Phthalocyanine dyes, colorants, colored resin compositions, color filters, display devices, and solid-state image sensors

Abstract

The present invention aims to provide a phthalocyanine-based dye that can be used to create a color filter with improved color separation from red light. [Solution] The phthalocyanine dye of the present invention consists of one or more compounds represented by formula (I), and is characterized in that the average number of groups represented by formula (II) for each M group in the compound represented by formula (I) is 4.5 or more and 7.2 or less. TIFF2026076873000039.tif60149

Description

[Technical Field]

[0001] The present invention relates to phthalocyanine dyes, colorants containing the dyes, colored resin compositions containing the colorants, color filters formed from the colored resin compositions, and display devices and solid-state image sensors containing the color filters. The present invention also relates to novel compounds. [Background technology]

[0002] Color filters used in display devices such as liquid crystal displays, electroluminescent displays, and plasma displays, as well as solid-state image sensors such as CCDs and CMOS sensors, are manufactured from colored resin compositions. Phthalocyanine compounds are known as colorants included in such colored resin compositions. For example, Patent Document 1 discloses a compound obtained by sulfonating a phthalocyanine compound having an etheraryl group or a thioetheraryl group at at least one of the 4th and 5th positions of the phthalocyanine skeleton, and it is stated that this compound has excellent solubility in alcoholic solvents. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 5-78364 [Overview of the project] [Problems that the invention aims to solve]

[0004] By the way, green color filters are required to efficiently absorb red light and improve color separation. Furthermore, each colorant contained in the colored resin composition for forming the green color filter is required to efficiently absorb red light.

[0005] Therefore, the present invention aims to provide a phthalocyanine-based dye that can be used to create a color filter with improved color separation from red light. Another object of the present invention is to provide a compound that can efficiently absorb red light. [Means for Solving the Problems]

[0006] The gist of the present invention is as follows. [1] A phthalocyanine-based dye composed of one or more compounds represented by formula (I), wherein the average number of groups represented by formula (II) is 4.5 or more and 7.2 or less with respect to M in the compound represented by formula (I). [Chemical formula] [In formula (I), M represents a divalent metal atom. X , 1 , x , , 1 , 5 , , 1 , , 8 , , x , 8 , , x , , , , x , , x , 1 , , <00 / 000017>, , 1 , , 8 , 1 , , x , , x ~X 8 each independently represents a fluorine atom or a chlorine atom. A 1 [[ID=3 8 each independently represents a fluorine atom, a chlorine atom, or a group represented by formula (II). In formula (II), B 1 ~B 5 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a COR < / x group, a CO2R x group, an OR x ​​​​​​​​​​​​​​​​​​​​​​​​​​​​5 At least one of them is CO2R x The phthalocyanine pigment described in [1] or [2] is the base. [4] A phthalocyanine pigment as described in any of [1] to [3], which is any of (i) to (v) below. (i) A compound having 4 groups represented by formula (II) in formula (I), and a compound having 5 groups represented by formula (II) in formula (I). (ii) A compound comprising a compound in which the number of groups represented by formula (II) in formula (I) is 5, and a compound in which the number of groups represented by formula (II) in formula (I) is 6. (iii) A compound comprising a compound in which the number of groups represented by formula (II) in formula (I) is 6, and a compound in which the number of groups represented by formula (II) in formula (I) is 7. (iv) A compound having 7 groups represented by formula (II) in formula (I), and a compound having 8 groups represented by formula (II) in formula (I). (v) A compound having 4 groups represented by formula (II) in formula (I), and a compound having 8 groups represented by formula (II) in formula (I). [5] A coloring agent containing a phthalocyanine-based dye as described in any of [1] to [4]. [6] The coloring agent according to [5], further comprising a coloring agent other than the compound represented by formula (I). [7] The coloring agent according to [5] or [6], wherein the content of the compound represented by formula (Ix) is 50 parts by mass or less per 100 parts by mass of the compound represented by formula (I). [ka] [In formula (Ix), M x This represents a divalent metal atom. X 1x ~X 8x and A 1x ~A 8x These represent, independently of each other, a fluorine atom, a chlorine atom, or a group represented by formula (II). However, X 1x ~X 8xOf these, at least one represents a base expressed by formula (II). * represents a bonding operation. A colored resin composition containing a coloring agent described in any of [8] [5] to [7] and an alkali-soluble resin. [9] The colored resin composition according to [8] further comprising a polymerizable compound and a polymerization initiator. A color filter formed from the colored resin composition described in

[10] [8] or [9].

[11] A display device including the color filter described in

[10] .

[12] A solid-state image sensor including the color filter described in

[10] .

[13] A compound represented by formula (IN). [ka] [In the formula (IN), M n This represents a divalent metal atom. X 1n ~X 8n These represent, independently of each other, a fluorine atom or a chlorine atom. A 1n ~A 8n These represent, independently of each other, a fluorine atom, a chlorine atom, or a group represented by formula (II). However, A 1n ~A 8n Of these, 5 to 7 represent the base expressed by formula (II). B 1 ~B 5 These are, independently of each other, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and COR x group, CO2R x Base, OR x Base, NHR x Base, or NR x This represents two units. R x R represents a hydrocarbon group with 1 to 10 carbon atoms. x If there are multiple instances, they may be identical or different. [Effects of the Invention]

[0007] The phthalocyanine-based dyes of the present invention enable the creation of color filters with enhanced color separation from red light. Furthermore, the compounds of the present invention allow for efficient absorption of red light. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a schematic diagram showing how to determine the distribution width. [Modes for carrying out the invention]

[0009] <<Phthalocyanine pigment (I)>> The phthalocyanine-based dye of the present invention (hereinafter referred to as phthalocyanine-based dye (I)) is a dye consisting of one or more compounds represented by formula (I) (hereinafter sometimes referred to as compound (I)).

[0010] The phthalocyanine dye (I) is characterized in that the average number of groups represented by formula (II) (hereinafter sometimes referred to as aryloxy group (II)) per M group in compound (I) is between 4.5 and 7.2. By using such a phthalocyanine dye (I), the transmittance of the resulting color filter in the 630-680 nm range can be lowered, and a color filter with improved color separation from red light can be provided. Furthermore, adjusting the average number of aryloxy groups (II) in the phthalocyanine dye (I) to the above range is preferable because it suppresses aggregation of compound (I) and improves solubility in solvents (particularly propylene glycol monomethyl ether acetate). It is also preferable because it suppresses the formation of precipitates even when a solution containing the phthalocyanine dye (I) (particularly a propylene glycol monomethyl ether acetate solution) is stored for a certain period of time, that is, it improves the storage stability of the solution. Furthermore, by adjusting the average number of aryloxy groups (II) in the phthalocyanine-based dye (I) to the above range, aggregation of compound (I) during high-temperature treatments such as post-baking is suppressed, which is also preferable because it suppresses the generation of foreign matter in the resulting color filter.

[0011] [ka] [In formula (I), M represents a divalent metal atom. X 1 ~X 8 These represent, independently of each other, a fluorine atom or a chlorine atom. A 1 ~A 8 These represent, independently of each other, a fluorine atom, a chlorine atom, or a group represented by formula (II). In formula (II), B 1 ~B 5 These are, independently of each other, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and COR x group, CO2R x Base, OR x Base, NHR x Base, or NR x This represents two units. R x R represents a hydrocarbon group with 1 to 10 carbon atoms. x If there are multiple instances, they may be identical or different. * represents a bonding operation.

[0012] In phthalocyanine dyes (I), the average number of aryloxy groups (II) per M molecule in compound (I) is 4.5 to 7.2, preferably 5.0 to 7.2, more preferably 5.1 to 7.0, and even more preferably 5.2 to 6.5. The molar ratio of each compound (specifically, compounds (I-1) to (I-9) below) contained in phthalocyanine dyes (I) is determined to be equal to the area ratio obtained by liquid chromatography (LC) area percentage method, and the average number of aryloxy groups (II) per M molecule can be calculated based on this molar ratio.

[0013] The compound (I) contained in the phthalocyanine dye (I) is determined by the number of aryloxy groups (II) that compound (I) possesses. A 1 ~A 8A compound in which one of the following is an aryloxy group (II) (hereinafter sometimes referred to as compound (I-1)); A 1 ~A 8 A compound in which any two of these are aryloxy groups (II) (hereinafter sometimes referred to as compound (I-2)); A 1 ~A 8 A compound in which any three of these are aryloxy groups (II) (hereinafter sometimes referred to as compound (I-3)); A 1 ~A 8 A compound in which any four of these are aryloxy groups (II) (hereinafter sometimes referred to as compound (I-4)); A 1 ~A 8 A compound in which any five of these are aryloxy groups (II) (hereinafter sometimes referred to as compound (I-5)); A 1 ~A 8 A compound in which any six of these are aryloxy groups (II) (hereinafter sometimes referred to as compound (I-6)); A 1 ~A 8 A compound in which any seven of these are aryloxy groups (II) (hereinafter sometimes referred to as compound (I-7)); A 1 ~A 8 Compounds in which all of them are aryloxy groups (II) (hereinafter sometimes referred to as compounds (I-8)); and A 1 ~A 8 These compounds can be classified into nine categories: compounds that do not contain an aryloxy group (II) (hereinafter sometimes referred to as compounds (I-9)); and compounds that do not contain an aryloxy group (II).

[0014] If compound (I) has two or more aryloxy groups (II), the multiple aryloxy groups (II) may be the same or different, but it is preferable that they be the same.

[0015] As long as the average number of aryloxy groups (II) per M is between 4.5 and 7.2, the phthalocyanine dye (I) may contain one compound (I) alone or a combination of two or more compounds.

[0016] The phthalocyanine dye (I) preferably contains at least one selected from the group consisting of compound (I-4), compound (I-5), compound (I-6), compound (I-7), and compound (I-8), and more preferably is any of the following (i) to (v). (i) containing compound (I-4) and compound (I-5) (ii) A compound comprising compound (I-5) and compound (I-6) (iii) A compound comprising compound (I-6) and compound (I-7) (iv) A compound comprising compound (I-7) and compound (I-8) (v) A compound containing compound (I-4) and compound (I-8)

[0017] In (i) above, it is preferable to further include at least one selected from the group consisting of compound (I-6), compound (I-7), and compound (I-8), more preferably compound (I-6), even more preferably compound (I-6) and compound (I-7), and particularly preferably compound (I-6), compound (I-7), and compound (I-8). In (ii) above, it is preferable to further include at least one selected from the group consisting of compound (I-4), compound (I-7), and compound (I-8), more preferably compound (I-7), and even more preferably compound (I-7) and compound (I-8). In (iii) above, it is preferable to further include at least one selected from the group consisting of compound (I-4), compound (I-5), and compound (I-8), more preferably compound (I-5), and even more preferably compound (I-5) and compound (I-8). In (iv) above, it is preferable to further include at least one selected from the group consisting of compound (I-4), compound (I-5), and compound (I-6), more preferably compound (I-6), and even more preferably compound (I-5) and compound (I-6). In (v) above, it is preferable to further include at least one selected from the group consisting of compound (I-5), compound (I-6), and compound (I-7), and it is more preferable to further include compound (I-5), compound (I-6), and compound (I-7).

