Negative photoresist composition, color filter and display device

Abstract

The present invention provides a negative photoresist composition that can be used to manufacture color filters with high transmittance of light at a wavelength of 440 nm. The negative photoresist composition of the present invention comprises a colorant and a resin, wherein the colorant contains a dye, and the spectroscopic spectrum of the hardened film formed by the negative photoresist composition satisfies the following condition 1. [Condition 1] It has a maximum absorption wavelength in the wavelength range of 500nm to 580nm. When the transmittance of this wavelength is set to 5%, the transmittance of the wavelength 440nm is more than 80%, and the transmittance of the wavelength 620nm is more than 80%.

Description

Technical Field

[0001] This invention relates to a negative photoresist composition. Prior Technology

[0002] Coloring compositions are used in the manufacture of color filters used in liquid crystal display devices and the like. Among such coloring compositions, those containing quinacrine-based pigments are known (Patent Document 1). [Previous Technical Documents] [Patent Literature]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-109487 Summary of the Invention

[0004] [The problem the invention aims to solve]

[0005] Magenta is known to be obtained by mixing blue and red. However, in previous magenta color filters, the transmittance of light at a wavelength of 440 nm was insufficient. The object of the present invention is to provide a negative photoresist composition that can be used to manufacture color filters with higher transmittance of light at a wavelength of 440 nm. [Technical means to solve the problem]

[0006] This invention includes the following inventions. [1] A negative photoresist composition, characterized in that: it comprises a colorant and a resin, and The above coloring agents contain 𠮿 dye, The spectroscopic spectrum of the hardened film formed from the above negative photoresist composition satisfies the following condition 1. [Condition 1] It has a maximum absorption wavelength in the wavelength range of 500 nm to 580 nm. When the transmittance of this wavelength is set to 5%, the transmittance of the wavelength 440 nm is more than 80%, and the transmittance of the wavelength 620 nm is more than 80%. [2] The negative photoresist composition described in [1] has a transmittance of 90% or more at the wavelength of 620 nm. [3] The negative photoresist composition as described in [1] or [2], wherein the above-mentioned 𠮿 The dye is represented by formula (I).

[0007] In formula (I), R1 to R4 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, wherein the -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR11-; R5 represents -OH, -SO3-, -SO3H, -SO3-Z+, -CO2H, -CO2-Z+, -CO2R8, -SO3R8, or -SO2NR9R10; R6 and R7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer from 0 to 5; when m is 2 or greater, the complex number of R5s can be the same or different; a represents an integer of 0 or 1; X represents a halogen atom; Z+ represents +N(R11)4, Na+, or K+, where the four R11 values ​​can be the same or different; R8 represents a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, in which the hydrogen atoms can be replaced by halogen atoms; R9 and R10 independently represent a hydrogen atom or a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents. The -CH2- in the saturated hydrocarbon group can be replaced by -O-, -CO-, -NH-, or -NR8-. R9 and R10 can form heterocycles with adjacent nitrogen atoms, consisting of 3 to 10 member rings. R11 represents a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, or an aralkyl group with 7 to 10 carbon atoms. [4] The negative photoresist composition as described in [3], wherein the above-mentioned 𠮿 The dyes are represented by formula (Ia) and / or formula (Ib1).

[0008] In formula (Ia), Ra1 and Ra4 are each independently monovalent aromatic hydrocarbon groups that can have two or fewer monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms; Ra2 and Ra3 are each independently a hydrogen atom, a methyl group, or an ethyl group; R5~R7, m, a, and X represent the same meaning as above.

[0009] In formula (Ib1), Rb1 to Rb4 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. Rb1 to Rb4 contain at least one saturated hydrocarbon group or aromatic hydrocarbon group having a halogen atom, -OH, -OR8, -CO2H, -CO2R8, -SO3-, -SO3H, -SO3-Z+, -SR8, -SO2R8, -SO3R8, -SO2NR9R10, or -Si(OR12)(OR13)(OR14) as a substituent, or Rb1 to Rb4 contain at least one aromatic hydrocarbon group having three or more monovalent saturated aliphatic hydrocarbon groups with one to four carbon atoms as substituents. R12, R13, and R14 independently represent monovalent saturated hydrocarbon groups with 1 to 4 carbon atoms, where the hydrogen atoms in these saturated hydrocarbon groups can be replaced by halogen atoms. R5 ~ R10, m, a, and X represent the same meaning as above. [5] The negative photoresist composition as described in [4], wherein the above-mentioned 𠮿 The dye is selected from two or more of those represented by formula (Ib1) above, or a combination of those represented by formula (Ib1) above and those represented by formula (Ia) above. [6] The negative photoresist composition described in any of [1] to [5], wherein the colorant is only a dye, or a combination of a dye and a red pigment or a purple pigment. [7] The negative photoresist composition described in any of [1] to [6] further comprises a polymerizable compound and a polymerization initiator. [8] The negative photoresist composition described in any of [1] to [7] is capable of forming a hardened film with a thickness of less than 1.5 μm. [9] A color filter formed from a negative photoresist composition as described in any one of [1] to [8].

[10] A display device comprising a color filter as described in [9]. [Effects of the Invention]

[0010] The negative photoresist composition of the present invention can produce a color filter with high transmittance of light with a wavelength of 440 nm. Implementation

[0011] <Negative Photoresist Composition> The negative photoresist composition of the present invention comprises a colorant (A) and a resin (C), wherein the colorant (A) contains α. The spectroscopic spectrum of the dye, which is a hardened film formed from a negative photoresist composition, satisfies the following condition 1. [Condition 1] It has a maximum absorption wavelength in the wavelength range of 500 nm to 580 nm. When the transmittance of this wavelength is set to 5%, the transmittance of the wavelength 440 nm is more than 80%, and the transmittance of the wavelength 620 nm is more than 80%.

[0012] With the above configuration, a magenta color filter with high transmittance of light at a wavelength of 440 nm can be obtained. The so-called negative photoresist composition is a photoresist that has the property of leaving residue in the exposed portion after development due to its lower solubility in the developer. Furthermore, compared to positive photoresist compositions with higher solubility in the developer, negative photoresist compositions tend to have a wider range of process conditions from exposure to development for modifying patterns to the desired size range, and are therefore superior.

[0013] The spectroscopic spectrum of the aforementioned hardened film can be obtained by the following method: a hardened film is fabricated on a glass substrate under the following conditions, and the spectrum is measured using a colorimeter. An example of a colorimeter is the OSP-SP-200 (manufactured by Olympus Corporation). [Method for making a hardened film] A negative photoresist composition was spin-coated onto a 5 cm square glass substrate, followed by pre-baking at 100°C for 3 minutes to form a colored composition layer. After cooling, the colored composition layer was irradiated with light at an exposure dose of 60 mJ / cm² (365 nm reference) under atmospheric conditions. Subsequently, it was baked at 230°C for 20 minutes.

[0014] When obtaining the transmittance of the hardened film, the film thickness can be adjusted so that the transmittance at the wavelength of maximum absorption is 5%, and then the transmittance at 440 nm and 620 nm can be measured. Alternatively, when obtaining the transmittance of the hardened film, the film thickness can be adjusted without the above method, and the transmittance at the wavelength of maximum absorption, the transmittance at 440 nm, and the transmittance at 620 nm can be measured. Then, the transmittance at 440 nm and the transmittance at 620 nm can be calculated by setting the transmittance at the wavelength of maximum absorption to 5%.

[0015] The transmittance at the aforementioned wavelength of 440 nm is 80% or higher, preferably 85% or higher, more preferably 90% or higher, and even more preferably 92% or higher. On the other hand, there is no particular upper limit; it can be below 100% or below 99%.

[0016] The transmittance at the aforementioned wavelength of 620 nm is 80% or higher, preferably 90% or higher, more preferably 93% or higher, and even more preferably 95% or higher, and especially preferably 97% or higher. On the other hand, there is no particular upper limit, and it can be below 100%.

[0017] The following is a detailed description of each component. Furthermore, unless otherwise specified, the compounds exemplified as components in this specification may be used alone or in combination of several.

[0018] <Coloring Agent (A)> Colorant (A) contains 𠮿 The dye (A1) content, relative to the solid content of the negative photoresist composition, is preferably 5-60% by mass, more preferably 8-55% by mass, and even more preferably 10-50% by mass. If the colorant content is within the above range, the color density when producing a color filter can be increased, and the composition contains the necessary amount of resin, etc. Here, the solid content of the negative photoresist composition refers to the total amount of components obtained by removing the solvent from the negative photoresist composition of the present invention. The solid content and the content of each component relative to it can be determined, for example, by known analytical methods such as liquid chromatography or gas chromatography.

[0019] <𠮿 Dye (A1)> 𠮿 The dye (A1) system contains molecules with intramolecular α-type... Dyes that are compounds with a skeletal structure. As a 𠮿 The dye (A1) is preferably a dye containing the compound represented by formula (I) (hereinafter, sometimes referred to as "compound (I)").

[0020] In formula (I), R1 to R4 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, wherein the -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR11-; R5 represents -OH, -SO3-, -SO3H, -SO3-Z+, -CO2H, -CO2-Z+, -CO2R8, -SO3R8, or -SO2NR9R10; R6 and R7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer from 0 to 5; when m is 2 or greater, the complex number of R5s can be the same or different; a represents an integer of 0 or 1; X represents a halogen atom; Z+ represents +N(R11)4, Na+, or K+, where the four R11 values ​​can be the same or different; R8 represents a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, in which the hydrogen atoms can be replaced by halogen atoms; R9 and R10 independently represent a hydrogen atom or a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents. The -CH2- in the saturated hydrocarbon group can be replaced by -O-, -CO-, -NH-, or -NR8-. R9 and R10 can form heterocycles with adjacent nitrogen atoms, consisting of 3 to 10 member rings. R11 represents a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, or an aralkyl group with 7 to 10 carbon atoms.

[0021] Compound (I) can also be its tautomer. When using compound (I), 𠮿 The content of compound (I) in the dye (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, and most preferably 100% by mass.

[0022] Examples of monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms in the R1 to R4 groups include: straight-chain alkyl groups such as methyl, ethyl, propyl, 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 2 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl. When substituents are present, the number of carbon atoms in the saturated hydrocarbon group includes the carbon atoms of the substituents. Examples of substituents that can be present in a saturated hydrocarbon group include: halogen atoms, -OH, -OR8, -SO3-, -SO3H, -SO3-Z+, -CO2H, -CO2R8, -SR8, -SO2R8, -SO3R8, -SO2NR9R10, or -Si(OR12)(OR13)(OR14). R12, R13, and R14 independently represent monovalent saturated hydrocarbon groups with 1 to 4 carbon atoms, in which the hydrogen atoms can be replaced by halogen atoms.

[0023] Examples of monovalent aromatic hydrocarbon groups with 6 to 20 carbon atoms in R1 to R4 include: monocyclic aromatic hydrocarbon groups such as phenyl; and polycyclic aromatic hydrocarbon groups such as naphthyl, anthraceneyl, phenanthryl, biphenyl, and triphenyl. Among polycyclic aromatic hydrocarbon groups, non-condensed polycyclic aromatic hydrocarbon groups such as biphenyl and triphenyl are preferred. Furthermore, polycyclic aromatic hydrocarbon groups are preferably unsubstituented. Examples of monovalent aromatic hydrocarbon groups with substituents include: toluene-methyl, xylene-methyl, etc. Benzyl, propylphenyl, butylphenyl, etc. When substituents are present, the number of carbon atoms in the aromatic hydrocarbon group includes the carbon atoms of the substituents. Examples of substituents that can be present in aromatic hydrocarbon groups include: halogen atoms, -R8, -OH, -OR8, -SO3-, -SO3H, -SO3-Z+, -CO2H, -CO2R8, -SR8, -SO2R8, -SO3R8, -SO2NR9R10, or -Si(OR12)(OR13)(OR14).

[0024] Examples of monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms in R8 to R11 include: 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.

[0025] The monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms in R9 and R10 may have substituents. Examples of such substituents include hydroxyl groups and halogen atoms.

[0026] Examples of monovalent saturated hydrocarbon groups with 1 to 4 carbons in R12 to R14 include: straight-chain alkyl groups such as methyl, ethyl, propyl, and butyl; and branched alkyl groups such as isopropyl and isobutyl, which are alicyclic saturated hydrocarbon groups with 1 to 4 carbons.

[0027] Z+ is +N(R11)4, Na+, or K+, preferably +N(R11)4. Preferably, at least two of the four R11 groups in +N(R11)4 are monovalent saturated hydrocarbon groups with 5 to 20 carbon atoms. Furthermore, the total number of carbon atoms in the four R11 groups is preferably 20 to 80, more preferably 20 to 60. When +N(R11)4 is present in compound (I), if the R11 groups are such groups, a color filter with fewer foreign matter can be formed from the negative photoresist composition of the present invention containing compound (I).

[0028] Examples of -OR8 compounds include: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, 2-ethylhexoxy, and eicosyloxy.

[0029] Examples of -CO2 R8 groups include: methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tributoxycarbonyl, hexoxycarbonyl, and eicosyloxycarbonyl.

[0030] Examples of -SR8 groups include: methyl thio, ethyl thio, butyl thio, hexyl thio, decyl thio, eicosyl thio, etc. Examples of -SO2 R8 groups include: methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, and eicosylsulfonyl. Examples of -SO3 R8 groups include: methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tributoxysulfonyl, hexoxysulfonyl, and eicosylsulfonyl.

