TW202229477A - Coloring composition, coloring film, and method for forming coloring film capable of forming a coloring film excellent in low-reflectivity and heat resistance - Google Patents

Abstract

An object of the present invention is to provide a coloring composition capable of forming a coloring film excellent in low-reflectivity and heat resistance, a coloring film that can be formed by using the coloring composition, and a method for forming a coloring film using the coloring composition. A pigment dispersion liquid containing a pigment, a polyamic acid, and an aprotic polar solvent is used in the coloring composition containing the pigment dispersion liquid and a hollow silica. Preferably, in the pigment dispersion liquid, the polyamic acid is used to disperse the pigment in the aprotic polar solvent. The polyamic acid includes at least one of a partial skeleton derived from an aromatic diamine having a specific structure and a partial skeleton derived from an alicyclic tetracarboxylic dianhydride having a specific structure.

Description

Colored composition, colored film, and method of forming a colored film

The present invention relates to a coloring composition, a coloring film that can be formed using the coloring composition, and a method for forming a coloring film using the coloring composition.

Conventionally, in order to color liquid compositions such as inks and various resin compositions, pigment dispersions containing various pigments have been used. As a representative pigment, carbon black is mentioned, for example. The colored compositions obtained using the carbon black dispersion are not only used for printing and coating applications, but also used as materials for forming light-shielding materials such as black matrices and black column spacers in various display panels.

For example, low-reflection properties are sometimes required for colored films such as black matrices. In order to impart low reflection characteristics to the colored film, it is proposed to use a composition (A) a color material, (B) an organic binder, and (C) fine particles such as silica particles (refer to the patent) in the process of forming the colored film. Reference 1).

Also, typically, the liquid coloring composition is prepared using a pigment dispersion. Pigment dispersions such as carbon black dispersions are mostly produced by dispersing pigments in solvents such as organic solvents using dispersants. As a method for producing such a pigment dispersion, for example, as a method for producing a carbon black dispersion, a method is known in which a low molecular weight compound such as an organic pigment derivative and a triazine derivative is used as a dispersant, and a Carbon black is dispersed in organic solvents such as solvents, ketones, and aprotic polar organic solvents (see Patent Document 2). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-067028 [Patent Document 2] Japanese Patent Laid-Open No. 2005-213405

[The problem to be solved by the invention]

However, when the carbon black dispersion liquid obtained by the method described in Patent Document 2 is used to color various compositions, there is a problem that the heat resistance of the obtained black composition is also poor due to the use of a dispersant with poor heat resistance. .

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a coloring composition capable of forming a colored film having excellent low reflectivity and heat resistance, a coloring film that can be formed using the coloring composition, and a coloring composition using the above-mentioned coloring composition. A method of forming a colored film. [Means for solving problems]

The inventors of the present invention found that the above-mentioned problems can be solved by using a pigment dispersion liquid containing a pigment, a polyamide acid, and an aprotic polar solvent in a coloring composition containing a pigment dispersion liquid and hollow silica, and completed the this invention.

The first aspect of the present invention is a coloring composition comprising a pigment dispersion liquid and hollow silica, The pigment dispersion liquid contains a pigment, a polyamide acid, and an aprotic polar organic solvent.

The 2nd aspect of this invention is a coloring film which dries the film containing the coloring composition of 1st aspect, or is dried and hardened.

The third aspect of the present invention is a method for forming a colored film, comprising: coating the coloring composition of the first form on a substrate to form a coating film; and The coating film is dried, or dried and cured. [Effect of invention]

According to the present invention, a coloring composition capable of forming a colored film having excellent low reflectivity and heat resistance, a colored film that can be formed using the coloring composition, and a method for forming a colored film using the coloring composition can be provided.

≪Coloring composition≫ The coloring composition includes a pigment dispersion and hollow silica. The pigment dispersion liquid contains a pigment, a polyamide, and an aprotic polar solvent. By containing the said pigment dispersion liquid and hollow silica together in a coloring composition, the coloring film excellent in low reflectivity and heat resistance can be formed using a coloring composition.

<Pigment dispersion> The pigment dispersion liquid contains polyamic acid and an aprotic polar organic solvent. Pigment dispersions are generally prepared by dispersing pigments in an aprotic polar organic solvent and in the presence of polyamic acid. In the pigment dispersion liquid prepared by this method, the polyamic acid acts as a dispersing agent to disperse the pigment rapidly and stably. Moreover, the cured film excellent in heat resistance can be formed using a coloring composition by making a coloring composition contain the pigment dispersion liquid containing polyamic acid. Hereinafter, the components which the pigment dispersion liquid must or optionally contain will be described in order.

[pigment] It does not specifically limit as a pigment, Various pigments can be used. The pigment may be an inorganic pigment or an organic pigment.

The pigment is not particularly limited. For example, it is preferable to use a compound classified as a pigment (Pigment) in the Color Index (C.I.; issued by The Society of Dyers and Colourists). Index (C.I.) numbered compound.

Examples of yellow pigments that can be suitably used include C.I. Pigment Yellow 1 (hereinafter, also referred to as "C.I. Pigment Yellow", and only the numbers are described), 3, 11, 12, 13, 14, 15, 16, 17, 20 , 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110 , 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167 , 168, 175, 180, and 185.

Examples of orange pigments that can be suitably used include C.I. Pigment Orange 1 (hereinafter, also referred to as "C.I. Pigment Orange", and only the numbers are described), 5, 13, 14, 16, 17, 24, 34, 36, 38 , 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, and 73.

Examples of purple pigments that can be suitably used include C.I. Pigment Violet 1 (hereinafter, also referred to as "C.I. Pigment Violet", only the numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39 , 40, and 50.

Examples of red pigments that can be suitably used include C.I. Pigment Red 1 (hereinafter, also referred to as "C.I. Pigment Red", and only the numbers are described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

Examples of blue pigments that can be suitably used include C.I. Pigment Blue 1 (hereinafter, also referred to as "C.I. Pigment Blue", only the number is described), 2, 15, 15:3, 15:4, 15:6, 16, 22, 28, 60, 64, and 66.

Examples of pigments with hues other than the above that can be suitably used include green pigments such as C.I. Pigment Green 7, C.I. Pigment Green 36, and C.I. Pigment Green 37; C.I. Pigment Brown 23, C.I. Pigment Brown 25, and C.I. Pigment Brown 26 , C.I. Pigment Brown 28 and other brown pigments; C.I. Pigment White 4, C.I. Pigment White 5, C.I. Pigment White 6, C.I. Pigment White 7 and other white pigments; C.I. Pigment Black 1, C.I. Pigment Black 7 and other black pigments.

In addition, the pigment may be an opacifier having a black color or a hue close to black. The pigment dispersion liquid containing the light-shielding agent can be suitably used for preparing the following photosensitive resin composition for forming black matrix or black column spacer in liquid crystal display panel, forming light emission in organic EL element Dividers are used for the division of layers.

As a light-shielding agent as a pigment, it is preferable to use a black pigment and a purple pigment. As a black pigment or a purple pigment, various pigments can be used, either an organic substance or an inorganic substance may be used. Examples of black pigments and purple pigments include carbon black, perylene-based pigments, lactamide-based pigments, titanium blacks such as titanium oxynitride and titanium nitride, metal oxides, composite oxides, metal sulfides, metal Sulfates or metal carbonates, etc. Examples of metals constituting metal oxides, metal composite oxides, metal sulfides, metal sulfates, or metal carbonates include copper, iron, manganese, cobalt, tungsten, chromium, nickel, zinc, calcium, and silver. .

Among these light-shielding agents, carbon black is preferred in view of easy availability and excellent light-shielding properties. As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used. Moreover, resin-coated carbon black can also be used.

As carbon black, the carbon black which performed the process to introduce|transduce an acidic group is also preferable. The acidic groups introduced into carbon black show functional groups based on the acidity defined by Brynster. As a specific example of an acidic group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned. Acid groups introduced into carbon black can form salts. The cation that forms a salt with an acidic group is not particularly limited in the range that does not inhibit the object of the present invention. Examples of cations include various metal ions, cations of nitrogen-containing compounds, ammonium ions, and the like, and preferred are alkali metal ions such as sodium ions, potassium ions, and lithium ions, and ammonium ions.

Among the carbon blacks that have been subjected to the treatment of introducing an acidic group as described above, from the viewpoint of realizing high resistance of the light-shielding cured film formed using the photosensitive resin composition, it is preferable to have a carbon black selected from the group consisting of carboxylic acid groups, carboxylic acid groups, and carboxylic acid groups. Carbon black with one or more functional groups in the group consisting of an acid group, a sulfonic acid group, and a sulfonic acid salt group.

The method of introducing an acidic group into carbon black is not particularly limited. As a method of introducing an acidic group, the following method is mentioned, for example. Method 1): introduce sulfonic acid groups into carbon black by direct substitution method and indirect substitution method. The above-mentioned direct substitution method uses concentrated sulfuric acid, oleum, chlorosulfonic acid, etc. Bisulfate, etc. Method 2): Diazo-coupling an organic compound having an amine group and an acidic group with carbon black. Method 3): Using the Williamson etherification method, an organic compound having a halogen atom and an acidic group and a carbon black having a hydroxyl group are reacted. Method 4): An organic compound having a halogenated carbonyl group and an acidic group protected by a protecting group is reacted with carbon black having a hydroxyl group. Method 5): Using an organic compound having a halogenated carbonyl group and an acidic group protected by a protecting group, a Friedel-Clayford reaction is performed on carbon black, followed by deprotection.

Among these methods, the method 2) is preferable from the viewpoint of easy and safe treatment of introducing an acidic group. The organic compound having an amine group and an acidic group used in the method 2) is preferably a compound in which an amine group and an acidic group are bonded to an aromatic group. Examples of such compounds include aminobenzenesulfonic acid such as p-aminobenzenesulfonic acid, and aminobenzoic acid such as 4-aminobenzoic acid.

The molar number of the acid group introduced into carbon black is not particularly limited within the range that does not hinder the object of the present invention. The molar number of the acidic group introduced into the carbon black is preferably 1 mmol or more and 200 mmol or less, more preferably 5 mmol or more and 100 mmol or less, relative to 100 g of carbon black.

For carbon black, coating treatment can be performed with resin. The coating treatment with resin can be applied to carbon black into which an acidic group is introduced. When a coloring composition containing a colorant dispersion containing resin-coated carbon black is used, it is easy to form a light-shielding coating film and a cured product with excellent light-shielding and insulating properties and low surface reflectance. Furthermore, by coating with resin, there is no particular adverse effect on the dielectric constant of the light-shielding coating film or cured product formed using the coloring composition. Examples of resins that can be used to coat carbon black include thermosetting resins such as phenol resins, melamine resins, xylene resins, diallyl phthalate resins, glycerol resins, epoxy resins, and alkylbenzene resins. ;Polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polystyrene, poly-p-phenylene terephthalate, polyamide Imide, polyimide, polyamine bismaleimide, polyether, polyphenylene, polyarylate, polyether ether ketone and other thermoplastic resins. The coating amount of the resin with respect to the carbon black is preferably 1 mass % or more and 30 mass % or less with respect to the sum of the mass of the carbon black and the mass of the resin.

In addition, carbon black may be treated with a silane coupling agent to improve the adhesion and the like between a colored molded body formed using a coloring composition containing carbon black and various substrates. The treatment with a silane coupling agent may be carried out before the treatment for introducing an acidic group into carbon black, or after the treatment for introducing an acidic group into carbon black, and may be carried out after the dispersion treatment using a polyamide acid as a dispersing agent It can be carried out before, or it can be carried out after the dispersion treatment using polyamic acid as a dispersant.