[0018] In the above compounds (I-4), (I-5), (I-6), (I-7), and (I-8), the position of the aryloxy group (II) is not particularly limited, however A 1 ~A 2 Either one or both, A 3 ~A 4 Either one or both, A 5 ~A 6 Either one or both, and A 7 ~A 8 It is preferable that the compound has one or both of the following positions. That is, compound (I-4) is preferably one compound selected from the compounds represented by the following formulas (I-4a) to (I-4d) or a mixture of two or more compounds, compound (I-5) is preferably one compound selected from the compounds represented by the following formulas (I-5a) to (I-5d) or a mixture of two or more compounds, compound (I-6) is preferably one compound selected from the compounds represented by the following formulas (I-6a) to (I-6e) or a mixture of two or more compounds, compound (I-7) is preferably a compound represented by the following formula (I-7a), and compound (I-8) is preferably a compound represented by the following formula (I-8a).

[0019] [ka]

[0020] [Chemistry]

[0021] [Chemistry]

[0022] [Chemistry]

[0023] In the above formula, AII represents a group represented by formula (II). When there are a plurality of AIIs, they may be the same or different from each other. In the above formula, A 11 ~~~ A 18 each independently represents a fluorine atom or a chlorine atom. In the above formula, M and X 1 ~ X 8 have the same meanings as described above.

[0024] Hereinafter, the present invention will be described more specifically by giving partial structures of the compound represented by formula (I) (hereinafter sometimes referred to as compound (I)).

[0025] Examples of the divalent metal atom represented by M include Mg, Mo, Mn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Cu, Zn, Si, Sn, Pb and the like. Among them, Cu, Ni, or Zn is preferable, Cu or Zn is more preferable, and Zn is particularly preferable from the viewpoint of coloring power.

[0026] X 1 ~ X 8 is preferably a fluorine atom.

[0027] A 1 ~ A 8 each independently is preferably a fluorine atom or a group represented by formula (II). A 11 ~ A 18 is preferably a fluorine atom.

[0028] B 1 ~B 5 and R x The hydrocarbon group having 1 to 10 carbon atoms represented by may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof, and the aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or cyclic (alicyclic hydrocarbon group).

[0029] Examples of saturated chain hydrocarbon groups (alkyl groups) include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group; and branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, tert-amyl group, 1,3-dimethylbutyl group, 2-ethylbutyl group, and 2-ethylhexyl group. The number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 1 to 4, and even more preferably 1 to 2.

[0030] Examples of unsaturated chain hydrocarbon groups include alkenyl groups such as ethenyl groups, propenyl groups (e.g., 1-propenyl groups, 2-propenyl groups), and butenyl groups (e.g., 1-butenyl groups, 3-butenyl groups); and alkynyl groups such as ethynyl groups, propynyl groups (e.g., 1-propynyl groups, 2-propynyl groups), and butynyl groups (e.g., 1-butynyl groups, 3-butynyl groups). The number of carbon atoms in the unsaturated chain hydrocarbon group is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 4.

[0031] Examples of saturated alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and 2-methylcyclohexyl.

[0032] Examples of the unsaturated alicyclic hydrocarbon group include cycloalkenyl groups such as cyclohexenyl group (e.g., cyclohex-1-en-1-yl group, cyclohex-2-en-1-yl group, cyclohex-3-en-1-yl group), cycloheptenyl group, cyclooctenyl group, etc.

[0033] Examples of the alicyclic hydrocarbon group include polycyclic saturated alicyclic hydrocarbon groups such as norbornyl group, adamantyl group, bicyclo[2.2.2]octyl group; polycyclic unsaturated alicyclic hydrocarbon groups such as norbornenyl group; etc.

[0034] The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 10, more preferably 4 to 8.

[0035] Examples of the aromatic hydrocarbon group include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-dimethylphenyl group, 2,6-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-vinylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, 1-naphthyl group, 2-naphthyl group, a group obtained by removing one hydrogen atom from tetralin, etc.

[0036] The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 10.

[0037] B 1 ~B 5 and R x As long as the total number of carbon atoms of the hydrocarbon group represented by is 10 or less, it may be a group formed by combining the hydrocarbon groups listed above. Examples of the group formed by combining the hydrocarbon groups include aralkyl group, an alkyl group to which an alicyclic hydrocarbon group is bonded, etc.

[0038] Examples of aralkyl groups include benzyl group, (2-methylphenyl)methyl group, (3-methylphenyl)methyl group, (4-methylphenyl)methyl group, (2-ethylphenyl)methyl group, (3-ethylphenyl)methyl group, (4-ethylphenyl)methyl group, (3,5-dimethylphenyl)methyl group, 1-phenylethyl group, and 1-methyl-1-phenylethyl group. The number of carbon atoms in the aralkyl group is preferably 7 to 10.

[0039] Examples of alkyl groups to which alicyclic hydrocarbon groups are attached include cyclopropylmethyl group, cyclopropylethyl group, cyclobutylmethyl group, cyclohexylmethyl group, and cyclohexylethyl group. The number of carbon atoms in the alkyl group to which the alicyclic hydrocarbon group is attached is preferably 4 to 10.

[0040] B 1 ~B 5 The hydrocarbon group having 1 to 10 carbon atoms represented is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms. COR x R in the base x Preferably, the alkyl group has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms. CO2R x R in the base x The alkyl group is preferably a C1-C10 alkyl group, more preferably a C1-C4 alkyl group, even more preferably a methyl group or an ethyl group, and particularly preferably an ethyl group. Ure x R in the base x Preferably, the alkyl group has 1 to 10 carbon atoms or an aromatic hydrocarbon group has 6 to 10 carbon atoms, more preferably an alkyl group has 1 to 10 carbon atoms, and even more preferably an alkyl group has 1 to 4 carbon atoms. NHR x R in the base xPreferably, the alkyl group has 1 to 10 carbon atoms or an aromatic hydrocarbon group has 6 to 10 carbon atoms, more preferably an alkyl group has 1 to 10 carbon atoms, and even more preferably an alkyl group has 1 to 4 carbon atoms. NR x R in 2 units x The C1-C10 alkyl group or the C6-C10 aromatic hydrocarbon group is preferred, more preferably the C1-C10 alkyl group, and even more preferably the C1-C4 alkyl group. Note that the two R x They may be the same or different.

[0041] From the viewpoint of further improving solubility (especially solubility in propylene glycol monomethyl ether acetate), B 1 ~B 5 At least one of them is COR x group, CO2R x Base, OR x Base, NHR x Base, and NR x It is preferable that the group consists of at least one group selected from the group of two groups (hereinafter sometimes referred to as a polar group). Among the polar groups, CO2R x The base is preferred. 1 ~B 5 If two or more of these have polar groups, they may be the same or different.

[0042] B 1 ~B 5 Preferably, one or more, more preferably one to three, and even more preferably one of these is the polar group. The position of the polar group is not particularly limited, but at least B 2 or B 3 Preferably, the group is a polar group, and at least B 3 It is more preferable that the group is a polar group.

[0043] B 1 ~B 5Of these, the portion other than the polar group is preferably a hydrogen atom and / or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom and / or an alkyl group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom.

[0044] Examples of the aryloxy group (II) represented by formula (II) include the groups represented by formulas (II-1) and (II-2) below.

[0045] [ka] [In equations (II-1) and (II-2), R z This represents a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-amyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, benzyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, or phenyl group.

[0046] As mentioned above, phthalocyanine pigments (I) are A 1 ~A 8 It is preferable that the compound contains 4 to 8 aryloxy groups (II), that is, it is preferable that it contains at least one selected from the group consisting of compound (I-4), compound (I-5), compound (I-6), compound (I-7), and compound (I-8). The total proportion of compound (I-4), compound (I-5), compound (I-6), compound (I-7), and compound (I-8) in the phthalocyanine dye (I) is, for example, 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 98% by mass or more, and may be 100% by mass.

[0047] In particular, in equation (I), A 1 ~A 8By making 5 to 7 of these groups aryloxy groups (II), the distribution width described later tends to be broadened. This broadening of the distribution width makes it possible to create a compound that can efficiently absorb red light, and therefore it can be preferably used as a colorant for green color filters. That is, from the viewpoint of more efficiently absorbing red light, it is preferable that the phthalocyanine dye (I) contains a compound represented by formula (IN) (hereinafter sometimes referred to as compound (IN)). Examples of compound (IN) include compound (I-5), compound (I-6), and compound (I-7), and the preferred embodiments thereof are the same. Among compound (IN), compound (I-5) and compound (I-6) are preferred from the viewpoint of even more efficiently absorbing red light, that is, in formula (IN), A 1n ~A 8n Of these, compounds in which 5 to 6 groups represent the group shown in formula (II) are preferred.

[0048] [ka] [In the formula (IN), M n This represents a divalent metal atom. X 1n ~X 8n These represent, independently of each other, a fluorine atom or a chlorine atom. A 1n ~A 8n These represent, independently of each other, a fluorine atom, a chlorine atom, or a group represented by formula (II). However, A 1n ~A 8n Of these, 5 to 7 represent the base expressed by formula (II).

[0049] M n The description of the divalent metal atom represented by M can be applied mutatis mutandis to the description of the divalent metal atom represented by M, including its preferred embodiment. X 1n ~X 8n Preferably, it is a fluorine atom. A 1n ~A 8nThe "group represented by formula (II)" can be described in accordance with the above explanation of the aryloxy group (II), including its preferred embodiment. A 1n ~A 8n Preferably, each of these is a fluorine atom or a group represented by formula (II), independently of the others.

[0050] From the viewpoint of more efficiently absorbing red light, the content of compound (IN) in 100% by mass of phthalocyanine dye (I) is, for example, 10 to 100% by mass or more, preferably 30 to 95% by mass, more preferably 50 to 90% by mass, and even more preferably 60 to 90% by mass.

[0051] Furthermore, the phthalocyanine dye (I) preferably contains compound (I-5), compound (I-6), or compound (I-7) as its main component. Here, "main component" refers to the component that is the most abundant in the phthalocyanine dye (I). The content of one compound selected from compound (I-5), compound (I-6), and compound (I-7) in 100% by mass of the phthalocyanine dye (I) is preferably 25 to 100% by mass, more preferably 30 to 85% by mass, and even more preferably 35 to 70% by mass.