[0031] As -SO2 NR9 R10, examples include: amine sulfonyl; N-Methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-isopropylaminesulfonyl, N-butylaminesulfonyl, N-isobutylaminesulfonyl, N-dibutylaminesulfonyl, N-tert-butylaminesulfonyl, N-pentylaminesulfonyl, N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl)aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)aminesulfonyl N-(3-methylbutyl)aminosulfonyl, N-cyclopentylaminosulfonyl, N-hexylaminosulfonyl, N-(1,3-dimethylbutyl)aminosulfonyl, N-(3,3-dimethylbutyl)aminosulfonyl, N-heptylaminosulfonyl, N-(1-methylhexyl)aminosulfonyl, N-(1,4-dimethylpentyl)aminosulfonyl, N-octylaminosulfonyl, N-(2-ethylhexyl)aminosulfonyl, N-(1,5-dimethyl)hexylaminosulfonyl, N-(1,1,2,2-tetramethylbutyl)aminosulfonyl and other N-1 substituted aminosulfonyl groups; N,N-dimethylaminesulfonyl, N,N-ethylmethylaminesulfonyl, N,N-diethylaminesulfonyl, N,N-propylmethylaminesulfonyl, N,N-isopropylmethylaminesulfonyl, N,N-tert-butylmethylaminesulfonyl, N,N-butylethylaminesulfonyl, N,N-bis(1-methylpropyl)aminesulfonyl, N,N-heptylmethylaminesulfonyl, and other N,N-2-substituted aminesulfonyl groups.

[0032] As -Si(OR12)(OR13)(OR14), examples include trimethoxysilyl, triethoxysilyl, etc.

[0033] R5 is preferably -CO2 H, -CO2 - Z+, -CO2 R8, -SO3 -, -SO3 - Z+, -SO3 H, or SO2 NHR9, and more preferably SO3 -, -SO3 - Z+, -SO3 H, or SO2 NHR9.

[0034] m represents an integer from 0 to 5, preferably from 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0035] As for the alkyl groups having 1 to 6 carbon atoms in R6 and R7, examples of alkyl groups having 1 to 6 carbon atoms can be given, with alkyl groups having 1 to 2 carbon atoms being more preferred. R6 and R7 are more preferably hydrogen atoms.

[0036] Examples of aralkyl groups with 7 to 10 carbon atoms in R11 include benzyl, phenylethyl, and phenylbutyl.

[0037] Examples of halogen atoms in X include chlorine, fluorine, and bromine atoms.

[0038] 'a' represents an integer of 0 or 1, preferably 0.

[0039] As for compound (I), the compound represented by formula (Ia) (hereinafter sometimes referred to as "compound (Ia)") is preferably exemplified. The compound represented by formula (Ia) may be used without being combined with other compounds in compound (Ia) (hereinafter sometimes referred to as "compound (Ib)"), or it may be used in combination with compound (Ia) and compound (Ib). Furthermore, compound (Ia) may also be used in combination with two or more compounds.

[0040] In formula (Ia), Ra1 and Ra4 are each independently monovalent aromatic hydrocarbon groups that can have two or fewer monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms; Ra2 and Ra3 are each independently a hydrogen atom, a methyl group, or an ethyl group; R5~R7, m, a, and X represent the same meaning as above.

[0041] Examples of Ra1 and Ra4 include monovalent aromatic hydrocarbon groups without substituents or monovalent aromatic hydrocarbon groups having two or fewer monovalent saturated aliphatic hydrocarbon groups having one to four carbons. Preferably, the monovalent aromatic hydrocarbon group has two or fewer monovalent saturated aliphatic hydrocarbon groups having one to four carbons.

[0042] Examples of monovalent aromatic hydrocarbon groups without substituents include: monocyclic aromatic hydrocarbon groups such as phenyl; and polycyclic aromatic hydrocarbon groups such as naphthyl, anthraceneyl, phenanthryl, biphenyl, and triphenyl. Among polycyclic aromatic hydrocarbon groups, non-condensed polycyclic aromatic hydrocarbon groups such as biphenyl and triphenyl are preferred. Examples of monovalent aromatic hydrocarbon groups having 1 to 4 carbon atoms include: toluenemethyl, xylenemethyl, etc. The aromatic hydrocarbon group includes methyl hydroxyl, monopropylphenyl, dipropylphenyl, monobutylphenyl, dibutylphenyl, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 7 to 20, more preferably 7 to 16, further preferably 7 to 10, and most preferably 8. The number of carbon atoms in the aromatic hydrocarbon group includes the carbon atoms of the substituents. The aromatic hydrocarbon group preferably does not have any substituents other than the saturated aliphatic hydrocarbon group.

[0043] 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 the ortho or meta position relative to the bond of the aromatic hydrocarbon group, more preferably to the ortho position. Examples of the saturated aliphatic hydrocarbon group include saturated aliphatic hydrocarbon groups without substituents. The number of carbon atoms in the saturated aliphatic hydrocarbon group is preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, and most preferably 1.

[0044] Examples of Ra2 and Ra3 include hydrogen atoms, methyl groups, and ethyl groups, with hydrogen atoms or methyl groups being preferred, and hydrogen atoms being even more preferred.

[0045] As compound (Ib), it is preferably the compound represented by formula (Ib1) (hereinafter sometimes referred to as "compound (Ib1)"). Compound formula (Ib1) is preferably used in combination with compound (Ia), but it can also be used without combination with compound (Ia). That is, 𠮿 The dye (A1) may be compound (Ia) and / or compound (Ib1), preferably compound (Ia), or compound (Ia) and compound (Ib1), and more preferably compound (Ia).

[0046] In formula (Ib1), Rb1 to Rb4 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. Rb1 to Rb4 contain at least one saturated hydrocarbon group or aromatic hydrocarbon group having a halogen atom, -OH, -OR8, -CO2H, -CO2R8, -SO3-, -SO3H, -SO3-Z+, -SR8, -SO2R8, -SO3R8, -SO2NR9R10, or -Si(OR12)(OR13)(OR14) as a substituent, or Rb1 to Rb4 contain at least one aromatic hydrocarbon group having three or more monovalent saturated aliphatic hydrocarbon groups with one to four carbon atoms as substituents. R12, R13, and R14 independently represent monovalent saturated hydrocarbon groups with 1 to 4 carbon atoms, where the hydrogen atoms in these saturated hydrocarbon groups can be replaced by halogen atoms. R5 ~ R10, m, a, and X represent the same meaning as above.

[0047] Examples of Rb1 and Rb4 that are similar to R1 and R4 include: hydrogen atoms, monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms that may have substituents, monovalent aromatic hydrocarbon groups with 6 to 20 carbon atoms that may have substituents, or aromatic hydrocarbon groups with 3 or more monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms as substituents. Preferably, these are monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms that may have substituents, monovalent aromatic hydrocarbon groups with 6 to 20 carbon atoms that have substituents, or aromatic hydrocarbon groups with 3 or more monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms as substituents.

[0048] The number of carbons in the monovalent saturated hydrocarbon group having 1 to 20 carbons of substituents is preferably 1 to 10, more preferably 2 to 8, and even more preferably 2 to 7. The number of carbons in the saturated aliphatic hydrocarbon group also includes the carbons of the substituents. As substituents, halogen atoms, -OH, -OR8, -CO2H, -CO2R8, -SO3-, -SO3H, -SO3-Z+, -SR8, -SO2R8, -SO3R8, -SO2NR9R10, or -Si(OR12)(OR13)(OR14) are preferred, more preferably -OH, -OR8, -CO2H, -CO2R8, -SO3-, -SO3H, -SO3-Z+, -SR8, -SO2R8, -SO3R8, or -Si(OR12)(OR13)(OR14), further preferably -OH, -OR8, -CO2H, -CO2R8, or -Si(OR12)(OR13)(OR14), and most preferably -Si(OR12)(OR13)(OR14). The number of substituents is preferably 1 to 5 per saturated aliphatic hydrocarbon group, more preferably 1 to 3, further preferably 1 to 2, and most preferably 1.

[0049] The monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms of substituents preferably has 7 to 20 carbon atoms, more preferably 7 to 16, further preferably 7 to 12, further preferably 7 to 10, especially preferably 7 to 8, and most preferably 8. The number of carbon atoms in the aromatic hydrocarbon group also includes the number of carbon atoms of the substituents. As substituents, preferred ones are monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms, halogen atoms, -OH, -OR8, -CO2H, -CO2R8, -SO3-, -SO3H, -SO3-Z+, -SR8, -SO2R8, -SO3R8, -SO2NR9R10, or -Si(OR12)(OR13)(OR14), more preferably monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms, -OH, -OR8, -CO2H, -CO2R8, -SO3-, -SO3H, -SO3-Z+, -SR8, -SO2R8, -SO3R8, or -SO2NR9R10. Preferably, the substituent is a monovalent saturated aliphatic hydrocarbon group with 1 to 4 carbon atoms, such as -OR8, -SO3-, -SO3H, -SO3-Z+, -SR8, -SO2R8, -SO3R8, or -SO2NR9R10. The number of substituents in each aromatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, and most preferably 2. The substituent is preferably bonded to the aromatic hydrocarbon group at the ortho and / or meta positions, more preferably at the ortho position.

[0050] The aromatic hydrocarbon group having three or more monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms as substituents preferably has 9 to 20 carbon atoms, more preferably 9 to 13, further preferably 9 to 12, and most preferably 9. The number of carbon atoms in the aromatic hydrocarbon group includes the carbon atoms of the substituents. The aromatic hydrocarbon group preferably does not have any substituents other than the saturated aliphatic hydrocarbon group. In each aromatic hydrocarbon group, the number of saturated aliphatic hydrocarbon groups is preferably 3 to 5, more preferably 3 to 4, and most preferably 3. The bond between the saturated aliphatic hydrocarbon group and the aromatic hydrocarbon group is preferably at the ortho and / or para positions, more preferably at the ortho and para positions. The number of carbon atoms in the monovalent saturated aliphatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, and most preferably 1.

[0051] As for Rb2 and Rb3, among the same groups as R2 and R3 mentioned above, hydrogen atoms or monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms that may have substituents can be preferred examples. More preferably, monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms that may have substituents are monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms that may have substituents are monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms that may have substituents are monovalent saturated hydrocarbon groups.

[0052] The number of carbons in the monovalent saturated hydrocarbon group having 1 to 20 carbons of substituents is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The number of carbons in the saturated aliphatic hydrocarbon group also includes the carbons of the substituents. Examples of substituents include: halogen atoms, -OH, -OR8, -CO2H, -CO2R8, -SO3-, -SO3H, -SO3-Z+, -SR8, -SO2R8, -SO3R8, -SO2NR9R10, or -Si(OR12)(OR13)(OR14), more preferably -OH, -OR8, -CO2H, -CO2R8, -SO3-, -SO3H, -SO3-Z+, -SR8, -SO2R8, -SO3R8, or -Si(OR12)(OR13)(OR14), further preferably -OH, -OR8, -CO2H, -CO2R8, or -Si(OR12)(OR13)(OR14), and most preferably -CO2H or -CO2R8. The number of substituents is preferably 1 to 5 per saturated aliphatic hydrocarbon group, more preferably 1 to 3, further preferably 1 to 2, and most preferably 1.

[0053] As compound (Ia), it is preferred to use formula (IaX) and compounds No. 1 to 48 specified in Table 1.

[0054]

[0055] [Table 1]

[0056] The symbols in the formula refer to the following bases (where * indicates a bond).

[0057]

[0058] As compound (Ib1), it is preferred to be a compound represented by formula (Ibx) and the compounds No. 49 to 74 specified in Table 2, and compounds A3-1 to A3-8.

[0059]

[0060] [Table 2]

[0061] The symbols in the formula refer to the following bases (where * indicates a bond).

[0062]

[0063]

[0064] Colorant (A) may be solely a dye, or a combination of dye and pigment. Preferably, colorant (A) is solely a dye, or a combination of dye and red or purple pigment, and even more preferably, solely a dye. Dye (A1), or 𠮿 The combination of dye (A1) with red or purple pigment, and preferably only for 𠮿 Dye (A1), or 𠮿 The combination of dye (A1) and purple pigment is even better for 𠮿 Dye (A1).

[0065] 𠮿 The dye (A1) is preferably compound (Ia) and / or compound (Ib1). That is, A1 The dye (A1) is preferably either compound (Ia) or compound (Ib1), or a combination of compound (Ia) and compound (Ib1).

[0066] 𠮿 The dye (A1) is preferably selected from a combination of two or more compounds (Ib), or a combination of compounds (Ib) and (Ia). More preferably, it is selected from a combination of two or more compounds (Ib1), or a combination of compounds (Ib1) and (Ia).

[0067] Regarding 𠮿 The content of dye (A1), relative to the total amount of colorant (A), is preferably 30-100% by mass, more preferably 60-100% by mass, and even more preferably 80-100% by mass, most preferably 100% by mass. When colorant (A) includes pigments, etc., The content of dye (A1) can also be below 90% by mass, below 80% by mass, or below 70% by mass.

[0068] 𠮿 The content of compound (Ia) in the dye (A1) is preferably 30-100% by mass, more preferably 60-100% by mass, further preferably 80-100% by mass, and most preferably 100% by mass. When the colorant (A) contains compound (Ib) or the like, the content of compound (Ia) may also be 80% by mass or less, 70% by mass or less, or 60% by mass or less.

[0069] 𠮿 The content of compound (Ib) in the dye (A1) is preferably 20-80% by mass, more preferably 30-70% by mass, and even more preferably 40-60% by mass.

[0070] The content of compound (Ib) relative to 100 parts by mass of compound (Ia) is preferably 20 to 150 parts by mass, more preferably 50 to 130 parts by mass, and even more preferably 80 to 110 parts by mass.

[0071] <Other Dyes (A2)> Colorant (A) may further include 𠮿 Dyes other than dye (A1) (sometimes referred to as "other dyes (A2)"). As for other dyes (A2), they are defined as follows: Dyes other than those classified as A1 are not specifically limited, but can include: oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, or sulfonamide derivatives of acid dyes. Examples include: compounds classified as dyes in the Dye Index (published by The Society of Dyens and Colourists), i.e., those with hues other than CI pigments, or well-known dyes recorded in dyeing notes (Shikiransha). Furthermore, based on chemical structure, examples include: azo dyes, anthraquinone dyes, cyanine dyes, phthalocyanine dyes, naphthoquinone dyes, quinone imine dyes, methylene dyes, methylimine dyes, squaric acid onion dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. <Pigment (A3)> Coloring agents (A) may also include pigments (A3). Examples of pigments (A3) include organic and inorganic pigments, and compounds classified as pigments in the Dye Index (published by The Society of Dyers and Colourists).

