhydride and the like. 2,6 2,6 2,6

[0227] Among them, as the resin (C), resin [Kl] and / or resin [K2] is preferred.

[0228] ​​​The weight average molecular weight of the resin (C) in terms of polystyrene is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, and further preferably from 5,000 to 30,000. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (C) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

[0229] The acid value of the resin (C) is preferably from 50 to 170 mgKOH / g, more preferably from 60 to 150 mgKOH / g, and further preferably from 70 to 135 mgKOH / g. Here, the acid value is a value determined as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

[0230] <Dispersant (D)>

[0231] The negative resist composition of the present application preferably further contains a dispersant (D). As the dispersant (D), if it is a dispersant used in the dispersion of a colorant, there is no particular limitation as long as it has an amine group and an amine value of from 0 to 55 mgKOH / g (preferably from 2 to 40 mgKOH / g), and a high molecular dispersant can be cited, for example.

[0232] As the above high molecular dispersant, an acrylic dispersant, a polyurethane dispersant, and the like can be cited.

[0233] As the above acrylic dispersant, for example, an acrylic block copolymer can be cited, and as the acrylic block copolymer, a block copolymer having a colorant adsorption block further containing an acid group as a colorant adsorption group in a colorant adsorption block containing a basic group as a colorant adsorption group (also referred to as a dye adsorption group), and a block not containing a colorant adsorption group is preferably used.

[0234] As the colorant adsorption block further containing an acid group in a colorant adsorption block containing a basic group as the above colorant adsorption group, a colorant adsorption block composed by using a monomer having an acid group together with a monomer having a basic group can be cited.

[0235] As the monomer having a basic group described above, a monomer having a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium group, specifically, (methyl) acrylate N,N-dimethylaminoethyl, (methyl) acrylate N,N-diethylaminoethyl, N,N-dimethylacrylamide, diethylacrylamide, dimethylaminopropyl methacrylamide, acryloyl morpholine, vinyl imidazole, 2-vinyl pyridine, a monomer having an amino group and a caprolactone skeleton, a reactant of a monomer having a glycidyl group such as glycidyl (methyl) acrylate and a compound having one secondary amino group in the molecule, a reactant of a (methyl) acryloyl alkyl isocyanate compound and 4-(2-aminomethyl)-pyridine, 4-(2-aminoethyl)-pyridine, 4-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)imidazole, N,N-diallyl melamine, N,N-dimethyl-1,3-propanediamine, and the like can be given.

[0236] As the monomer having an acidic group described above, a monomer having a carboxyl group, a sulfonic acid group, a phosphoric acid group, specifically, as the monomer having a carboxyl group, an unsaturated monocarboxylic acid compound such as acrylic acid, methacrylic acid, crotonic acid, an unsaturated dicarboxylic acid compound such as maleic acid, fumaric acid, itaconic acid, and a half ester thereof, as the monomer having a sulfonic acid group, 2-acrylamido-2-methyl-1-propane sulfonic acid, 2-methacrylamido-2-methyl-1-propane sulfonic acid, styrene sulfonic acid, and the like, as the monomer having a phosphoric acid group, acid phosphono (methyl) acrylate, acid phosphono ethyl (methyl) acrylate, and the like can be given.

[0237] As the component of the block not containing a colorant adsorbing group described above, aromatic vinyl compounds such as styrene, α-methyl styrene, vinyl toluene, benzyl chloride, unsaturated carboxylic acid alkyl esters such as methyl (methyl) acrylate, ethyl (methyl) acrylate, butyl (methyl) acrylate, unsaturated carboxylic acid aralkyl esters such as benzyl (methyl) acrylate, a monomer containing a polycaprolactone, a polyalkylene glycol monoester-based monomer, and the like can be given. The above-described acrylic block copolymer can be obtained by living anion polymerization or the like, and a polymerization method known in the past can be used.

[0238] The amine value of the above-mentioned acrylic block copolymer is 0 to 55 mgKOH / g, preferably 0 to 50 mgKOH / g, and more preferably 2 to 40 mgKOH / g. Note that the amine value indicates the amine value of the solid content of 1 g of the acrylic block copolymer, and is the value converted into the equivalent of potassium hydroxide after measurement using 0.1 mol / L hydrochloric acid aqueous solution by potentiometric titration (for example, COMTITE (AUTOTITRATOR COM-900, BURET B-900, TITSTATION K-900) manufactured by Hiranuma Industries Co., Ltd.).

[0239] As commercially available products of the above-mentioned acrylic block copolymer, "Disperbyk (registered trademark) -112 (amine value 36 mgKOH / g)", "Disperbyk (registered trademark) -2000 (amine value 4 mgKOH / g)", "Disperbyk-2001 (amine value 29 mgKOH / g)", "Disperbyk (registered trademark) -2020 (amine value 38 mgKOH / g)", "Disperbyk (registered trademark) -2050 (amine value 30 mgKOH / g)", "Disperbyk (registered trademark) -2070 (amine value 20 mgKOH / g)", and the like manufactured by BYK-Chemie Japan Co., Ltd. can be given.

[0240] As the above-mentioned polyurethane-based dispersant, a compound obtained by reacting a compound having a number average molecular weight of 300 to 10,000 and having one or more hydroxyl groups in the molecule with a polyisocyanate compound and a basic group-containing compound having a functional group reactive with the isocyanate group in the molecule can be used. As a method for obtaining such a polyurethane-based dispersant, the method described in Japanese Patent Application Laid-Open No. 60-166318, and the like can be used.

[0241] As the polyisocyanate compound constituting the above polyurethane-based dispersant, there are isocyanate compounds having two or more isocyanate groups, for example, aromatic diisocyanate compounds such as 2,4-toluene diisocyanate, 2-polymer of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, and the like; aliphatic, alicyclic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methylcyclohexane-2,4(or 2,6)diisocyanate, 1,3-(isocyanatomethylene)cyclohexane, and the like; polyisocyanates having isocyanuric acid groups based on the above diisocyanates (polyisocyanates having isocyanuric acid groups formed by trimerization of the above diisocyanates, and the like), polyisocyanates obtained by reacting diisocyanates with polyols, polyisocyanates obtained by biuret reaction of diisocyanate compounds, and the like. Among the above polyisocyanate compounds, for example, polyisocyanates having isocyanuric acid groups based on diisocyanates such as toluene diisocyanate and isophorone diisocyanate are preferred.

[0242] As the compound having one or more hydroxyl groups in the molecule constituting the above polyurethane-based dispersant, there are, for example, polyether compounds, polyester compounds, and the like.

[0243] As the above polyether compound, there are, for example, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, and the like; alkylene glycols such as ethylene glycol, propane diol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexane diol, neopentyl glycol, glycerol, trimethylolpropane, pentaerythritol, di(glycerol), di(trimethylolpropane), dipentaerythritol, and the like; oxirane-modified products of low molecular monohydric alcohols such as methanol and ethanol, propylene oxide-modified products, butylene oxide-modified products, tetrahydrofuran-modified products, and the like.

[0244] As the polyester compound, for example, ethylene glycol, propane diol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexane diol, neopentyl glycol, glycerol, trimethylolpropane, pentaerythritol, di-glycerol, di(trimethylolpropane), di-pentaerythritol, and the like alkylene glycols, methanol, ethanol, and the like low molecular monohydric alcohols, ε-caprolactone adducts, γ-butyrolactone adducts, δ-valerolactone adducts, methylvalerolactone adducts, esterification products of aliphatic dicarboxylic acids such as adipic acid, dimer acid, and the like with polyols such as neopentyl glycol, methylpentane diol, and the like, i.e., aliphatic polyester polyols, esterification products of aromatic dicarboxylic acids such as terephthalic acid with polyols such as neopentyl glycol, and the like, i.e., aromatic polyester polyols, polycarbonate polyols, acrylic polyols, polytetramethylene hexaglycol ether (tetrahydrofuran-modified hexaglycol), and the like polyhydric alcohols, esterification products of dicarboxylic acids such as fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid, and the like with polyhydric hydroxyl compounds such as glycerol and the like polyhydric hydroxyl compounds, and the like. Of the above compounds having one or more hydroxyl groups within the molecule, ε-caprolactone adducts of alcohols are preferred.