[0052] In particular, from the viewpoint of further improving the color separation of the resulting color filter from red light, the phthalocyanine dye (I) preferably contains at least one selected from the group consisting of compound (I-5), compound (I-6), and compound (I-7), more preferably contains compound (I-5), compound (I-6), and compound (I-7), even more preferably contains compound (I-5), compound (I-6), compound (I-7), and compound (I-8), and particularly preferably contains compound (I-4), compound (I-5), compound (I-6), compound (I-7), and compound (I-8).

[0053] Specifically, compound (I) includes compounds (I-4a-1) to (I-4a-8), compounds (I-4b-1) to (I-4b-8), compounds (I-4c-1) to (I-4c-8), compounds (I-4d-1) to (I-4d-8), compounds (I-5a-1) to (I-5a-8), compounds (I-5b-1) to (I-5b-8), compounds (I-5c-1) to (I-5c-8), and compounds (I-5c-1) to (I-5c-8). Examples include substances (I-5d-1)~(I-5d-8), compounds (I-6a-1)~(I-6a-8), compounds (I-6b-1)~(I-6b-8), compounds (I-6c-1)~(I-6c-8), compounds (I-6d-1)~(I-6d-8), compounds (I-6e-1)~(I-6e-8), compounds (I-7a-1)~(I-7a-8), compounds (I-8a-1)~(I-8a-8), etc.

[0054] [Table 1]

[0055] [Table 2]

[0056] [Table 3]

[0057] [Table 4]

[0058] [Table 5]

[0059] [Table 6]

[0060] [Table 7]

[0061] [Table 8]

[0062] In Tables 1-8, F represents a fluorine atom, and II-a to II-d represent groups represented by the following formulas (II-a) to (II-d).

[0063] [ka]

[0064] Phthalocyanine dyes (I) can be produced, for example, by cyclizing compounds represented by formulas (i-1) to (i-4) with a compound represented by formula (iii). Conventional known methods can be used for the cyclization reaction.

[0065] [ka]

[0066] In the formula, Y represents a halogen atom, a hydroxyl group, or an OR group. R represents a hydrocarbon group having 1 to 6 carbon atoms. M, X 1 ~X 8 , and A 1 ~A 8 This has the same meaning as above.

[0067] In formula (iii), the halogen atom represented by Y includes fluorine, chlorine, bromine, and iodine atoms, with iodine being the preferred choice.

[0068] As for the hydrocarbon group with 1 to 6 carbon atoms represented by R, B 1 ~B 5 and R x Among the hydrocarbon groups having 1 to 10 carbon atoms represented by the formula, hydrocarbon groups having 1 to 6 carbon atoms are mentioned, and among these, aliphatic hydrocarbon groups having 1 to 6 carbon atoms are preferred, and alkyl groups having 1 to 4 carbon atoms are more preferred. Examples of OR groups include alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy groups, as well as phenoxy groups. Among these, alkoxy groups having 1 to 6 carbon atoms are preferred, and alkoxy groups having 1 to 4 carbon atoms are more preferred.

[0069] In the above manufacturing method, depending on the number of aryloxy groups in each compound represented by formulas (i-1) to (i-4) and the ratio of each compound, a dye containing two or more compounds from compounds (I-1) to (I-9) may be obtained. If such a dye is obtained, each compound may be isolated from the dye. Furthermore, if the average number of aryloxy groups (II) per M group in compound (I) in the dye is 4.5 to 7.2, the dye may be used as is as a phthalocyanine dye (I).

[0070] Furthermore, phthalocyanine dye (I) can also be prepared by mixing two or more compounds from the obtained compounds (I-1) to (I-9). In this case, it is preferable that the two or more compounds be mixed so as to be homogeneous. As a method for mixing to be homogeneous, for example, it is preferable to stir the two or more compounds in the presence of an organic solvent such as propylene glycol monomethyl ether acetate, then distill off the solvent and dry as necessary.

[0071] The phthalocyanine-based dye (I) of the present invention has enhanced solubility in solvents (particularly propylene glycol monomethyl ether acetate). The solubility of the phthalocyanine-based dye (I) in propylene glycol monomethyl ether acetate is preferably 4.0% by mass or more, more preferably 4.5% by mass or more, and even more preferably 5.0% by mass or more at a temperature of 23°C. There is no particular upper limit, but it may be, for example, around 10% by mass.

[0072] <<Coloring agent>> The present invention also includes colorants containing the aforementioned phthalocyanine-based dye (I) (hereinafter sometimes referred to as colorant (A)).

[0073] The content of phthalocyanine dye (I) is preferably 5 to 100% by mass, more preferably 10 to 100% by mass, and even more preferably 20 to 100% by mass, of the total amount of colorant (A), and may be 50 to 100% by mass or 30 to 90% by mass.

[0074] The coloring agent (A) may contain a phthalocyanine dye (I) along with other coloring agents other than compound (I) (hereinafter sometimes referred to as "other coloring agents"). The other coloring agents may be either dyes or pigments.

[0075] Examples of the aforementioned dyes include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, thiazole dyes, oxazine dyes, quinophthalone dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and phthalocyanine dyes. Of these, organic solvent-soluble dyes are preferred.

[0076] Specifically, the dyes used are CI Solvent Yellow 4 (hereafter, the designation "CI Solvent Yellow" will be omitted, and only the numbers will be listed; the same applies to others), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, and 189; CI Solvent Red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99; CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; and other CI solvent dyes. CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 1 82, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, ​​383, 388, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123 ,126,127,129,130,131,138,140,142,143,147,150,151,154,158,161,166,167,168,170,171,175,182,183,184,187,192,199,203,204,205,210,213,229,234,236,242,243,249,256,259,267,269,278,280,285,290,296,315,324:1,335,340; CI Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109; and other CI Acid dyes. CI Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 16 6, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; and other CI Direct dyes. CI Disperse Yellow 51, 54, 76; CI Disperse Violet 26, 27; CI Disperse Blue 1, 14, 56, 60; and other CI disperse dyes. CI Basic Red 1, 9, 10; CI Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; CI Basic Violet 2; CI Basic Green 1; and other CI Basic dyes, CI Reactive Yellow 2, 76, 116; CI Reactive Orange 16; CI Reactive Red 36; and other CI reactive dyes, CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI Modant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; CI Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; CI Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; CI Modant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53; and other CI Modant dyes. Examples include CI bat green 1 and other CI bat dyes. These dyes may be made using one or more dyes for each color, or a combination of dyes for each color.

[0077] Examples of the aforementioned pigments include those classified as pigments in the Color Index (published by The Society of Dyers and Colourists). Examples of pigments classified as pigments include yellow pigments such as CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, and 231; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, and other orange pigments; CI Pigment Red 9, 97, 105, 122, 144, 166, 168, 176, 177, 180, 190, 192, 209, 215, 216, 224, 242, 246, 254, 255, 264, 265, 266, 268, 269, 273, 291, and other red pigments; CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, and other blue pigments; CI Pigment Violet 1, 19, 23, 32, 36, 38, and other violet color pigments; Green pigments such as CI Pigment Green 7, 58, 59, 62, 63; CI Pigment Brown 23, 25, and other brown pigments; Examples include black pigments such as CI Pigment Black 1 and 7. These pigments may use one or more pigments for each color, or a combination of pigments for each color.

[0078] The pigment may be subjected to rosin treatment, surface treatment using pigment derivatives into which acidic or basic groups have been introduced, grafting treatment of the pigment surface with polymer compounds, atomization treatment by sulfuric acid atomization method, washing treatment with organic solvents or water to remove impurities, removal treatment of ionic impurities by ion exchange method, etc., as needed. The particle size of the pigment is preferably substantially uniform.

[0079] Furthermore, the coloring agent (A) may contain a compound represented by the following formula (Ix) (hereinafter referred to as compound (Ix)), but it is preferable that the content be small. The content of compound (Ix) is preferably 50 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of compound (I), and it is particularly preferable that it be 0 parts by mass, i.e., no compound (Ix) is present. By adjusting the content of compound (Ix) to the above range, the lightfastness can be improved.

[0080] [ka] [In formula (Ix), M x This represents a divalent metal atom. X 1x ~X 8x and A 1x ~A 8x These represent, independently of each other, a fluorine atom, a chlorine atom, or a group represented by formula (II). However, X 1x ~X 8x Of these, at least one represents the base expressed by formula (II).

[0081] Note that in equation (Ix), the base represented by equation (II) has the same meaning as the base represented by equation (II) in equation (I).

[0082] <<Colored resin composition>> The present invention encompasses a colored resin composition containing a coloring agent (i.e., coloring agent (A)) containing a phthalocyanine-based dye (I), and an alkali-soluble resin (hereinafter sometimes referred to as resin (B)). The colored resin composition of the present invention may further contain a polymerizable compound (hereinafter sometimes referred to as polymerizable compound (C)) and a polymerization initiator (hereinafter sometimes referred to as polymerization initiator (D)). The colored resin composition of the present invention may further contain a solvent (hereinafter sometimes referred to as solvent (E)). The colored resin composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as leveling agent (F)). In this specification, the compounds exemplified as components may be used individually or in combination, unless otherwise specified.

[0083] <Coloring agent (A)> The coloring agent (A) is as described above.

[0084] The content of colorant (A) is preferably 0.5 to 80% by mass, more preferably 1 to 70% by mass, even more preferably 2 to 50% by mass, and particularly preferably 3 to 40% by mass, based on the total amount of solids in the colored resin composition. When the content of colorant (A) is within the above range, it becomes easier to obtain the desired spectral characteristics and color density while suppressing the generation of foreign matter. In this specification, "total amount of solids" refers to the total amount of components from the colored resin composition of the present invention, excluding the solvent. The total amount of solids and the content of each component therein can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0085] <Resin (B)> Resin (B) is an alkali-soluble resin. Examples of resin (B) include the following resins [K1] to [K6], and it is preferable that at least one is selected from resins [K1] to [K6]. Resin [K1]; a copolymer having structural units derived from at least one monomer (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and structural units derived from monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond; Resin [K2]; a copolymer having structural units derived from (a) and structural units derived from structural units derived from (b) and a monomer (c) copolymerizable with (a) (however different from (a) and (b)) (hereinafter sometimes referred to as "(c)"); Resin [K3]; a copolymer having structural units derived from (a) and structural units derived from (c); Resin [K4]; a copolymer having structural units obtained by adding (b) to structural units derived from (a) and structural units derived from (c), wherein the copolymer includes structural units derived from (a) to which (b) is not added; Resin [K4']; a copolymer having structural units obtained by adding (b) to structural units derived from (a) and structural units derived from (c), and not containing structural units derived from (a) to which (b) is not added; Resin [K5]; a copolymer having structural units obtained by adding (a) to structural units derived from (b) and structural units derived from (c) (it may include structural units derived from (b) to which (a) is not added, but it is preferable that it not be included); Resin [K6]; A copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride, and a structural unit derived from (c).