The silane coupling agent used for the treatment of carbon black can be appropriately selected from previously known silane coupling agents. The silane coupling agent used for the treatment of carbon black is preferably a silane coupling agent represented by the following formula (I).

R ^A1 _a R ^A2 _{(3 - a)} Si-R ^A3 -NH-C(O)-YR ^A4 -X・・・(I) (In formula (I), R ^A1 is an alkoxy group, and R ^A2 is an alkane group, a is an integer of 1 or more and 3 or less, R ^A3 is an alkylene group, Y is -NH-, -O-, or -S-, R ^A4 is a single bond or an alkylene group, and X is an optionally substituted group The monocyclic or polycyclic nitrogen-containing heteroaryl group, the ring bonded with -YR ^A4 - in X is a nitrogen-containing six-membered aromatic ring, -YR ^A4 - is bonded with the carbon atom in the above-mentioned nitrogen-containing six-membered aromatic ring Knot)

In formula (I), R ^A1 is an alkoxy group. As for R ^A1 , the number of carbon atoms of the alkoxy group is preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and particularly preferably 1 or 2 from the viewpoint of the reactivity of the silane coupling agent. Preferable specific examples of R ^A1 include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, 2nd butoxy, 3rd butoxy group, n-pentyloxy, and n-hexyloxy. Among these alkoxy groups, a methoxy group and an ethoxy group are particularly preferred.

The silanol group generated by the hydrolysis of R ^A1 , which is an alkoxy group, reacts with functional groups containing active hydrogen atoms such as hydroxyl and carboxyl groups present on the surface of the carbon black, whereby the silane coupling agent is bonded to the surface of the carbon black. Therefore, a is preferably 3 from the viewpoint of easily bonding the silane coupling agent to the surface of the carbon black.

In formula (I), R ^A2 is an alkyl group. As for R ^A2 , the number of carbon atoms of the alkyl group is preferably 1 or more and 12 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or 2 from the viewpoint of the reactivity of the silane coupling agent. Preferable specific examples of R ^A2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl.

In formula (I), R ^A3 is an alkylene group. As for R ^A3 , the number of carbon atoms in the alkylene group is preferably 1 or more and 12 or less, more preferably 1 or more and 6 or less, and particularly preferably 2 or more and 4 or less. Preferable specific examples of R ^A3 include methylene, 1,2-ethylene, 1,1-ethylene, propane-1,3-diyl, propane-1,2-diyl , propane-1,1-diyl, propane-2,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-1,2-diyl, butane Alkane-1,1-diyl, butane-2,2-diyl, butane-2,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, and Hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, Undecane-1,11-diyl, and dodecane-1,12-diyl. Among these alkylene groups, 1,2-ethylene, propane-1,3-diyl, and butane-1,4-diyl are preferable.

Y is -NH-, -O-, or -S-, preferably -NH-. The reason for this is that the bond represented by -CO-NH- is less prone to hydrolysis than the bond represented by -CO-O- or -CO-S-. As for the carbon black obtained by using the compound whose Y is -NH- as the silane coupling agent, the structure of the silane coupling agent is not easily changed by the action of acid, alkali, etc., so it is easy to obtain the carbon black by using the silane coupling agent. the desired effect.

R ^A4 is a single bond or an alkylene group, preferably a single bond. The preferable example when R ^A4 is an alkylene group is the same as that of R ^A3 .

X is a monocyclic or polycyclic nitrogen-containing heteroaryl group that may have substituents, the ring bonded to -YR ^A4 - in X is a nitrogen-containing six-membered aromatic ring, -YR ^A4 - and the nitrogen-containing six-membered aromatic ring The carbon atoms in the ring are bonded. Although the reason is not clear, when a coloring composition containing a compound having such X as a silane coupling agent is used, a colored molded body excellent in adhesion to a substrate, water resistance, and solvent resistance can be formed.

When X is a polycyclic heteroaryl group, the heteroaryl group may be a group formed by condensing a plurality of monocyclic rings, or a group formed by bonding a plurality of monocyclic rings through a single bond. When X is a polycyclic heteroaryl group, the number of rings contained in the polycyclic heteroaryl group is preferably 1 or more and 3 or less. When X is a polycyclic heteroaryl group, the ring condensed or bonded to the nitrogen-containing six-membered aromatic ring in X may or may not contain a heteroatom, and may or may not be an aromatic ring.

As the substituent that X of the nitrogen-containing heteroaryl group may have, an alkyl group having 1 to 6 carbon atoms or less, an alkoxy group having 1 to 6 carbon atoms or less, and an alkene having 2 to 6 carbon atoms or less can be mentioned. group, alkenyloxy group with 2 to 6 carbon atoms, aliphatic aryl group with 2 to 6 carbon atoms, benzyl group, nitro group, nitroso group, amine group, hydroxyl group, mercapto group, cyano group, sulfonyl group Acid group, carboxyl group, and halogen atom, etc. The number of substituents that X has is not particularly limited as long as the object of the present invention is not inhibited. The number of substituents that X has is preferably 5 or less, more preferably 3 or less. When X has a plurality of substituents, the plurality of substituents may be the same or different.

As a preferable example of X, the base of the following formula can be mentioned. [hua 1]

Among the above-mentioned groups, X is more preferably a group of the following formula. [hua 2]

As a preferable specific example of the compound represented by formula (I) demonstrated above, the following compounds 1-8 can be mentioned. [hua 3]

The treatment method of carbon black with a silane coupling agent is not particularly limited, and the treatment with a silane coupling agent is performed according to a known method. Typically, the following method is preferred: the carbon black and the silane coupling agent are reacted in the presence of water in an organic solvent in which the silane coupling agent can be dissolved.

The amount of the silane coupling agent used is not particularly limited as long as the desired effect can be obtained. The amount of the silane coupling agent used is preferably 0.5 parts by mass or more and 15 parts by mass or less, more preferably 3 parts by mass or more and 7 parts by mass or less, relative to 100 parts by mass of carbon black.

The treatment of carbon black with a silane coupling agent is carried out in the presence of water. Water may be added to the treatment liquid containing carbon black and a silane coupling agent, but it is not necessary to add water to the treatment liquid. When the treatment with the silane coupling agent is carried out in an air atmosphere containing sufficient moisture, the alkoxy group of the silane coupling agent is hydrolyzed by the moisture in the air, thereby generating a silanol group.

The temperature when the carbon black is treated with the silane coupling agent is not particularly limited as long as the reaction between the silane coupling agent and the carbon black proceeds well. The treatment of carbon black with a silane coupling agent is typically performed at a temperature of not less than 25°C and not more than 100°C.

Moreover, as a pigment, a perylene type pigment is also preferable. Specific examples of the perylene-based pigment include a perylene-based pigment represented by the following formula (A-1), a perylene-based pigment represented by the following formula (A-2), and a perylene-based pigment represented by the following formula (A-3). Perylene pigments. Among the commercially available products, product names K0084, K0086, Pigment Black 21, 30, 31, 32, 33, and 34 manufactured by BASF can be preferably used as the perylene-based pigment.

式(A-1)中，R ^A11及R ^A12各自獨立地表示碳原子數1以上3以下之伸烷基，R ^A13及R ^A14各自獨立地表示氫原子、羥基、甲氧基、或乙醯基。 [hua 4]

In formula (A-1), R ^A11 and R ^A12 each independently represent an alkylene group having 1 to 3 carbon atoms, and R ^A13 and R ^A14 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or an acetyl group base.

式(A-2)中，R ^A15及R ^A16各自獨立地表示碳原子數1以上7以下之伸烷基。 [hua 5]

In formula (A-2), R ^A15 and R ^A16 each independently represent an alkylene group having 1 to 7 carbon atoms.

式(A-3)中，R ^A17及R ^A18各自獨立地為氫原子、碳原子數1～22之烷基，亦可以包含N、O、S、或P之類之雜原子。R ^A17及R ^A18為烷基時，該烷基可以為直鏈狀，亦可以為支鏈狀。 [hua 6]

In formula (A-3), R ^A17 and R ^A18 are each independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and may also contain a hetero atom such as N, O, S, or P. When R ^A17 and R ^A18 are alkyl groups, the alkyl groups may be linear or branched.

As the compound represented by the above formula (A-1), the compound represented by the formula (A-2), and the compound represented by the formula (A-3), for example, Japanese Patent Laid-Open No. 62-1753 and Japanese Patent Laid-Open No. 63 can be used. Synthesis was carried out by the method described in -26784 Gazette. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines are used as raw materials, and a heating reaction is performed in water or an organic solvent. Then, the obtained crude product is reprecipitated in sulfuric acid, or recrystallized in water, an organic solvent, or a mixed solvent of these, whereby the target product can be obtained.

In order to disperse the perylene-based pigment well in the colorant dispersion liquid, the average particle size of the perylene-based pigment is preferably 10 nm or more and 1000 nm or less.

Moreover, as a light-shielding agent, a lactamide-type pigment may be contained. As a lactamide type pigment, the compound represented by following formula (A-4) is mentioned, for example.

[hua 7]

In the formula (A-4), X ^A1 represents a double bond, and as geometric isomers, each independently is an E body or a Z body, and R ^A19 each independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, a bromine group atom, chlorine atom, fluorine atom, carboxyl group, or sulfo group, R ^A20 each independently represents a hydrogen atom, methyl group, or phenyl group, and R ^A21 each independently represents a hydrogen atom, methyl group, or chlorine atom. The compounds represented by the formula (A-4) may be used alone or in combination of two or more. From the viewpoint of easy production of the compound represented by the formula (A-4), R ^A19 is preferably bonded to the 6-position of the indoline ring, and R ^A21 is preferably bonded to the 4-position of the indoline ring. superior. From the same viewpoint, R ^A19 , R ^A20 , and R ^A21 are preferably hydrogen atoms. The compound represented by the formula (A-4) has EE, ZZ, and EZ isomers as geometric isomers, and may be a single compound of any of these, or may be these geometric isomers mixture of things. The compound represented by formula (A-4) can be produced by the method described in, for example, International Publication No. 2000/24736 and International Publication No. 2010/081624.

In order to disperse the lactamide-based pigment well in the colorant dispersion liquid, the average particle diameter of the lactamide-based pigment is preferably 10 nm or more and 1000 nm or less.

Moreover, as a pigment, a metal particle can also be used. Such metal particles are preferably formed of a metal or formed of a metal and a metal compound, and particularly preferably formed of a metal. The metal particles may contain two or more metals or metal compounds in combination. In particular, the metal particles preferably contain a metal selected from the group consisting of the 4th period, the 5th period, and the 6th period of the long periodic table (IUPAC 1991) as a main component. Further, the metal particles preferably contain a metal selected from the group consisting of Groups 2 to 14 as a main component, and more preferably contain a metal selected from Groups 2, 8, 9, 10, and 11 The metal in the group consisting of Group, Group 12, Group 13, and Group 14 is used as the main component. The metal particles are more preferably a metal of the fourth period, the fifth period or the sixth period, and the particles of the metal of the second group, the tenth group, the 11th group, the 12th group or the 14th group.

Preferred examples of the metal contained in the metal particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, At least one of tungsten, niobium, tantalum, titanium, bismuth, antimony, lead, and their alloys. Preferred metals among these are copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, calcium, iridium, and alloys thereof, and more preferred metals are selected from copper, silver, gold, platinum, palladium , tin, calcium, and at least one of these alloys, and a particularly preferred metal is at least one selected from copper, silver, gold, platinum, tin, and these alloys. Also, such metal particles may adopt a core-shell structure.

Among the metal particles exemplified above, inorganic pigments containing particles mainly composed of silver-tin (AgSn) alloy (hereinafter, referred to as "AgSn alloy particles") can also be preferably used as sunscreens. In the AgSn alloy fine particles, the AgSn alloy may be the main component, and for example, Ni, Pd, Au and the like may be contained as other metal components. The average particle size of the AgSn alloy fine particles is preferably 1 nm or more and 300 nm or less.