[0245] The number average molecular weight of the above compound having one or more hydroxyl groups within the molecule is 300 to 10,000, and preferably 300 to 6,000. Note that the number average molecular weight and the weight average molecular weight can be measured by column chromatography.

[0246] As the compound having a basic group within the molecule which can react with an isocyanate group constituting the above polyurethane-based dispersant, there is no particular limitation, and at least one compound selected from the group consisting of polyols having N,N-disubstituted amino groups or heterocyclic nitrogen atoms, polythiols, and amines is preferred. As these compounds, compounds conventionally used in the technical field of dispersants can be used. These compounds have Zerewitinoff active hydrogen atoms and at least one basic group containing nitrogen atoms. As such compounds, for example, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,4-butanediamine, 2-dimethylaminoethanol, 1-(2-aminoethyl)-piperazine, 2-(1-pyrrolidinyl)-ethylamine, 4-amino-2-methoxy-pyrimidine, 4-(2-aminoethyl)-pyridine, 1-(2-hydroxyethyl)-piperazine, 4-(2-hydroxyethyl)-morpholine, 2-mercapto-pyrimidine, 2-mercapto-benzimidazole, 2-amino-6-methoxy-benzothiazole, N,N-diallyl melamine, 3-amino-1,2,4-triazole, 1-(2-hydroxyethyl)-imidazole, 3-mercapto-1,2,4-triazole, and the like can be given. Of these, amines having heterocyclic nitrogen atoms are preferred.

[0247] As the reaction in the synthesis of the above polyurethane-based dispersant, there is no particular limitation, and it can be performed using a method known in the past. In addition, the amine value of the above polyurethane-based dispersant is also 0 to 55 mgKOH / g, and preferably 5 to 40 mgKOH / g.

[0248] In addition, as the commercially available product of the above polyurethane-based dispersant, Disperbyk-161 (amine value 11 mgKOH / g, manufactured by BYK-Chemie), Disperbyk-162 (amine value 13 mgKOH / g, manufactured by BYK-Chemie), Disperbyk-167 (amine value 13 mgKOH / g, manufactured by BYK-Chemie), Disperbyk-182 (amine value 13 mgKOH / g, manufactured by BYK-Chemie), and the like can be given.

[0249] As the dispersant, the above acrylic-based dispersant is preferred.

[0250] The negative resist composition of the present application preferably further contains a polymerizable compound (E) and a polymerization initiator (F). Thereby, the curing property at the time of exposure and the like is exerted.

[0251] < Polymerizable compound (E) >

[0252] The polymerizable compound (E) is a compound which can be polymerized by active radicals and acids and the like generated from the polymerization initiator (F) described later, and for example, a compound having a polymerizable ethylenic unsaturated bond and the like can be given, and a (meth) acrylate compound can be preferably given.

[0253] Among them, as the polymerizable compound (E), a polymerizable compound having 3 or more (preferably 4 to 10, further preferably 5 to 8) ethylenic unsaturated bonds, and further preferably an ester of an alcohol (for example, pentaerythritol, a condensate thereof, or a modified product thereof) having 3 or more (preferably 4 to 10, further preferably 5 to 8) OH groups and (meth)acrylic acid are preferable. As such a polymerizable compound, for example, 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) isocyanurate, 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, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like are exemplified. Among them, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like are preferable.

[0254] The weight average molecular weight of the polymerizable compound (E) is preferably 150 to 2900, more preferably 250 to 1500.

[0255] The content of the polymerizable compound (E) with respect to the solid content of the negative resist composition is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, further preferably 17 to 55% by mass. When the content of the above-mentioned polymerizable compound (E) is within the above-mentioned range, sufficient curing proceeds, the residual film rate at the time of development increases, and there is a tendency that the adhesion of the colored pattern becomes good without occurrence of undercut, and thus it is preferable.

[0256] <Polymerization initiator (F)>

[0257] As the above-mentioned polymerization initiator (F), there is no particular limitation as long as it is a compound capable of generating an active radical, an acid, or the like under the action of light or heat and initiating polymerization, and a publicly known polymerization initiator can be used.

[0258] As the polymerization initiator (F), a compound generating an active radical under the action of light is preferable, and an alkyl phenone compound, a triazine compound, an acyl phosphine oxide compound, an oxime compound, and a bisimidazole compound are more preferable.

[0259] The above-mentioned alkyl phenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring can have a substituent. In the formula, * indicates a bonding site.

[0260]

[0261] As the compound having a partial structure represented by formula (d2), for example, 2-methyl-2-morpholino-l-(4-methylthiophenyl)propan-l-one, 2-dimethylamino-l-(4-morpholinophenyl)-2-benzylbutan-l-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-l-[4-(4-morpholinyl)phenyl]butan-l-one, and the like can be given. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (all of which are manufactured by BASF Corporation) can be used.

[0262] As the compound having a partial structure represented by formula (d3), for example, 2-hydroxy-2-methyl-l-phenylpropan-l-one, 2-hydroxy-2-methyl-l-[4-(2-hydroxyethoxy)phenyl]propan-l-one, l-hydroxycyclohexyl phenyl ketone, an oligomer of 2-hydroxy-2-methyl-l-(4-isopropenylphenyl)propan-l-one, α,α-diethoxyacetophenone, benzil dimethyl ketal, and the like can be given.

[0263] As the above-mentioned alkylphenone compound, in terms of sensitivity, a compound having a partial structure represented by formula (d2) is preferred, and 2-methyl-2-morpholino-l-(4-methylthiophenyl)propan-l-one and 2-dimethylamino-l-(4-morpholinophenyl)-2-benzylbutan-l-one are more preferred.

[0264] As the above-mentioned triazine compound, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-l,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-l,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-l,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-l,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-l,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-l,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-l,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-l,3,5-triazine, and the like can be given.

[0265] As the above-mentioned acylphosphine oxide compound, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like can be given. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can be used.

[0266] The oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * indicates a bonding site.

[0267]

[0268] As the oxime compound, N-benzoyloxy-l-(4-phenylthiophenyl)butane-l-ketone-2-imine, N-benzoyloxy-l-(4-phenylthiophenyl)octane-l-ketone-2-imine, N-benzoyloxy-l-(4-phenylthiophenyl)-3-cyclopentylpropane-l-ketone-2-imine, N-acetyloxy-l-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-l-imine, N-acetyloxy-l-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxocyclopentylmethoxy)benzoyl}-9H-carbazol-3-yl]ethane-l-imine, N-acetyloxy-l-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-l-imine, N-benzoyloxy-l-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-l-ketone-2-imine, and the like can be given. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (both of which are manufactured by BASF Corporation), N-1919 (manufactured by ADEKA Corporation), and the like can also be used. Among them, N-benzoyloxy-l-(4-phenylthiophenyl)butane-l-ketone-2-imine, N-benzoyloxy-l-(4-phenylthiophenyl)octane-l-ketone-2-imine, and N-benzoyloxy-l-(4-phenylthiophenyl)-3-cyclopentylpropane-l-ketone-2-imine are preferred. When these oxime compounds are used in the case where the negative resist composition of the present application is prepared into a blue negative resist composition, there is a tendency that the brightness of the obtained color filter becomes higher.

[0269] As the above-mentioned bisimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (for example, refer to Japanese Patent Application Publication No. 6-75372, Japanese Patent Application Publication No. 6-75373, and the like), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxylphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxylphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxylphenyl)bisimidazole (for example, refer to Japanese Patent Application Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, and the like), a bisimidazole compound in which the phenyl group at the 4,4',5,5'-position is substituted with a carbalkoxy group (for example, refer to Japanese Patent Application Publication No. 7-10913, and the like), and the like can be mentioned. 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, and 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole can be preferably mentioned.