[0086] (a) specifically includes, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, p-vinylbenzoic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid; Bicyclounsaturated compounds containing carboxyl groups, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; Unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride; Unsaturated mono(meth)acryloyloxyalkyl) esters of divalent or higher polycarboxylic acids such as mono(2-(meth)acryloyloxyethyl) succinate and mono(2-(meth)acryloyloxyethyl) phthalate; Examples include unsaturated acrylates containing both a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid. Of these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferred in terms of copolymerization reactivity and the solubility of the resulting resin in alkaline aqueous solutions.

[0087] (b) refers to a polymerizable compound having, for example, a cyclic ether structure with 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether with 2 to 4 carbon atoms and a (meth)acryloyloxy group. In this specification, "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid. The terms "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[0088] Examples of (b) include monomers having an oxyranyl group and an ethylenically unsaturated bond (b1) (hereinafter sometimes referred to as "(b1)"), monomers having an oxetanyl group and an ethylenically unsaturated bond (b2) (hereinafter sometimes referred to as "(b2)"), and monomers having a tetrahydrofuryl group and an ethylenically unsaturated bond (b3) (hereinafter sometimes referred to as "(b3)").

[0089] Examples of (b1) include monomers having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized (b1-1) (hereinafter sometimes referred to as "(b1-1)") and monomers having a cyclic unsaturated hydrocarbon structure that has been epoxidized (b1-2) (hereinafter sometimes referred to as "(b1-2)").

[0090] (b1-1) includes glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, α-methyl-o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyl Examples include oxymethylstyrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, and 2,4,6-tris(glycidyloxymethyl)styrene.

[0091] Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer-M100; manufactured by Daicel Corporation), compounds represented by formula (BI), and compounds represented by formula (BII).

[0092] [ka]

[0093] [In formulas (BI) and (BII), R e and R f This represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X e and X f This is a single bond, *-R g -, *-R g -O-, *-R g -S- or *-R g Represents -NH- R g This represents an alkanediyl group with 1 to 6 carbon atoms. * represents a bond with O.

[0094] Examples of alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. Examples of alkyl groups in which a hydrogen atom is substituted with hydroxyl include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, and 4-hydroxybutyl group. R e and R f Preferably, the group can be a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

[0095] Examples of alkanediyl groups include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl. X e and X fPreferably, the bonds include single bonds, methylene groups, ethylene groups, *-CH2-O- and *-CH2CH2-O-, and more preferably, single bonds and *-CH2CH2-O- (* represents a bond with O).

[0096] Compounds represented by formula (BI) include those represented by any of formulas (BI-1) to (BI-15). Among these, compounds represented by formulas (BI-1), (BI-3), (BII-5), (BI-7), (BI-9), or (BI-11) to (BI-15) are preferred, and compounds represented by formulas (BI-1), (BI-7), (BI-9), or (BI-15) are more preferred.

[0097] [ka]

[0098] Compounds represented by formula (BII) include compounds represented by any of formulas (BII-1) to (BII-15). Among these, compounds represented by formulas (BII-1), (BII-3), (BII-5), (BII-7), (BII-9), or (BII-11) to (BII-15) are preferred, and compounds represented by formulas (BII-1), (BII-7), (BII-9), or (BII-15) are more preferred.

[0099] [ka]

[0100] The compound represented by formula (BI) and the compound represented by formula (BII) may be used individually or in combination of two or more. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, their content ratio [compound represented by formula (BI):compound represented by formula (BII)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20, on a molar basis.

[0101] For (b2), monomers having an oxetanyl group and a (meth)acryloyloxy group are more preferred. Examples of (b2) include 3-methyl-3-(meth)acryloyloxymethyl oxetane, 3-ethyl-3-(meth)acryloyloxymethyl oxetane, 3-methyl-3-(meth)acryloyloxyethyl oxetane, and 3-ethyl-3-(meth)acryloyloxyethyl oxetane.

[0102] For (b3), monomers having a tetrahydrofurfuryl group and a (meth)acryloyloxy group are more preferred. Specifically for (b3), examples include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0103] (b) is preferable because it allows for greater reliability of the heat resistance, chemical resistance, etc., of the resulting color filter. Furthermore, (b1-2) is more preferable because it provides excellent storage stability for the colored resin composition.

[0104] Examples of (c) include (meth)acrylic acid ester monomers, unsaturated carboxylic acid esters such as unsaturated dicarboxylic acid esters; vinyl monomers such as vinyl monomers having an unsaturated aliphatic hydrocarbon ring or an aromatic ring; maleimides; and the like. Examples of (meth)acrylic acid ester monomers include (meth)acrylic acid esters having linear or branched aliphatic saturated hydrocarbon groups, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and cyclopentyl (meth)acrylate; (Meth)acrylic acid esters having straight-chain or branched aliphatic unsaturated hydrocarbon groups, such as allyl (meth)acrylate and propargyl (meth)acrylate; Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 (Meth)acrylic acid esters having cyclic saturated hydrocarbon groups, such as decane-8-yl(meth)acrylate (commonly known in the relevant technical field as "dicyclopentanyl(meth)acrylate," and sometimes as "tricyclodecyl(meth)acrylate"), isobornyl(meth)acrylate, and adamantyl(meth)acrylate; Tricyclo[5.2.1.0 2,6 (meth)acrylic acid esters having cyclic unsaturated aliphatic hydrocarbon groups, such as decen-8-yl (meth)acrylate (commonly known in the art as "dicyclopentenyl (meth)acrylate") and dicyclopentanyloxyethyl (meth)acrylate; Aromatic ring-containing (meth)acrylic acid esters such as phenyl(meth)acrylate, naphthyl(meth)acrylate, benzyl(meth)acrylate, and phenoxybenzyl(meth)acrylate; Examples include hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Examples of unsaturated dicarboxylic acid esters include diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0105] Among these unsaturated carboxylic acid esters, C such as methyl methacrylate and 2-ethylhexyl acrylate 1-10 Alkyl (meth)acrylate; Tricyclo[5.2.1.0 2,6 (meth)acrylic acid esters having cyclic saturated hydrocarbon groups, such as decane-8-yl(meth)acrylate; Tricyclo[5.2.1.0 2,6 (meth)acrylic acid esters having cyclic unsaturated aliphatic hydrocarbon groups, such as decen-8-yl(meth)acrylate; (Meth)acrylic acid esters having aromatic rings, such as benzyl (meth)acrylate and phenoxybenzyl (meth)acrylate, are preferred.

[0106] Examples of vinyl monomers having an unsaturated aliphatic hydrocarbon ring include bicyclo[2.2.1]hept-2-ene (also known as 2-norbornene), 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, and 5-(2'-hydroxy Ethyl)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 Examples of bicyclounsaturated compounds include 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, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene. Examples of vinyl monomers having aromatic rings include styrene-based monomers such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene. Other vinyl monomers include nitrile group-containing monomers such as acrylonitrile and methacrylonitrile; Halogen atom-containing monomers such as vinyl chloride and vinylidene chloride; Examples include acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. Among these vinyl monomers, styrene monomers such as styrene and vinyltoluene, and bicyclounsaturated compounds such as bicyclo[2.2.1]hepto-2-ene (also known as 2-norbornene) are preferred from the viewpoint of copolymerization reactivity and heat resistance.

[0107] Examples of maleimides include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl)maleimide. Among these maleimides, maleimides having alicyclic hydrocarbon groups or aromatic hydrocarbon groups, such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide, are preferred from the viewpoint of copolymerization reactivity and heat resistance.

[0108] A structural unit obtained by adding (b) to a structural unit derived from (a) is a unit formed by adding (b) to a structural unit derived from (a) that constitutes the main chain of the copolymer, and has a pendant unsaturated group derived from (b). In this structural unit, (a) may be any of the examples above, and (b) may also be any of the examples above. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As (b), a monomer (b1) having an oxiranil group and an ethylenically unsaturated bond is preferred, and a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized is more preferred.

[0109] A structural unit obtained by adding (a) to a structural unit derived from (b) is a unit formed by adding (a) to a structural unit derived from (b) that constitutes the main chain of the copolymer, and has a pendant unsaturated group derived from (a). In this structural unit, (b) may be any of the examples above, and (a) may also be any of the examples above. As (b), a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferred, and a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized is more preferred. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred.

[0110] A structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride is a structural unit in which a hydroxyl group formed by the addition of (a) to a structural unit derived from (b) constituting the main chain of the copolymer is bonded to by the carboxylic acid anhydride through half-esterification, and has a pendant carboxyl group derived from the carboxylic acid anhydride and a pendant unsaturated group derived from (a). In this structural unit, (b) may be any of the above examples, and (a) may also be any of the above examples. As (b), a monomer (b1) having an oxiranil group and an ethylenically unsaturated bond is preferred, and a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized is more preferred. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. Examples of carboxylic acid anhydrides include saturated aliphatic polycarboxylic acid anhydrides such as malonic acid anhydride, succinic acid anhydride, glutaric acid anhydride, and adipic acid anhydride; unsaturated aliphatic polycarboxylic acid anhydrides such as maleic acid anhydride, citraconic acid anhydride, and itaconic acid anhydride; aromatic polycarboxylic acid anhydrides such as 3-vinylphthalic acid anhydride and 4-vinylphthalic acid anhydride; and polycarboxylic acid anhydrides such as alicyclic polycarboxylic acid anhydrides such as 3,4,5,6-tetrahydrophthalic acid anhydride, 1,2,3,6-tetrahydrophthalic acid anhydride, dimethyltetrahydrophthalic acid anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.

[0111] In resin [K1], the ratio of structural units derived from each is, among all structural units constituting resin [K1], (a) Structural units derived from (a); 2-60 mol% (b) Structural units derived from (b); 40-98 mol% It is preferable that this be the case. (a) Structural units derived from (a); 10-50 mol% (b) Structural units derived from (b); 50-90 mol% It is preferable that it be so. Furthermore, it is preferable that the structural units derived from (c) are substantially omitted. The sum of structural units derived from (a) and structural units derived from (b) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of the total structural units constituting the resin [K1]. When the ratio of structural units of resin [K1] falls within the above range, the storage stability of the colored resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter tend to be excellent.

[0112] The resin [K1] can be manufactured, for example, by referring to the method described in the literature "Experimental Methods for Polymer Synthesis" (by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, March 1, 1972) and the cited literature.

[0113] Specifically, a method involves placing predetermined amounts of (a) and (b), a polymerization initiator, and a solvent into a reaction vessel, creating a deoxygenated atmosphere by, for example, replacing oxygen with nitrogen, and heating and maintaining the temperature while stirring. The polymerization initiator and solvent used here are not particularly limited and can be those commonly used in the field. For example, examples of polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc.), and the solvent can be any solvent that dissolves each monomer. Examples of solvents include those described later as solvent (E) of the colored resin composition of the present invention.