When the AgSn alloy is represented by the chemical formula AgxSn, the range of x that can obtain chemically stable AgSn alloy is 1≦x≦10, and the range of x that can simultaneously obtain chemical stability and blackness is 3≦x≦4. Here, within the range of the above x, the mass ratio of Ag in the AgSn alloy is obtained, and the result is: When x=1, Ag/AgSn=0.4762 When x=3, 3・Ag/Ag3Sn=0.7317 When x=4, 4・Ag/Ag4Sn=0.7843 When x=10, 10・Ag/Ag10Sn=0.9008 Therefore, in this AgSn alloy, when Ag is contained in an amount of 47.6 to 90 mass %, the chemical properties are stable, and when Ag is contained in an amount of 73.17 to 78.43 wt %, chemical stability and blackness can be effectively obtained according to the amount of Ag.

The AgSn alloy fine particles can be produced by an ordinary fine particle synthesis method. As the microparticle synthesis method, a gas-phase reaction method, a spray thermal decomposition method, an atomization method, a liquid-phase reaction method, a freeze-drying method, a hydrothermal synthesis method, etc. may be mentioned.

Although the insulating properties of AgSn alloy particles are relatively high, depending on the application of the coloring composition prepared by using the pigment dispersion liquid, the surface can also be covered with an insulating film to further improve the insulating properties. As a material of such an insulating film, a metal oxide or an organic polymer compound is suitable. As the metal oxide, an insulating metal oxide such as silicon oxide (silicon dioxide), aluminum oxide (alumina), zirconia (zirconia), yttria (yttria), and titanium oxide (titania) can be suitably used. Moreover, as an organic polymer compound, the resin which has insulating property, for example, polyimide, polyether, polyacrylate, polyamine compound, etc. can be used suitably.

When the insulating film is formed using the coloring composition described later, in order to sufficiently improve the insulating properties of the surface of the AgSn alloy fine particles, the thickness of the insulating film is preferably 1 nm or more and 100 nm or less, more preferably 5 nm or more and 50 nm or less. The insulating film can be easily formed using a surface modification technique or a surface coating technique. In particular, if an alkoxide such as tetraethoxysilane and aluminum triethoxide is used, an insulating film with a uniform thickness can be formed at a relatively low temperature, which is preferable.

As the light-shielding agent, the above-mentioned perylene-based pigments, lactamide-based pigments, and AgSn alloy fine particles may be used alone or in combination. In addition, for the purpose of adjusting the hue, etc., the sunscreen agent may simultaneously contain the above-mentioned black pigment, purple pigment, and pigments of hues such as red, blue, green, and yellow. Pigments for hues other than black pigments and purple pigments can be appropriately selected from known pigments. For example, the above-mentioned various pigments can be used as pigments of hues other than black pigments and violet pigments. The usage-amount of the pigments of other hues other than the black pigment and the purple pigment is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total mass of the sunscreen agent.

In addition, the inorganic pigments and the organic pigments may be used alone or in combination of two or more. When used together, the amount is preferably 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the total amount of the inorganic pigments and the organic pigments. An organic pigment is used in the range, and it is more preferable to use it in the range of 20 mass parts or more and 40 mass parts or less.

The pigment described above forms a pigment dispersion liquid together with a polyamide acid described later, and a dispersion medium containing an aprotic polar organic solvent. In the pigment dispersion liquid, the content of the pigment in the solid content is not particularly limited. The content of the pigment in the solid content of the pigment dispersion liquid is preferably 40% by mass or more and 99% by mass in view of the ease of dispersing the pigment well and the ease of preparation of a coloring composition containing the pigment at a desired concentration Below, it is more preferable that it is 40 mass % or more and 90 mass % or less, and it is still more preferable that it is 40 mass % or more and 80 mass % or less.

By dispersing the pigment in a dispersion medium containing an aprotic polar organic solvent in the presence of a polyamide of a specific structure described later, the pigment is stably dispersed in the pigment dispersion liquid for a short time without aggregation. The smaller the dispersed particle size is, the less the pigment is aggregated and the better the dispersibility, for example, it is dispersed so that the dispersed particle size becomes 90 nm or less.

[Polyamide] Polyamides are used as dispersants for dispersing pigments. It is believed that the molecular chain of the polyamide acid is bound to the surface of the primary particle of the pigment in the form of dots by hydrogen bonding, such as the interaction of the intermolecular force with the surface of the pigment. Therefore, it is considered that on the surface of the primary particle of the pigment, the molecular chain of the polyamic acid acts as a spacer to promote the dispersion of the pigment and stabilize the dispersion.

It is preferable that the pigment dispersion liquid does not contain resin components other than polyamic acid. When the pigment dispersion liquid contains resin components other than polyamic acid, the aggregates of the primary particles of the pigment may be coated with the resin, so that the aggregates are not easily disintegrated, or the adsorption of the molecules of the polyamic acid to the primary particles of the pigment may be hindered. surface, making it difficult for the pigment to disperse.

The molecular weight of the polyamic acid is preferably 5,000 or more and 30,000 or less, more preferably 10,000 or more and 20,000 or less, in terms of mass average molecular weight. When the molecular weight of the polyamic acid is within the above-mentioned range, the pigment can be well and stably dispersed by using the polyamic acid in an amount that does not greatly affect the properties of various compositions to which the pigment dispersion liquid is formulated.

The usage-amount of polyamide is not specifically limited. From the viewpoint of the dispersibility of the pigment, the polyamic acid is preferably used in an amount of not less than 20 parts by mass and not more than 80 parts by mass, more preferably not less than 30 parts by mass and not more than 70 parts by mass, relative to 100 parts by mass of the pigment. amount used.

As the polyamic acid, previously known polyamic acid can be used without particular limitation. Polyamic acid is usually a polymer obtained by polycondensation of a diamine component and a tetracarboxylic dianhydride component. It does not specifically limit as a diamine component. The diamine component may be an aliphatic diamine compound or a diamine compound having an aromatic group in the structure. It does not specifically limit as a tetracarboxylic dianhydride component. The tetracarboxylic dianhydride component may be an aliphatic tetracarboxylic dianhydride, or may be a dianhydride of a tetracarboxylic acid having an aromatic group in its structure. For example, as a diamine component and a tetracarboxylic dianhydride component, the compound mentioned later can be used without a restriction|limiting in particular.

(式(a1)中，A ¹為四價有機基，A ²為二價有機基) 所表示之結構單元，且 A ¹為下述式(a2)表示之基， [化9]

(式(a2)中，R ^a11、R ^a12、及R ^a13各自獨立地為選自由氫原子、碳原子數1以上5以下之烷基及氟原子所組成之群中之1種，a為0以上12以下之整數) 或者，A ²為下述式(a3)表示之基， -Ar ¹-X-Ar ²-・・・(a3) (式(a3)中，Ar ¹及Ar ²各自獨立地為可具有取代基之伸苯基或伸萘基，X為-CO-NH-)。 Since the dispersibility of the pigment is particularly good, and it is particularly easy to obtain a coloring composition capable of forming a coloring film excellent in heat resistance, it is preferable to use a polymer containing a structural unit represented by the following formula (a1) as the polyamic acid. Amino acid. That is, the following polyamic acid, which contains [Chemical 8]

(In formula (a1), A ¹ is a tetravalent organic group, A ² is a divalent organic group) represented by a structural unit, and A ¹ is a group represented by the following formula (a2), [Chemical 9]

(In formula (a2), R ^a11 , R ^a12 , and R ^a13 are each independently one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms and a fluorine atom, and a is 0 Integer above 12 or less) Alternatively, A ² is a group represented by the following formula (a3), -Ar ¹ -X-Ar ² -・・・(a3) (In formula (a3), Ar ¹ and Ar ² are each independently X is phenylene or naphthylene which may have substituents, and X is -CO-NH-).

In formula (a1), A ¹ is a tetravalent organic group, and the number of carbon atoms thereof is preferably 2 or more and 50 or less, more preferably 2 or more and 30 or less. A ¹ may be an aliphatic group, an aromatic group, or a group formed by combining these structures. Usually, A ¹ is a residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride used for the production of polyamic acid. However, in the formula (a1), when A2 is ^a group other than the group represented by the above ^- mentioned formula (a3), A1 in the formula (a1) must be the group represented by the formula (a2). A ¹ may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to a carbon atom and a hydrogen atom. When A ¹ contains an oxygen atom, nitrogen atom, or sulfur atom, the oxygen atom, nitrogen atom, or sulfur atom may be selected from nitrogen-containing heterocyclic groups, -CONH-, -NH-, -N=N-, -CH=N -, -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS- are included in A ¹ in the form of groups, more preferably selected from -O The forms of the radicals in -, -CO-, -SO-, -SO ₂ -, -S-, and -SS- are included in A ¹ .

A ¹ in the formula (a1) is preferably the above formula (a2) from the viewpoint of the dispersion stability of the pigment in the pigment dispersion liquid and the good heat resistance of the colored molded article formed by using the coloring composition prepared from the pigment dispersion liquid ) represents the base.

The alkyl group that can be selected as R ^a11 in the formula (a2) is an alkyl group having 1 or more and 5 or less carbon atoms. By making the number of carbon atoms of the alkyl group as R ^a11 within the above-mentioned range, it becomes easy to form a colored molded article excellent in heat resistance using the coloring composition containing the pigment dispersion liquid. The number of carbon atoms of the alkyl group is further preferably 1 or more and 4 or less, and particularly preferably 1 or more and 3 or less. When R ^a11 is an alkyl group, the alkyl group may be linear or branched.

R ^a11 in formula (a2) is more preferably a hydrogen atom, methyl group, ethyl group, normal A propyl group or an isopropyl group is particularly preferably a hydrogen atom or a methyl group. From the viewpoint of easy purification of the tetracarboxylic dianhydride that provides the tetravalent organic group represented by the formula (a2), the plurality of R ^a11 in the formula (a2) are preferably the same group.

a in formula (a2) represents an integer of 0 or more and 12 or less. When the value of a exceeds 12, purification of the tetracarboxylic dianhydride that provides the tetravalent organic group represented by the formula (a2) becomes difficult. The upper limit of a is preferably 5, more preferably 3, from the viewpoint of easy purification of the tetracarboxylic dianhydride that provides the tetravalent organic group represented by the formula (a2). The lower limit of a is preferably 1, more preferably 2, from the viewpoint of providing the chemical stability of the tetravalent organic group represented by the formula (a2) of the tetracarboxylic dianhydride. In the formula (a2), a is particularly preferably 2 or 3.

The alkyl group having 1 to 5 carbon atoms that can be selected as R ^a12 and R ^a13 in formula (a2) is the same as the alkyl group having 1 to 5 carbon atoms that can be selected as R ^a11 . R ^a12 and R ^a13 are preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, particularly from the viewpoint of easy purification of the tetracarboxylic dianhydride that provides the tetravalent organic group represented by the formula (a2). Preferably, it is a hydrogen atom or a methyl group.