[0270] Further, as the polymerization initiator (F), benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like benzoin compounds; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, and the like quinone compounds; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, a titanocene compound, and the like can be mentioned. These are preferably used in combination with the polymerization initiation aid (F1) (particularly, an amine) described later.

[0271] As the acid generator which generates an acid under the action of light, for example, onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetyloxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetyloxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and the like, nitrobenzyltoluenesulfonates, benzoin toluenesulfonates, and the like can be mentioned.

[0272] The content of the polymerization initiator (F) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (C) (including the resin (C') described later) and the polymerizable compound (E) in the negative resist composition of the present application. When the content of the photopolymerization initiator is within the above range, high sensitivity is achieved and the exposure time can be shortened, thereby improving the productivity.

[0273] The negative resist composition of the present application can further contain at least one selected from a polymerization initiation aid (F1) and a leveling agent (G).

[0274] The polymerization initiation aid (F1) is a compound or a sensitizer for promoting the polymerization of the polymerizable compound initiated by the polymerization initiator, and is generally used in combination with the polymerization initiator (F).

[0275] The negative resist composition of the present application can further contain a polymerization initiation aid (F1). The polymerization initiation aid (F1) is a compound or a sensitizer for promoting the polymerization of the polymerizable compound initiated by the polymerization initiator, and is generally used in combination with the polymerization initiator (F).

[0276] As the polymerization initiation aid (F1), an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxylic acid compound, and the like can be given.

[0277] As the amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-diethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, and the like can be given, of which 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by DKS Co., Ltd.) can also be used.

[0278] As the alkoxyanthracene compound, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like can be given.

[0279] As the thioxanthone compound, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like can be given.

[0280] As the above carboxylic acid compound, benzylthioacetic acid, methylbenzylthioacetic acid, ethylbenzylthioacetic acid, methylethylbenzylthioacetic acid, dimethylbenzylthioacetic acid, methoxybenzylthioacetic acid, dimethoxybenzylthioacetic acid, chlorobenzylthioacetic acid, dichlorobenzylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like can be given.

[0281] When the polymerization initiator aid (F1) is used, the amount thereof used is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (C) (including the resin (C') described later when the resin (C') is included) and the polymerizable compound (E) in the negative resist composition of the present application. When the amount of the polymerization initiator aid (F1) is within this range, it is possible to further form a pattern with high sensitivity, and there is a tendency that the productivity of the pattern is improved.

[0282] <Leveling agent (G)>

[0283] As the leveling agent (G), an organosilicon surfactant, a fluorine-based surfactant, and an organosilicon surfactant having a fluorine atom, and the like can be given. They can have a polymerizable group in a side chain.

[0284] As the organosilicon surfactant, a surfactant having a siloxane bond in the molecule, and the like can be given. Specifically, Toray Silicone (trade name) DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan KK), and the like can be given.

[0285] As the above-mentioned fluorine-based surfactant, a surfactant having a fluorocarbon chain, etc. can be given. Specifically, FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Corp.), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi Materials Electronic Materials Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemicals Ltd.), etc. can be given.

[0286] As the above-mentioned organosilicon-based surfactant having a fluorine atom, a surfactant having a siloxane bond and a fluorocarbon chain in the molecule, etc. can be given. Specifically, MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC Corp.), etc. can be given.

[0287] The content of the leveling agent (G) is preferably 0.001 to 0.2 mass%, preferably 0.002 to 0.1 mass%, and more preferably 0.005 to 0.05 mass% with respect to the total amount of the negative resist composition of the present application. When the content of the leveling agent (G) is within the above range, the planarity of the color filter is made good.

[0288] <Other Components>

[0289] An additive (hereinafter, referred to as "other components") known in the technical field, such as a filler, another high molecular compound, an adhesion promoter, an antioxidant, a light stabilizer, a chain transfer agent, etc. can be contained as needed.

[0290] <Manufacturing Method of Negative Resist Composition>

[0291] The negative resist composition can be obtained by, for example, dispersing the colorant (A) and the resin (C) in the solvent (B) containing the dispersant (D) to obtain a colorant dispersion liquid, and mixing the polymeric compound (E), the polymerization initiator (F), the leveling agent (G), etc. as needed to obtain the negative resist composition.

[0292] The dispersion treatment refers to mixing the particles of the colorant (A), the resin (C), and the like to be in a dispersed state. The particles are pulverized to be very small by this dispersion treatment. In addition, the dispersed state refers to a state in which the particles float in the solvent (B) in the mixed solution.

[0293] The content of the colorant (A) in the colorant dispersion liquid 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, with respect to the total amount of the colorant dispersion liquid.

[0294] In addition, 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, with respect to the total amount of the colorant dispersion liquid.

[0295] When the colorant dispersion liquid contains the resin (C), the content of the resin (C) is preferably 1% by mass or more, more preferably 2% by mass or more, and is preferably 15% by mass or less, more preferably 7% by mass or less, with respect to the total amount of the colorant dispersion liquid. When the content of the resin (C) is within the above range, there is a tendency that the dispersed state becomes stable.

[0296] The content of the dispersant (D) in the colorant dispersion liquid is preferably 1% by mass or more, more preferably 2% by mass or less, and is preferably 20% by mass or less, more preferably 10% by mass or less, with respect to the total amount of the colorant dispersion liquid. When the content of the dispersant (D) is within the above range, there is a tendency that the dispersed state becomes stable.

[0297] The temperature at the time of dispersing the colorant (A) in the solvent (B) and at the time of mixing the dispersion is preferably 120°C or lower, more preferably 70°C or lower. The lower limit of the temperature at the time of dispersing is not particularly limited, and is usually 20°C. The dispersion time is preferably 0.5 hours or more, more preferably 2 hours or more, and is preferably 48 hours or less, more preferably 20 hours or less. As a device used in the dispersion, for example, a roll mill, a high-speed stirring device, a bead mill, a ball mill, a sand mill, a Paint Conditioner, an ultrasonic disperser, a high-pressure disperser, and the like can be given. The obtained colorant dispersion liquid is preferably filtered using a filter having a pore diameter of about 1.0 to 5.0 μm.

[0298] When the polymerizable compound (E) and the polymerization initiator (F) are added to the above-described colorant dispersion liquid, a resin ("resin (C')) is preferably further added. As the resin (C'), the same resins as the resin (C) can be given. The resin (C') can be the same resin as the resin (C) or a different kind of resin from the resin (C). As the resin (C'), the resin [Kl], the resin [K2], the resin [K5], and the resin [K6] are preferable, the resin [K5] and the resin [K6] are more preferable, and the resin [K6] is further preferable.

[0299] The total content of the resin (C) and the resin (C') with respect to the total amount of the solid components is preferably 7 to 65 mass%, more preferably 10 to 60 mass%, further preferably 13 to 60 mass%, and particularly preferably 13 to 55 mass%. When the content of the resin is within the above-described range, there is a tendency that the resolution of the colored pattern and the residual film rate of the colored pattern are improved.

[0300] When the polymerizable compound (E) and the polymerization initiator (F) are added to the above-described colorant dispersion liquid, a solvent (B') is preferably further added.

[0301] As the solvent (B'), the same solvents as the solvent (B) can be given. From the viewpoint of coatability and dryability, an organic solvent having a boiling point of 120°C to 180°C at 1 atm is preferable, and more preferably, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionic acid ethyl ester, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, 3-methoxybutyl acetate, 3-methoxy-l-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, and the like are preferable, and further preferably, propylene glycol monomethyl ether acetate, ethyl lactate, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol ethyl methyl ether, 3-methoxybutyl acetate, 3-methoxy-l-butanol, 3-ethoxypropionic acid ethyl ester, and the like are preferable.