[0114] The resulting copolymer may be used as is after the reaction, or after being concentrated or diluted, or after being extracted as a solid (powder) by methods such as reprecipitation. In particular, by using the solvent contained in the colored resin composition of the present invention as the solvent during polymerization, the solution after the reaction can be used directly in the preparation of the colored resin composition of the present invention, thereby simplifying the manufacturing process of the colored resin composition of the present invention.

[0115] In resin [K2], the ratio of structural units derived from each is, among all structural units constituting resin [K2], (a) Structural units derived from (a); 1-70 mol% (b) Structural units derived from (b); 1-60 mol% (c) Structural units derived from this structure; 20-95 mol% It is preferable that this be the case. (a) Structural units derived from (a); 3-50 mol% (b) Structural units derived from (b); 3-40 mol% (c) Structural units derived from (c); 30-90 mol% It is more preferable that, (a) Structural units derived from (a); 5-40 mol% (b) Structural units derived from (b); 5-30 mol% (c) Structural units derived from (c); 40-80 mol% It is even more preferable that it be so. The sum of structural units derived from (a), (b), and (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of the total structural units constituting the resin [K2]. When the ratio of structural units of resin [K2] is within the above range, the colored resin composition tends to have excellent storage stability, developability when forming colored patterns, and solvent resistance, heat resistance, and mechanical strength of the resulting color filter.

[0116] In resin [K2], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid. For (b), a monomer (b1) having an oxiranil group and an ethylenically unsaturated bond is preferred, and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized is more preferred. For (c), (meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, (meth)acrylic acid esters having an aromatic ring, and dicarbonylimide derivatives are preferred.

[0117] Resin [K2] can be manufactured, for example, in the same manner as described as the method for manufacturing resin [K1].

[0118] In resin [K3], the ratio of structural units derived from each is, out of the total structural units constituting resin [K3], (a) Structural units derived from (a); 2-60 mol% (c) Structural units derived from (c); 40-98 mol% It is preferable that this be the case. (a) Structural units derived from (a); 10-50 mol% (c) Structural units derived from (c); 50-90 mol% It is more preferable that, (a) Structural units derived from (a); 35-45 mol% (c) Structural units derived from (c); 55-65 mol% It is even more preferable that it be so. It is also preferable that the resin substantially does not contain structural units derived from (b). The total of the structural units derived from (a) and the structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% in all the structural units constituting the resin [K3].

[0119] In the resin [K3], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid. (c) is preferably (meth)acrylic acid esters having an aromatic ring. The resin [K3] can be produced, for example, in the same manner as the method described as the production method of the resin [K1].

[0120] In the resin [K4], the ratio of the structural units derived from each is among all the structural units constituting the resin [K4], Structural units derived from (a) (where (b) is not added); 1 to 60 mol% Structural units obtained by adding (b) to the structural units derived from (a); 1 to 50 mol% Structural units derived from (c); 30 to 90 mol% It is preferable that it is as follows, Structural units derived from (a) (where (b) is not added); 5 to 50 mol% Structural units obtained by adding (b) to the structural units derived from (a); 5 to 40 mol% Structural units derived from (c); 35 to 80 mol% It is more preferable that it is as follows, Structural units derived from (a) (where (b) is not added); 10 to 40 mol% Structural units obtained by adding (b) to the structural units derived from (a); 10 to 25 mol% Structural units derived from (c); 40 to 75 mol% It is even more preferable that it is as follows. The sum of structural units derived from (a) (without (b) added), structural units derived from (a) with (b) added, and structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of the total structural units constituting the resin [K4].

[0121] As structural units derived from (a) (without (b) being added), structural units derived from unsaturated monocarboxylic acids such as (meth)acrylic acid are preferred. As structural units obtained by adding (b) to structural units derived from (a), structural units obtained by adding a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure to a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid are preferred. As structural units derived from (c), one or more selected from (meth)acrylic acid esters having linear or branched aliphatic saturated hydrocarbon groups, (meth)acrylic acid esters having cyclic saturated hydrocarbon groups, (meth)acrylic acid esters having aromatic rings, bicyclounsaturated compounds, and styrene monomers are preferred, and two or more are more preferred. When (c) has two constituent units derived from (c), it is preferable to select two from unsaturated carboxylic acid esters such as (meth)acrylic acid esters, (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, and (meth)acrylic acid esters having an aromatic ring, and to select two or more from bicyclounsaturated compounds and vinyl monomers such as styrene monomers.

[0122] The resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms of (b) to the carboxylic acid and / or carboxylic acid anhydride of (a). First, a copolymer of (a) and (c) is produced in the same manner as described for the production of resin [K1]. In this case, it is preferable that the ratio of structural units derived from each is the same as that given for resin [K3].

[0123] Next, a portion of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms that (b) possesses. Following the production of the copolymer of (a) and (c), the atmosphere inside the flask is replaced from nitrogen to air, and (b), a reaction catalyst for the reaction between a carboxylic acid or carboxylic acid anhydride and a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, triphenylphosphine, etc.) and a polymerization inhibitor (e.g., hydroquinone, methoquinone, etc.) are added to the flask and the mixture is reacted at, for example, 60 to 130°C for 1 to 10 hours to produce resin [K4]. The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). This range tends to result in a good balance of storage stability of the colored resin composition, developability when forming patterns, and solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting patterns. The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b), and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b), and (c). The reaction conditions, such as the preparation method, reaction temperature, and time, can be adjusted as appropriate, taking into account the manufacturing equipment and the amount of heat generated by polymerization. Similarly, the preparation method and reaction temperature can be adjusted as appropriate, taking into account the manufacturing equipment and the amount of heat generated by polymerization.

[0124] In resin [K4'], the ratio of structural units derived from each is, among all structural units constituting resin [K4'], A structural unit obtained by adding (b) to a structural unit derived from (a); 5-95 mol% (c) Structural units derived from (c); 5-95 mol% It is preferable that this be the case. A structural unit obtained by adding (b) to a structural unit derived from (a); 15-90 mol% (c) Structural units derived from (c); 10-85 mol% It is more preferable that, A structural unit obtained by adding (b) to a structural unit derived from (a); 20-80 mol% (c) Structural units derived from (c); 20-80 mol% It is even more preferable that it be so. Furthermore, structural units derived from (a) but without (b) attached are not substantially included. The sum of structural units derived from (a) with (b) added, and structural units derived from (c), is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of the total structural units constituting the resin [K4'].

[0125] As a structural unit obtained by adding (b) to a structural unit derived from (a), a preferred structural unit is one obtained by adding a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure to a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid. As a structural unit derived from (c), one or more selected from (meth)acrylic acid esters having linear or branched aliphatic saturated hydrocarbon groups and (meth)acrylic acid esters having cyclic saturated hydrocarbon groups are preferred, and two or more are more preferred. The resin [K4'] may be prepared by referring to the above method for producing resin [K4], and the amount of (b) used is preferably 100 moles or more, and more preferably 100 moles, per 100 moles of (a).

[0126] In resin [K5], the ratio of structural units derived from each is, among all structural units constituting resin [K5], (b) Structural units derived from (a) (without addition of (a)); 0-30 mol% Structural units obtained by adding (a) to structural units derived from (b); 5-95 mol% (c) Structural units derived from (c); 5-95 mol% It is preferable that this be the case. (b) Structural units derived from (a) (without addition); 0-10 mol% Structural units obtained by adding (a) to structural units derived from (b); 15-90 mol% (c) Structural units derived from (c); 10-85 mol% It is more preferable that, (b) Structural units derived from (a) (without addition); 0-5 mol% Structural units obtained by adding (a) to structural units derived from (b); 20-80 mol% (c) Structural units derived from (c); 20-80 mol% It is even more preferable that it be so. The sum of structural units derived from (b) (without (a) added), structural units derived from (b) with (a) added, and structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of the total structural units constituting the resin [K5].

[0127] As structural units derived from (b) (without (a) attached), structural units derived from monomers (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized are preferred. As structural units obtained by attaching (a) to structural units derived from (b), structural units obtained by attaching an unsaturated monocarboxylic acid such as (meth)acrylic acid to structural units derived from monomers (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized are preferred. As structural units derived from (c), one or more selected from (meth)acrylic acid esters having linear or branched aliphatic saturated hydrocarbon groups and (meth)acrylic acid esters having cyclic saturated hydrocarbon groups are preferred, and two or more are more preferred.

[0128] As a first step, resin [K5] is produced in the same manner as the production method for resin [K1] described above to obtain a copolymer of (b) and (c). As described above, the obtained copolymer may be used as is after the reaction, or a concentrated or diluted solution may be used, or it may be used after being extracted as a solid (powder) by methods such as reprecipitation. The ratios of structural units derived from (b) and (c) are, in relation to the total number of moles of all structural units constituting the copolymer, respectively: Structural unit derived from (b); 5 to 95 mol% Structural unit derived from (c); 5 to 95 mol% It is preferable that it is Structural unit derived from (b); 10 to 90 mol% Structural unit derived from (c); 10 to 90 mol% It is more preferable that it is

[0129] Furthermore, under the same conditions as the production method of resin [K4] or resin [K4'], by reacting the carboxylic acid or carboxylic anhydride of (a) with the cyclic ether derived from (b) in the copolymer of (b) and (c), resin [K5] can be obtained. The amount of (a) used for reacting with the copolymer is preferably 5 to 100 mol, more preferably 60 to 100 mol, per 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) is unlikely to remain, (b1) is preferable as (b) used for resin [K5], and further (b1-1) is preferable.

[0130] In resin [K6], the ratio of the structural units derived therefrom is among all the structural units constituting resin [K6], Structural unit derived from (b) (without addition of (a)); 0 to 30 mol% Structural unit obtained by adding (a) to the structural unit derived from (b) (without addition of carboxylic anhydride); 20 to 85 mol% Structural unit obtained by adding (a) to the structural unit derived from (b) and further adding carboxylic anhydride; 2 to 40 mol% Structural unit derived from (c); 10 to 60 mol% It is preferable that it is Structural unit derived from (b) (without addition of (a)); 0 to 10 mol% Structural unit obtained by adding (a) to the structural unit derived from (b) (without addition of carboxylic anhydride); 40 to 80 mol% Structural unit obtained by adding (a) to the structural unit derived from (b) and further adding carboxylic anhydride; 3 to 30 mol% (c) Structural units derived from (c); 15-50 mol% It is more preferable that, (b) Structural units derived from (a) (without addition); 0-5 mol% (b) is a structural unit to which (a) is added (no carboxylic acid anhydride is added); 50-70 mol% A structural unit obtained by adding (a) to a structural unit derived from (b), and then adding a carboxylic acid anhydride; 5-20 mol% (c) Structural units derived from this structure; 20-40 mol% It is even more preferable that it be so.