As the tetracarboxylic dianhydride which provides the tetravalent organic group represented by the formula (a2), for example, norcan-2-spiro-α-cyclopentanone-α'-spiro-2''-norcan -5,5'',6,6''-tetracarboxylic dianhydride (alias "nor-2-spiro-2'-cyclopentanone-5'-spiro-2''-nor-nor-5 ,5'',6,6''-tetracarboxylic dianhydride"), methyl nor alkane-2-spiro-α-cyclopentanone-α'-spiro-2''-(methyl nor alkane) -5,5'',6,6''-tetracarboxylic dianhydride, nor𦯉alkane-2-spiro-α-cyclohexanone-α'-spiro-2''-noralkane-5,5'' ,6,6''-tetracarboxylic dianhydride (alias is "nor alkane-2-spiro-2'-cyclohexanone-6'-spiro-2''-nor alkane-5,5'',6 ,6''-Tetracarboxylic dianhydride"), methylnoroxane-2-spiro-α-cyclohexanone-α'-spiro-2''-(methylnoroxane)-5,5'' ,6,6''-Tetracarboxylic dianhydride, Noroxane-2-spiro-α-cycloacetone-α'-spiro-2''-noroxane-5,5'',6,6''- Tetracarboxylic dianhydride, nor-2-spiro-α-cyclobutanone-α'-spiro-2''-nor-5,5'',6,6''-tetracarboxylic dianhydride, nor 𦯉alkane-2-spiro-α-cycloheptanone-α'-spiro-2''-noralkane-5,5'',6,6''-tetracarboxylic dianhydride, noralkane-2-spiro -α-Cyclooctanone-α'-spiro-2''-noroxane-5,5'',6,6''-tetracarboxylic dianhydride, noroxane-2-spiro-α-cyclononanone -α'-spiro-2''-nor𦯉alkane-5,5'',6,6''-tetracarboxylic dianhydride, nor𦯉alkane-2-spiro-α-cyclodecanone-α'-spiro- 2''-nor𦯉alkane-5,5'',6,6''-tetracarboxylic dianhydride, nor𦯉alkane-2-spiro-α-cycloundecanone-α'-spiro-2''- Nor𦯉alkane-5,5'',6,6''-tetracarboxylic dianhydride, nor𦯉alkane-2-spiro-α-cyclododecanone-α'-spiro-2''-nor𦯉alkane- 5,5'',6,6''-tetracarboxylic dianhydride, nor𦯉alkane-2-spiro-α-cyclotridecone-α'-spiro-2''-nor𦯉alkane-5,5' ',6,6''-tetracarboxylic dianhydride, nor𦯉alkane-2-spiro-α-cyclotetradecanone-α'-spiro-2''-nor𦯉alkane-5,5'',6, 6''-Tetracarboxylic dianhydride, nor𦯉alkane-2-spiro-α-cyclopentadecanone-α'-spiro-2''-nor𦯉alkane-5,5'',6,6''- Tetracarboxylic dianhydride, nor𦯉alkane-2-spiro-α-(methylcyclopentanone)-α'-spiro-2''-nor𦯉alkane-5,5'',6,6''-tetracarboxylic acid Dianhydride, noralkane-2-spiro-α-(methylcyclohexanone)-α'-spiro-2''-noralkane-5,5'',6,6''-tetracarboxylic dianhydride Wait.

(式(a2-1)中，R ^a11、R ^a12、R ^a13、a係與式(a2)中之R ^a11、R ^a12、R ^a13、a之含義相同) [化11]

(式(a2-2)中，R ^a11、R ^a12、R ^a13、a係與式(a2)中之R ^a11、R ^a12、R ^a13、a之含義相同) In addition, as the tetracarboxylic dianhydride that provides the tetravalent organic group represented by the formula (a2), from the viewpoint of good thermal properties, mechanical properties, optical properties, and electrical properties of the polyimide resin for purifying polyamide acid, Preferably, it contains at least one of the compound (A2-1) represented by the following formula (a2-1) and the compound (A2-2) represented by the following formula (a2-2), and the compound (A2-1) And the total amount of compound (A2-2) is 30 mol% or more. [Chemical 10]

(In formula (a2-1), R ^a11 , R ^a12 , R ^a13 , and a have the same meanings as R ^a11 , R ^a12 , R ^a13 , and a in formula (a2))

(In formula (a2-2), R ^a11 , R ^a12 , R ^a13 , and a have the same meanings as R ^a11 , R ^a12 , R ^a13 , and a in formula (a2))

The compound (A2-1) represented by the formula (a2-1) is an isomer of the tetracarboxylic dianhydride that will provide the tetravalent organic group represented by the formula (a2) as follows, that is, 2 noralkyi groups are in a trans group. The carbonyl group of cycloalkanone is in an inward stereoscopic configuration relative to each of the two nor-alkane groups. The compound (A2-2) represented by the formula (a2-2) is an isomer of the tetracarboxylic dianhydride which will provide the tetravalent organic group represented by the formula (a2) as follows, that is, 2 noralkyi groups are in a cis group. The carbonyl group of cycloalkanone is in an inward stereoscopic configuration relative to each of the two nor-alkane groups. In addition, the manufacturing method of the tetracarboxylic dianhydride containing such an isomer at the said ratio is also not specifically limited, A well-known method can be suitably used, for example, the method of International Publication No. 2014/034760 can be suitably used.

As the tetracarboxylic dianhydride that provides the tetravalent organic group, that is, A1, an aromatic tetracarboxylic dianhydride is also preferable. As the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 3,3',4,4'- Oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4, 4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, etc.

Moreover, as an aromatic tetracarboxylic dianhydride, the compound represented by following general formula (a2a) - (a2c) can be used, for example. [Chemical 12]

In the above formulas (a2a) and (a2b), R ^a1 , R ^a2 and R ^a3 each represent an aliphatic group which may be substituted by halogen, an oxygen atom, a sulfur atom, an aromatic group interposed by one or more divalent elements Either one, or a bivalent group consisting of a combination of these. R ^a2 and R ^a3 may be the same or different. That is, R ^a1 , R ^a2 and R ^a3 may contain a carbon-carbon single bond, a carbon-oxygen-carbon ether bond, or a halogen element (fluorine, chlorine, bromine, iodine). As the compound represented by the formula (a2a), 2,2-bis(3,4-dicarboxyphenoxy)propane dianhydride and 1,4-bis(3,4-dicarboxyphenoxy)benzene may, for example, be mentioned Dianhydride, etc.

Furthermore, in the above formula (a2c), R ^a4 and R ^a5 represent an aliphatic group which may be substituted by halogen, an aromatic group interposed by one or more divalent elements, halogen, or any of these The combination constitutes a valent substituent. Each of R ^a4 and R ^a5 may be the same or different. As the compound represented by the formula (a2c), difluoropymellitic dianhydride, dichloropymellitic dianhydride, and the like can also be used.

As tetracarboxylic dianhydride containing fluorine in the molecule, for example, (trifluoromethyl) pyromellitic dianhydride, bis(trifluoromethyl) pyromellitic dianhydride, bis(heptafluoropropyl) may be mentioned. ) pyromellitic dianhydride, pentafluoroethyl pyromellitic dianhydride, bis{3,5-bis(trifluoromethyl)phenoxy}pymellitic dianhydride, 2,2-bis(3 ,4-Dicarboxyphenyl)hexafluoropropane dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxybiphthalic anhydride, 2,2',5 ,5'-Tetrakis(trifluoromethyl)-3,3',4,4'-tetracarboxybiphthalic anhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4 '-Tetracarboxydiphenyl ether dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxybenzophenone dianhydride, bis{(trifluoromethyl) ) dicarboxyphenoxy}phthalic anhydride, bis{(trifluoromethyl)dicarboxyphenoxy}(trifluoromethyl)phthalic anhydride, bis(dicarboxyphenoxy)(trifluoromethyl)benzene Dianhydride, bis(dicarboxyphenoxy)bis(trifluoromethyl)phthalic anhydride, bis(dicarboxyphenoxy)tetrakis(trifluoromethyl)phthalic anhydride, 2,2-bis{4-( 3,4-Dicarboxyphenoxy)phenyl}hexafluoropropane dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}biphenyl dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy base}bis(trifluoromethyl)biphenyl dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}diphenyl ether dianhydride, bis(dicarboxyphenoxy)bis(trifluoromethyl) Biphthalic anhydride, difluoropyromellitic dianhydride, 1,4-bis(3,4-dicarboxytrifluorophenoxy)tetrafluorophthalic anhydride, 1,4-bis(3,4-dicarboxylate) Trifluorophenoxy) octafluorobiphthalic anhydride and the like.

In formula (a1), A ² is a divalent organic group, and the number of carbon atoms thereof is preferably 2 or more and 50 or less, more preferably 6 or more and 30 or less. A ² may be an aliphatic group, an aromatic group, or a group formed by combining these structures. Generally, A ² is the residue obtained by removing two amine groups from the diamine used for the production of polyamic acid. However, in the formula (a1), when A ¹ is a group other than the group represented by the above-mentioned formula (a2), A ² in the formula (a1) must be the group represented by the formula (a3).

A2 in ^formula (a1) is preferably the following formula ( a3) represents the basis. -Ar ¹ -X-Ar ² -・・・(a3) (In formula (a3), Ar ¹ and Ar ² are each independently an optionally substituted phenylene or naphthylene, and X is -CO- NH-)

Ar ¹ and Ar ² are each independently a phenylene group or a naphthylene group which may have a substituent. The substituent is not particularly limited. Preferred examples of the substituent which the phenylene group and the naphthylene group may have include alkyl groups having 1 to 4 carbon atoms, haloalkyl groups having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. The following alkoxy groups, halogenated alkoxy groups having 1 to 4 carbon atoms, aryl groups having 2 to 4 carbon atoms, aryloxy groups having 2 to 4 carbon atoms, halogen atoms, and cyano groups.

The number of substituents that the phenylene group or naphthylene group as Ar ¹ and Ar ² may have is not particularly limited within a range that does not inhibit the purpose of the present invention. The number of substituents is preferably 0 or more and 4 or less, more preferably 0 or more and 2 or less, and still more preferably 0 or 1.

The phenylene which may have a substituent as Ar ¹ and Ar ² may be any of ortho-phenylene, meta-phenylene, and para-phenylene, preferably meta-phenylene and para-phenylene group, more preferably p-phenylene group. The positions of the two bonding bonds of the optionally substituted naphthylene group as Ar ¹ and Ar ² are not particularly limited as long as the object of the present invention is not inhibited. The naphthylene extended group is preferably naphthalene-1,4-diyl, naphthalene-1,3-diyl, naphthalene-1,2-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl Diyl and naphthalene-2,7-diyl, more preferably naphthalene-1,4-diyl, naphthalene-2,6-diyl, and naphthalene-2,7-diyl.

As the group represented by the formula (a3), it is preferable that Ar ¹ and Ar ² are each independently p-phenylene, m-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, or The base of naphthalene-2,7-diyl, more preferably Ar ¹ and Ar ² are each independently a base of p-phenylene or m-phenylene, particularly preferably Ar ¹ and Ar ² are both p-phenylene foundation. That is, the unit represented by the formula (a3) is preferably selected from 4,4'-diaminobenzylaniline, 3,4'-diaminobenzylaniline, or 4,3'-diaminobenzylaniline The residue obtained by removing two amine groups from aniline is more preferably the residue obtained by removing two amine groups from 4,4'-diaminobenzylaniline.

When A ² is an organic group containing one or more aromatic rings, the organic group may be one aromatic group itself, or two or more aromatic groups through an aliphatic hydrocarbon group and a halogenated aliphatic hydrocarbon group, or A base formed by bonds with heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of bonds containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms contained in A ² include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS-, etc., preferably -O-, -CO-, -SO-, -SO ₂ -, -S- , and -SS-.

The aromatic ring bonded to the amino group in A ² is preferably a benzene ring. When the ring bonded to the amino group in A2 is a condensed ring containing ^two or more rings, the ring bonded to the amino group in the condensed ring is preferably a benzene ring. Moreover, the aromatic ring contained in ^A2 may be an aromatic heterocyclic ring.