[0072] Examples of organic pigments include: CI pigments Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265. CI pigments include blue (15, 15:3, 15:4, 15:6, 60, etc.) and purple (1, 19, 23, 29, 32, 36, 38, etc.). CI pigments include green pigments such as green 7, 36, and 58.

[0073] Among them, red pigment and purple pigment are preferred, purple pigment is even more preferred, and CI pigment purple 19 is even more preferred.

[0074] As inorganic pigments, examples include metal compounds such as metal oxides or metal salts. Specifically, examples include oxides or composite metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony.

[0075] The aforementioned pigment (A3) may also undergo surface treatment as needed, such as rosin treatment, surface treatment using pigment derivatives or dispersants incorporating acidic or basic groups, grafting treatment of the pigment surface using polymeric compounds, micronization treatment using sulfuric acid micronization, or washing treatment using organic solvents or water to remove impurities, or treatment to remove ionic impurities using ion exchange. Furthermore, it is preferable that the pigment (A3) has a uniform particle size.

[0076] Furthermore, 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.

[0077] Solvent (B) The negative photoresist composition may also include a solvent (B). Solvent (B) is not particularly limited and may be any solvent commonly used in the field. For example, it may be selected from ester solvents (solvents containing -COO- but not -O-), ether solvents (solvents containing -O- but not -COO-), ether-ester solvents (solvents containing both -COO- and -O-), ketone solvents (solvents containing -CO- but not -COO-), alcohol solvents (solvents containing OH but not -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

[0078] 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, 1,3-butanediol diacetate, etc.

[0079] Examples of ether solvents include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and other ethylene glycol monoalkyl ethers; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and other diethylene glycol monoalkyl ethers; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and other propylene glycol monoalkyl ethers; tetrahydrofuran, tetrahydropyran Cyclic ethers such as 1,4-dimethyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether; phenolic ethers such as anisole, phenethyl ether, and methyl anisole; 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, etc.

[0080] Examples of ether ester solvents include: ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and other ethylene glycol monoalkyl ether acetates; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and other propylene glycol monoalkyl ether acetates; diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and other diethylene glycol monoalkyl ether acetates; dipropylene glycol monomethyl ether acetate and other dipropylene glycol monoalkyl ether acetates; methyl methoxyacetate, ethyl methoxyacetate, methyl ... Butyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc.

[0081] Examples of ketone solvents include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, etc.

[0082] Examples of alcohol solvents include: methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

[0083] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0084] Examples of acetamide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0085] Among the above solvents, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and / or 4-hydroxy-4-methyl-2-pentanone are preferred.

[0086] The solvent is preferably an ether ester solvent. In this case, the content of the ether ester solvent relative to the total amount of solvent (B) is preferably 40% by mass or more and 100% by mass or less, and from the perspective of dispersion stability, it is more preferably 40% by mass or more and 99% by mass or less. The lower limit of the above-mentioned content of the ether ester solvent is preferably 60% by mass, and more preferably 70% by mass. The ether solvent is preferably selected from at least one of the group consisting of ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates and diethylene glycol monoalkyl ether acetates, and more preferably propylene glycol monomethyl ether acetate. When solvent (B) is a mixed solvent, the solvent combined with the ether ester solvent is preferably selected from at least one of the group consisting of ether solvents and ketone solvents, and more preferably from at least one of the group consisting of propylene glycol monomethyl ether and 4-hydroxy-4-methyl-2-pentanone. If solvent (B) is this type of solvent, then a high-brightness color filter can be manufactured using the negative photoresist composition prepared from the negative photoresist composition of the present invention, which is therefore preferable. As solvent (B), it is preferably a solvent in which the solubility (at 23°C) of colorant (A) is 5% by mass or less, more preferably a solvent in which the solubility (at 23°C) of colorant (A) is 0.3 to 3% by mass. It is especially preferred to use solvent B. Solvent (B) whose solubility of dye (A1) is within the above range.

[0087] <Resin(C)> The negative photoresist composition of the present invention comprises a resin (C). Preferably, the resin (C) is an alkali-soluble resin. By comprising an alkali-soluble resin in the negative photoresist composition, the solubility of the developer in the non-exposed portion is improved. Furthermore, the alkali-soluble resin exhibits excellent compatibility with dispersants having the following amine groups. Examples of resin (C) include the following resins [K1] to [K6]. The resin [K1] is selected from at least one (a) of the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "(a)"), and a monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylene-unsaturated bond (hereinafter sometimes referred to as "(b)"); A copolymer of resins [K2](a), (b), and monomer (c) capable of copolymerizing with (a) (wherein, it is different from (a) and (b)) (hereinafter sometimes referred to as "(c)"); A copolymer of resins [K3](a) and (c); Resin [K4] is a resin obtained by reacting (b) and (a) with (c) to form a copolymer; Resin [K5] is a resin obtained by reacting a copolymer of (a) and (b) with (c); Resin [K6] is a resin obtained by reacting the copolymer of (a) and (b) with (c) and then reacting the carboxylic anhydride.

[0088] As in (a), specifically, examples include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, ortho-, meta-, and p-vinylbenzoic acid; Unsaturated dicarboxylic acids such as maleic acid, trans-butenedioic acid, citrate, methyl-trans-butenedioic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexene dicarboxylic acid; Methyl-5-norcamphen-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 other carboxyl-containing bicyclic unsaturated compounds; Unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citrate anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxylic bicyclic [2.2.1]hept-2-enoic anhydride; Unsaturated mono[(meth)acryloxyethyl] esters of di- or higher polycarboxylic acids, such as succinate mono[2-(meth)acryloxyethyl] ester and phthalate mono[2-(meth)acryloxyethyl] ester; Examples include unsaturated acrylates such as α-(hydroxymethyl)acrylic acid, which contain both hydroxyl and carboxyl groups in the same molecule. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred from the perspective of copolymerization reactivity or the solubility of the obtained resin in alkaline aqueous solution.

[0089] (b) For example, it refers to a polymeric compound having a cyclic ether structure having 2 to 4 carbon atoms (e.g., selected from at least one of the group consisting of ethylene oxide ring, oxobutane ring and tetrahydrofuran ring) and an ethylene unsaturated bond. (b) Preferably, it is a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acrylic acid oxy group. Furthermore, in this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The terms "(meth)acrylyl" and "(meth)acrylate" have the same meaning.

[0090] Examples of (b) include monomers having ethylene oxide and vinyl unsaturated bonds (b1) (hereinafter sometimes referred to as "(b1)"), monomers having oxobutyl and vinyl unsaturated bonds (b2) (hereinafter sometimes referred to as "(b2)"), monomers having tetrahydrofuranyl and vinyl unsaturated bonds (b3) (hereinafter sometimes referred to as "(b3)"), etc.

[0091] Examples of (b1) include: monomers having a structure of epoxidized aliphatic unsaturated hydrocarbons (b1-1) (hereinafter sometimes referred to as "(b1-1)") and monomers having a structure of epoxidized alicyclic unsaturated hydrocarbons (b1-2) (hereinafter sometimes referred to as "(b1-2)").

[0092] Examples of (b1-1) include: glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl) 2,4-Bis(glycidoxymethyl)styrene, 2,5-Bis(glycidoxymethyl)styrene, 2,6-Bis(glycidoxymethyl)styrene, 2,3,4-Tris(glycidoxymethyl)styrene, 2,3,5-Tris(glycidoxymethyl)styrene, 2,3,6-Tris(glycidoxymethyl)styrene, 3,4,5-Tris(glycidoxymethyl)styrene, 2,4,6-Tris(glycidoxymethyl)styrene, etc.

[0093] Examples of (b1-2) include: vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Inc.), 3,4-epoxycyclohexyl methyl methacrylate (e.g., Cyclomer A400; manufactured by Daicel Inc.), 3,4-epoxycyclohexyl methyl methacrylate (e.g., Cyclomer M100; manufactured by Daicel Inc.), compounds represented by formula (BI), and compounds represented by formula (BII).

[0094]

[0095] In formulas (BI) and (BII), Ra and Rb represent hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, wherein the hydrogen atoms in the alkyl group may be replaced by hydroxyl groups; Xa and Xb represent single bonds, -Rc-, *-Rc-O-, *-Rc-S-, or *-Rc-NH-; Rc indicates an alkyldiyl group with 1 to 6 carbon atoms; * indicates a bond with O.

[0096] Examples of alkyl groups having 1 to 4 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, and tributyl. Examples of alkyl groups in which hydrogen atoms are replaced by hydroxyl groups include: hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc. For Ra and Rb, examples of the following are preferred: hydrogen atom, methyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, and more preferably hydrogen atom and methyl.

[0097] Examples of alkyldiyl groups include: methylene, ethyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, etc. For Xa and Xb, examples of the following are preferred: single bond, methylene, ethyl, *-CH2-O- and *-CH2CH2-O-, and more preferably single bond and *-CH2CH2-O- (* indicates a bond with O).

[0098] Examples of compounds represented by formula (BI) include compounds represented by formulas (BI-1) to (BI-15). More preferably, examples include compounds represented by formulas (BI-1), (BI-3), (BI-5), (BI-7), (BI-9), or (BI-11) to (BI-15). Even more preferably, examples include compounds represented by formulas (BI-1), (BI-7), (BI-9), or (BI-15).

[0099]

[0100]

[0101] Examples of compounds represented by formula (BII) include compounds represented by formulas (BII-1) to (BII-15). Preferably, examples include compounds represented by formulas (BII-1), (BII-3), (BII-5), (BII-7), (BII-9), or (BII-11) to (BII-15). Even more preferably, examples include compounds represented by formulas (BII-1), (BII-7), (BII-9), or (BII-15).

[0102]

[0103]

[0104] The compounds represented by formula (BI) and formula (BII) may be used individually or in combination. When used in combination, the ratio of the compounds represented by formula (BI) and formula (BII) on a molar basis is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20.

[0105] As (b2), it is more preferably a monomer having an oxetyl group and a (meth)propenyloxy group. Examples of (b2) include: 3-methyl-3-methpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3-ethyl-3-methpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methpropenyloxyethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methpropenyloxyethyloxetane, 3-ethyl-3-propenyloxyethyloxetane, etc.

[0106] As (b3), it is more preferably a monomer having a tetrahydrofuran group and a (meth)acryloxy group. Specifically, examples of (b3) include: tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemicals Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.

[0107] As for (b), from the perspective of further improving the reliability of the obtained color filter, such as heat resistance and chemical resistance, (b1) is preferred. Furthermore, from the perspective of excellent storage stability of the negative photoresist composition, (b1-2) is even more preferred.

[0108] Examples of (c) include: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, dibutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, and tricyclo[5.2.1.02,6]dec-8-yl methacrylate (commonly referred to as "dicyclopentyl methacrylate" in this art). Examples of other meth esters include: tricyclodecyl methacrylate, tricyclo[5.2.1.02,6]decen-8-yl methacrylate (commonly known in this field as dicyclopentenyl methacrylate), dicyclopentoxyethyl methacrylate, isomethacrylate, adamantyl methacrylate, allyl methacrylate, propargyl methacrylate, phenyl methacrylate, naphthyl methacrylate, benzyl methacrylate, etc. Hydroxyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and other hydroxyl-containing methacrylates; Dicarboxylic acid diesters such as diethyl maleate, diethyl transbutenedioate, and diethyl isocarboxylate; 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-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo [2.2.1]Hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, etc., are bicyclic unsaturated compounds; N-Phenylacetinibimide, N-Cyclohexylcisbutenetinibimide, N-Benzylcisbutenetinibimide, N-Butadienetinibimino-3-cisbutenetinibimide benzoate, N-Butadienetinibimino-4-cisbutenetinibimide butyrate, N-Butadienetinibimino-6-cisbutenetinibimide hexanoate, N-Butadienetinibimino-3-cisbutenetinibimide propionate, N-(9-acridyl)cisbutenetinibimide, and other dicarbonyl acetimine derivatives; Styrene monomers such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene; nitrile monomers such as acrylonitrile and methacrylonitrile; halogenated vinylides such as vinyl chloride and vinylidene chloride; acetylamine monomers such as acrylamide and methacrylamide; vinyl acetate; diene monomers such as 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. Among these, styrene, vinyltoluene, N-phenylcis-butene diimide, N-cyclohexylcis-butene diimide, N-benzylcis-butene diimide, and bicyclo[2.2.1]hept-2-ene are preferred in terms of copolymerization reactivity and heat resistance.

[0109] In resin [K1], the ratio of structural units derived from each monomer is preferably, among all the structural units constituting resin [K1], as follows: Structural unit derived from (a); 2~60 mol% Structural unit derived from (b); 40-98 mol%. Better Structural unit derived from (a); 10~50 mol% Structural units derived from (b); 50-90 moles. If the ratio of the structural units of resin [K1] is within the above range, there is a tendency for the negative photoresist composition to have excellent storage stability, developability when forming colored patterns, and solvent resistance of the obtained color filter.

[0110] The resin [K1] can be manufactured, for example, by referring to the method described in the literature "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, Chemical Publishers Co., Ltd., 1st Edition, 1st Printing, March 1, 1972) and the references cited in that literature.

[0111] Specifically, the following method can be used: specific amounts of (a) and (b), the polymerization initiator, and the solvent are added to a reaction vessel, for example, by replacing oxygen with nitrogen to create a deoxygenated atmosphere, and the mixture is heated and kept at a constant temperature while stirring. Furthermore, the polymerization initiator and solvent used here are not particularly limited, and those commonly used in the field can be used. For example, examples of polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile) etc.) or organic peroxides (benzoyl peroxide, etc.). As for the solvent, any solvent that dissolves the monomers is acceptable; examples include solvents described below as solvent (B) for the negative photoresist composition of the present invention.