[0302] The total content of the solvent (B) and the solvent (B') in the negative resist composition with respect to the total amount of the negative resist composition is preferably 40 to 95 mass%, and more preferably 45 to 92 mass%. In other words, the solid components of the negative resist composition are preferably 5 to 60 mass%, and more preferably 8 to 55 mass%. When the content of the solvent is within the above-described range, the planarity at the time of coating becomes good, and furthermore, the color density does not become insufficient when a color filter is formed, and thus there is a tendency that the display characteristics become good.

[0303] As a method of producing a colored pattern of a color filter from the negative resist composition of the present application, a photolithography method, an inkjet method, a printing method, and the like can be given. Among them, the photolithography method is preferred. The photolithography method is a method of forming a composition layer by applying the above-mentioned negative resist composition to a substrate and drying it, and exposing the composition layer through a photomask, and developing it. In the photolithography method, a colored coating film which is a cured product of the above-mentioned composition layer can be formed without using a photomask at the time of exposure and / or without developing.

[0304] The film thickness of the color filter (cured film) is preferably 20 μm or less, more preferably 6 μm or less, further preferably 3 μm or less, more further preferably 1.5 μm or less, particularly preferably 0.5 μm or less, preferably 0.1 μm or more, more preferably 0.2 μm or more, further preferably 0.3 μm or more.

[0305] As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass coated with silicon dioxide, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, a substrate on which an aluminum, silver, silver / copper / palladium alloy thin film, or the like is formed on the above-mentioned substrate can be used. Other color filter layers, resin layers, transistors, circuits, and the like can be formed on these substrates. A substrate subjected to HMDS treatment on a silicon substrate can also be used.

[0306] The formation of each color pixel based on the photolithography method can be performed using a publicly known or conventional device and conditions. For example, it can be produced as follows. First, the negative resist composition is applied to a substrate, and heated drying (pre-baking) and / or reduced pressure drying is performed to remove volatile components such as solvents and dry to obtain a smooth composition layer. As the application method, a spin coating method, a slit coating method, a slit spin coating method, and the like can be given. The temperature at the time of heated drying is preferably 30°C to 120°C, more preferably 50°C to 110°C. In addition, as the heating time, 10 seconds to 60 minutes is preferred, more preferably 30 seconds to 30 minutes. At the time of reduced pressure drying, it is preferred to be performed at a temperature in the range of 20 to 25°C under a pressure of 50 to 150 Pa. The film thickness of the composition layer is not particularly limited, and it can be appropriately selected depending on the film thickness of the target color filter.

[0307] Next, the composition layer is exposed through a photomask used to form the target color pattern. The pattern on the photomask is not particularly limited; a pattern corresponding to the target application is used. As the light source used for exposure, a light source that generates light with wavelengths of 250–450 nm is preferred. For example, light with wavelengths less than 350 nm can be cut off using a filter that cuts off this wavelength region, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength regions. Specifically, examples include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps. To ensure uniform illumination of the entire exposure surface with parallel light and precise alignment of the photomask and substrate, a reduction projection exposure apparatus or a close-proximity exposure apparatus, such as a mask aligner and a stepper, is preferred.

[0308] The exposed composite layer is brought into contact with a developing solution for development, thereby forming a colored pattern on the substrate. The unexposed portions of the composite layer are dissolved and removed by the developing solution. As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferred. 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. Furthermore, the developing solution may contain a surfactant. The developing method can be any of the following: spin-dip, immersion, or spray. Furthermore, the substrate can be tilted at any angle during development.

[0309] After development, it is preferable to wash with water.

[0310] Preferably, the obtained colored pattern is further subjected to a post-baking process. The post-baking temperature is preferably 80–250°C, more preferably 100–245°C. The post-baking time is preferably 1–120 minutes, more preferably 2–30 minutes.

[0311] The resulting colored pattern and colored coating are useful as color filters, which are used in display devices (e.g., liquid crystal displays, organic EL devices, etc.), electronic paper, solid-state imaging elements, etc.

[0312] Example

[0313] The following examples illustrate the invention in more detail, but the invention is not limited to these examples. Appropriate modifications can be made to suit the above and following spirit, and all such modifications are included within the technical scope of the invention. Unless otherwise specified, "%" and "parts" in the examples refer to mass percentage and mass parts, respectively. The structure of the compound was determined by mass analysis (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

[0314] <Synthesis of Dyes>

[0315] Synthesis Example 1

[0316] Pink Base (manufactured by TAIYO Fine Chemicals Co., Ltd.) 50.0 parts, N-methylpyrrolidone (NMP) (manufactured by FUJIFILM Wako Pure Chemical Corporation) 300 parts, iodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.) 247.0 parts, potassium carbonate (manufactured by FUJIFILM Wako Pure Chemical Corporation) 120.3 parts represented by formula (1) were mixed at room temperature, and warmed to 80°C while stirring for 4 hours. After the reaction solution was cooled to room temperature, iodomethane was distilled off under reduced pressure, and 1 equivalent of hydrochloric acid 3300 parts was added to the obtained slurry. The obtained precipitate was taken as a residue of suction filtration, washed with ion exchange water 1000 parts, and dried to obtain a compound represented by formula (2) 50.6 parts. The yield was 97%.

[0317]

[0318] Confirmation of the compound represented by formula (2)

[0319] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 603.2

[0320] Exact molecular weight: 602.2

[0321] Synthesis Example 2

[0322] The compound represented by formula (3) 10.0 parts, 2,4,6-trimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 20.0 parts, NMP (manufactured by FUJIFILM Wako Pure Chemical Corporation) 60 parts were mixed at room temperature, and warmed to 160°C while stirring for 7 hours. After the reaction solution was cooled to room temperature, 1 equivalent of hydrochloric acid 120 parts was added, and the obtained precipitate was taken as a residue of suction filtration, washed with ion exchange water 100 parts, and dried to obtain a compound represented by formula (4) 12.4 parts. The yield was 83%.

[0323]

[0324] Confirmation of the compound represented by formula (4)

[0325]

[0326] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 603.8

[0327] Exact molecular weight: 602.2

[0328] Synthesis Example 3

[0329] Using the same method as in Synthesis Example 2, except that 2,4,6-trimethylaniline was changed to 5-methoxy-2-methylaniline, synthesis was performed to obtain a compound represented by Formula (5). The yield was 78%.

[0330] Determination of the compound represented by Formula (5)

[0331]

[0332] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 607.2

[0333] Exact molecular weight: 606.2

[0334] [Synthesis Example 4]

[0335] Using the same method as in Synthesis Example 2, except that 2,4,6-trimethylaniline was changed to 6-methoxy-2-methylaniline, synthesis was performed to obtain a compound represented by Formula (6). The yield was 31%.

[0336] Determination of the compound represented by Formula (6)

[0337]

[0338] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 607.2

[0339] Exact molecular weight: 606.2

[0340] [Synthesis Example 5]

[0341] A compound represented by Formula (7) 2.0 parts, N-methylpyrrolidone (NMP) (manufactured by FUJIFILM Wako Pure Chemical Corporation) 20.0 parts, iodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.) 16.4 parts, potassium carbonate (manufactured by FUJIFILM Wako Pure Chemical Corporation) 8.0 parts were mixed at room temperature, warmed to 80°C, and stirred for 16 hours. After the reaction solution was cooled to room temperature, iodomethane was distilled off under reduced pressure, and 1 equivalent of hydrochloric acid 220.0 parts was added to the obtained slurry. The obtained precipitate was obtained as a residue of suction filtration, washed with ion exchange water 40 parts, and dried to obtain a compound represented by Formula (8) 1.0 part. The yield was 49%.

[0342] Determination of the compound represented by Formula (7)

[0343]

[0344] (Mass Analysis) Ionization Mode = ESI + m / z = [M + H] + 519.1

[0345] Precise molecular weight: 518.1

[0346] Determination of the compound represented by equation (8)

[0347]

[0348] (Mass Analysis) Ionization Mode = ESI + m / z = [M + H] + 547.2

[0349] Precise molecular weight: 546.2

[0350] [Synthesis Example 6]

[0351] 40.6 parts of the compound represented by formula (3) and 8 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in the presence of 50 parts of 1-methyl-2-pyrrolidone under light-shielding conditions and stirred at 30°C for 3 hours. After cooling the resulting reaction solution to room temperature, it was added to a mixture of 400 parts of water and 20 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour, resulting in crystal precipitation. The precipitated crystals were collected as a residue by vacuum filtration and dried to obtain 44 parts of the compound represented by formula (I-1-A).