(式(21)～(24)中，R ¹¹¹表示選自由氫原子、氟原子、羥基、碳原子數1以上4以下之烷基、及碳原子數1以上4以下之鹵代烷基所組成之群中之1種。式(24)中，Q表示選自由9,9'-亞茀基、或式：-C ₆H ₄-、-CONH-C ₆H ₄-NHCO-、-NHCO-C ₆H ₄-CONH-、-O-C ₆H ₄-CO-C ₆H ₄-O-、-OCO-C ₆H ₄-COO-、-OCO-C ₆H ₄-C ₆H ₄-COO-、-OCO-、-O-、-S-、-CO-、-SO ₂-、-C(CF ₃) ₂-、-C(CH ₃) ₂-、-CH ₂-、-O-C ₆H ₄-SO ₂-C ₆H ₄-O-、-C(CH ₃) ₂-C ₆H ₄-C(CH ₃) ₂-、-O-C ₁₀H ₆-O-、及-O-C ₆H ₄-O-表示之基所組成之群中之1種。 Q之示例中，-C ₆H ₄-為伸苯基，較佳為間伸苯基、及對伸苯基，更佳為對伸苯基。又，-C ₁₀H ₆-為萘二基，較佳為萘-1,2-二基、萘-1,4-二基、萘-2,3-二基、萘-2,6-二基、及萘-2,7-二基，更佳為萘-1,4-二基、及萘-2,6-二基) When A2 is an organic group containing an aromatic ring, the organic group is preferably at least one of the groups represented by the following formulae ( ²¹ ) to (24) from the viewpoint of the heat resistance of the cured product formed using the resin composition. 1 type. [Chemical 13]

(In formulae (21) to (24), R ¹¹¹ represents a group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, and a haloalkyl group having 1 to 4 carbon atoms One of them. In formula (24), Q represents a group selected from 9,9'-perlenylene, or formula: -C ₆ H ₄ -, -CONH-C ₆ H ₄ -NHCO-, -NHCO-C ₆ H ₄ -CONH-, -OC ₆ H ₄ -CO-C ₆ H ₄ -O-, -OCO-C ₆ H ₄ -COO-, -OCO-C ₆ H ₄ -C ₆ H ₄ -COO-, - OCO-, -O-, -S-, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -CH ₂ -, -OC ₆ H ₄ -SO ₂ -C ₆ H ₄ -O-, -C(CH ₃ ) ₂ -C ₆ H ₄ -C(CH ₃ ) ₂ -, -OC ₁₀ H ₆ -O-, and -OC ₆ H ₄ -O- represent 1 in the group formed by the bases. In the example of Q, -C ₆ H ₄ - is a phenylene, preferably a m-phenylene and a p-phenylene, more preferably a p-phenylene. , -C ₁₀ H ₆ - is naphthalene diyl, preferably naphthalene-1,2-diyl, naphthalene-1,4-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl , and naphthalene-2,7-diyl, more preferably naphthalene-1,4-diyl, and naphthalene-2,6-diyl)

R ¹¹¹ in the formulae (21) to (24) is more preferably a hydrogen atom from the viewpoint of the heat resistance of the polyamic acid and the heat resistance of the polyimide resin imparted by the polyamic acid , a hydroxyl group, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group, particularly preferably a hydrogen atom, a hydroxyl group, or a trifluoromethyl group.

As Q in the formula (24), from the viewpoint of the heat resistance of the formed polyimide resin, 9,9'-perylene, -OC ₆ H ₄ -O-, -C(CF ₃ ) ₂ -, -O-, -C(CH ₃ ) ₂ -, or -CH ₂ -.

When an aromatic diamine is used as a diamine compound that provides A ² other than the group represented by the formula (a3), for example, the aromatic diamine shown below can be suitably used. That is, as the aromatic diamine, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 4,4'-diamino -2,2'-Bis(trifluoromethyl)biphenyl, 3,3'-diaminodiphenyl, 4,4'-diaminodiphenyl, 4,4'-diamino Diphenyl sulfide, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diamine diphenyl ether, 4,4'-diaminobenzylaniline, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene , 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl] benzene, bis[4-(3-aminophenoxy)phenyl ] bismuth, 9,9-bis(4-aminophenyl) fluoride, 9,9-bis(4-amino-3-methylphenyl) fluoride, and 4,4'-[1,4-extendane Phenylbis(1-methylethane-1,1-diyl)]diphenylamine, etc. Among these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl ether are preferred in terms of price, availability, and the like. 4'-Diaminobenzylaniline.

In addition, as A2, a chain ^- like aliphatic group and/or a silicon atom-containing group which may have an aromatic ring can be used. As such a silicon atom-containing group, typically, the groups shown below can be used. [Chemical 14]

(式(Si-1)中，R ¹¹²及R ¹¹³各自獨立地為單鍵或亞甲基、碳原子數2以上20以下之伸烷基、碳原子數3以上20以下之伸環烷基、或者碳原子數6以上20以下之伸芳基等，R ¹¹⁴、R ¹¹⁵、R ¹¹⁶、及R ¹¹⁷各自獨立地為碳原子數1以上20以下之烷基、碳原子數3以上20以下之環烷基、碳原子數6以上20以下之芳基、碳原子數20以下之含有胺基之基、-O-R ¹¹⁸表示之基(R ¹¹⁸為碳原子數1以上20以下之烴基)、碳原子數2以上20以下之含有1個以上之環氧基之有機基，l為3以上50以下之整數) Moreover, as A2, the group represented by the following formula (Si- ¹ ) can also be used suitably. [Chemical 15]

(In formula (Si-1), R ¹¹² and R ¹¹³ are each independently a single bond or a methylene group, an alkylene group having 2 to 20 carbon atoms, a cycloextended alkyl group having 3 to 20 carbon atoms, Or an aryl group having 6 to 20 carbon atoms, etc., R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , and R ¹¹⁷ are each independently an alkyl group having 1 to 20 carbon atoms, and a ring having 3 to 20 carbon atoms. Alkyl group, aryl group with 6 to 20 carbon atoms, amine group-containing group with 20 or less carbon atoms, group represented by -OR ¹¹⁸ (R ¹¹⁸ is a hydrocarbon group with 1 to 20 carbon atoms), number of carbon atoms 2 or more and 20 or less organic groups containing 1 or more epoxy groups, and l is an integer of 3 or more and 50 or less)

The alkylene group having 2 to 20 carbon atoms in R ¹¹² and R ¹¹³ in the formula (Si-1) is preferably an alkylene group having 2 to 10 carbon atoms from the viewpoint of heat resistance, A dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc. are mentioned.

As the cycloextended alkyl group having 3 to 20 carbon atoms in R ¹¹² and R ¹¹³ in the formula (Si-1), from the viewpoint of heat resistance, a cycloextended alkyl group having 3 to 10 carbon atoms is preferable The group may, for example, be a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptide group, or the like. The aryl group having 6 to 20 carbon atoms in R ¹¹² and R ¹¹³ in the formula (Si-1) is preferably an aromatic group having 6 to 20 carbon atoms from the viewpoint of heat resistance, A phenylene extension, a naphthylene extension group, etc. are mentioned.

The alkyl group having 1 to 20 carbon atoms in R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , and R ¹¹⁷ in the formula (Si-1) is preferably from 1 to 10 carbon atoms from the viewpoint of heat resistance As the following alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, etc. are mentioned specifically,. The cycloalkyl group having 3 or more carbon atoms and 20 or less carbon atoms in R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , and R ¹¹⁷ in formula (Si-1) is preferably 3 or more carbon atoms from the viewpoint of heat resistance The cycloalkyl group of 10 or less, specifically, a cyclopentyl group, a cyclohexyl group, and the like can be mentioned. The aryl group having 6 or more carbon atoms and 20 or less carbon atoms in R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , and R ¹¹⁷ in the formula (Si-1) is preferably 6 or more and 12 carbon atoms from the viewpoint of heat resistance. As the following aryl group, a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned specifically,. Examples of the amine group-containing group having 20 or less carbon atoms in R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , and R ¹¹⁷ in the formula (Si-1) include amine groups, substituted amine groups (for example, bis (trialkylsilyl)amine) and the like. Examples of groups represented by R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , and -OR ¹¹⁸ in R ¹¹⁷ in formula (Si-1) include methoxy, ethoxy, propoxy, isopropoxy, Butoxy, phenoxy, tolyloxy, naphthoxy, propenyloxy (eg, allyloxy), cyclohexyloxy, and the like. Among them, as R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , and R ¹¹⁷ , methyl, ethyl, propyl, and phenyl are preferred.

The group represented by the formula (Si-1) can be introduced by reacting an acid anhydride with a silicon-containing compound having an amine group at both ends. Specific examples of such silicon-containing compounds include: two-terminal amino group-modified methylphenyl silicone (for example, X-22-1660B-3 (number average molecular weight about 4,400) manufactured by Shin-Etsu Chemical Co., Ltd.) and X -22-9409 (number average molecular weight about 1,300)), two-terminal amino group modified dimethyl silicone (such as X-22-161A (number average molecular weight about 1,600) manufactured by Shin-Etsu Chemical Co., Ltd., X-22-161B ( Number average molecular weight is about 3,000) and KF8012 (number average molecular weight is about 4,400); BY16-835U (number average molecular weight is about 900) manufactured by Toray Dow Corning; and Silaplane FM3311 (number average molecular weight is about 1000) manufactured by JNC Corporation).

(式(a4)中，A ³為上述式(a2)表示之基以外之四價有機基，A ⁴為上述式(a3)表示之基以外之二價有機基) The polyamic acid may contain a structural unit represented by the following formula (a4). [Chemical 16]

(In the formula (a4), A ³ is a tetravalent organic group other than the group represented by the above formula (a2), and A ⁴ is a divalent organic group other than the group represented by the above formula (a3))

As A ³ , a tetravalent organic group other than the group represented by the formula (a2) described with respect to the formula (a1) can be appropriately used. As A ⁴ , a divalent organic group other than the group represented by the formula (a3) described with respect to the formula (a1) can be appropriately used.

The ratio of the structural unit represented by the above formula (a1) in the polyamide acid is preferably 30 mol % or more, more preferably 50 mol % or more, and further preferably 70 mol % with respect to the molar amount of all the structural units. More preferably, it is 90 mol% or more, and particularly preferably 100 mol%.

(Method for producing polyamide acid) Polyamic acid is usually prepared by reacting a tetracarboxylic dianhydride component and a diamine component. Typically, a polyamic acid can be obtained by reacting a tetracarboxylic dianhydride component and a diamine component in a solvent capable of dissolving both. The amount of the tetracarboxylic dianhydride component and the diamine component to be used in the synthesis of the polyamic acid is not particularly limited, but it is preferable to use two of the tetracarboxylic dianhydride components in an amount of 0.50 mol or more and 1.50 mol or less with respect to 1 mol of the tetracarboxylic dianhydride component. The amine component is more preferably 0.60 mol or more and 1.30 mol or less, and particularly preferably 0.70 mol or more and 1.20 mol or less.

As a solvent that can be used in the synthesis of polyamide acid, for example, N,N,N',N'-tetramethylurea, N-methyl-2-pyrrolidone, N,N-dimethyl Aprotic polar organic solvents such as methylformamide, N,N-dimethylacetamide, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, and γ-butyrolactone , or diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, and propylene glycol monoalkyl ether propylene Glycol ethers such as acid esters. These solvents may be used in combination of two or more. Among them, N,N,N',N'-tetramethylurea is preferably used.

The usage-amount of the solvent at the time of synthesizing the polyamic acid is not particularly limited as long as it can synthesize the polyamic acid of the desired molecular weight. Typically, the amount of the solvent used is preferably 100 parts by mass or more and 4,000 parts by mass or less, more preferably 150 parts by mass or more and 2,000 parts by mass with respect to 100 parts by mass in total of the amount of the tetracarboxylic dianhydride component and the amount of the diamine component. parts by mass or less.