[0112] Furthermore, the obtained copolymer can be used directly from the reaction solution, or from a concentrated or diluted solution, or extracted in solid (powder) form by methods such as reprecipitation. In particular, by using the solvent contained in the negative photoresist composition of the present invention as the solvent during polymerization, the reaction solution can be directly used in the preparation of the negative photoresist composition of the present invention, thus simplifying the manufacturing steps of the negative photoresist composition of the present invention.

[0113] In resin [K2], the ratio of structural units derived from each monomer is preferably, among all the structural units constituting resin [K2], as follows: Structural unit derived from (a); 2~45 mol% Structural unit derived from (b); 2~95 mol% Structural units derived from (c); 1~65 mol%. Better Structural unit derived from (a); 5~40 mol% Structural units derived from (b); 5~80 mol% Structural units derived from (c); 5-60 mol%. If the ratio of the structural units of resin [K2] is within the above range, the negative photoresist composition tends to have excellent storage stability, developability when forming colored patterns, and solvent resistance, heat resistance and mechanical strength of the obtained color filter.

[0114] Resin [K2] can be manufactured, for example, in the same manner as the method described in the manufacturing method of resin [K1].

[0115] In resin [K3], the ratio of structural units derived from each monomer is preferably, among all the structural units constituting resin [K3], as follows: Structural unit derived from (a); 2~60 mol% Structural unit derived from (c); 40~98 mol%. Better Structural unit derived from (a); 10~50 mol% Structural units derived from (c); 50-90 moles. Resin [K3] can be manufactured, for example, in the same manner as the method described in the manufacturing method of resin [K1].

[0116] The resin [K4] can be manufactured by obtaining a copolymer of (a) and (c), and adding the cyclic ether of (b) having 2 to 4 carbon atoms to the carboxylic acid and / or carboxylic anhydride of (a). First, the copolymer of (a) and (c) is manufactured in the same manner as described in the method for manufacturing resin [K1]. In this case, the ratio of structural units derived from each monomer is preferably the same as that exemplified in resin [K3].

[0117] Next, the cyclic ether having 2 to 4 carbon atoms in (b) is reacted with a portion of the carboxylic acid and / or carboxylic anhydride derived from (a) of the copolymer described above. Following the production of the copolymer of (a) and (c), the atmosphere inside the flask is replaced with air instead of nitrogen. Then, (b), the reaction catalyst of carboxylic acid or carboxylic anhydride with cyclic ether (e.g., tris(dimethylaminomethyl)phenol) and polymerization inhibitor (e.g., hydroquinone) are added to the flask, and the reaction is carried out at 60-130°C for 1-10 hours to produce resin [K4]. Regarding the amount of (b) used, it is preferably 5 to 80 mol, and more preferably 10 to 75 mol, relative to 100 mol in (a). By setting it within this range, there is a tendency for the storage stability of the negative photoresist composition, the developability when forming a pattern, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern to become better. Considering the higher reactivity of cyclic ethers and the fact that unreacted (b) is less likely to remain, (b1) is preferred as (b) used in resin [K4], and more preferably (b1-1). The amount of the above-mentioned reaction catalyst used is preferably 0.001 to 5 parts by mass relative to the combined amount of 100 parts by mass 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 the combined amount of 100 parts by mass of (a), (b), and (c). The reaction conditions, such as the method of addition, reaction temperature, and time, can be appropriately adjusted considering factors such as the manufacturing equipment or the heat generated by polymerization. Furthermore, similarly to polymerization conditions, the method of addition or reaction temperature can be appropriately adjusted considering factors such as the manufacturing equipment or the heat generated by polymerization.

[0118] Regarding resin [K5], as the first stage, copolymers of (b) and (c) are obtained in the same manner as resin [K1] described above. Similarly, the obtained copolymer can be used directly from the reaction solution, from a concentrated or diluted solution, or extracted in solid (powder) form by methods such as reprecipitation. Regarding the ratio of structural units derived from (b) and (c), relative to the total mole number of all structural units constituting the copolymer, it is preferably as follows: Structural units derived from (b); 5~95 mol% Structural unit derived from (c); 5~95 mol%. Better Structural units derived from (b); 10~90 mol% Structural units derived from (c); 10~90 moles.

[0119] Furthermore, under the same conditions as the manufacturing method of resin [K4], the carboxylic acid or carboxylic anhydride contained in (a) and the cyclic ether derived from (b) in the copolymer of (b) and (c) are reacted to obtain resin [K5]. Compared to 100 moles of (b), the amount of (a) reacting with the above copolymer is preferably 5 to 80 moles. Considering the higher reactivity of cyclic ethers and the less likely unreacted (b) to remain, (b1) is preferred as (b) for use in resin [K5], and even more preferably (b1-1).

[0120] Resin [K6] is obtained by further reacting carboxylic anhydride with resin [K5]. This involves reacting a carboxylic anhydride with a hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic anhydride. Examples of carboxylic anhydrides include: succinic anhydride, maleic anhydride, citrate anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxylic bicyclic [2.2.1]hept-2-enoic anhydride (bicyclic heptenic anhydride). The preferred amount of carboxylic anhydride used is 0.5 to 1 mol relative to the amount used in (a).

[0121] As a resin (C), specifically, examples include: methyl 3,4-epoxycyclohexyl methacrylate / (meth)acrylate copolymer, decyl 3,4-epoxytricyclo[5.2.1.02,6]acrylate / (meth)acrylate copolymer, etc. [K1]; glycidyl methacrylate / benzyl methacrylate / (meth)acrylate copolymer, glycidyl methacrylate / styrene / (meth)acrylate copolymer, decyl 3,4-epoxytricyclo[5.2.1.02,6]acrylate / (meth)acrylate / N-cyclohexylcis-butene diimide copolymer, decyl 3,4-epoxytricyclo[5.2.1.02,6]acrylate / (meth)acrylate / N-cyclohexylcis-butene diimide copolymer, decyl 3,4-epoxytricyclo[5.2.1.02,6]acrylate / (meth)acrylate / N-cyclohexylcis-butene diimide copolymer, etc. Resins such as decyl acrylate / (meth)acrylic acid / styrene monomer copolymers and 3-methyl-3-(meth)acrylic acid oxymethyloxetane / (meth)acrylic acid / styrene copolymers [K2]; resins such as benzyl acrylate / (meth)acrylic acid copolymers and styrene / (meth)acrylic acid copolymers [K3]; resins formed by the addition reaction of glycidyl acrylate and benzyl acrylate / (meth)acrylic acid copolymers; resins formed by the addition reaction of glycidyl acrylate and tricyclodecyl acrylate / styrene / (meth)acrylic acid copolymers; resins formed by the addition reaction of glycidyl acrylate and (methyl)acrylic acid copolymers. Resins such as those formed by the addition reaction of tricyclodecyl acrylate / benzyl methacrylate / (meth)acrylic acid copolymer [K4]; resins formed by reacting (meth)acrylic acid with a copolymer of tricyclodecyl methacrylate / (meth)acrylic acid glycidyl acrylate; resins formed by reacting (meth)acrylic acid with a copolymer of tricyclodecyl methacrylate / styrene / (meth)acrylic acid glycidyl acrylate [K5]; resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl methacrylate / (meth)acrylic acid glycidyl acrylate; and resins formed by reacting tetrahydrophthalic anhydride with the resin [K6]. Among them, resin (C) is preferably resin [K1] and / or resin [K2].

[0122] The weight-average molecular weight of the polystyrene-based resin (C) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. The molecular weight distribution of the resin (C) [weight-average molecular weight (Mw) / number-average molecular weight (Mn)] is preferably 1.1 to 6, more preferably 1.2 to 4.

[0123] The acid value of resin (C) is preferably 50~170 mgKOH / g, more preferably 60~150 mgKOH / g, and even more preferably 70~135 mgKOH / g. Here, the acid value is determined by the amount of potassium hydroxide (mg) required to neutralize 1 g of the resin, for example, by titration using an aqueous solution of potassium hydroxide.

[0124] <Dispersant (D)> The negative photoresist composition of the present invention preferably further includes a dispersant (D). As a dispersant (D), it is not particularly limited as long as it is used in the dispersion of the colorant and has an amine group and an amine value of 0 to 55 mgKOH / g (preferably 2 to 40 mgKOH / g), such as polymeric dispersants.

[0125] Examples of such polymeric dispersants include acrylic dispersants and carbamate dispersants.

[0126] As an acrylic dispersant, an acrylic block copolymer can be cited as an example. As an acrylic block copolymer, it is preferred to use a block copolymer that further includes a colorant adsorption block containing an acid group as a colorant adsorption group (also known as a dye adsorption group) and a block without a colorant adsorption group in a colorant adsorption block containing a basic group as a colorant adsorption group (also known as a dye adsorption group).

[0127] As a colorant adsorption block that includes an acidic group in a colorant adsorption block containing a basic group as the above-mentioned colorant adsorption group, an example can be formed by using a monomer having a basic group and a monomer having an acidic group.

[0128] The monomers with basic groups mentioned above are monomers possessing primary, secondary, tertiary, or quaternary ammonium groups. Specifically, examples include: N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylacrylamide, diethylacrylamide, dimethylaminopropylmethacrylamide, acrylmorpholine, vinylimidazole, 2-vinylpyridine, monomers with an amino group and a caprolactone backbone, glycidyl methacrylate, and other monomers with a glycidyl group and molecules containing one [unclear character]. Reactants of compounds with secondary amino groups, reactants of (meth)acrylic alkyl isocyanates with 4-(2-aminomethyl)-pyridine, 4-(2-aminoethyl)-pyridine, 4-(2-hydroxyethyl)pyridine, 1-(2-aminoethyl)-piperazine, 2-amino-6-methoxybenzothiazole, 1-(2-hydroxyethylimidazolium), N,N-diallyl melamine, N,N-dimethyl-1,3-propanediamine, etc.

[0129] The monomers with acidic groups mentioned above are monomers with carboxyl, sulfonic acid, or phosphoric acid groups. Specifically, examples of monomers with carboxyl groups include: unsaturated monocarboxylic acid compounds such as acrylic acid, methacrylic acid, and butenoic acid; unsaturated dicarboxylic acid compounds such as maleic acid, fumaric acid, and itconic acid, and their half-esters; examples of monomers with sulfonic acid groups include: 2-acrylamide-2-methyl-1-propanesulfonic acid, 2-methacrylamide-2-methyl-1-propanesulfonic acid, and styrene sulfonic acid; examples of monomers with phosphoric acid groups include: (meth)acrylate acid phosphonic acid ester and (meth)acrylate acid phosphonic acid ethyl ester.

[0130] Examples of components constituting the aforementioned blocks without colorant adsorbent groups include: aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and benzyl chloride; unsaturated alkyl carboxylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; unsaturated aralkyl carboxylic acid esters such as benzyl (meth)acrylate; monomers containing polycaprolactone; and polyalkylene glycol monoester monomers. The aforementioned acrylic block copolymers can be obtained by living anionic polymerization, and previously known polymerization methods can be used.

[0131] The amine value of the aforementioned acrylic block copolymer is 0~55 mgKOH / g, preferably 0~50 mgKOH / g, and more preferably 2~40 mgKOH / g. Furthermore, the amine value refers to the amine value of the solid component of each 1 g of the acrylic block copolymer, which is the value obtained by converting it to the equivalent of potassium hydroxide after determination using a 0.1 mol / L hydrochloric acid aqueous solution by potentiometric titration (e.g., COMTITE (AUTOTITRATOR COM-900, BURET B-900, TITSTATION K-900), manufactured by Hiranuma Sangyo Co., Ltd.).

[0132] Examples of commercially available acrylic block copolymers include: "Disperbyk-112 (amine value 36 mgKOH / g)," "Disperbyk-2000 (amine value 4 mgKOH / g)," "Disperbyk-2001 (amine value 29 mgKOH / g)," "Disperbyk-2020 (amine value 38 mgKOH / g)," "Disperbyk-2050 (amine value 30 mgKOH / g)," and "Disperbyk-2070 (amine value 20 mgKOH / g)" manufactured by BYK-Chemie Japan.

[0133] As the aforementioned carbamate-based dispersant, it can be obtained by reacting the isocyanate groups of a polyisocyanate compound with compounds having one or more hydroxyl groups on average with a molecular weight of 300 to 10,000, and compounds containing basic groups with functional groups capable of reacting with isocyanate groups. As a method for obtaining such a carbamate-based dispersant, the method described in Japanese Patent Application Publication No. 60-166318, etc., can be used.

[0134] Examples of polyisocyanate compounds constituting the above-mentioned carbamate-based dispersants include isocyanate compounds having two or more isocyanate groups, such as: 2,4-toluene diisocyanate, dimers of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, and other aromatic diisocyanate compounds; hexamethylene diisocyanate, isocyanate, etc. Aliphatic or alicyclic polyisocyanates such as phorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, and 1,3-(isocyanate methylene)cyclohexane; polyisocyanates with isotricyanate groups based on the above diisocyanates (polyisocyanates with isotricyanate groups formed by trimerization of the above diisocyanates, etc.); polyisocyanates obtained by reacting diisocyanates with polyols; and polyisocyanates obtained by reacting diisocyanate compounds with biuret. Among the above polyisocyanate compounds, toluene diisocyanate, isophorone diisocyanate, and other polyisocyanates with isotricyanate groups based on diisocyanates are preferred, for example.