[0131] The sum of structural units derived from (b) (without (a) added), structural units obtained by adding (a) to structural units derived from (b) (without carboxylic acid anhydride added), structural units obtained by adding (a) to structural units derived from (b) and further adding carboxylic acid anhydride, and structural units derived from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of the total structural units constituting the resin [K6].

[0132] As a structural unit derived from (b) (without (a) being added), a structural unit derived from a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized is preferred. As a structural unit obtained by adding (a) to a structural unit derived from (b) (without carboxylic acid anhydride being added), a structural unit obtained by adding an unsaturated monocarboxylic acid such as (meth)acrylic acid to a structural unit derived from a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized is preferred. As a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride, a structural unit obtained by adding an unsaturated monocarboxylic acid such as (meth)acrylic acid to a structural unit derived from a monomer (b1-1) having a linear or branched aliphatic unsaturated hydrocarbon structure that has been epoxidized is preferred, and further adding a saturated aliphatic polycarboxylic acid anhydride such as succinic anhydride is preferred. The structural unit derived from (c) is preferably one or more selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, and more preferably two or more.

[0133] As a first step, resin [K6] is produced in the same manner as the production method for resin [K1] described above to obtain a copolymer of (b) and (c). As described above, the obtained copolymer may be used as is after the reaction, or a concentrated or diluted solution may be used, or it may be used after being extracted as a solid (powder) by methods such as reprecipitation. The ratios of structural units derived from (b) and (c) are, in relation to the total number of moles of all structural units constituting the copolymer, respectively: (b) Structural units derived from (b); 5-95 mol% (c) Structural units derived from (c); 5-95 mol% It is preferable that this be the case. (b) Structural units derived from (b); 10-90 mol% (c) Structural units derived from (c); 10-90 mol% It is preferable that it be so.

[0134] Furthermore, under the same conditions as for the production of resin [K4], the cyclic ether derived from (b) in the copolymer of (b) and (c) is reacted with the carboxylic acid or carboxylic acid anhydride of (a). The amount of (a) used is preferably 80 to 100 moles per 100 moles of (b).

[0135] The hydroxyl group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic acid anhydride of (a) is reacted with the carboxylic acid anhydride. The amount of carboxylic acid anhydride used is preferably 0.05 to 1 mole, more preferably 0.10 to 0.8 moles, and even more preferably 0.13 to 0.7 moles, relative to 1 mole of (a) used (in other words, 1 mole of hydroxyl groups produced by the use of (a)).

[0136] Specifically, resin (B) is 3,4-epoxycyclohexylmethyl(meth)acrylate / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Resins such as decyl acrylate / (meth)acrylic acid copolymer [K1]; Glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 Decyl acrylate / (meth)acrylic acid / N-cyclohexyl maleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 Decyl acrylate / (meth)acrylic acid / N-cyclohexyl maleimide / tricyclo[5.2.1.0 2,6 ] Decen-8-yl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 Decyl acrylate / (meth)acrylic acid / benzyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6] Resins such as decyl acrylate / (meth)acrylic acid / phenoxybenzyl(meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyl oxetane / (meth)acrylic acid / styrene copolymer [K2]; Resins such as benzyl (meth)acrylate / (meth)acrylic acid copolymers and styrene / (meth)acrylic acid copolymers [K3]; Resins such as those obtained by adding glycidyl (meth)acrylate to some of the carboxylic acid groups of a benzyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to some of the carboxylic acid groups of a tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to some of the carboxylic acid groups of a tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to some of the carboxylic acid groups of a norbornene / vinyltoluene / (meth)acrylic acid copolymer, and resins obtained by adding glycidyl (meth)acrylate to some of the carboxylic acid groups of a norbornene / styrene / (meth)acrylic acid copolymer [K4]; Resins such as resins obtained by reacting a tricyclodecyl (meth)acrylate / (meth)acrylic acid copolymer with glycidyl (meth)acrylate, and resins obtained by reacting a tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer with glycidyl (meth)acrylate [K4']; Resins such as resins obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid, and resins obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate with (meth)acrylic acid [K5]; Examples of resins include those obtained by reacting a tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymer with (meth)acrylic acid and then reacting that with tetrahydrophthalic anhydride; a resin obtained by reacting a 2-ethylhexyl (meth)acrylate / tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymer with (meth)acrylic acid and then reacting that with succinic anhydride; a resin obtained by reacting a methyl (meth)acrylate / 2-ethylhexyl (meth)acrylate / tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymer with (meth)acrylic acid and then reacting that with succinic anhydride; and so on [K6].

[0137] Resins [K1] to [K6] may be used individually or in combination of two or more types.

[0138] Among these, resin [K1] and / or resin [K2] are preferred, and resin [K1] is more preferred.

[0139] The weight-average molecular weight of resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed areas in the developer is good, and the resolution of the color pattern tends to improve. The degree of dispersion of resin (B) [weight-average molecular weight (Mw) / number-average molecular weight (Mn)] is preferably 1.1 to 6, and more preferably 1.2 to 4.

[0140] The acid value of resin (B) is preferably 20 to 170 mg-KOH / g, more preferably 30 to 150 mg-KOH / g, and even more preferably 40 to 135 mg-KOH / g, based on solid content. Here, the acid value is measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

[0141] The content of resin (B) is preferably 2 to 65% by mass, more preferably 10 to 60% by mass, and even more preferably 15 to 55% by mass, relative to the total amount of solids in the colored resin composition. When the content of resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film rate of the colored pattern tend to improve.

[0142] <Polymerizable compound (C)> The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D), and examples include compounds having polymerizable ethylenically unsaturated bonds, and is preferably a (meth)acrylic acid ester compound.

[0143] In particular, polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol poly(meth)acrylate (e.g., pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate), dipentaerythritol poly(meth)acrylate (e.g., dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate), tripentaerythritol poly(meth)acrylate (e.g., tri Pentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate), tetrapentaerythritol poly(meth)acrylate (e.g., tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate), tris(2-(meth)acryloyloxyethyl) isocyanurate, alkoxylated pentaerythritol poly(meth)acrylate (e.g., ethoxylated pentaerythritol tri(meth)acrylate, ethoxylated Xylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate), alkoxylated dipentaerythritol poly(meth)acrylate (e.g., ethoxylated dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol penta(meth)acrylate, propoxylated dipentaerythritol Examples include hexa(meth)acrylate, caprolactone-modified pentaerythritol poly(meth)acrylate (e.g., caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate), caprolactone-modified dipentaerythritol poly(meth)acrylate (e.g., caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate), etc. In particular, it is preferable that it be at least one selected from the group consisting of trimethylolpropane tri(meth)acrylate and dipentaerythritol poly(meth)acrylate.

[0144] The weight-average molecular weight of the polymerizable compound (C) is preferably 150 to 2,900, more preferably 250 to 1,500.

[0145] The content of polymerizable compound (C) is, for example, 5 to 80% by mass, preferably 20 to 70% by mass, and more preferably 40 to 65% by mass, relative to the total amount of solids in the colored resin composition. When the content of polymerizable compound (C) is within the above range, the residual film rate when forming the colored pattern and the chemical resistance of the color filter tend to improve.

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

[0147] Examples of polymerization initiators that generate active radicals include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

[0148] The O-acyloxime compound is a compound having a substructure represented by formula (d1). Hereinafter, * represents a bond.

[0149] [ka]

[0150] Examples of the O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-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-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine, N- Examples include acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-[4-(2-hydroxyethyloxy)phenylsulfanylphenyl]propan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, and 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propan-1-one. Commercially available products such as Irgacure OXE01, OXE02, OXE03 (all manufactured by BASF), N-1919 (manufactured by ADEKA), PBG-314, PBG-317, PBG-326, PBG-327, PBG-329 (all manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) may also be used.Among them, O-acyloxime compounds include N-acetyloxy-1-[4-(2-hydroxyethyloxy)phenylsulfanylphenyl]propan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propan-1-one, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1- At least one selected from the group consisting of on-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-on-2-imine is preferred, and at least one selected from the group consisting of 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propane-1-one, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-on-2-imine, and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-on-2-imine is more preferred. These O-acyloxime compounds tend to yield high-brightness color filters.

[0151] The alkylphenone compound is a compound having a substructure represented by formula (d2) or formula (d3). In these substructures, the benzene ring may have substituents.

[0152] [ka]

[0153] Examples of compounds having the substructure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) may also be used.

[0154] Examples of compounds having the substructure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethyl ketal. In terms of sensitivity, alkylphenone compounds having the substructure represented by formula (d2) are preferred.

[0155] Examples of the aforementioned triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[ Examples include 2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0156] Examples of the aforementioned acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure® 819 (manufactured by BASF) may also be used.

[0157] Examples of the biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, 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(alkoxyphen Examples include (nyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), and biimidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Application Publication No. 7-10913, etc.).

[0158] Furthermore, examples of polymerization initiators (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; and 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with polymerization initiators (D1) (especially amine compounds) described later.

[0159] Examples of polymerization initiators that generate acids include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate, as well as nitrobenzyl tosylates and benzoin tosylates.

[0160] The polymerization initiator (D) is preferably at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds, with O-acyloxime compounds being more preferred.

[0161] The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 2 to 10 parts by mass, based on 100 parts by mass of the total amount of resin (B) and polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, sensitivity tends to increase and exposure time is shortened, thus improving the productivity of color filters.

[0162] <Polymerization initiator (D1)> Polymerization initiator (D1) is a compound or sensitizer used to accelerate the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator. When polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D). Examples of polymerization initiators (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0163] Examples of the amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michla's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, with 4,4'-bis(diethylamino)benzophenone being preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.

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

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

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

[0167] When these polymerization initiators (D1) are used, their content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of resin (B) and polymerizable compound (C). When the amount of polymerization initiator (D1) is within this range, it is possible to form a colored pattern with even higher sensitivity, and the productivity of color filters tends to improve.

[0168] <Solvent (E)> The solvent (E) is not particularly limited, and any solvent commonly used in the art may be used. Examples include 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 both -CO- and -COO-), alcohol solvents (solvents containing OH but not -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxides, and the like.

[0169] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0170] Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethole, and methylanisole.

[0171] Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxypropionate Examples include ethyl xy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0172] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0173] Examples of alcoholic solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0174] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0175] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0176] Of the above solvents, organic solvents with a boiling point of 120°C or higher and 180°C or lower at 1 atm are preferred from the viewpoint of applicability and drying properties. As the solvent, at least one selected from the group consisting of 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, 4-hydroxy-4-methyl-2-pentanone, and N,N-dimethylformamide is preferred, and at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate, and ethyl 3-ethoxypropionate is more preferred.

[0177] The solvent (E) content is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, relative to the total amount of the colored resin composition. In other words, the solid content of the colored resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the solvent (E) content is within the above range, the flatness during coating is good, and when a color filter is formed, there is no shortage of color density, which tends to result in good display characteristics and sensitivity.