[0352]

[0353] 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. After cooling the resulting reaction solution to room temperature, it was 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).

[0354] Determination of the compound represented by formula (I-1)

[0355]

[0356] (Mass Analysis) Ionization Mode = ESI + m / z = [M + H] + 599.2

[0357] Precise molecular weight: 598.2

[0358] [Synthesis Example 7]

[0359] To a flask equipped with a cooling tube and a stirring device were added 4.1 parts of the compound represented by the formula (A-6-IM1), 9.8 parts of methanol, and 3.5 parts of an 8% sodium hydroxide aqueous solution, and the mixture was stirred at room temperature for 6 hours. The resulting reaction solution was added to 30 parts of 2N hydrochloric acid, and the mixture was stirred at room temperature for 30 minutes, and then crystals were precipitated. The precipitated crystals were filtered off, washed with ion exchange water, and dried under reduced pressure at 60°C to obtain 1.0 parts of the compound (A-6-IM2).

[0360] Determination of the compound represented by the formula (A-6-IM2)

[0361]

[0362] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 803.5

[0363] Exact molecular weight: 802.3

[0364] To a flask equipped with a cooling tube and a stirring device were added 4.1 parts of the compound represented by the formula (A-6-IM1), 9.8 parts of methanol, and 3.5 parts of an 8% sodium hydroxide aqueous solution, and the mixture was stirred at room temperature for 6 hours. The resulting reaction solution was added to 30 parts of 2N hydrochloric acid, and the mixture was stirred at room temperature for 30 minutes, and then crystals were precipitated. The precipitated crystals were filtered off, washed with ion exchange water, and dried under reduced pressure at 60°C to obtain 1.0 parts of the compound (A-6-IM2).

[0365] Determination of the compound represented by the formula (A-6-IM2)

[0366]

[0367] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 747.5

[0368] Exact molecular weight: 746.3

[0369] 〔Synthesis Example 8〕

[0370] To a flask equipped with a cooling tube and a stirring device, 15 parts of the pigment represented by A0-3, 150 parts of chloroform and 8.9 parts of N,N-dimethylformamide were charged, and kept at 20°C or lower with stirring, while adding 10.9 parts of thionyl chloride dropwise. After the completion of the dropwise addition, the temperature was raised to 50°C, and the reaction was allowed to proceed for 5 hours at a temperature of 50°C, and then cooled to 20°C. The cooled reaction solution was kept at 20°C or lower with stirring, while adding a mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine dropwise. Thereafter, the reaction was allowed to proceed for 5 hours at a temperature of 20°C with stirring. Subsequently, the obtained reaction mixture was distilled to remove the solvent using a rotary evaporator, and a small amount of methanol was added with vigorous stirring. This mixture was added to a mixture of 375 parts of ion exchange water with stirring, and crystals were precipitated. The precipitated crystals were filtered, washed thoroughly with ion exchange water, and dried at 60°C under reduced pressure to obtain 11.3 parts of the dye A3 (a mixed dye of dyes A3-1 to A3-8).

[0371]

[0372] (In the formula (A3), R g , R h and R i each independently represent a hydrogen atom, -SO3 - , -SO3H or -SO2NHRa. Ra represents a 2-ethylhexyl group.)

[0373]

[0374] [Synthesis Example 9]

[0375] A compound represented by the formula (9) was obtained by using the same method as that of the synthesis example 2, except that 2,4,6-trimethylaniline was changed to o-toluidine. The yield was 90%.

[0376] Determination of the compound represented by the formula (9)

[0377]

[0378] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 575.2

[0379] Exact molecular weight: 574.2

[0380] [Synthesis Example 10]

[0381] A compound represented by formula (3) 4.00 parts, 2-aminobiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 parts, and N-methylpyrrolidone (manufactured by FUJIFILM Wako Pure Chemical Corporation) 24.0 parts were mixed at room temperature, warmed to 170°C, and stirred for 9 hours. After the reaction solution was cooled to room temperature, 1 equivalent of hydrochloric acid 48.0 parts was added, and the resulting precipitate was obtained as a residue of suction filtration, and further washed with 1 equivalent of hydrochloric acid 96.0 parts. To the resulting residue, acetone 267 parts and methanol 267 parts were added, warmed to 50°C, and stirred for 1 hour, and the precipitate was obtained as a residue of suction filtration. The resulting residue was dried to obtain a compound represented by formula (11) 4.67 parts. The yield was 71%.

[0382] Determination of the compound represented by formula (11)

[0383]

[0384] (Mass analysis) Ionization mode = MALDI-TOF + : m / z = [M+H] + 671.1

[0385] Exact molecular weight: 670.2

[0386] [Synthesis Example 11]

[0387] A compound represented by formula (3) 4.00 parts, 3-aminobiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 parts, and N-methylpyrrolidone (manufactured by FUJIFILM Wako Pure Chemical Corporation) 24.0 parts were mixed at room temperature, warmed to 170°C, and stirred for 9 hours. After the reaction solution was cooled to room temperature, 1 equivalent of hydrochloric acid 48.0 parts was added, and the resulting precipitate was obtained as a residue of suction filtration, and further washed with 1 equivalent of hydrochloric acid 96.0 parts. To the resulting residue, acetone 300 parts and methanol 300 parts were added, warmed to 50°C, and stirred for 1 hour, and the precipitate was obtained as a residue of suction filtration. The resulting residue was dried to obtain a compound represented by formula (12) 5.13 parts. The yield was 78%.

[0388] Determination of the compound represented by formula (12)

[0389]

[0390] (Mass analysis) Ionization mode = MALDI-TOF + : m / z = [M+H] + 671.1

[0391] Exact molecular weight: 670.2

[0392] [Synthesis Example 12]

[0393] A compound represented by formula (3) 4.00 parts, 4-tert-butylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 8.84 parts, and N-methylpyrrolidone (manufactured by FUJIFILM Wako Pure Chemical Corporation) 24.0 parts were mixed at room temperature, warmed to 170°C, and stirred for 9 hours. After the reaction solution was cooled to room temperature, 1 equivalent of hydrochloric acid 48.0 parts was added, and the resulting precipitate was obtained as a residue of suction filtration, and further washed with 1 equivalent of hydrochloric acid 96.0 parts. To the resulting residue, acetone 357 parts and methanol 357 parts were added, warmed to 50°C, and stirred for 1 hour, and the precipitate was obtained as a residue of suction filtration. The resulting residue was dried to obtain a compound represented by formula (13) 5.59 parts. The yield was 90%.

[0394] Determination of the compound represented by formula (13)

[0395]

[0396] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 631.2

[0397] Exact molecular weight: 630.3

[0398] [Synthesis Example 13]

[0399] A compound represented by formula (3) 4.00 parts, 3,5-di-tert-butylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 parts, and N-methylpyrrolidone (manufactured by FUJIFILM Wako Pure Chemical Corporation) 24.0 parts were mixed at room temperature, warmed to 170°C, and stirred for 9 hours. After the reaction solution was cooled to room temperature, 1 equivalent of hydrochloric acid 48.0 parts was added, and the resulting precipitate was obtained as a residue of suction filtration, and further washed with 1 equivalent of hydrochloric acid 96.0 parts. To the resulting residue, acetone 264 parts and methanol 264 parts were added, warmed to 50°C, and stirred for 1 hour, and the precipitate was obtained as a residue of suction filtration. The resulting residue was dried to obtain a compound represented by formula (14) 4.70 parts. The yield was 64%.