[0135] Compounds having one or more hydroxyl groups within their molecules that constitute the above-mentioned carbamate-based dispersants include, for example, polyether compounds and polyester compounds. Examples of the aforementioned polyether compounds include: polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutane glycol, and polytetramethylene glycol; alkylene glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexane glycol, neopentyl glycol, glycerol, trimethylolpropane, pentaerythritol, diglycerol, di-trimethylolpropane, and dipentaerythritol; and modified forms of low-molecular-weight monohydric alcohols such as methanol and ethanol, including ethylene oxide modified forms, propylene oxide modified forms, butane oxide modified forms, and tetrahydrofuran modified forms.

[0136] Examples of the aforementioned polyester compounds include: ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerol, trimethylolpropane, pentaerythritol, diglycerol, di-trimethylolpropane, dipentaerythritol and other alkyl glycols, methanol, ethanol and other low molecular weight monohydric alcohols such as ε-caprolactone, γ-butyrolactone, δ-valerolactone and methylvalerolactone; aliphatic polyester polyols as esterifications of aliphatic dicarboxylic acids such as adipic acid or dimer acids with polyols such as neopentyl glycol or methylpentyl glycol; terephthalic acid. Esterifications of aromatic dicarboxylic acids and polyols such as neopentyl glycol, i.e., aromatic polyester polyols and other polyester polyols; esterifications of polyhydroxy compounds such as polycarbonate polyols, acrylic polyols, and polytetramethylene hexaglycerol ether (a tetrahydrofuran-modified hexaglycerol) with dicarboxylic acids such as fumaric acid, phthalic acid, isophthalic acid, itconic acid, adipic acid, sebacic acid, and maleic acid; and monoglycerides and other compounds containing polyhydroxy compounds, obtained through transesterification reactions of glycerol and other compounds containing polyhydroxy compounds with fatty acid esters. Among the above-mentioned compounds having one or more hydroxyl groups in their molecules, ε-caprolactone adducts of alcohols are preferred.

[0137] The number-average molecular weight of the compounds having one or more hydroxyl groups is 300 to 10,000, preferably 300 to 6,000. Furthermore, the number-average molecular weight and weight-average molecular weight can be determined by column chromatography.

[0138] The compounds constituting the above-mentioned carbamate-based dispersants, which contain a basic functional group capable of reacting with an isocyanate group, are not particularly limited, but are preferably selected from at least one compound from the group consisting of polyols, polythiols, and amines having N,N-disubstituted amino groups or heterocyclic nitrogen atoms. Such compounds are those commonly used in the field of dispersants. These compounds have a Zerewitinoff active hydrogen atom and at least one basic nitrogen-containing group. Examples of such compounds include: N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,4-butanediamine, 2-dimethylaminoethanol, 1-(2-aminoethyl)-piperazine, 2-(1-pyrrolidinyl)-ethylamine, 4-amino-2-methoxypyrimidine, 4-(2-aminoethyl)-pyridine, 1-(2-hydroxyethyl)-piperazine, 4-(2-hydroxyethyl)-morpholine, 2-mercaptopyrimidine, 2-mercaptobenzimidazole, 2-amino-6-methoxybenzothiazole, N,N-diallyl-melamine, 3-amino-1,2,4-triazole, 1-(2-hydroxyethyl)-imidazole, 3-mercapto-1,2,4-triazole, etc. Among these, amines having a heterocyclic nitrogen atom are preferred.

[0139] The reaction in the synthesis of the above-mentioned carbamate-based dispersant is not particularly limited and can be carried out by previously known methods. Furthermore, the amine value of the above-mentioned carbamate-based dispersant is 0~55 mgKOH / g, preferably 5~40 mgKOH / g.

[0140] Furthermore, commercially available products that are carbamate-based dispersants include: 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), and Disperbyk-182 (amine value 13 mgKOH / g, manufactured by BYK-Chemie).

[0141] The acrylic dispersant described above is preferred as the dispersant.

[0142] The negative photoresist composition of the present invention preferably further comprises a polymerizable compound (E) and a polymerization initiator (F). This allows it to exhibit curing properties such as those required for exposure.

[0143] <Polymerizing Compounds (E)> The polymerizable compound (E) is a compound that can be polymerized using active free radicals and acids generated by the polymerization initiator (F). Examples include compounds with polymerizable vinyl unsaturated bonds, and preferably (meth)acrylate compounds.

[0144] Among them, the polymerizable compound (E) is preferably a polymerizable compound having 3 or more (preferably 4 to 10, and more preferably 5 to 8) vinyl unsaturated bonds, and more preferably an ester of an alcohol (e.g., pentaerythritol, its condensate, or a modified form thereof) and (meth)acrylic acid having 3 or more (preferably 4 to 10, and more preferably 5 to 8) OH groups. Examples of such polymerizable compounds include: pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloxyethyl) 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, and caprolactone-modified dipentaerythritol hexa(meth)acrylate. Among these, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

[0145] The weight average molecular weight of the polymeric compound (E) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

[0146] Regarding the content of the polymeric compound (E), relative to the solid content of the negative photoresist composition, it is preferably 7-65% by mass, more preferably 13-60% by mass, and even more preferably 17-55% by mass. If the content of the polymeric compound (E) is within the above range, the curing is more thorough, the residual film rate under development is improved, undercutting is less likely to occur in the colored pattern, and the adhesion is better, which is therefore preferable.

[0147] <Polymerization Initiator (F)> As for the aforementioned polymerization initiator (F), there are no particular limitations as long as it is a compound that generates active free radicals, acids, etc. through the action of light or heat and can initiate polymerization; any known polymerization initiator can be used.

[0148] As a polymerization initiator (F), it is preferably a compound that generates active free radicals by the action of light, and more preferably an alkyl phenyl ketone compound, a triphenyl ketone compound, a phenyl phosphine oxide compound, an oxime compound, and a bimidazole compound.

[0149] The aforementioned alkyl phenyl ketone compounds are compounds having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have substituents. In the formula, * represents a bond.

[0150]

[0151] Examples of compounds having the partial structure represented by formula (d2) include: 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one, etc. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (and above, manufactured by BASF) can be used. Examples of compounds having the partial structure represented by formula (d3) include: 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, benzodiazepine dimethyl ketal, etc. From a sensitivity perspective, the aforementioned alkyl phenyl ketone compound is preferably a compound having a partial structure represented by formula (d2), and more preferably 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one.

[0152] Examples of the aforementioned trichloromethyl compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-trichloromethyl, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-trichloromethyl, 2,4-bis(trichloromethyl)-6-helianthyl-1,3,5-trichloromethyl, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-trichloromethyl, 2,4-bis(trichloromethyl)-6-[ [2-(5-methylfuran-2-yl)vinyl]-1,3,5-trisyl, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-trisyl, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-trisyl, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-trisyl, etc.

[0153] Examples of the aforementioned acetylated phosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can be used.

[0154] The above-mentioned oxime compounds are compounds having a partial structure represented by formula (d1). Hereinafter, * indicates a bond.

[0155]

[0156] Examples of the aforementioned oxime compounds include: N-benzoxoxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoxoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoxoxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[ 9-Ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentylmethoxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-one-2-imine, etc. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (and above, manufactured by BASF), and N-1919 (manufactured by ADEKA) can be used. Preferably, the compounds are N-benzoxyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoxyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, and N-benzoxyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine. When the oxime compound is one of these compounds, the brightness of the obtained color filter tends to increase when the negative photoresist composition of the present invention is prepared in the form of a blue negative photoresist composition.

[0157] Examples of the aforementioned biimidazole compounds include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, see Japanese Patent Publication No. 6-75372, Japanese Patent Publication No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkyl) Imidazole compounds with the 4,4',5,5'-phenyl group replaced by an alkoxyphenyl group, such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (e.g., see Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), and imidazole compounds in which the 4,4',5,5'-phenyl group is replaced by an alkoxycarbonyl group (e.g., see Japanese Patent Publication No. 7-10913, etc.). Preferred examples include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

[0158] Furthermore, examples of polymerization initiators (F) include: benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butyl carbonyl peroxide)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthroquinone, 2-ethylanthraquinone, and camphorquinone; and 10-butyl-2-chloroacridone, benzoin, methyl phenylglyoxylate, and titanium dioxide compounds. These are preferably used in combination with the following polymerization initiators (F1) (especially amines).

[0159] Examples of acid-generating agents that produce acid through light include: 4-hydroxyphenyl dimethyl strontium p-toluenesulfonate, 4-hydroxyphenyl dimethyl strontium hexafluoroantimonate, 4-acetoxyphenyl dimethyl strontium p-toluenesulfonate, 4-acetoxyphenyl-methyl-benzyl strontium hexafluoroantimonate, triphenyl strontium p-toluenesulfonate, triphenyl strontium hexafluoroantimonate, diphenyl strontium p-toluenesulfonate, diphenyl strontium hexafluoroantimonate, and other onium salts, or nitrobenzyl toluenesulfonates, benzoin toluenesulfonates, etc.

[0160] Regarding the content of the polymerization initiator (F), it is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of resin (C) (including resin (C') in the case of resin (C') described below) and polymerizable compound (E) in the negative photoresist composition of the present invention. If the content of the photopolymerization initiator is within the above range, high sensitivity can be achieved while shortening the exposure time and improving productivity.

[0161] The negative photoresist composition of the present invention may further include at least one selected from the group consisting of polymerization initiators (F1) and leveling agents (G).

[0162] <Polymerization Initiator (F1)> The negative photoresist composition of the present invention may further include a polymerization initiator (F1). The polymerization initiator (F1) is a compound or sensitizer used to promote the polymerization of a polymerizable compound that is initiated by a polymerization initiator, and is usually used in combination with the polymerization initiator (F).

[0163] Examples of polymerization initiators (F1) include: amine compounds, alkoxyanthracene compounds, and 9-oxosulfuron. Compounds, carboxylic acid compounds, etc.

[0164] Examples of amine compounds include: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as milchnerone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, among which 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) can be used.

[0165] Examples of the above-mentioned alkoxyanthracene compounds include: 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

[0166] As mentioned above, 9-oxosulfur Compounds, for example: 2-isopropyl-9-oxosulfuron 4-Isopropyl-9-Oxysulfur 2,4-Diethyl-9-oxosulfur 2,4-Dichloro-9-oxosulfur 1-Chloro-4-propoxy-9-oxosulfur wait.

[0167] Examples of the aforementioned carboxylic acid compounds include: phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

[0168] When using the polymerization initiator (F1), its amount 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 resin (C) (including resin (C') in the case of resin (C') described below) and polymerizable compound (E) in the negative photoresist composition of the present invention. If the amount of polymerization initiator (F1) is within this range, patterns can be formed with high sensitivity, and there is a tendency to improve the productivity of patterns.

[0169] <Leveling Agent (G)> Examples of leveling agents (G) include polysiloxane surfactants, fluorinated surfactants, and polysiloxane surfactants containing fluorine atoms. These may have polymerizable groups on their side chains.

[0170] Examples of polysiloxane surfactants include surfactants with siloxane bonds. Specifically, examples include: Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, 8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Momentive Advanced Materials Japan Co., Ltd.).

[0171] Examples of fluorinated surfactants include those with fluorocarbon chains. Specifically, examples include: Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Co., Ltd.), Eftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics & Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Precision Chemical Research Institute Co., Ltd.).

[0172] Examples of polysiloxane surfactants containing fluorine atoms include surfactants containing siloxane bonds and fluorocarbon chains. Specifically, examples include: MEGAFAC (registered trademark) R08, BL20 (same series), F475 (same series), F477 (same series), and F443 (same series, manufactured by DIC Corporation).

[0173] Regarding the content of the leveling agent (G), relative to the total amount of the negative photoresist composition of the present invention, it is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, and more preferably 0.005% by mass or more and 0.05% by mass or less. If the content of the leveling agent (G) is within the above range, the flatness of the color filter can be improved.

[0174] <Other Ingredients> The negative photoresist composition of the present invention may, as needed, include fillers, other polymeric compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and other additives known in the art (hereinafter referred to as "other components").

[0175] <Method for manufacturing negative photoresist composition> For example, a negative photoresist composition can be obtained by dispersing a colorant (A) and a resin (C) in a solvent (B) containing a dispersant (D) to obtain a colorant dispersion, and then, as needed, by mixing a polymerizable compound (E), a polymerization initiator (F), a leveling agent (G), etc.

[0176] The term "dispersion treatment" refers to mixing until the particles of the colorant (A) or resin (C) are dispersed. Through this dispersion treatment, the particles are broken down into smaller pieces. Furthermore, the term "dispersion state" refers to the state in which the particles float in the solvent (B) within the mixture.

[0177] Regarding the content of colorant (A) in the colorant dispersion, it is preferably 2% by mass or more, more preferably 5% by mass or more, and more preferably 30% by mass or less, and more preferably 20% by mass or less, relative to the total amount of the colorant dispersion.

[0178] Furthermore, regarding the content of solvent (B), relative to the total amount of colorant dispersion, it is preferably 60% by mass or more, more preferably 75% by mass or more, and preferably 93% by mass or less, more preferably 90% by mass or less, and most preferably 85% by mass or less.

[0179] When the colorant dispersion contains resin (C), the content of resin (C) relative to the total amount of the colorant dispersion is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 15% by mass or less, more preferably 7% by mass or less. If the content of resin (C) is within the above range, the dispersion tends to become more stable.

[0180] Regarding the content of dispersant (D) in the colorant dispersion, it is preferably 1% by mass or more, more preferably 2% by mass or less, and more preferably 20% by mass or less, and more preferably 10% by mass or less, relative to the total amount of the colorant dispersion. If the content of dispersant (D) is within the above range, the dispersion tends to become more stable.

[0181] The temperature for dispersing the colorant (A) in the solvent (B) and for dispersing the mixture is preferably below 120°C, more preferably below 70°C. There is no particular limitation on the lower limit of the dispersion temperature, which is typically 20°C. The dispersion time is preferably 0.5 hours or more, more preferably 2 hours or more, and preferably 48 hours or less, more preferably 20 hours or less. Examples of apparatus used in the dispersion include: roller mills, high-speed stirring devices, bead mills, ball mills, sand mills, paint conditioners, ultrasonic dispersers, and high-pressure dispersers. The obtained colorant dispersion is preferably filtered using a filter with a pore size of approximately 1.0 to 5.0 μm.