[0178] <Leveling agent (F)> Examples of leveling agents (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants containing fluorine atoms. These may have polymerizable groups in their side chains.

[0179] Examples of silicone-based surfactants include surfactants that have siloxane bonds in their molecules. Specifically, examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (product name: 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, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC).

[0180] Examples of the aforementioned fluorine-based surfactants include surfactants having fluorocarbon chains in their molecules. Specifically, these include Florard® FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac® F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), F-Top® EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon® S381, S382, SC101, SC105 (manufactured by AGC Inc. (formerly Asahi Glass Co., Ltd.)), and E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.).

[0181] Examples of silicone-based surfactants containing fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in their molecules. Specifically, examples include Megafac® R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0182] The content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.002 to 0.1% by mass, and even more preferably 0.005 to 0.05% by mass, relative to the total amount of the colored resin composition. Note that this content does not include the content of the pigment dispersant described later. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

[0183] <Other ingredients> The colored resin composition may optionally contain additives known in the art, such as pigment dispersants, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents.

[0184] <Method for producing colored resin composition> A colored resin composition can be prepared, for example, by mixing a colorant (A) and a resin (B), along with a polymerizable compound (C), polymerization initiator (D), solvent (E), leveling agent (F), polymerization initiator aid (D1), and other components as needed. The mixed colored resin composition may be filtered through a filter with a pore size of approximately 0.01 to 10 μm.

[0185] The coloring agent (A) may be pre-mixed with part or all of the resin (B) and part or all of the solvent (E) to prepare a coloring agent solution. The desired colored resin composition can be prepared by mixing the remaining components to such a coloring agent solution to a predetermined concentration.

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

[0187] The film thickness of the color filter (colored coating or colored pattern) is, for example, 30 μm or less, preferably 20 μm or less, more preferably 6 μm or less, even more preferably 3 μm or less, even more preferably 1.5 μm or less, particularly preferably 0.5 μm or less, preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0188] As substrates, glass plates such as quartz glass, borosilicate glass, aluminasilate glass, and soda-lime glass with a silica coating on the surface are used; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used; silicon is used; and aluminum, silver, and silver / copper / palladium alloy thin films are formed on the substrate. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates. Alternatively, a substrate treated with HMDS on a silicon substrate may be used.

[0189] The formation of each color pixel (colored filter for each color) by photolithography can be carried out using known or conventional equipment and conditions. For example, it can be manufactured as follows: First, a colored resin composition is applied to a substrate, and volatile components such as solvents are removed by heat drying (pre-baking) and / or vacuum drying to obtain a smooth composition layer. Application methods include spin coating, slit coating, and slit and spin coating. When performing heat drying, the temperature is preferably 30 to 120°C, and more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. When performing vacuum drying, it is preferable to do so under a pressure of 50 to 150 Pa and at a temperature range of 20 to 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 desired color filter.

[0190] Next, the composition layer is exposed via a photomask to form the desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern appropriate to the intended application is used. A light source that generates light with a wavelength of 250 to 450 nm is preferred for exposure. For example, light below 250 nm can be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Specifically, examples include mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, etc. It is preferable to use a reduction projection exposure apparatus or proximity exposure apparatus such as a mask aligner and stepper, as this allows for uniform irradiation of the entire exposure surface with parallel light rays and precise alignment of the photomask and the substrate.

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

[0192] Furthermore, it is preferable to perform a post-bake on the obtained coloring pattern. The post-bake temperature is preferably 80 to 250°C, and more preferably 100 to 245°C. The post-bake time is preferably 1 to 120 minutes, and more preferably 2 to 40 minutes.

[0193] The colored patterns and colored coatings obtained in this manner are useful as color filters, and these color filters are useful as color filters used in display devices (e.g., liquid crystal display devices, organic EL devices, etc.), electronic paper, solid-state image sensors, etc. [Examples]

[0194] The present invention will be described in more detail below with reference to examples, but the present invention is not limited by the following examples, and it is certainly possible to implement it with appropriate modifications within the scope that is consistent with the spirit of the preceding and following descriptions, and all such modifications are included within the technical scope of the present invention. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "percent mass".

[0195] In the following examples, the structure of the compounds was confirmed by mass spectrometry (LC: Agilent 1200; MASS: Agilent LC / MSD6130; and MALDI-TOF MS: JEOL JMS-S3000).

[0196] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the resin, calculated on a polystyrene basis, were measured using the GPC method under the following conditions. Equipment: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40℃ Solvent: Tetrahydrofuran Flow rate: 1.0mL / min Solid content concentration of the analytical sample: 0.001~0.01% by mass Injection volume: 50μL Detector: RI Calibration standards: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation) The ratio of the weight-average molecular weight to the number-average molecular weight (Mw / Mn) obtained above in polystyrene terms was defined as the degree of dispersion.

[0197] [Synthesis Example 1] <Synthesis of the compound represented by formula (B-1)> 100 parts of tetrafluorophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), 29.0 parts of p-ethoxycarbonylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 19.3 parts of potassium fluoride (manufactured by Kanto Chemical Co., Ltd.), and 800 parts of acetone were charged and stirred at 45°C for 12 hours. After cooling to room temperature, the resulting solid was filtered off, washed with methanol and then warm water to purify it, and 45.0 parts of the compound represented by formula (B-1) (hereinafter, compound (B-1)) were obtained (yield 78%). [ka]

[0198] <Identification of compound (B-1)> (Mass Spectrometry) Ionization Mode = ESI+: m / z = 347 [M+H] + Exact Mass: 346

[0199] [Synthesis Example 2] <Synthesis of the compound represented by formula (C-1)> 50.0 parts of tetrafluorophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), 29.1 parts of p-ethoxycarbonylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 14.5 parts of potassium fluoride (manufactured by Kanto Chemical Co., Ltd.), and 400 parts of acetone were charged and stirred at 45°C for 19 hours. After cooling to room temperature, the resulting solid was filtered off, washed with methanol and then warm water to purify it, and 41.0 parts of the compound represented by formula (C-1) (hereinafter, compound (C-1)) were obtained (yield 83%). [ka]

[0200] <Identification of compound (C-1)> (Mass Spectrometry) Ionization Mode = ESI+: m / z = 493 [M+H] + Exact Mass: 492

[0201] [Example 1A] 23.4 parts of compound (B-1) obtained in Synthesis Example 1, 100 parts of compound (C-1) obtained in Synthesis Example 2, 21.6 parts of zinc iodide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 132 parts of benzonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and heated to 170°C, and stirred for 17 hours. When 1990 parts of methanol were added dropwise, a dark green precipitate was formed. The mixture containing this dark green precipitate was filtered, and the residue after filtering was washed with 663 parts of deionized water. The obtained residue was dried under reduced pressure at 60°C to obtain 71.6 parts of phthalocyanine dye (I-a1) (yield 56%). Here, phthalocyanine dye (I-a1) is a mixture of compounds represented by the following formula (Ian) (hereinafter also referred to as compound (Ian)), where n represents the number of 4-ethoxycarbonylphenyloxy groups. Based on the LC area percentages obtained under the following LC conditions, the ratios of compound (Ia-4): compound (Ia-5): compound (Ia-6): compound (Ia-7): compound (Ia-8) were 0%:5%:21%:42%:32%, and the average number of n was 7.0.

[0202] [ka]

[0203] <Identification of compound (Ia-5)> (Mass Spectrometry) Ionization Mode = ESI+: m / z = 1595 [M+H] + Exact Mass: 1594 <Identification of compound (Ia-6)> (Mass Spectrometry) Ionization Mode = ESI+: m / z = 1741 [M+H] + Exact Mass: 1740 <Identification of compound (Ia-7)> (Mass Spectrometry) Ionization Mode = ESI+: m / z = 1887 [M+H] + Exact Mass: 1886 <Identification of compound (Ia-8)> (Mass spectrometry) Ionization mode = ESI+: m / z = 2033 [M+H] + Exact Mass: 2032

[0204] (LC conditions) The analysis conditions of high performance liquid chromatography (HPLC) are shown below. <HPLC analysis condition 1> (1) Instrument: Agilent 1260 Infinity LC series (2) Detector: DAD (254 nm) (3) Column: Wakosil II 3C18HG (3.0 mm φ × 150 mm) (4) Column temperature: 40 °C (5) Mobile phase: Mobile phase A: Ion-exchanged water, 0.1 wt% formic acid Mobile phase B: THF / acetonitrile = 50 / 50 (v / v), 0.1 wt% formic acid (6) Flow rate: 1.0 mL / min (7) Gradient conditions: 0 min Mobile phase A / Mobile phase B = 90 / 10 5 min Mobile phase A / Mobile phase B = 90 / 10 15 min Mobile phase A / Mobile phase B = 0 / 100 30 min Mobile phase A / Mobile phase B = 0 / 100 Regarding the identification of the detected LC peaks, mass spectrometry (LC; Agilent 1260 type, MASS; Agilent LC / MSD6130 type, and MALDI-TOF MS; JEOL JMS-S3000) was used for confirmation.

[0205] <Measurement of the spectral distribution width> Using the photodiode array (PDA) detector attached to the aforementioned LC apparatus, the absorption spectra of each component corresponding to compounds (Ia-5) to (Ia-8) were measured, and the spectral distribution width was calculated. In the absorption spectra of all components, there was a first maximum absorption peak with the maximum absorbance at its peak, and a second maximum absorption peak with the next highest peak peak (second maximum absorbance). As shown in Figure 1, the spectral distribution width can be calculated by the difference (x2-x1) between the wavelength x1 at the second maximum absorbance and the longer wavelength x2 at the wavelength that shows the same absorbance as the second maximum absorbance at the first maximum absorption. As is clear from the results below, compounds (Ia-5) to (Ia-7), which correspond to compound (IN), have the maximum absorbance and second maximum absorbance in the 650-710 nm range, and their spectral distribution width is broadened. The broadened distribution of this compound indicates that it can efficiently absorb red light. [Table 9]

[0206] [Example 2A] The procedure was carried out in the same manner as in Example 1A, except that 23.4 parts of compound (B-1) were replaced with 46.9 parts and 100 parts of compound (C-1) were replaced with 50 parts, yielding 60.2 parts of phthalocyanine dye (I-a2) (yield 51%). Based on the LC area percentages obtained under the same LC conditions as in Example 1A, the ratio of compounds (Ia-4):compound(Ia-5):compound(Ia-6):compound(Ia-7):compound(Ia-8) was 6%:25%:38%:25%:6%, and the average number of n was 6.0.