[0400] Determination of the compound represented by formula (14)

[0401]

[0402] (Mass analysis) Ionization mode = MALDI-TOF + : m / z = [M+H] + 743.5

[0403] Exact molecular weight: 742.4

[0404] [Synthesis Example 14]

[0405] A compound represented by formula (15) was synthesized according to the literature (Chun Liu, Xiaoxiao Song, Qijian Ni and Jieshan Qiu; ARKIVOC, 2012, 9, 62-75.). Then, a compound represented by formula (3) 4.00 parts, 2,6-diphenylphenylamine 9.69 parts, zinc chloride (manufactured by FUJIFILM Wako Pure Chemical Corporation) 2.69 parts, and sulfolane (manufactured by Tokyo Chemical Industry Co., Ltd.) 24.0 parts were mixed at room temperature, warmed to 250°C, and stirred for 4 hours. After the reaction solution was cooled to room temperature, 1 equivalent of hydrochloric acid 48.0 parts was added, and the resulting precipitate was obtained as a residue of suction filtration, and further washed with toluene 24.0 parts, N,N-dimethylformamide 18.0 parts, and N,N-dimethylformamide 20.0 parts in this order. The resulting residue was dried to obtain a compound represented by formula (15) 5.18 parts. The yield was 64%.

[0406] Determination of the compound represented by formula (15)

[0407]

[0408] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 823.3

[0409] Exact molecular weight: 822.3

[0410] 〔Synthesis Example 15〕

[0411] A compound represented by formula (3) 10.0 parts, 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 16.5 parts, and N-methylpyrrolidone (manufactured by FUJIFILM Wako Pure Chemical Corporation) 70.0 parts were mixed at room temperature, warmed to 80°C, and stirred for 2 hours. After the reaction solution was cooled to room temperature, 1 equivalent of hydrochloric acid 140 parts was added, and the resulting precipitate was obtained as a residue of suction filtration, and further washed with 1 equivalent of hydrochloric acid 280 parts. The resulting residue was dried to obtain a compound represented by formula (16) 9.06 parts. The yield was 75%.

[0412] Determination of the compound represented by formula (16)

[0413]

[0414] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 490.2

[0415] Exact molecular weight: 489.1

[0416] A mixture of the compound represented by formula (16) 4.00 parts, aniline (manufactured by FUJIFILM Wako Pure Chemical Corporation) 3.80 parts and N-methylpyrrolidone (manufactured by FUJIFILM Wako Pure Chemical Corporation) 24.0 parts was mixed at room temperature, warmed to 170°C and stirred for 3 hours. After the reaction solution was cooled to room temperature, 1 equivalent of hydrochloric acid 48.0 parts was added, and the resulting precipitate was obtained as a residue of suction filtration, and further washed with 1 equivalent of hydrochloric acid 96.0 parts and N,N-dimethylformamide 36.8 parts. The resulting residue was dried to obtain a compound represented by formula (17) 3.28 parts. The yield was 74%.

[0417] Determination of the compound represented by formula (17)

[0418]

[0419] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 547.2

[0420] Exact molecular weight: 546.2

[0421] [Synthesis Example 16]

[0422] A mixture of the compound represented by formula (16) 4.00 parts, 2,4-dimethoxyaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.25 parts and N-methylpyrrolidone (manufactured by FUJIFILM Wako Pure Chemical Corporation) 24.0 parts was mixed at room temperature, warmed to 170°C and stirred for 3 hours. After the reaction solution was cooled to room temperature, 1 equivalent of hydrochloric acid 48.0 parts was added, and the resulting precipitate was obtained as a residue of suction filtration, and further washed with 1 equivalent of hydrochloric acid 96.0 parts and N,N-dimethylformamide 42.4 parts. The resulting residue was dried to obtain a compound represented by formula (18) 2.88 parts. The yield was 58%.

[0423] Determination of the compound represented by formula (18)

[0424]

[0425] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 607.2

[0426] Exact molecular weight: 606.2

[0427] [Synthesis Example 17]

[0428] A mixture of the compound represented by formula (16) 4.00 parts, 4-methoxyaniline (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 5.03 parts and N-methylpyrrolidone (manufactured by Fuji Photo Film Co., Ltd. and Wako Pure Chemical Industries, Ltd.) 24.0 parts was mixed at room temperature, warmed to 170°C and stirred for 3 hours. After the reaction solution was cooled to room temperature, 1 equivalent of hydrochloric acid 48.0 parts was added, and the resulting precipitate was obtained as a residue of suction filtration, and further washed with 1 equivalent of hydrochloric acid 96.0 parts and N,N-dimethylformamide 41.9 parts. The resulting residue was dried to obtain a compound represented by formula (19) 5.00 parts. The yield was 69%.

[0429] Determination of the compound represented by formula (19)

[0430]

[0431] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 577.3

[0432] Exact molecular weight: 576.2

[0433] [Synthesis Example 18]

[0434] A mixture of the compound represented by formula (16) 4.00 parts, 3- aminobiphenyl (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 6.91 parts and N-methylpyrrolidone (manufactured by Fuji Photo Film Co., Ltd. and Wako Pure Chemical Industries, Ltd.) 24.0 parts was mixed at room temperature, warmed to 170°C and stirred for 5 hours. After the reaction solution was cooled to room temperature, 1 equivalent of hydrochloric acid 48.0 parts was added, and the resulting precipitate was obtained as a residue of suction filtration, and further washed with 1 equivalent of hydrochloric acid 96.0 parts and N,N-dimethylformamide 75.2 parts. The resulting residue was dried to obtain a compound represented by formula (20) 3.79 parts. The yield was 75%.

[0435] Determination of the compound represented by formula (20)

[0436]

[0437] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 623.2

[0438] Exact molecular weight: 622.2

[0439] [Synthesis Example 19]

[0440] A mixture of 4.00 parts of the compound represented by the 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.) was mixed at room temperature, warmed to 170°C, and stirred for 3 hours. After the reaction solution was cooled to room temperature, 48.0 parts of 1 equivalent of hydrochloric acid was added, and the resulting precipitate was obtained as a residue of suction filtration, and further washed with 96.0 parts of 1 equivalent of 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 the formula (21). The yield was 70%.

[0441] Determination of the compound represented by the formula (21)

[0442]

[0443] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 623.2

[0444] Exact molecular weight: 622.2

[0445] (Synthetic Example 20)

[0446] A mixture of 13.0 parts of the compound represented by the formula (3), 39.3 parts of 2,6-diphenylphenylamine, and 78.0 parts of N-methylpyrrolidone (manufactured by Fuji Photo Film Co., Ltd. and Wako Pure Chemical Industries, Ltd.) was mixed at room temperature, warmed to 85°C, and stirred for 5 hours. After the reaction solution was cooled to room temperature, 156 parts of 1 equivalent of hydrochloric acid was added, and the resulting precipitate was obtained as a residue of suction filtration, and further washed with 312 parts of 1 equivalent of hydrochloric acid. The resulting residue was dried to obtain 16.2 parts of the compound represented by the formula (22). The yield was 82%.

[0447] Determination of the compound represented by the formula (22)

[0448]

[0449] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 614.5

[0450] Exact molecular weight: 613.1

[0451] A mixture of the compound represented by formula (22) 4.00 parts, 2,6-xylylenediamine (manufactured by FUJIFILM Wako Pure Chemical Corporation) 3.95 parts, zinc chloride (manufactured by FUJIFILM Wako Pure Chemical Corporation) 1.78 parts, and sulfolane (manufactured by Tokyo Chemical Industry Co., Ltd.) 24.0 parts was mixed at room temperature, warmed to 250°C, and stirred for 3 hours. After the reaction solution was cooled to room temperature, 1 equivalent of hydrochloric acid 48.0 parts was added, and the resulting precipitate was obtained as a residue of suction filtration, and further washed with 1 equivalent of hydrochloric acid 96.0 parts and N,N-dimethylformamide 69.5 parts. The resulting residue was dried to obtain a compound represented by formula (23) 3.05 parts. The yield was 67%.