[0182] When adding a polymerizable compound (E) and a polymerization initiator (F) to the above-mentioned colorant dispersion, it is preferable to further add a resin ("resin (C')"). Examples of resin (C') are the same as resin (C). Resin (C') may be the same as resin (C) or may be a different type. Resin (C') is preferably resin [K1], resin [K2], resin [K5], or resin [K6], more preferably resin [K5] or resin [K6], and even more preferably resin [K6].

[0183] Regarding the total content of resin (C) and resin (C'), relative to the total amount of solid components, it is preferably 7-65% by mass, more preferably 10-60% by mass, further preferably 13-60% by mass, and even more preferably 13-55% by mass. If the resin content is within the above range, there is a tendency to increase the resolution of the colored pattern and the residual film rate of the colored pattern.

[0184] When adding a polymerizable compound (E) and a polymerization initiator (F) to the above-mentioned colorant dispersion, it is preferable to further add a solvent (B').

[0185] As a solvent (B'), examples similar to solvent (B) can be cited. From the perspective of coatability and drying properties, organic solvents with a boiling point of 1 atm above 120°C and below 180°C are preferred, and more preferably are propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, etc., and even more preferably are propylene glycol monomethyl ether acetate, ethyl lactate, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol ethyl methyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, etc.

[0186] Regarding the total content of solvent (B) and solvent (B') in the negative photoresist composition, it is preferably 40-95% by mass, more preferably 45-92% by mass, relative to the total amount of the negative photoresist composition. In other words, the solid content of the negative photoresist composition is preferably 5-60% by mass, more preferably 8-55% by mass. If the solvent content is within the above range, the flatness during coating becomes better, and since the color concentration is not insufficient when forming a color filter, the display characteristics tend to be better.

[0187] Methods for manufacturing colored patterns for color filters using the negative photoresist composition of the present invention include photolithography, inkjet printing, and printing. Photolithography is preferred. Photolithography involves coating the aforementioned negative photoresist composition onto a substrate, drying it to form a composition layer, and then exposing and developing the composition layer using a photomask. In photolithography, a photomask is not used during exposure, and / or development is not performed, thereby forming a colored coating film that is a hardened form of the aforementioned composition layer.

[0188] The thickness of the color filter (hardened film) is preferably less than 20 μm, more preferably less than 6 μm, further preferably less than 3 μm, further preferably less than 1.5 μm, especially preferably less than 0.5 μm, and preferably more than 0.1 μm, more preferably more than 0.2 μm, and further preferably more than 0.3 μm.

[0189] As a substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda-lime glass with a silicon dioxide coating can be used; or resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; and aluminum, silver, or silver / copper / palladium alloy thin films formed on the above-mentioned substrates. Other color filter layers, resin layers, transistors, circuits, etc., can also be formed on these substrates. Furthermore, substrates treated with HMDS (hexamethyl disilazane) can also be used.

[0190] The formation of individual color pixels using photolithography can be performed using known or conventional apparatus or conditions. For example, it can be fabricated as follows: First, a negative photoresist composition is coated onto a substrate, followed by heat drying (pre-baking) and / or vacuum drying to remove volatile components such as solvents and achieve a smooth composition layer. Examples of coating methods include spin coating, slit coating, and a combination of slit and spin coating. The temperature during heat drying is preferably 30–120°C, more preferably 50–110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. During vacuum drying, it is preferably performed at a pressure of 50–150 Pa and a temperature range of 20–25°C. The film thickness of the composition layer is not particularly limited, and can be appropriately selected according to the film thickness of the target color filter.

[0191] Secondly, the composite layer system is used to form a photomask for exposure, thereby creating the target colored pattern. The pattern on the photomask is not particularly limited; any pattern appropriate to the intended use can be used. The light source used in the exposure is preferably a light source that generates light with wavelengths in the range of 250–450 nm. For example, light wavelengths below 350 nm can be cut off using a filter that cuts off that wavelength region, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts those wavelength regions. Specifically, examples include mercury lamps, light-emitting diodes (LEDs), metal halide lamps, and halogen lamps. Since parallel light can be uniformly irradiated across the entire exposure surface, or accurate alignment of the photomask and substrate can be achieved, it is preferable to use a photomask alignment exposure machine, a stepper exposure machine, or a proximity exposure device, which allows for reduced projection exposure or close-in exposure.

[0192] Developing is performed by contacting the exposed composite layer with a developing solution to form a colored pattern on the substrate. During development, the unexposed portions of the composite layer dissolve in the developing solution and are removed. The developing solution is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of this alkaline compound 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 also contain a surfactant. The developing method can be any of the following: immersion method, dipping method, or spray method. Furthermore, the substrate can be tilted at any angle during development. After development, it is best to wash with water.

[0193] Furthermore, it is preferable to bake the obtained colored pattern afterward. The baking temperature is preferably 80~250℃, more preferably 100~245℃. The baking time is preferably 1~120 minutes, more preferably 2~30 minutes.

[0194] The colored patterns and colored coatings obtained in the above manner are more useful as color filters, which are more useful as color filters used in display devices (such as liquid crystal display devices, organic EL (Electroluminescence) devices, electronic paper, solid-state imaging elements, etc.). [Example]

[0195] The present invention is described in more detail below with examples, but the present invention is not limited to the following examples and can be implemented by appropriate modifications within the scope of the above and below principles, all of which are included within the technical scope of the present invention. Unless otherwise specified, "%" and "parts" in the examples refer to mass percentage and mass parts, respectively. The structure of the compounds was identified using mass spectrometry (LC; Agilent 1200 model, MASS; Agilent LC / MSD model).

[0196] <Synthesis of Dyes> [Synthesis example 1] 50.0 parts of Pink Base (manufactured by TAIYO Fine Chemicals), 300 parts of N-methylpyrrolidone (NMP) (manufactured by Fujifilm and Koh Genuine Chemicals Co., Ltd.), 247.0 parts of iodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 120.3 parts of potassium carbonate (manufactured by Fujifilm and Koh Genuine Chemicals Co., Ltd.) were mixed at room temperature, heated to 80°C, and stirred for 4 hours. After cooling the reaction solution to room temperature, the iodomethane was removed by distillation under reduced pressure, and 3300 parts of hydrochloric acid with a concentration of 1 equivalent was added to the obtained slurry. The precipitate was obtained as a residue from vacuum filtration, washed with 1000 parts of deionized water, and dried to obtain 50.6 parts of the compound represented by formula (2). The yield was 97%.

[0197]

[0198] Identification of the compound represented by formula (2) (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 603.2 Exact Mass: 602.2

[0199] [Synthesis example 2] 10.0 parts of the compound represented by formula (3), 20.0 parts of 2,4,6-trimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), and 60 parts of NMP (manufactured by Fujifilm and Wako Pure Chemical Industries Co., Ltd.) were mixed at room temperature, heated to 160°C, and stirred for 7 hours. After cooling the reaction solution to room temperature, 120 parts of hydrochloric acid with a concentration of 1 equivalent were added. The precipitate was obtained as a residue after vacuum filtration, washed with 100 parts of deionized water, and dried to obtain 12.4 parts of the compound represented by formula (4). The yield was 83%.

[0200]

[0201] Identification of the compound represented by formula (4)

[0202] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 603.8 Precision quality: 602.2

[0203] [Synthesis example 3] Except for replacing 2,4,6-trimethylaniline with 5-methoxy-2-methylaniline, the compound represented by formula (5) was synthesized by the same method as in Synthesis Example 2. The yield was 78%.

[0204] Identification of the compound represented by formula (5)

[0205] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 607.2 Precision mass: 606.2

[0206] [Synthesis Example 4] Except for replacing 2,4,6-trimethylaniline with 6-methoxy-2-methylaniline, the compound represented by formula (6) was synthesized by the same method as in Synthesis Example 2. The yield was 31%.

[0207] Identification of the compound represented by formula (6)

[0208] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 607.2 Precision mass: 606.2

[0209] [Synthesis example 5] 2.0 parts of the compound represented by formula (7), 20.0 parts of N-methylpyrrolidone (NMP) (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.), 16.4 parts of iodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 8.0 parts of potassium carbonate (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.) were mixed at room temperature, heated to 80°C, and stirred for 16 hours. After cooling the reaction solution to room temperature, the iodomethane was removed by distillation under reduced pressure, and 220.0 parts of hydrochloric acid with a concentration of 1 equivalent was added to the obtained slurry. The precipitate was obtained as a residue from vacuum filtration, washed with 40 parts of deionized water, and dried to obtain 1.0 part of the compound represented by formula (8). The yield was 49%.

[0210] Identification of the compound represented by formula (7)

[0211] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 519.1 Precision quality: 518.1

[0212] Identification of the compound represented by formula (8)

[0213] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 547.2 Precision mass: 546.2

[0214] [Synthesis example 6] 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 obtained 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 crystallization. The precipitated crystals were obtained as residue by vacuum filtration and dried to obtain 44 parts of the compound represented by formula (I-1-A).

[0215]

[0216] Subsequently, 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 obtained reaction solution to room temperature, it was filtered, washed with 100 parts of water, and the obtained crystals were dried to obtain 52 parts of the compound represented by formula (I-1).

[0217] Identification of compounds represented by formula (I-1)

[0218] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 599.2 Precision quality: 598.2

[0219] [Synthesis Example 7] One part of Pink Base (manufactured by TAIYO Fine Chemicals), seven parts of N-methylpyrrolidone, one part of potassium carbonate, and two parts of ethyl 4-bromobutyrate (represented by formula (1)) were added, and the mixture was stirred at 100°C for seven and a half hours. After cooling, 20 parts of 2 N hydrochloric acid were added to the obtained reaction solution, and the mixture was extracted twice with 45 parts of chloroform. The chloroform layers were combined, washed with saturated brine, and dried with anhydrous magnesium sulfate. The solvent was removed by distillation under reduced pressure, and the mixture was dried under reduced pressure at 60°C to obtain 4.1 parts of the crude product of the compound represented by formula (A-6-IM1).

[0220] Identification of compounds represented by formula (A-6-IM1)

[0221] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 803.5 Precision quality: 802.3

[0222] 4.1 parts of the compound represented by formula (A-6-IM1), 9.8 parts of methanol, and 3.5 parts of 8% sodium hydroxide aqueous solution were added to a flask equipped with a condenser and a stirrer, and the mixture was stirred at room temperature for 6 hours. The resulting reaction solution was added to 30 parts of 2 N hydrochloric acid, and stirred at room temperature for 30 minutes, resulting in crystallization. The precipitated crystals were filtered, thoroughly washed with deionized water, and dried under reduced pressure at 60°C to obtain 1.0 part of compound (A-6-IM2).

[0223] Identification of compounds represented by formula (A-6-IM2)

[0224] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 747.5 Precision mass: 746.3

[0225] [Synthesis example 8] 15 parts of a pigment (manufactured by TAIYO Fine Chemicals) represented by formula A0-3, 150 parts of chloroform, and 8.9 parts of N,N-dimethylformamide were added to a flask equipped with a condenser and a stirrer. While maintaining the temperature below 20°C with stirring, 10.9 parts of thionyl chloride were added dropwise. After the addition was complete, the temperature was raised to 50°C and maintained at the same temperature for 5 hours to allow the reaction to proceed. The temperature was then cooled to 20°C. While maintaining the cooled reaction solution below 20°C with stirring, a mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. The reaction was then carried out at the same temperature with stirring for 5 hours. The resulting reaction mixture was then subjected to solvent distillation using a rotary evaporator, and a small amount of methanol was added with vigorous stirring. While stirring, this mixture was added to a mixture of 375 parts of deionized water to induce crystallization. The precipitated crystals were filtered and separated, thoroughly washed with ion-exchange water, and dried under reduced pressure at 60°C to obtain 11.3 parts of dye A3 (a mixed dye of dyes A3-1 to A3-8).

[0226] (In formula (A3), Rg, Rh, and Ri independently represent hydrogen atoms, -SO3-, -SO3H, or -SO2NHRa, respectively; Ra represents 2-ethylhexyl.)

[0227]

[0228] [Synthesis Example 9] Except for replacing 2,4,6-trimethylaniline with o-toluidine, the compound represented by formula (9) was synthesized by the same method as in Synthesis Example 2. The yield was 90%.

[0229] Identification of the compound represented by formula (9)

[0230] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 575.2 Precision mass: 574.2

[0231] [Synthesis Example 10] 4.00 parts of the compound represented by formula (3), 10.0 parts of 2-aminobiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (manufactured by Fujifilm and Koko Pure Chemical Industries Co., Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 9 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 equivalent hydrochloric acid were added, and the precipitate was obtained as a residue after vacuum filtration. The precipitate was then washed with 96.0 parts of 1 equivalent hydrochloric acid. 267 parts of acetone and 267 parts of methanol were added to the obtained residue, heated to 50°C, and stirred for 1 hour. The precipitate was obtained as a residue after vacuum filtration. The obtained residue was dried to obtain 4.67 parts of the compound represented by formula (11). The yield was 71%.

[0232] Identification of the compound represented by formula (11)

[0233] (Mass spectrometry analysis) Ionization mode = MALDI-TOF + : m / z = [M + H] + 671.1 Precision mass: 670.2

[0234] [Synthesis Example 11] 4.00 parts of the compound represented by formula (3), 10.0 parts of 3-aminobiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (manufactured by Fujifilm and Kako Pure Chemical Industries Co., Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 9 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 equivalent hydrochloric acid were added, and the precipitate was obtained as a residue after vacuum filtration. The precipitate was then washed with 96.0 parts of 1 equivalent hydrochloric acid. 300 parts of acetone and 300 parts of methanol were added to the obtained residue, heated to 50°C, and stirred for 1 hour. The precipitate was obtained as a residue after vacuum filtration. The obtained residue was dried to obtain 5.13 parts of the compound represented by formula (12). The yield was 78%.