The temperature at the time of the reaction of the tetracarboxylic dianhydride component and the diamine component is not particularly limited, as long as the reaction proceeds well. Typically, the reaction temperature of the tetracarboxylic dianhydride component and the diamine component is preferably -5°C or higher and 150°C or lower, more preferably 0°C or higher and 120°C or lower, and particularly preferably 0°C or higher and 70°C or lower. In addition, the time for reacting the tetracarboxylic dianhydride component and the diamine component varies depending on the reaction temperature, but typically, it is preferably 1 hour or more and 50 hours or less, more preferably 2 hours or more and 40 hours or less. Particularly preferred is 5 hours or more and 30 hours or less.

[Aprotic polar organic solvent] The pigment dispersion liquid contains an aprotic polar organic solvent. By dispersing the pigment in a dispersion medium containing an aprotic polar organic solvent using the above-mentioned polyamic acid, the pigment can be easily dispersed to a desired degree.

The content of the aprotic polar organic solvent in the dispersion medium is not particularly limited as long as the dispersed state of the pigment is well maintained. Typically, the content of the aprotic polar organic solvent in the dispersion medium is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass.

The kind of aprotic polar organic solvent is not specifically limited in the range which does not inhibit the objective of this invention. Examples of suitable aprotic polar organic solvents include N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylacetamide Isobutylamide, N,N-diethylacetamide, N,N-dimethylformamide (DMF), N,N-diethylformamide, N-methylcaprolactamide , 1,3-dimethyl-2-imidazolidinone (DMI), pyridine, and N,N,N',N'-tetramethylurea (TMU) and other nitrogen-containing polar solvents; β-propiolactone, Lactone-based polar solvents such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone; dimethyl sulfoxide; hexamethylphosphoric triamine ; Acetonitrile; Fatty acid esters such as ethyl lactate and butyl lactate; Ketones such as cyclopentanone and cyclohexanone.

(式(S1)中，R ^S1及R ^S2各自獨立地為碳原子數1以上3以下之烷基，R ^S3為下述式(S1-1)或下述式(S1-2)表示之基。 [化18]

式(S1-1)中，R ^S4為氫原子或羥基，R ^S5及R ^S6各自獨立地為碳原子數1以上3以下之烷基。式(S1-2)中，R ^S7及R ^S8各自獨立地為氫原子、或者碳原子數1以上3以下之烷基) The aprotic polar solvent is preferably a nitrogen-containing polar organic solvent represented by the following formula (S1) from the viewpoints of good solubility of the polyamide and easy to disperse the pigment well and stably. [Chemical 17]

(In formula (S1), R ^S1 and R ^S2 are each independently an alkyl group having 1 to 3 carbon atoms, and R ^S3 is a group represented by the following formula (S1-1) or the following formula (S1-2) .[Chemical 18]

In formula (S1-1), R ^S4 is a hydrogen atom or a hydroxyl group, and R ^S5 and R ^S6 are each independently an alkyl group having 1 to 3 carbon atoms. In formula (S1-2), R ^S7 and R ^S8 are each independently a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms)

In the nitrogen-containing polar organic solvent represented by the formula (S1), specific examples when R ^S3 is a group represented by the formula (S1-1) include N,N,2-trimethylpropionamide, N- Ethyl-N,2-dimethylpropionamide, N,N-diethyl-2-methylpropionamide, N,N,2-trimethyl-2-hydroxypropionamide, N-ethylpropionamide base-N,2-dimethyl-2-hydroxypropionamide, and N,N-diethyl-2-hydroxy-2-methylpropionamide, etc.

In the nitrogen-containing polar organic solvent represented by the formula (S1), specific examples when R ^S3 is a group represented by the formula (S1-2) include N,N,N',N'-tetramethylurea, N,N,N',N'-tetraethylurea, etc.

Among the nitrogen-containing polar organic solvents represented by the formula (S1) described above, N,N,N',N' is preferred from the viewpoints of good solubility of the polyamic acid and the ease of dispersing the pigments well and stably -Tetramethylurea and N,N,N',N'-tetraethylurea, particularly preferably N,N,N',N'-tetramethylurea.

When the dispersion medium contains other dispersion mediums other than aprotic polar organic solvents, such as aprotic polar organic solvents, nonpolar solvents, etc., suitable examples of the other solvents include: water; ethylene glycol, diethylene glycol Alcohol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, isopropylene glycol, polypropylene glycol, pentamethylene glycol, trimethylene glycol, Butanediol, isobutanediol, thiodiethanol, 1,2-hexanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1,2-pentanediol , 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,3-propanediol, 1,4-butanediol, 1,7-heptanediol, 1,8-octanediol Alcohols, 2-butene-1,4-diol, glycerin and other polyols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether Tributyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monophenyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monotert-butyl ether, triethylene glycol monoethyl ether, triethyl ether Glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol mono-tert-butyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropylene ether, propylene glycol monophenyl ether , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monoisopropyl ether and other polyol ethers.

The amount of the dispersion medium in the pigment dispersion liquid is not particularly limited, as long as the dispersed state of the pigment is well maintained. The pigment dispersion liquid usually contains the dispersion medium in such an amount that the solid content concentration of the pigment dispersion liquid is 5 mass % or more and 60 mass % or less, preferably 20 mass % or more and 40 mass % or less.

[other ingredients] The pigment dispersion may also contain various additives previously formulated in the pigment dispersion. As such an additive, a viscosity modifier, a surfactant, an antioxidant, an ultraviolet absorber, a pH adjuster, an antifoamer, etc. are mentioned. These additives are used in the same amounts as those previously formulated in the pigment dispersion within the range that does not adversely affect the properties of the pigment dispersion and the coloring composition.

The pigment dispersion liquid described above contains a well and stably dispersed pigment, and is formulated into a coloring composition together with the hollow silica described later, thereby providing a coloring combination that can form a coloring film excellent in low reflectivity and heat resistance thing.

[Pigment dispersion method] After the pigment and the above-mentioned polyamic acid are blended in a dispersion medium containing an aprotic polar organic solvent so that the content of the pigment is 50% by mass to 99% by mass, the pigment is dispersed in the dispersion medium.

As the dispersing apparatus used for the dispersing treatment of the pigment, various dispersing apparatuses previously used for dispersing the pigment can be used. Specific examples of suitable dispersing devices include kneaders, salt mill kneaders, roll mills, planetary mixers, paint shakers, ball mills, sand mills, attritors, bead mills, annular ball mills , Homogeneous mixer, homogenizer, wet jet mill, high pressure homogenizer, ultrasonic homogenizer, etc. When a medium is used for the dispersion device, as the medium, glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads, or the like can be used.

When the dispersion treatment is performed using an ultrasonic homogenizer, it is preferable to use the above-mentioned kneader, salt mill kneader, roll mill, planetary mixer, homomixer, homogenizer, wet jet mill, Pigments after pre-dispersion by high pressure homogenizer and bead mill.

When dispersing the pigment, the pigment, the polyamide acid, and the dispersion medium containing the aprotic polar organic solvent are each used in an amount within the above-mentioned range.

By dispersing the pigment by the method described above, the pigment can be dispersed well and stably in a short time, and a carbon black dispersion liquid can be prepared to provide the following coloring composition, which can provide a coating with excellent heat resistance. Cloth film, molded products.

＜Hollow silica＞ The coloring composition contains hollow silica. The refractive index of hollow silica is significantly lower than that of ordinary silica, which is 1.46. The reason for this is that the hollow silica contains air which exhibits a low refractive index of 1.0. Therefore, by using the coloring composition containing hollow silica, a coloring film excellent in low reflectivity can be formed. As a refractive index of hollow silica, 1.2 or more and 1.3 or less are typically preferable.

In the coloring composition, previously known hollow silica can be formulated without particular limitation. The hollow silica may be a commercial product or a synthetic product. The hollow silica is preferably selected from known hollow silicas in consideration of particle size and refractive index.

The average particle size of the hollow silica is preferably 5 nm or more and 100 nm or less, more preferably 60 nm or more and 80 nm or less. The average particle diameter of the hollow silica can be measured using a light scattering particle size distribution analyzer LB-550 (manufactured by HORIBA, Ltd.).

The content of the hollow silica in the coloring composition is not particularly limited as long as the object of the present invention is not hindered. The content of hollow silica in the coloring composition is preferably 0.5 mass % or more and 25 mass % or less with respect to the entire solid content in the coloring composition from the viewpoint of easily forming a coloring film with excellent low reflectivity, and more It is preferably 1 mass % or more and 15 mass % or less, and particularly preferably 2 mass % or more and 8 mass % or less.

<Substrate composition> It is preferable that a coloring composition contains a base material component. In this case, the content of the pigment in the solid content of the coloring composition is 0.1 mass % or more and less than 60 mass %, preferably 0.1 mass % or more and less than 55 mass %, more preferably 0.1 mass % or more and less than 50% by mass.

The base material component is a component that imparts formability to the coloring composition so that the coloring composition can be formed into a film shape and various three-dimensional three-dimensional shapes. The base material component is not particularly limited as long as it is a material capable of imparting desired shapeability to the coloring composition. As the base material component, typically, a resin material containing a polymer compound, and a low-molecular-weight compound that is cross-linked by heating to generate the reactivity of the polymer compound can be used.

As the base material component contained in the coloring composition, a precursor for forming a cured product of various thermosetting resins can be used. The colored cured product is formed into a colored molded body by heating the cured product precursor of the thermosetting resin and the coloring composition of the above-mentioned pigment dispersion liquid. Specific examples of the precursor of the cured product of the thermosetting resin that can be formulated in the coloring composition or the resin material containing the above-mentioned polymer compound include epoxy resin, phenol resin, polyimide resin, polybenzoyl Precursors of thermosetting resins such as azole resins, urea resins, melamine resins, alkyd resins, and polyurethane resins; polyacetal resins, polyamide resins, polycarbonate resins, polyester resins (polybutylene terephthalate) ester, polyethylene terephthalate, polyarylate, etc.), FR-AS resin, FR-ABS resin, AS resin, ABS resin, polyphenylene ether resin, polyphenylene sulfide resin, polysilicon resin, polyether Resin, polyether ether ketone resin, fluorine resin, polyimide resin, polyimide resin, polyamide bismaleimide resin, polyetherimide resin, polybenzoxazole resin, polybenzothiazole resin, polybenzimidazole resin, silicone resin, BT resin, polymethylpentene, ultra-high molecular weight polyethylene, FR-polypropylene, (meth)acrylic resin (polymethylmethacrylate) esters, etc.), and resin materials such as polystyrene. Such a precursor or resin material for forming a cured product is formulated into a coloring composition together with a curing agent, a crosslinking agent, a curing catalyst, and the like as necessary. As the curing agent, a heat-sensitive curing agent or a photosensitive curing agent may be used. When a heat-sensitive curing agent is used, the coloring film is formed by heating the coating film containing the coloring composition. When a photosensitive curing agent is used, the colored film is formed by exposing the coating film containing the colored composition.

For example, when the cured product is an epoxy resin, an epoxy compound and a curing agent are blended as base components in the coloring composition. When the cured product is a phenol resin, phenols such as phenol and cresol as base components, and aldehydes such as formaldehyde or hexamethylenetetramine as crosslinking agents are blended in the coloring composition. When the cured product is a polyimide resin, a polyimide as a base component is blended in the coloring composition.

From the viewpoints of the mechanical properties, solvent resistance, chemical resistance, etc. of the formed colored molded body, the colored composition preferably contains an epoxy compound or a polyamic acid as a base material component. Moreover, from the viewpoint of the dispersibility of the pigment in the colored film, a coloring composition containing a polyamide as a base component is more preferable. The content of the polyamic acid is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass with respect to the entire base material component (precursor or resin material) contained in the coloring composition More than 100 mass % or less. Regarding the polyamic acid used as the base material component, the same polyamic acid as the polyamic acid prepared in the pigment dispersion liquid can be used.