[0452]

[0453] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 699.2

[0454] Exact molecular weight: 698.2

[0455] [Synthesis Example 21]

[0456] A mixture of the compound represented by formula (22) 4.00 parts, 3-aminobiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.51 parts, and N-methylpyrrolidone (manufactured by FUJIFILM Wako Pure Chemical Corporation) 24.0 parts was mixed at room temperature, warmed to 170°C, and stirred for 6 hours. After the reaction solution was cooled to room temperature, 1 equivalent of hydrochloric acid 48.0 parts was added, and the resulting precipitate was obtained as a residue of suction filtration, and further washed with 1 equivalent of hydrochloric acid 96.0 parts and N,N-dimethylformamide 28.5 parts. The resulting residue was dried to obtain a compound represented by formula (24) 2.85 parts. The yield was 59%.

[0457]

[0458] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 747.2

[0459] Exact molecular weight: 746.2

[0460] [Synthesis Example 22]

[0461] A compound represented by formula (22) 4.00 parts, 2- aminobiphenyl (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 5.51 parts, and N-methylpyrrolidone (manufactured by Fuji Photo Film Co., Ltd. and Wako Pure Chemical Industries, Ltd.) 24.0 parts were mixed at room temperature, and the mixture was warmed to 170°C and stirred for 6 hours. After the reaction solution was cooled to room temperature, 1 equivalent of hydrochloric acid 48.0 parts was added, and the resulting precipitate was obtained as a residue by suction filtration, and further washed with 1 equivalent of hydrochloric acid 96.0 parts and N,N-dimethylformamide 49.2 parts. The resulting residue was dried to obtain a compound represented by formula (25) 2.88 parts. The yield was 59%.

[0462]

[0463] (Mass analysis) Ionization mode = ESI + : m / z = [M+H] + 747.2

[0464] Exact molecular weight: 746.2

[0465] <Synthesis of resin>

[0466] [Synthesis Example 23 Resin C-1]

[0467] Propylene glycol monomethyl ether acetate 276.8 g was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and stirred while being replaced with nitrogen, and warmed to 120°C. Next, 35.3 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator) was added to a monomer mixture composed of 2-ethylhexyl acrylate 92.4 g, glycidyl methacrylate 184.9 g, and dicyclopentyl methacrylate 12.3 g, and the resulting solution was added dropwise to the above flask from the dropping funnel over 2 hours. After the completion of the dropwise addition, the copolymerization reaction was performed by further stirring at 120°C for 30 minutes. Then, the inside of the flask was replaced with air, and acrylate 93.7 g, triphenylphosphine (catalyst) 1.5 g, and p-methoxyphenol (inhibitor) 0.8 g were added to the above addition copolymer solution, and the reaction was continued at 110°C for 10 hours, whereby the epoxy group was cleaved by the reaction of the epoxy group derived from glycidyl methacrylate with acrylate, and a polymerizable unsaturated bond was introduced into the side chain of the polymer. Next, succinic anhydride 24.2 g was added to the reaction system, and the reaction was continued at 110°C for 1 hour, whereby the hydroxyl group generated by the cleavage of the epoxy group was reacted with the succinic anhydride to introduce a carboxyl group into the side chain, and a polymer was obtained. Finally, propylene glycol monomethyl ether acetate 383.3 g was added to the reaction solution to obtain a polymer (resin (C-1)) solution having a polymer solid content of 40%. The weight average molecular weight Mw of the resulting copolymer (polymer; resin (C-1)) was 6.3 x 10 3The acid value of the solid component was 34 mg-KOH / g.

[0468] [Synthesis Example 24 Resin C-2]

[0469] A nitrogen atmosphere was created by flowing nitrogen into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, and propylene glycol monomethyl ether acetate 280 parts was introduced into the flask. The mixture was heated to 80°C while stirring. Next, a solution in which a mixture of acrylic acid 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-8-yl ester and acrylic acid 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-9-yl ester (1:1) 289 parts was dissolved in propylene glycol monomethyl ether acetate 125 parts was added dropwise to the flask over a period of about 5 hours using a dropping pump. On the other hand, a solution in which a polymerization initiator, 2,2'-azobis(2,4-dimethylvaleronitrile) 33 parts was dissolved in propylene glycol monomethyl ether acetate 235 parts was added dropwise to the flask over a period of about 6 hours using another dropping pump. After the dropwise addition was completed, the temperature was maintained at 80°C for 4 hours, and then the mixture was cooled to room temperature. A polymer solution was obtained, and the solid content of the polymer was 35.1%. The weight average molecular weight Mw of the copolymer (polymer; resin (C-2)) was 9200, the dispersity was 2.08, and the acid value of the solid component was 77 mg-KOH / g. The copolymer had the following structural units.

[0470]

[0471] (Preparation of Dispersion 1)

[0472] C.I. Pigment Red 122 8 parts, dispersant (BYK LPN-6919 manufactured by BYK Co.) 3.0 parts, the above resin (C-2) (solid component) 3.0 parts, propylene glycol monomethyl ether acetate 81 parts, and diacetone alcohol 5 parts were mixed, and 300 parts of 0.4 mm zirconia beads were added. The mixture was shaken for 1 hour using a paint shaker (manufactured by LAU Co.). Thereafter, the zirconia beads were removed by filtration to obtain dispersion 1.

[0473] (Preparation of Dispersion 2)

[0474] C.I. Pigment Red 122 was replaced with C.I. Pigment Violet 19, and dispersion 2 was obtained in the same manner as dispersion 1.

[0475] (Preparation of Dispersion 3)

[0476] Pink Base manufactured by TAIYO Fine Chemicals Co. was used instead of C.I. Pigment Red 122, and dispersion 3 was obtained in the same manner as dispersion 1.

[0477] (Production of Dispersion 4)

[0478] A compound obtained in Synthesis Example 1 was used instead of C.I. Pigment Red 122, and otherwise, similarly to Dispersion 1, Dispersion 4 was obtained.

[0479] (Production of Dispersion 5)

[0480] A compound obtained in Synthesis Example 2 was used instead of C.I. Pigment Red 122, and otherwise, similarly to Dispersion 1, Dispersion 5 was obtained.

[0481] (Production of Dispersion 6)

[0482] A compound obtained in Synthesis Example 3 was used instead of C.I. Pigment Red 122, and otherwise, similarly to Dispersion 1, Dispersion 6 was obtained.

[0483] (Production of Dispersion 7)

[0484] A compound obtained in Synthesis Example 4 was used instead of C.I. Pigment Red 122, and otherwise, similarly to Dispersion 1, Dispersion 7 was obtained.

[0485] (Production of Dispersion 8)

[0486] A compound obtained in Synthesis Example 5 was used instead of C.I. Pigment Red 122, and otherwise, similarly to Dispersion 1, Dispersion 8 was obtained.

[0487] (Production of Dispersion 9)

[0488] A compound obtained in Synthesis Example 9 was used instead of C.I. Pigment Red 122, and otherwise, similarly to Dispersion 1, Dispersion 9 was obtained.

[0489] (Production of Dispersion 10)

[0490] A compound obtained in Synthesis Example 10 was used instead of C.I. Pigment Red 122, and otherwise, similarly to Dispersion 1, Dispersion 10 was obtained.

[0491] (Production of Dispersion 11)

[0492] A compound obtained in Synthesis Example 11 was used instead of C.I. Pigment Red 122, and otherwise, similarly to Dispersion 1, Dispersion 11 was obtained.

[0493] (Production of Dispersion 12)

[0494] A compound obtained in Synthesis Example 12 was used instead of C.I. Pigment Red 122, and otherwise, similarly to Dispersion 1, Dispersion 12 was obtained.

[0495] (Preparation of Dispersion 13)

[0496] The compound obtained in Synthesis Example 13 was used instead of CI Pigment Red 122, and otherwise dispersion 13 was obtained in the same manner as dispersion 1.