[0235] Identification of the compound represented by formula (12)

[0236] (Mass spectrometry analysis) Ionization mode = MALDI-TOF + : m / z = [M + H] + 671.1 Precision mass: 670.2

[0237] [Synthesis Example 12] 4.00 parts of the compound represented by formula (3), 8.84 parts of 4-tert-butylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (manufactured by Fujifilm and Koko Pure Chemical Industries Co., Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 9 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 equivalent hydrochloric acid were added, and the precipitate was obtained as a residue after vacuum filtration. The precipitate was then washed with 96.0 parts of 1 equivalent hydrochloric acid. 357 parts of acetone and 357 parts of methanol were added to the obtained residue, heated to 50°C, and stirred for 1 hour. The precipitate was obtained as a residue after vacuum filtration. The obtained residue was dried to obtain 5.59 parts of the compound represented by formula (13). The yield was 90%.

[0238] Identification of the compound represented by formula (13)

[0239] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 631.2 Precision mass: 630.3

[0240] [Synthesis Example 13] 4.00 parts of the compound represented by formula (3), 10.0 parts of 3,5-di-tert-butylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (manufactured by Fujifilm and Wako Pure Chemical Industries Co., Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 9 hours. After cooling the reaction solution to room temperature, 48.0 parts of hydrochloric acid with a concentration of 1 equivalent were added, and the precipitate was obtained as a residue after vacuum filtration. The precipitate was then washed with 96.0 parts of hydrochloric acid with a concentration of 1 equivalent. 264 parts of acetone and 264 parts of methanol were added to the obtained residue, heated to 50°C, and stirred for 1 hour. The precipitate was obtained as a residue after vacuum filtration. The obtained residue was dried to obtain 4.70 parts of the compound represented by formula (14). The yield was 64%.

[0241] Identification of the compound represented by formula (14)

[0242] (Mass spectrometry analysis) Ionization mode = MALDI-TOF + : m / z = [M + H] + 743.5 Precision mass: 742.4

[0243] [Synthesis Example 14] 2,6-Diphenylaniline was synthesized using references (Chun Liu, Xiaoxiao Song, Qijian Ni and Jieshan Qiu; ARKIVOC, 2012, 9, 62-75.). Subsequently, 4.00 parts of the compound represented by formula (3), 9.69 parts of 2,6-diphenylaniline, 2.69 parts of zinc chloride (manufactured by Fujifilm and Koh Genuine Chemicals Co., Ltd.), and 24.0 parts of cyclobutane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed at room temperature, heated to 250°C, and stirred for 4 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 equivalent hydrochloric acid were added, and the precipitate was obtained as a residue obtained by vacuum filtration. The precipitate was then washed sequentially with 24.0 parts of toluene, 18.0 parts of N,N-dimethylformamide, and 20.0 parts of N,N-dimethylformamide. The obtained residue was dried to obtain 5.18 parts of the compound represented by formula (15). The yield was 64%.

[0244] Identification of the compound represented by formula (15)

[0245] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 823.3 Precision quality: 822.3

[0246] [Synthesis Example 15] 10.0 parts of the compound represented by formula (3), 16.5 parts of 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), and 70.0 parts of N-methylpyrrolidone (manufactured by Fujifilm and Kako Pure Chemical Industries Co., Ltd.) were mixed at room temperature, heated to 80°C, and stirred for 2 hours. After cooling the reaction solution to room temperature, 140 parts of hydrochloric acid with a concentration of 1 equivalent were added, and the precipitate was obtained as a residue by vacuum filtration. The precipitate was then washed with 280 parts of hydrochloric acid with a concentration of 1 equivalent. The obtained residue was dried to obtain 9.06 parts of the compound represented by formula (16). The yield was 75%.

[0247] Identification of the compound represented by formula (16)

[0248] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 490.2 Precision quality: 489.1

[0249] 4.00 parts of the compound represented by formula (16), 3.80 parts of aniline (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 3 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 equivalent hydrochloric acid were added, and the precipitate was obtained as a residue by vacuum filtration. The precipitate was then washed with 96.0 parts of 1 equivalent hydrochloric acid and 36.8 parts of N,N-dimethylformamide. The obtained residue was dried to obtain 3.28 parts of the compound represented by formula (17). The yield was 74%.

[0250] Identification of the compound represented by formula (17)

[0251] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 547.2 Precision mass: 546.2

[0252] [Synthesis Example 16] 4.00 parts of the compound represented by formula (16), 6.25 parts of 2,4-dimethoxyaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (manufactured by Fujifilm and Koimitsu Chemical Co., Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 3 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 equivalent hydrochloric acid were added, and the precipitate was obtained as a residue by vacuum filtration. The precipitate was then washed with 96.0 parts of 1 equivalent hydrochloric acid and 42.4 parts of N,N-dimethylformamide. The obtained residue was dried to obtain 2.88 parts of the compound represented by formula (18). The yield was 58%.

[0253] Identification of the compound represented by formula (18)

[0254] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 607.2 Precision mass: 606.2

[0255] [Synthesis Example 17] 4.00 parts of the compound represented by formula (16), 5.03 parts of 4-methoxyaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (manufactured by Fujifilm and Koimitsu Chemical Co., Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 3 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 equivalent hydrochloric acid were added, and the precipitate was obtained as a residue by vacuum filtration. The precipitate was then washed with 96.0 parts of 1 equivalent hydrochloric acid and 41.9 parts of N,N-dimethylformamide. The obtained residue was dried to obtain 5.00 parts of the compound represented by formula (19). The yield was 69%.

[0256] Identification of the compound represented by formula (19)

[0257] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 577.3 Precision mass: 576.2

[0258] [Synthesis Example 18] 4.00 parts of the compound represented by formula (16), 6.91 parts of 3-aminobiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (manufactured by Fujifilm and Koko Pure Chemical Industries Co., Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 5 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 equivalent hydrochloric acid were added, and the precipitate was obtained as a residue by vacuum filtration. The precipitate was then washed with 96.0 parts of 1 equivalent hydrochloric acid and 75.2 parts of N,N-dimethylformamide. The obtained residue was dried to obtain 3.79 parts of the compound represented by formula (20). The yield was 75%.

[0259] Identification of the compound represented by formula (20)

[0260] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 623.2 Precision quality: 622.2

[0261] [Synthesis Example 19] 4.00 parts of the compound represented by formula (16), 6.91 parts of 2-aminobiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 3 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 equivalent hydrochloric acid were added, and the precipitate was obtained as a residue by vacuum filtration. The precipitate was then washed with 96.0 parts of 1 equivalent hydrochloric acid and 44.8 parts of N,N-dimethylformamide. The obtained residue was dried to obtain 3.55 parts of the compound represented by formula (21). The yield was 70%.

[0262] Identification of the compound represented by formula (21)

[0263] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 623.2 Precision quality: 622.2

[0264] [Synthesis Example 20] 13.0 parts of the compound represented by formula (3), 39.3 parts of 2,6-diphenylaniline, and 78.0 parts of N-methylpyrrolidone (manufactured by Fujifilm and Koko Pure Chemical Industries, Ltd.) were mixed at room temperature, heated to 85°C, and stirred for 5 hours. After cooling the reaction solution to room temperature, 156 parts of hydrochloric acid with a concentration of 1 equivalent were added, and the precipitate was obtained as a residue by vacuum filtration. The precipitate was then washed with 312 parts of hydrochloric acid with a concentration of 1 equivalent. The obtained residue was dried to obtain 16.2 parts of the compound represented by formula (22). The yield was 82%.

[0265] Identification of the compound represented by formula (22)

[0266] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 614.5 Precision quality: 613.1

[0267] 4.00 parts of the compound represented by formula (22), 3.95 parts of 2,6-dimethylamine (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.), 1.78 parts of zinc chloride (manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.), and 24.0 parts of cyclobutane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed at room temperature, heated to 250°C, and stirred for 3 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 equivalent concentration hydrochloric acid were added, and the precipitate was obtained as a residue by vacuum filtration. The precipitate was then washed with 96.0 parts of 1 equivalent concentration hydrochloric acid and 69.5 parts of N,N-dimethylformamide. The obtained residue was dried to obtain 3.05 parts of the compound represented by formula (23). The yield was 67%.

[0268] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 699.2 Precision quality: 698.2

[0269] [Synthesis Example 21] 4.00 parts of the compound represented by formula (22), 5.51 parts of 3-aminobiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (manufactured by Fujifilm and Kako Pure Chemical Industries Co., Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 6 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 equivalent hydrochloric acid were added, and the precipitate was obtained as a residue by vacuum filtration. The precipitate was then washed with 96.0 parts of 1 equivalent hydrochloric acid and 28.5 parts of N,N-dimethylformamide. The obtained residue was dried to obtain 2.85 parts of the compound represented by formula (24). The yield was 59%.

[0270] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 747.2 Precision mass: 746.2

[0271] [Synthesis Example 22] 4.00 parts of the compound represented by formula (22), 5.51 parts of 2-aminobiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.), and 24.0 parts of N-methylpyrrolidone (manufactured by Fujifilm and Kako Pure Chemical Industries Co., Ltd.) were mixed at room temperature, heated to 170°C, and stirred for 6 hours. After cooling the reaction solution to room temperature, 48.0 parts of 1 equivalent hydrochloric acid were added, and the precipitate was obtained as a residue by vacuum filtration. The precipitate was then washed with 96.0 parts of 1 equivalent hydrochloric acid and 49.2 parts of N,N-dimethylformamide. The obtained residue was dried to obtain 2.88 parts of the compound represented by formula (25). The yield was 59%.

[0272] (Mass spectrometry analysis) Ionization mode = ESI+ : m / z = [M+H]+ 747.2 Precision mass: 746.2

[0273] <Resin Synthesis> [Synthesis Example 23 Resin C-1] 276.8 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube. Nitrogen purging was performed while stirring and the temperature was raised to 120°C. Then, 35.3 g of tributylperoxide-2-ethyl hexanoate (polymerization initiator) was added to a monomer mixture containing 92.4 g of 2-ethylhexyl acrylate, 184.9 g of glycidyl methacrylate, and 12.3 g of dicyclopentyl methacrylate. The resulting mixture was added dropwise to the flask over a period of 2 hours using a dropping funnel. After the addition was complete, the mixture was stirred at 120°C for 30 minutes to induce a copolymerization reaction, resulting in an addition copolymer. Subsequently, the flask was purged with air, and 93.7 g of acrylic acid, 1.5 g of triphenylphosphine (catalyst), and 0.8 g of p-methoxyphenol (polymerization inhibitor) were added to the above addition copolymer solution. The reaction was continued at 110°C for 10 hours. The epoxy groups from glycidyl methacrylate reacted with acrylic acid to break the epoxy groups, simultaneously introducing polymerizable unsaturated bonds into the side chains of the polymer. Next, 24.2 g of succinic anhydride was added to the reaction system, and the reaction was continued at 110°C for 1 hour. The hydroxyl groups generated by the breaking of the epoxy groups reacted with succinic anhydride to introduce carboxyl groups into the side chains, thereby obtaining the polymer. Finally, 383.3 g of propylene glycol monomethyl ether acetate was added to the reaction solution to obtain a polymer (resin (C-1)) solution with a polymer solids content of 40%. The weight-average molecular weight (Mw) of the resulting copolymer (polymer; resin (C-1)) is 6.3 × 10³, and the acid value converted from solid content is 34 mg-KOH / g.

[0274] [Synthesis Example 24 Resin C-2] A nitrogen atmosphere was created by introducing an appropriate amount of nitrogen gas into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer. 280 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 80°C while stirring. Then, using a dropping pump, a solution was added dropwise to the flask over approximately 5 hours. This solution was prepared by dissolving 289 parts of a mixture (1:1) of 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.02,6]decane-8-yl acrylate, and 3,4-epoxytricyclo[5.2.1.02,6]decane-9-yl acrylate in 125 parts of propylene glycol monomethyl ether acetate. Meanwhile, using another dropping pump, a solution was added dropwise to the flask over approximately 6 hours. This solution was prepared by dissolving 33 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylpentanonitrile) in 235 parts of propylene glycol monomethyl ether acetate. After the addition was complete, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a polymer (resin (C-2)) solution with a polymer solids content of 35.1%. The resulting copolymer (polymer; resin (C-2)) had a weight average molecular weight (Mw) of 9200, a dispersion of 2.08, and an acid value converted from the solids content of 77 mg-KOH / g. The resulting copolymer has the following structural units.

[0275]

[0276] (Preparation of Dispersion 1) Eight parts of CI Pigment Red 122, 3.0 parts of dispersant (BYKLPN-6919 manufactured by BYK Corporation), 3.0 parts of the above-mentioned resin (C-2) (solid content conversion), 81 parts of propylene glycol monomethyl ether acetate, and 5 parts of diacetone alcohol were mixed together. 300 parts of 0.4 mm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU Corporation). Subsequently, the zirconia beads were removed by filtration to obtain dispersion 1.

[0277] (Preparation of Dispersion 2) Dispersion 2 was obtained in the same manner as dispersion 1, except that CI pigment violet 19 was used instead of CI pigment red 122.

[0278] (Preparation of Dispersion 3) Dispersion 3 was obtained in the same manner as dispersion 1, except that Pink Base manufactured by TAIYO Fine Chemicals was used instead of CI Pigment Red 122.

[0279] (Preparation of Dispersion 4) Dispersion 4 was obtained in the same manner as dispersion 1, except that the compound obtained in Synthesis Example 1 was used instead of CI pigment red 122.

[0280] (Preparation of Dispersion 5) Dispersion 5 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 2 was used instead of CI pigment red 122.

[0281] (Preparation of Dispersion 6) Dispersion 6 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 3 was used instead of CI pigment red 122.

[0282] (Preparation of Dispersion 7) Dispersion 7 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 4 was used instead of CI pigment red 122.