When performing lithography patterning etc. using a coloring composition, it is preferable that a coloring composition contains the polymerizable compound (A) which has a radically polymerizable group as a base material component, for example. Moreover, it is preferable that a coloring composition contains the polymerizable compound (A) as a base material component, and an initiator (B) in combination.

<Polymerizable compound (A)> As the polymerizable compound (A), a compound having a radically polymerizable group can be used. The polymerizable compound (A) may be a monofunctional compound having one radically polymerizable group, or a polyfunctional compound having two or more radically polymerizable groups, preferably a polyfunctional compound. The polymerizable compound (A) having a radically polymerizable group is preferably a compound having one or more (meth)acrylamide groups such as a (meth)acrylate compound or a (meth)acrylamide compound, and more preferably Preferably, it is a (meth)acrylate compound which has one or more (meth)acryloyl groups.

As a monofunctional compound which has a radically polymerizable group, (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethyl Oxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol (methyl) Acrylamide, N-Hydroxymethyl(meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride , crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid Butyl, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylate 2-Hydroxybutyl acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerol mono(methyl) ) acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylamino (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate , (meth)acrylic acid 2,2,3,3-tetrafluoropropyl ester, (meth)acrylic acid half ester of phthalic acid derivatives, etc. These monofunctional compounds may be used alone or in combination of two or more.

As the polyfunctional compound having a radically polymerizable group, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate may, for example, be mentioned. , propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate base) acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4) -(Meth)acrylooxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acrylooxypolyethoxyphenyl)propane, 2-(meth)acrylic acid Hydroxy-3-(meth)acryloyloxypropyl ester, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, ortho Diglycidyl phthalate di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (ie, toluene diacrylate) isocyanate), trimethylhexamethylene diisocyanate and reaction product of hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate, methylenebis(meth)acrylamide, (meth) Polyfunctional compounds such as acrylamide methylene ether, polyol and N-methylol (meth)acrylamide condensate, triacrylamide formal, etc. These polyfunctional compounds may be used alone or in combination of two or more.

When the polymerizable compound (A) is used, the content of the polymerizable compound (A) in the solid content of the coloring composition may be appropriately adjusted, for example, 0.1% by mass or more and 30% by mass or less, preferably 1% by mass or more and 20% by mass. mass % or less.

<Starter (B)> The initiator (B) is not particularly limited, and various previously known polymerization initiators can be used.

、2-氯9-氧硫𠮿

、2,4-二甲基9-氧硫𠮿

、1-氯-4-丙氧基9-氧硫𠮿

、硫𠮿

、2-氯𠮿

、2,4-二乙基𠮿

、2-甲基𠮿

、2-異丙基𠮿

、2-乙基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-二苯基蒽醌、偶氮雙異丁腈、過氧化苯甲醯、氫過氧化異丙苯、2-巰基苯并咪唑、2-巰基苯并㗁唑、2-巰基苯并噻唑、2-(鄰氯苯基)-4,5-二(間甲氧基苯基)-咪唑基二聚物、二苯甲酮、2-氯二苯甲酮、p,p'-雙二甲基胺基二苯甲酮、4,4'-雙二乙基胺基二苯甲酮、4,4'-二氯二苯甲酮、3,3-二甲基-4-甲氧基二苯甲酮、苯偶醯、安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香正丁醚、安息香異丁醚、安息香丁醚、苯乙酮、2,2-二乙氧基苯乙酮、對二甲基苯乙酮、對二甲基胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、對第三丁基苯乙酮、對二甲基胺基苯乙酮、對第三丁基三氯苯乙酮、對第三丁基二氯苯乙酮、α,α-二氯-4-苯氧基苯乙酮、9-氧硫𠮿

、2-甲基9-氧硫𠮿

、2-異丙基9-氧硫𠮿

、二苯并環庚酮、4-二甲基胺基苯甲酸戊酯、9-苯基吖啶、1,7-雙-(9-吖啶基)庚烷、1,5-雙-(9-吖啶基)戊烷、1,3-雙-(9-吖啶基)丙烷、對甲氧基三嗪、2,4,6-三(三氯甲基)均三嗪、2-甲基-4,6-雙(三氯甲基)均三嗪、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)均三嗪、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)均三嗪、2-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)均三嗪、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)均三嗪、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)均三嗪、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)均三嗪、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)均三嗪、2,4-雙三氯甲基-6-(3-溴-4-甲氧基)苯基均三嗪、2,4-雙三氯甲基-6-(2-溴-4-甲氧基)苯基均三嗪、2,4-雙三氯甲基-6-(3-溴-4-甲氧基)苯乙烯基苯基均三嗪、2,4-雙三氯甲基-6-(2-溴-4-甲氧基)苯乙烯基苯基均三嗪等。該等光自由基聚合起始劑可以單獨使用或組合2種以上使用。Specific examples of photoradical polymerization initiators that can be used as radical polymerization initiators capable of polymerizing the polymerizable compound (A) having a radically polymerizable group include: 1-hydroxycyclohexylbenzene ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1- Propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2 -Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl) ketone, 2-methyl -1-[4-(Methylthio)phenyl]-2-morpholino (morpholino)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholine Phenyl)-butan-1-one, O-acetyl-1-[6-(2-methylbenzyl)-9-ethyl-9H-carbazol-3-yl]ethanone Oxime, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetoxime, 2-(benzyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, 2,4,6-trimethylbenzyl Acrylodiphenylphosphine oxide, 4-benzyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4- Ethyl dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamyl benzoic acid, benzalkonium-β-methoxyethyl acetal, benzalkonium dimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) Oxime, methyl o-benzoylbenzoate, 2,4-diethyl 9-oxothioate

, 2-chloro-9-oxysulfur

, 2,4-dimethyl 9-oxothio

, 1-chloro-4-propoxy 9-oxothio

, sulfur

, 2-Chlorine

, 2,4-diethyl

, 2-methyl

, 2-isopropyl 𠮿

, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzyl peroxide, isohydroperoxide Propylbenzene, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)-imidazolyl Dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4 ,4'-Dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzoin, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl Ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, Trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α -Dichloro-4-phenoxyacetophenone, 9-oxysulfur 𠮿

, 2-methyl 9-oxothio

, 2-isopropyl 9-oxothio

, Dibenzocycloheptanone, Amyl 4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-( 9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)s-triazine, 2- Methyl-4,6-bis(trichloromethyl)s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)s-s-triazine Triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)s-triazine, 2-[2-(4-diethylamino-2- Methylphenyl)vinyl]-4,6-bis(trichloromethyl)s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis (Trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)- 4,6-bis(trichloromethyl)s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)s-triazine, 2,4-bistrichloro Methyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bistrichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine , 2,4-bistrichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bistrichloromethyl-6-(2-bromo- 4-methoxy) styrylphenyl s-triazine and the like. These photoradical polymerization initiators may be used alone or in combination of two or more.

Among the photoradical polymerization initiators, an oxime ester compound is preferred from the viewpoint of the sensitivity of the curable composition. The oxime ester compound is preferably a compound having a partial structure represented by the following formula (b1).

(式(b1)中， n1為0或1， R ^b2為一價有機基， R ^b3為氫原子、可具有取代基之碳原子數1以上20以下之脂肪族烴基、或者可具有取代基之芳基， *為鍵結鍵) [Chemical 19]

(In formula (b1), n1 is 0 or 1, R ^b2 is a monovalent organic group, R ^b3 is a hydrogen atom, an aliphatic hydrocarbon group which may have 1 to 20 carbon atoms, or an optionally substituted aliphatic hydrocarbon group Aryl, * is a bond)

The compound having the partial structure represented by the formula (b1) preferably has a carbazole skeleton, a perylene skeleton, a diphenyl ether skeleton, and a phenylene sulfide skeleton. The compound having the partial structure represented by the formula (b1) preferably has one or two partial structures represented by the formula (b1).

As a compound which has a partial structure represented by formula (b1), the compound represented by following formula (b2) is mentioned.

(式(b2)中，R ^b1為下述式(b3)、(b4)、或(b5)表示之基， n1為0或1， R ^b2為一價有機基， R ^b3為氫原子、可具有取代基之碳原子數1以上20以下之脂肪族烴基、或可具有取代基之芳基) [hua 20]

(In formula (b2), R ^b1 is a group represented by the following formula (b3), (b4), or (b5), n1 is 0 or 1, R ^b2 is a monovalent organic group, R ^b3 is a hydrogen atom, or Aliphatic hydrocarbon group having 1 to 20 carbon atoms, or aryl group which may have substituent)

(式(b3)中，R ^b4及R ^b5各自獨立地為一價有機基， n2為0以上3以下之整數， n2為2或3時，複數個R ^b5可以相同亦可以不同，複數個R ^b5可以彼此鍵結而形成環。 *為鍵結鍵) [Chemical 21]

(In formula (b3), R ^b4 and R ^b5 are each independently a monovalent organic group, n2 is an integer of 0 or more and 3 or less, when n2 is 2 or 3, a plurality of R ^b5 may be the same or different, and a plurality of R ^b5 can be bonded to each other to form a ring. * is a bonding bond)

(式(b4)中，R ^b6及R ^b7各自獨立地為可具有取代基之鏈狀烷基、可具有取代基之鏈狀烷氧基、可具有取代基之環狀有機基、或氫原子， R ^b6與R ^b7可以彼此鍵結而形成環， R ^b7與茀骨架中之苯環可以彼此鍵結而形成環， R ^b8為硝基、或一價有機基， n3為0以上4以下之整數， *為鍵結鍵) [Chemical 22]

(In formula (b4), R ^b6 and R ^b7 are each independently an optionally substituted chain alkyl group, an optionally substituted chain alkoxy group, an optionally substituted cyclic organic group, or a hydrogen atom , R ^b6 and R ^b7 can be bonded to each other to form a ring, R ^b7 and the benzene ring in the perylene skeleton can be bonded to each other to form a ring, R ^b8 is a nitro group or a monovalent organic group, and n3 is 0 or more and 4 or less. Integer, * is the bond key)

(式(b5)中，R ^b9為一價有機基、鹵素原子、硝基、或氰基， A為S或O， n4為0以上4以下之整數， *為鍵結鍵) [Chemical 23]

(In formula (b5), R ^b9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group, A is S or O, n4 is an integer of 0 or more and 4 or less, and * is a bond)

In formula (b3), R ^b4 is a monovalent organic group. R ^b4 may be selected from various organic groups within a range that does not hinder the purpose of the present invention. The organic group is preferably a group containing a carbon atom, more preferably one or more carbon atoms, and a group selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms group of one or more atoms. The number of carbon atoms of the carbon atom-containing group is not particularly limited, but is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less. Suitable examples of R ^b4 include an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, and an optionally substituted cycloalkyl group having 2 to 20 carbon atoms. Optionally substituted saturated aliphatic aliphatic group, optionally substituted alkoxycarbonyl group with 2 to 20 carbon atoms, optionally substituted phenyl, optionally substituted benzyl group, optionally substituted phenoxycarbonyl group, optionally substituted phenylalkyl group with 7 to 20 carbon atoms, optionally substituted naphthyl, optionally substituted naphthylcarboxyl, optionally substituted naphthyloxy Carbonyl, optionally substituted naphthylalkyl having 11 to 20 carbon atoms, optionally substituted heterocyclic group, and optionally substituted heterocyclic carbonyl, and the like.