[0497] (Preparation of Dispersion 14)

[0498] The compound obtained in Synthesis Example 14 was used instead of CI Pigment Red 122, and otherwise dispersion 14 was obtained in the same manner as dispersion 1.

[0499] (Preparation of Dispersion 15)

[0500] The compound obtained in Synthesis Example 15 was used instead of CI Pigment Red 122, and otherwise dispersion 15 was obtained in the same manner as dispersion 1.

[0501] (Preparation of Dispersion 16)

[0502] The compound obtained in Synthesis Example 16 was used instead of CI Pigment Red 122, and otherwise dispersion 16 was obtained in the same manner as dispersion 1.

[0503] (Preparation of Dispersion 17)

[0504] The compound obtained in Synthesis Example 17 was used instead of CI Pigment Red 122, and otherwise dispersion 17 was obtained in the same manner as dispersion 1.

[0505] (Preparation of Dispersion 18)

[0506] The compound obtained in Synthesis Example 18 was used instead of CI Pigment Red 122, and otherwise dispersion 18 was obtained in the same manner as dispersion 1.

[0507] (Preparation of Dispersion 19)

[0508] The compound obtained in Synthesis Example 19 was used instead of CI Pigment Red 122, and otherwise dispersion 19 was obtained in the same manner as dispersion 1.

[0509] (Preparation of Dispersion 20)

[0510] The compound obtained in Synthesis Example 20 was used to replace CI Pigment Red 122, and otherwise dispersion 20 was obtained in the same manner as dispersion 1.

[0511] (Preparation of Dispersion 21)

[0512] The compound obtained in Synthesis Example 21 was used to replace CI Pigment Red 122, and otherwise dispersion 21 was obtained in the same manner as dispersion 1.

[0513] (Preparation of Dispersion 22)

[0514] The compound obtained in Synthesis Example 22 was used to replace CI Pigment Red 122, and otherwise dispersion 22 was obtained in the same manner as dispersion 1.

[0515] [Examples 1-27, Comparative Examples 1 and 2]

[0516] The negative resist compositions of Examples 1 to 27 and Comparative Examples 1 and 2 were obtained by mixing dispersions 1 to 22, compounds (A-9) to (A-11) of Synthetic Examples 6 to 8, resin, polymerizable compound, polymerization initiator, leveling agent and solvent in such a manner as shown in Tables 3 and 4 below.

[0517] [Table 3]

[0518]

[0519] [Table 4]

[0520]

[0521] In Tables 3 and 4, each component represents the following compounds.

[0522] Compound (A-9): Compound from Synthesis Example 6

[0523] Compound (A-10): The compound from Synthesis Example 7

[0524] Compound (A-11): Compound of Synthesis Example 8 Resin (C-1): Resin (C-1) (Solid Component)

[0525] Polymerizable compound (E-1): Dipentaerythritol polyacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "A9550")

[0526] Polymerization initiator (F-1): N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine (PBG-327; O-acyl oxime compound; manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0527] Leveling agent (G-1): Polyether modified silicone oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.)

[0528] Solvent (B-1): Diacetone alcohol (DAA)

[0529] Solvent (B-2): Ethyl lactate (EL)

[0530] Solvent (B-3): Propylene glycol monomethyl ether acetate (PGMA)

[0531] <Production of cured film>

[0532] A 5 cm square glass substrate (EAGLE 2000; manufactured by CORNING) was coated with the negative resist composition by a spin coating method, and prebaked at 100°C for 3 minutes to form a colored composition layer. After cooling, the colored composition layer was subjected to light irradiation under an atmosphere at an exposure amount of 60 mJ / cm2(365 nm basis) using an exposure machine (TME-150RSK; manufactured by TOPCON). Thereafter, a postbake was performed at 230°C for 20 minutes in an oven to obtain a cured film. Note that the film thickness was adjusted so that the transmittance at the maximum absorption wavelength described later was 5% when the cured film was produced. 2

[0533] <Measurement of film thickness>

[0534] A film thickness measuring device (DEKTAK3; manufactured by ULTRASPEC) was used to measure the film thickness of the cured film on the glass substrate obtained. The results are shown in Tables 5 and 6.

[0535] <Measurement of maximum absorption wavelength and transmittance>

[0536] A colorimeter (OSP-SP-200; manufactured by OLYMPUS) was used to measure the spectral transmittance of the cured film on the glass substrate obtained. Specifically, the transmittance at wavelengths of 400 to 700 nm and the maximum absorption wavelength were measured, respectively. The maximum absorption wavelength, the transmittance at the maximum absorption wavelength (T(λmax)), the transmittance at a wavelength of 440 nm (T(440 nm)), and the transmittance at a wavelength of 620 nm (T(620 nm)) are shown in Tables 5 and 6. Furthermore, the ratio (mass parts) of each colorant contained in the cured film and the concentration (mass %) of the colorant contained in the cured film are shown in Tables 5 and 6.

[0537] [Table 5]

[0538]

[0539] [Table 6]

[0540]

[0541] ​From Tables 5 and 6, it is known that the negative resist compositions of Examples 1 to 27 contain the compound represented by the above formula (I), and the cured films obtained therefrom have a maximum absorption wavelength in the wavelength range of 500 nm to 580 nm, the transmittance at the wavelength is set to 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. On the other hand, the negative resist compositions of Comparative Examples 1 and 2 do not contain the compound represented by the above formula (I), and the cured films obtained therefrom have a transmittance at a wavelength of 440 nm of less than 80%.

[0542] Industrial applicability

[0543] A color filter having a high transmittance of light at a wavelength of 440 nm can be obtained from the negative resist composition of the present application.

Claims

1. A negative resist composition, characterized in that, Contains colorants and resins, The colorant contains xaton dye, the content of which is 60-100% by mass relative to the total amount of the colorant, and the xaton dye is a compound represented by formula (I). The spectroscopic spectrum of the cured film formed by the negative resist composition satisfies the following condition 1. Condition 1: The negative resist composition was spin-coated onto a 5cm square glass substrate, pre-baked at 100°C for 3 minutes to form a colored composition layer, and then cooled. The substrate was then exposed to atmospheric light at a reference wavelength of 60mJ / cm² at 365nm. 2 The coloring composition layer was irradiated with light of a certain exposure amount, and then baked in an oven at 230°C for 20 minutes to obtain a cured film. The obtained cured film has a maximum absorption wavelength in the wavelength range of 500nm to 580nm. When the transmittance at this wavelength is set to 5%, the transmittance at a wavelength of 440nm is greater than 80%, and the transmittance at a wavelength of 620nm is greater than 80%. In equation (I), R 2 and R 3 Each independently represents a hydrogen atom, methyl, ethyl, or -(CH2)3-CO-OH group, R 1 and R 4 Each of these groups independently represents 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-methyl-5-methoxyphenyl, 2-methyl-6-methoxyphenyl, phenyl, ethyl, -(CH2)3-Si(OCH3)3-yl, 2-methylphenyl, biphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, 2,6-diphenylphenyl, 2,4-dimethoxyphenyl, 4-methoxyphenyl, or the following groups. * indicates a bonding site. R 5 Indicates -SO3 - 、or -SO2NR 9 R 10 R 9 R represents a hydrogen atom. 10 It represents 2-ethylhexyl. R 6 and R 7 Represents a hydrogen atom. m represents an integer from 0 to 5. When m is 2 or higher, multiple R... 5 They can be the same or different. a represents an integer that is either 0 or 1. X represents a halogen atom.

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

3. The negative resist composition according to claim 2, wherein, The zeatin dye is a combination of two or more compounds selected from those represented by formula (I).

4. The negative resist composition according to claim 1 or 2, wherein, The colorant is either a dye or a combination of a dye and a red or purple pigment.

5. The negative resist composition according to claim 1 or 2, wherein, It further includes polymerizable compounds and polymerization initiators.

6. The negative resist composition according to claim 1 or 2, wherein, It can form a cured film with a thickness of less than 1.5 μm.

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 of claim 7.

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