[0283] (Preparation of Dispersion 8) Dispersion 8 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 5 was used instead of CI pigment red 122.

[0284] (Preparation of Dispersion 9) Dispersion 9 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 9 was used instead of CI pigment red 122.

[0285] (Preparation of Dispersion 10) Dispersion 10 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 10 was used instead of CI pigment red 122.

[0286] (Preparation of Dispersion 11) Dispersion 11 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 11 was used instead of CI pigment red 122.

[0287] (Preparation of Dispersion 12) Dispersion 12 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 12 was used instead of CI pigment red 122.

[0288] (Preparation of Dispersion 13) Dispersion 13 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 13 was used instead of CI pigment red 122.

[0289] (Preparation of Dispersion 14) Dispersion 14 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 14 was used instead of CI pigment red 122.

[0290] (Preparation of Dispersion 15) Dispersion 15 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 15 was used instead of CI pigment red 122.

[0291] (Preparation of Dispersion 16) Dispersion 16 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 16 was used instead of CI pigment red 122.

[0292] (Preparation of Dispersion 17) Dispersion 17 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 17 was used instead of CI pigment red 122.

[0293] (Preparation of Dispersion 18) Dispersion 18 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 18 was used instead of CI pigment red 122.

[0294] (Preparation of Dispersion 19) Dispersion 19 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 19 was used instead of CI pigment red 122.

[0295] (Preparation of Dispersion 20) Dispersion 20 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 20 was used instead of CI pigment red 122.

[0296] (Preparation of Dispersion 21) Dispersion 21 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 21 was used instead of CI pigment red 122.

[0297] (Preparation of Dispersion 22) Dispersion 22 was obtained in the same manner as dispersion 1, except that the compound obtained in synthesis example 22 was used instead of CI pigment red 122.

[0298] [Examples 1-27, Comparative Examples 1 and 2] Dispersions 1-22, compounds (A-9)-(A-11) of Synthetic Examples 6-8, resin, polymerizable compound, polymerization initiator, leveling agent, and solvent were mixed in such a manner that the final composition was shown in Tables 3 and 4 below, to obtain the negative photoresist compositions of Examples 1-27 and Comparative Examples 1 and 2.

[0299] [Table 3] The unit is parts by mass. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 1 Comparative Example 2 Dispersion 1 A-1 657.9 Dispersion 2 A-2 230.3 223.8 394.7 657.9 Dispersion 3 A-3 657.9 328.9 300.2 300.2 328.9 319.8 328.9 328.9 328.9 Dispersion 4 A-4 328.9 657.9 98.7 263.2 Dispersion 5 A-5 328.9 Dispersion 6 A-6 328.9 Dispersion 7 A-7 328.9 Dispersion 8 A-8 657.9 Compound (A-9) A-9 24.0 7.7 Compound (A-10) A-10 24.0 Compound (A-11) A-11 44.2 Dispersion 9 A-12 657.9 Resin (C') C-1 40.3 40.3 51.0 51.0 40.3 40.3 43.7 40.3 60.0 40.3 40.3 40.3 40.3 40.3 40.3 40.3 Polymerizable compounds (E) E-1 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Polymerization initiator (F) F-1 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Leveling agent (G) G-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Solvent (B') B-1 66.5 66.5 484 484 66.5 66.5 359.4 66.5 66.5 66.5 66.5 66.5 66.5 66.5 66.5 B-2 417.1 B-3 361.8 361.8 165.1 165.1 361.8 361.8 139.5 361.8 417.1 361.8 361.8 361.8 361.8 361.8 361.8 361.8

[0300] [Table 4] The unit is parts by mass. Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Dispersion 3 A-3 328.9 592.1 625.0 592.1 328.9 592.1 625.0 625.0 526.3 328.9 328.9 625.0 328.9 Dispersion 10 A-13 328.9 Dispersion 11 A-14 65.8 Dispersion 12 A-15 32.9 Dispersion 13 A-16 65.8 Dispersion 14 A-17 328.9 Dispersion 15 A-18 65.8 Dispersion 16 A-19 32.9 Dispersion 17 A-20 32.9 Dispersion 18 A-21 131.6 Dispersion 19 A-22 328.9 Dispersion 20 A-23 328.9 Dispersion 21 A-24 32.9 Dispersion 22 A-25 328.9 Resin (C') C-1 40.3 40.3 40.3 40.3 40.3 40.3 40.3 40.3 40.3 40.3 40.3 40.3 40.3 Polymerizable compounds (E) E-1 40 40 40 40 40 40 40 40 40 40 40 40 40 Polymerization initiator (F) F-1 3 3 3 3 3 3 3 3 3 3 3 3 3 Leveling agent (G) G-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Solvent (B') B-1 66.5 66.5 66.5 66.5 66.5 66.5 66.5 66.5 66.5 66.5 66.5 66.5 66.5 B-3 361.8 361.8 361.8 361.8 361.8 361.8 361.8 361.8 361.8 361.8 361.8 361.8 361.8

[0301] In Tables 3 and 4, each component represents the following compound. Compound (A-9): Compound from Synthesis Example 6 Compound (A-10): Compound from Synthesis Example 7 Compound (A-11): Compound from Synthesis Example 8 Resin (C-1): Resin (C-1) (Solids composition) Polymerizable compound (E-1): Dipentaerythritol polyacrylate ("A9550" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Polymerization initiator (F-1): N-ethoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine (PBG-327; O-acetylgoxime compound; manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) Leveling agent (G-1): Polyether modified polysiloxane oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) Solvent (B-1): Diacetone alcohol (DAA) Solvent (B-2): Ethyl lactate (EL) Solvent (B-3): Propylene glycol monomethyl ether acetate (PGMA)

[0302] <Creation of Hardening Film> A negative photoresist composition was spin-coated onto a 5 cm square glass substrate (Eagle2000; manufactured by Corning Incorporated), followed by pre-baking at 100°C for 3 minutes to form a colored composition layer. After cooling, the colored composition layer was irradiated with light using an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) under atmospheric conditions at an exposure dose of 60 mJ / cm² (365 nm reference). Subsequently, it was baked in an oven at 230°C for 20 minutes to obtain a hardened film. Furthermore, during the fabrication of the hardened film, the film thickness was adjusted so that the transmittance at the maximum absorption wavelength was 5%.

[0303] <Film Thickness Measurement> The thickness of the hardened film on the obtained glass substrate was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Tables 5 and 6.

[0304] <Determination of Maximum Absorption Wavelength and Transmittance> The obtained hardened film on the glass substrate was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). Specifically, the transmittance and maximum absorption wavelength were measured at wavelengths of 400–700 nm. The transmittance at the maximum absorption wavelength (T(λmax)), the transmittance at 440 nm (T(440 nm)), and the transmittance at 620 nm (T(620 nm)) are shown in Tables 5 and 6. Furthermore, the proportions (parts by mass) of each colored material contained in the hardened film and the concentrations (%) of the colored materials contained in the hardened film are shown in Tables 5 and 6.

[0305] [Table 5] The unit is parts by mass. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 1 Comparative Example 2 PR122 100 PV19 35 35 60 100 PinkBase Compound (Ia) 100 50 50 50 50 50 50 50 50 Synthesis example 1 Compound (Ia) 50 100 15 40 Synthesis example 2 Compound (Ib1) 50 Synthesis example 3 Compound (Ib1) 50 Synthesis example 4 Compound (Ib1) 50 Synthesis example 5 Compound (Ia) 100 Synthesis example 6 Compound (Ib1) 50 15 Synthesis Example 7 Compound (Ib1) 50 Synthesis example 8 Compound (Ib1) 100 Synthesis example 9 Compound (Ia) 100 Concentration of colored materials 30% Film thickness (μm) 0.28 0.28 0.35 0.27 0.24 0.40 0.44 0.50 0.43 0.26 0.39 0.35 0.32 0.28 2.70 0.91 T(λmax) 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% T(440 nm) 93% 93% 91% 92% 95% 88% 86% 83% 92% 92% 82% 87% 89% 88% 59% 65% T(620 nm) 99% 98% 98% 98% 98% 98% 97% 95% 99% 93% 99% 84% 98% 80% 91% 91% Maximum absorption wavelength (nm) 535 540 535 540 545 535 535 550 535 550 535 535 535 555 565 575

[0306] [Table 6] The unit is parts by mass. Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 PinkBase Compound (Ia) 50 90 95 90 50 90 95 95 80 50 50 95 50 Synthesis example 10 Compound (Ia) 50 Synthesis example 11 Compound (Ia) 10 Synthesis example 12 Compound (Ia) 5 Synthesis example 13 Compound (Ia) 10 Synthesis example 14 Compound (Ia) 50 Synthesis Example 15 Compound (Ia) 10 Synthesis example 16 Compound (Ib1) 5 Synthesis Example 17 Compound (Ib1) 5 Synthesis Example 18 Compound (Ia) 20 Synthesis example 19 Compound (Ia) 50 Synthesis example 20 Compound (Ia) 50 Synthesis Example 21 Compound (Ia) 5 Synthesis example 22 Compound (Ia) 50 Concentration of colored materials 30% Film thickness (μm) 0.36 0.30 0.29 0.30 0.40 0.28 0.29 0.29 0.30 0.37 0.36 0.29 0.37 T(λmax) 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% T(440 nm) 88% 90% 92% 91% 87% 91% 93% 93% 90% 82% 90% 92% 91% T(620 nm) 92% 82% 89% 92% 92% 94% 95% 94% 87% 94% 95% 90% 97% Maximum absorption wavelength (nm) 535 535 535 535 535 535 535 535 535 535 535 535 535

[0307] As shown in Tables 5 and 6, the negative photoresist compositions of Examples 1 to 27 contain the compound represented by Formula (I) above, and the cured films obtained therefrom have a maximum absorption wavelength in the wavelength range of 500 nm to 580 nm. 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. On the other hand, the negative photoresist compositions of Comparative Examples 1 and 2 do not contain the compound represented by Formula (I) above, and the cured films obtained therefrom have a transmittance of less than 80% at a wavelength of 440 nm. [Industrial Applicability]

[0308] The negative photoresist composition of the present invention can produce a color filter with high transmittance of light with a wavelength of 440 nm.

Claims

1. A negative photoresist composition, characterized in that: it comprises a colorant and a resin, wherein the colorant contains a dye, and the dye is represented by formula (I), [in formula (I), R1 to R4 independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms that may have substituents, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms that may have substituents, wherein the -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR11-; R5 represents -OH, -SO3-, -SO3H, -SO3-Z+, -CO2H, -CO2-Z+, -CO2R8, -SO3R8, or -SO2NR9R10; R6 and R7 independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer from 0 to 5; when m is 2 or more, the plurality of R5s may be the same or different; a represents an integer of 0 or 1; X represents a halogen atom;] Z+ represents +N(R11)4, Na+, or K+, and the four R11s can be the same or different; R8 represents a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, in which the hydrogen atom can be replaced by a halogen atom; R9 and R10 independently represent hydrogen atoms or monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms that may have substituents, in which the -CH2- can be replaced by -O-, -CO-, -NH-, or -NR8-, and R9 and R10 can bond together with the adjacent nitrogen atom to form a 3 to 10-membered heterocycle; R11 represents hydrogen atoms, monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms, or aralkyl groups with 7 to 10 carbon atoms. The spectroscopic spectrum of the hardened film formed by the above negative photoresist composition based on the following hardened film preparation method satisfies the following condition 1: [Condition 1] in the wavelength range of 500 nm to 580 nm. It has a maximum absorption wavelength within nm. When the transmittance of this wavelength is set to 5%, the transmittance of wavelength 440 nm is more than 80%, and the transmittance of wavelength 620 nm is more than 80%. [Curing film preparation method] On a 5 cm square glass substrate, a negative photoresist composition is coated by spin coating. After pre-baking at 100°C for 3 minutes, a colored composition layer is formed. After cooling, the colored composition layer is irradiated with light at an exposure dose of 60 mJ / cm2 (365 nm reference) in an atmospheric atmosphere using an exposure machine. After that, it is baked at 230°C for 20 minutes.

2. The negative photoresist composition of claim 1, having a transmittance of 90% or more at the aforementioned wavelength of 620 nm.

3. The negative photoresist composition of claim 1 or 2, wherein the dye is represented by formula (Ia) and / or formula (Ib1), [in formula (Ia), Ra1 and Ra4 are each independently a monovalent aromatic hydrocarbon group having 1 to 4 carbon atoms; Ra2 and Ra3 are each independently a hydrogen atom, methyl, or ethyl; R5 to R7, m, a, and X represent the same meaning as above] [in formula (Ib1), Rb1 to Rb4 are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms having substituents, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms having substituents,] At least one saturated hydrocarbon group or aromatic hydrocarbon group contained in Rb1 to Rb4 has a halogen atom, -OH, -OR8, -CO2H, -CO2R8, -SO3-, -SO3H, -SO3-Z+, -SR8, -SO2R8, -SO3R8, -SO2NR9R10, or -Si(OR12)(OR13)(OR14) as a substituent, or at least one aromatic hydrocarbon group contained in Rb1 to Rb4 has three or more monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms as substituents, R12, R13, and R14 each independently represent a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, R5 to R10, m, a, and X represent the same meaning as above).

4. The negative photoresist composition of claim 3, wherein the dye is a combination of two or more selected from those represented by formula (Ib1) above, or a combination of those represented by formula (Ib1) above and those represented by formula (Ia) above.

5. The negative photoresist composition of claim 1 or 2, wherein the colorant is only a dye, or a combination of a dye and a red pigment or a purple pigment.

6. The negative photoresist composition of claim 1 or 2, further comprising a polymerizable compound and a polymerization initiator.

7. The negative photoresist composition of claim 1 or 2, which is capable of forming a hardened film with a thickness of less than 1.5 μm.

8. A color filter formed from a negative photoresist composition of any one of claims 1 to 7.

9. A display device comprising a color filter as claimed in claim 8.