[0207] <Identification of compound (Ia-4)> (Mass Spectrometry) Ionization Mode = ESI+: m / z = 1449 [M+H] + Exact Mass: 1448

[0208] [Example 3A] The procedure was carried out in the same manner as in Example 1A, except that 23.4 parts of compound (B-1) were replaced with 65.4 parts and 100 parts of compound (C-2) were replaced with 40.0 parts, yielding 59.4 parts of phthalocyanine dye (I-a3) (yield 55%). Based on the LC area percentages obtained under the same LC conditions as in Example 1A, the ratios of compound (Ia-4): compound (Ia-5): compound (Ia-6): compound (Ia-7): compound (Ia-8) were 24%:41%:26%:8%:1%, and the average number of n was 5.2.

[0209] [Comparative Example 1A] The procedure was carried out in the same manner as in Example 1A, except that 23.4 parts of compound (B-1) were replaced with 0 parts and 100 parts of compound (C-2) were replaced with 133 parts, yielding 79.9 parts of phthalocyanine dye (I-ac1) (yield 58%). Based on the LC area percentage obtained under the same LC conditions as in Example 1A, the phthalocyanine dye (I-ac1) was compound (Ia-8) = 100%, and the average number of n was 8.0.

[0210] [ka]

[0211] [Synthesis Example 3] The procedure was carried out in the same manner as in Example 1A, except that 23.4 parts of compound (B-1) were replaced with 93.6 parts and 100 parts of compound (C-2) were replaced with 0 parts, yielding 57.8 parts of phthalocyanine dye (I-a4) (yield 55%). Based on the LC area percentage obtained under the same LC conditions as in Example 1A, the phthalocyanine dye (I-a4) was compound (Ia-4) = 100%, and the average number of n was 4.0.

[0212] [ka]

[0213] [Example 4A] 30.0 parts of the compound (I-a-4) obtained in Synthesis Example 3, 42.0 parts of the compound (I-a-8) obtained in Comparative Example 1A, and 1440 parts of propylene glycol monomethyl ether acetate were added and stirred at 23 °C for 6 hours. The solvent was distilled off, and the obtained dark green residue was dried under reduced pressure at 60 °C to obtain the phthalocyanine-based dye (I-a4). Based on the LC area percentage determined under the same LC conditions as in Example 1A, compound (I-a-4): compound (I-a-5): compound (I-a-6): compound (I-a-7): compound (I-a-8) = 50%: 0%: 0%: 0%: 50%, and the average value of n was 6.0.

[0214] <Solubility in propylene glycol monomethyl ether acetate (PGMEA)> The solubility of each phthalocyanine-based dye obtained in Examples 1A to 4A and Comparative Example 1A in PGMEA was measured by the following method. The results are as shown in Table 10. (Method for measuring solubility) Approximately 50 mg of the dye whose solubility was to be measured (hereinafter sometimes referred to as the solute) was weighed into a screw tube, and approximately 500 mg of PGMEA was added thereto. The total amount of the solute and PGMEA was weighed and stirred at 23 °C for 30 minutes using a mix rotor (manufactured by AS ONE, MR-3S, rotation speed 40 rpm). Thereafter, when dissolution was visually confirmed, the solubility was determined from the following formula (h). When dissolution was not visually confirmed, an additional 100 mg of PGMEA was added, and stirring was performed under the same conditions for 30 minutes to visually confirm the presence or absence of dissolution of the solute. This operation was repeated until dissolution was visually confirmed. When dissolution was visually confirmed, the solubility was determined from the following formula (h). The results are shown in Table 10. Note that the size of the screw tube was such that the amount of the solution when dissolution was complete was 1 to 80% of the volume of the screw tube. Solubility [%] = (mass of solute) / (total mass of solute and PGMEA) × 100 (h)

[0215] <Storage stability test of PGMEA solution>[ PGMEA was added to each phthalocyanine dye obtained in Examples 1A to 4A and Comparative Example 1A to prepare a 2% by mass PGMEA solution. The obtained PGMEA solution was incubated at 40°C for 24 hours, and then visually inspected for the presence or absence of precipitates. The results are shown in Table 10. ○ indicates no precipitates, and × indicates the presence of precipitates. If precipitates are present, haze will occur in the resulting color filter, causing a decrease in transmittance. Therefore, long-term stability of the dye solution is required to prevent precipitate formation.

[0216] [Example of resin synthesis 1] A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, dropping funnel, and stirrer to replace the atmosphere with nitrogen. 280 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 80°C while stirring. Then, 38 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 A mixture of 289 parts of decane-9-yl acrylate (with a molar ratio of 1:1) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a solution of 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the addition was complete, the mixture was held at 80°C for 4 hours, then cooled to room temperature to obtain a copolymer (resin B1) solution with a solid content of 35.1% and a viscosity of 125 mPa·s measured with a B-type viscometer (23°C). The weight-average molecular weight Mw of the resulting copolymer was 9.2 × 10⁻⁶. 3 The dispersion was 2.08, and the acid value on a solid content basis was 77 mg-KOH / g. Resin B1 has the following structural units.

[0217] [ka]

[0218] [Example 1B] (1) Preparation of colored resin composition 1 The following components were mixed in the following proportions to obtain colored resin composition 1. (A) Coloring agent: Phthalocyanine dye (I-a1) 2.6 parts (B) Resin: 54 parts of resin B1 solution (E) Solvent: Propylene glycol monomethyl ether acetate 420 parts

[0219] (2) Preparation of colored resin composition 1' Next, the components were mixed in the following proportions to obtain colored resin composition 1'. Colored resin composition 1 478 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayalad® DPHA; manufactured by Nippon Kayaku Co., Ltd.) 40 copies (D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure® OXE 01; manufactured by BASF) 2 parts (F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts

[0220] (3) Preparation of colored coating film (color filter) A colored resin composition 1' was applied by spin coating onto a 5cm square glass substrate (Eagle XG; Corning Corporation) to a post-baking thickness of 2μm. The substrate was then pre-baked at 100°C for 3 minutes to form a colored composition layer. After cooling, the colored composition layer formed on the substrate was exposed to air at 80mJ / cm² using an exposure unit (TME-150RSK; Topcon Corporation) in an atmospheric environment. 2 The sample was irradiated with light at the specified exposure level (based on 365 nm). After light irradiation, post-baking was performed in an oven at 230°C for 30 minutes to obtain a colored coating.

[0221] [Examples 2B-4B, Comparative Example 1B] A colored coating film was obtained in the same manner as in Example 1B, except that the phthalocyanine dye (I-a1) was replaced with the following phthalocyanine dye. Example 2B: Phthalocyanine dye (I-a2) obtained in Example 2A Example 3B: Phthalocyanine dye (I-a3) obtained in Example 3A Example 4B: Phthalocyanine dye (I-a4) obtained in Example 4A Comparative Example 1B: Phthalocyanine-based dye (I-ac1) obtained in Comparative Example 1A

[0222] <Foreign object detection> The presence or absence of foreign matter in the colored coating after post-baking was inspected visually. The results are shown in Table 10.

[0223] [Table 10]

[0224] <Coating film spectrum> The colored coating film after post-baking was spectrally measured at 1 nm intervals in the wavelength range of 380 nm to 780 nm using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). The transmittance at three wavelengths, 630 nm, 650 nm, and 680 nm, was measured. The low transmittance in the 630-680 nm region indicates that it can efficiently absorb red light, suggesting high suitability as a green color filter.

[0225] [Table 11]

Claims

1. A phthalocyanine dye consisting of one or more compounds represented by formula (I), A phthalocyanine dye in which the average number of groups represented by formula (II) per M group in the compound represented by formula (I) is 4.5 or more and 7.2 or less. 【Chemistry 1】 [In formula (I), M represents a divalent metal atom. X 1 ~X 8 These represent, independently of each other, a fluorine atom or a chlorine atom. A 1 ~A 8 These independently represent a fluorine atom, a chlorine atom, or a group represented by formula (II). In formula (II), B 1 to B 5 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a COR x group, a CO 2 R x group, an OR x group, an NHR x group, or an NR x 2 group. R x R represents a hydrocarbon group having 1 to 10 carbon atoms. x If there are multiple instances, they may be identical or different. * indicates a bonding operation.

2. X 1 ~X 8 is a fluorine atom, and A 1 ~A 8 The phthalocyanine dye according to claim 1, wherein each is independently a fluorine atom or a group represented by formula (II).

3. B 1 ~B 5 At least one of them is CO 2 R x The phthalocyanine-based dye according to claim 1, which is the base.

4. A phthalocyanine-based dye according to claim 1, which is any of (i) to (v) below. (i) A compound comprising a compound in which the number of groups represented by formula (II) in formula (I) is 4, and a compound in which the number of groups represented by formula (II) in formula (I) is 5. (ii) A compound comprising a compound in which the number of groups represented by formula (II) in formula (I) is 5, and a compound in which the number of groups represented by formula (II) in formula (I) is 6. (iii) A compound comprising a compound in which the number of groups represented by formula (II) in formula (I) is 6, and a compound in which the number of groups represented by formula (II) in formula (I) is 7. (iv) A compound comprising a compound in which the number of groups represented by formula (II) in formula (I) is 7, and a compound in which the number of groups represented by formula (II) in formula (I) is 8. (v) A compound comprising a compound in which the number of groups represented by formula (II) in formula (I) is 4, and a compound in which the number of groups represented by formula (II) in formula (I) is 8.

5. A coloring agent comprising a phthalocyanine-based dye as described in claim 1.

6. The coloring agent according to claim 5, further comprising a coloring agent other than the compound represented by formula (I).

7. The coloring agent according to claim 5, wherein the content of the compound represented by formula (Ix) is 50 parts by mass or less per 100 parts by mass of the compound represented by formula (I). 【Chemistry 2】 [In formula (Ix), M x This represents a divalent metal atom. X 1x ~X 8x and A 1x ~A 8x These represent, independently of each other, a fluorine atom, a chlorine atom, or a group represented by formula (II). However, X 1x ~X 8x Of these, at least one represents a base represented by formula (II). * indicates a bonding operation.

8. A colored resin composition comprising the coloring agent described in claim 5 and an alkali-soluble resin.

9. Furthermore, the colored resin composition according to claim 8 contains a polymerizable compound and a polymerization initiator.

10. A color filter formed from the colored resin composition described in claim 8.

11. A display device including the color filter described in claim 10.

12. A solid-state image sensor including the color filter described in claim 10.

13. A compound represented by the formula (I-N). 【Transformation 3】 [In formula (IN), M n This represents a divalent metal atom. X 1n ~X 8n These represent, independently of each other, a fluorine atom or a chlorine atom. A 1n ~A 8n These independently represent a fluorine atom, a chlorine atom, or a group represented by formula (II). However, A 1n ~A 8n Of these, 5 to 7 represent the base expressed by formula (II). B 1 ~B 5 These are, independently of each other, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and COR x Group, CO 2 R x Base, OR x Group, NHR x Base, or NR x 2 It represents the basis. R x R represents a hydrocarbon group having 1 to 10 carbon atoms. x If there are multiple instances, they may be identical or different.

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