Among R ^b4 , an alkyl group having 1 to 20 carbon atoms is preferred. The alkyl group may be linear or branched. From the viewpoint of good solubility in the curable composition of the compound represented by the formula (b3), the number of carbon atoms of the alkyl group of R ^b4 is preferably 2 or more, more preferably 5 or more, particularly preferably 7 or more . Moreover, from the viewpoint of good compatibility between the compound represented by formula (b3) and other components in the curable composition, the number of carbon atoms of the alkyl group as R ^b4 is preferably 15 or less, more preferably 10 or less.

When R ^b4 has a substituent, suitable examples of the substituent include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 2 to 20 carbon atoms. The following aliphatic aryl groups, aliphatic aryloxy groups having 2 to 20 carbon atoms, phenoxy, benzyloxy, benzyloxy, groups represented by -PO(OR) ₂ (R is a carbon atom) 1 or more alkyl groups of 6 or less), halogen atoms, cyano groups, heterocyclic groups and the like.

When R ^b4 is a heterocyclic group, the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. When R ^b4 is a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing at least one N, S, O, or the above-mentioned monocyclic rings are condensed with each other, or the above-mentioned monocyclic rings are condensed with a benzene ring. of heterocyclyl. When the heterocyclic group is a condensed ring, the number of rings is at most 3. Examples of the heterocyclic ring constituting the above-mentioned heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine, and pyrimidine , pyridoxine, benzofuran, benzothiophene, indole, isoindole, indole azine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, iso Quinoline, quinazoline, quinoline, quinoline, quinoline, piperidine, piperidine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran, etc. When R ^b4 is a heterocyclic group, examples of the substituent which the heterocyclic group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, and a nitro group.

Suitable specific examples of R ^b4 described above include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl , isopentyl, neopentyl, pentan-3-yl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, and 2-ethylhexyl. Furthermore, from the viewpoint of good solubility in the curable composition of the compound represented by the formula (b3), n-octyl and 2-ethylhexyl are preferred, and 2-ethylhexyl is more preferred.

In formula (b3), R ^b5 is a monovalent organic group. R ^b5 can be selected from various organic groups within a range that does not hinder the purpose of the present invention. The organic group is preferably a group containing a carbon atom, more preferably one or more carbon atoms, and a group selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms group of one or more atoms. The number of carbon atoms of the carbon atom-containing group is not particularly limited, but is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less. Examples of suitable monovalent organic groups for R ^b5 include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acid group, an alkoxycarbonyl group, and a saturated aliphatic acid group. , a phenyl group that can have a substituent, a phenoxy group that can have a substituent group, a benzyl group that can have a substituent group, a phenoxycarbonyl group that can have a substituent group, a benzyloxy group that can have a substituent group, Substitutable phenylalkyl, optional substituted naphthyl, optional substituted naphthyl, optional substituted naphthyl, optional substituted naphthyloxycarbonyl, optional substituted naphthyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclic group, optionally substituted heterocyclic carbonyl, optionally substituted amine group, substituted with one or two organic groups, olin-1-yl, piperazine-1-yl, halogen, nitro, cyano, substituents including a group represented by HX ₂ C- or H ₂ XC- (wherein X is each independently a halogen atom) and the like.

When R ^b5 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. In addition, when R ^b5 is an alkyl group, it may be a straight chain or a branched chain. Specific examples when R ^b5 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl , isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-decyl base, and isodecyl, etc. In addition, when R ^b5 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxy ethoxyethyl, and methoxypropyl.

When R ^b5 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. In addition, when R ^b5 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples when R ^b5 is an alkoxy group include: methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, second butoxy group, 3rd-butoxy, n-pentyloxy, isopentyloxy, second-pentoxy, third-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second-octyl Oxy group, tertiary octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. In addition, when R ^b5 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy group, propoxyethoxyethoxy, and methoxypropoxy, etc.

When R ^b5 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Specific examples when R ^b5 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. As a specific example when R ^b5 is a cycloalkoxy group, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, etc. may be mentioned.

When R ^b5 is a saturated aliphatic alkoxy group or a saturated aliphatic alkoxy group, the carbon number of the saturated aliphatic alkanoyl group or saturated aliphatic alkoxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less. Specific examples when R ^b5 is a saturated aliphatic acyl group include an acetyl group, a propionyl group, an n-butyryl group, a 2-methylpropionyl group, an n-pentyl group, and a 2,2-dimethylpropyl group. Acyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecanyl, n-dodecyl, n-tridecyl, n-tetradecane Acyl group, n-pentadecanyl group, n-hexadecyl group, etc. Specific examples when R ^b5 is a saturated aliphatic alkoxy group include acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, n-pentanoyloxy, 2,2-Dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecanyloxy, n-undecanyloxy Dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanyloxy, n-hexadecanoyloxy, and the like.

When R ^b5 is an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples when R ^b5 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, and isobutoxycarbonyl. , the second butoxycarbonyl, the third butoxycarbonyl, n-pentoxycarbonyl, isopentyloxycarbonyl, the second pentoxycarbonyl, the third pentoxycarbonyl, n-hexyloxycarbonyl, n-heptyloxy Carbonyl, n-octoxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxy carbonyl, etc.

When R ^b5 is a phenylalkyl group, the carbon number of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. Moreover, when R ^b5 is a naphthyl alkyl group, the carbon number of the naphthyl alkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. Specific examples when R ^b5 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples when R ^b5 is naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl) ) ethyl. When R ^b5 is a phenylalkyl group or a naphthylalkyl group, R ^b5 may further have a substituent on the phenyl group or the naphthyl group.

When R ^b5 is a heterocyclic group, the heterocyclic group is the same as the case where R ^b4 in the formula (b3) is a heterocyclic group, and the heterocyclic group may further have a substituent. When R ^b5 is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as when R ^b5 is a heterocyclic group.

When R ^b5 is an amine group substituted with one or two organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, and a cycloalkane having 3 to 10 carbon atoms. group, saturated aliphatic aryl group with 2 to 21 carbon atoms, optionally substituted phenyl group, optionally substituted benzyl group, optionally substituted with 7 to 20 carbon atoms, phenylalkane group, an optionally substituted naphthyl group, an optionally substituted naphthyl carboxyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and a heterocyclic group. Specific examples of these suitable organic groups are the same as for R ^b5 . Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamine Propylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decyl Amino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-decylamino, benzylamino, α-naphthylamino, β-naphthylamino, and the like.

As a substituent when the phenyl group, naphthyl group, and heterocyclic group contained in R ^b5 further has a substituent, a substituent including a group represented by HX ₂ C- or H ₂ XC- (for example, a substituent including a HX ₂ C- or H ₂ XC- group represented by haloalkoxy group, including HX ₂ C- or H ₂ XC- group represented by haloalkyl group), alkyl group with 1 to 6 carbon atoms, 1 or more carbon atoms Alkoxy group with 6 or less carbon atoms, saturated aliphatic alkoxy group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic alkoxy group with 2 to 7 carbon atoms, Monoalkylamine group of alkyl group with 1 to 6 carbon atoms, dialkylamine group of alkyl group with 1 to 6 carbon atoms, morpholin-1-yl, piperazine-1-yl, benzene Formyl, halogen, nitro, and cyano, etc. When the phenyl group, naphthyl group, and heterocyclic group included in R ^b5 further have substituents, the number of the substituents is not limited within the range that does not inhibit the object of the present invention, but preferably 1 or more and 4 or less. When the phenyl group, naphthyl group, and heterocyclic group included in R ^b5 have plural substituents, the plural substituents may be the same or different.

As a substituent when the benzalyl group contained in R ^b5 further has a substituent, an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazine-1-yl, 2- Thienocarboxyl (thiophen-2-ylcarbonyl), furan-3-ylcarbonyl and phenyl, etc.

As a halogen atom represented by X, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, Preferably it is a fluorine atom.

As a substituent containing a group represented by HX ₂ C- or H ₂ XC-, a halogenated alkoxy group containing a group represented by HX ₂ C- or H ₂ XC-, a haloalkoxy group containing a group represented by HX ₂ C- or H ₂ XC-, haloalkoxy group represented by group, haloalkyl group containing group represented by HX ₂ C- or H ₂ XC-, group having haloalkyl group represented by HX ₂ C- or H ₂ XC-, etc., more preferably It is a haloalkoxy group containing a group represented by HX ₂ C- or H ₂ XC-, or a group having a haloalkoxy group containing a group represented by HX ₂ C- or H ₂ XC-.

As the group having a haloalkyl group containing a group represented by HX ₂ C- or H ₂ XC-, an aromatic group (eg, benzene) substituted with a haloalkyl group containing a group represented by HX ₂ C- or H ₂ XC- can be exemplified (e.g., cyclopentyl, cyclohexyl, etc.), cycloalkyl (for example, cyclopentyl, cyclohexyl, etc.) substituted by a haloalkyl group containing a group represented by HX ₂ C- or H ₂ XC-, etc., preferably a group containing HX ₂ C A halogenated alkyl-substituted aromatic group of a group represented by - or H ₂ XC-.

As the group having a haloalkoxy group containing a group represented by HX ₂ C- or H ₂ XC-, an aromatic group substituted with a haloalkoxy group containing a group represented by HX ₂ C- or H ₂ XC- (for example, , phenyl, naphthyl, etc.), an alkyl group substituted by a halogenated alkoxy group containing a group represented by HX ₂ C- or H ₂ XC- (for example, methyl, ethyl, n-propyl, isopropyl, etc.), Cycloalkyl group (for example, cyclopentyl, cyclohexyl, etc.) substituted by a haloalkoxy group containing a group represented by HX ₂ C- or H ₂ XC-, and the like, preferably a group containing HX ₂ C- or H ₂ XC- The halogenated alkoxy substituted aromatic group represented by the group.

Moreover, as R ^b5 , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R ^b5 may have.

Among the monovalent organic groups, R ^b5 is preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group or a phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or less, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group base. Among the optionally substituted phenyl groups, methylphenyl groups are preferred, and 2-methylphenyl groups are more preferred. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl is preferred.

In the group represented by the formula (b3), when a plurality of R ^b5 are present and a plurality of R ^b5 are bonded to each other to form a ring, the formed ring may, for example, be a hydrocarbon ring or a heterocyclic ring. As a hetero atom contained in a heterocyclic ring, N, O, and S are mentioned, for example. An aromatic ring is particularly preferable as a ring formed by bonding a plurality of R ^b5 to each other. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. As the aromatic ring, an aromatic hydrocarbon ring is preferred. In formula (b3), a specific example when a plurality of R ^b5 are bonded to each other to form a benzene ring is shown below.

[Chemical 24]

In the group represented by the formula (b4), R ^b8 is a nitro group or a monovalent organic group. R ^b8 is bonded to a six-membered aromatic ring different from the aromatic ring bonded to the group represented by -(CO) _n1 - on the condensed ring in the formula (b4). In formula (b4), the bonding position of R ^b8 is not particularly limited. When the group represented by the formula (b4) has one or more R ^b8 , from the viewpoint of ease of synthesis of the compound represented by the formula (b4), it is preferable that one of the one or more R ^b8 is bonded to the pyrene skeleton. at the 7th position. That is, when the group represented by the formula (b4) has one or more R ^b8 , the group represented by the formula (b4) is preferably represented by the following formula (b6). When R ^b8 is plural, the plural R ^b8 may be the same or different.

(式(b6)中，R ^b6、R ^b7、R ^b8、n3各自與式(b4)中之R ^b6、R ^b7、R ^b8、n3相同) [Chemical 25]

(In formula (b6), R ^b6 , R ^b7 , R ^b8 , and n3 are the same as R ^b6 , R ^b7 , R ^b8 , and n3 in formula (b4), respectively.)

When R ^b8 is a monovalent organic group, R ^b8 is not particularly limited as long as the object of the present invention is not inhibited. The organic group is preferably a group containing a carbon atom, more preferably one or more carbon atoms, and a group selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms group of one or more atoms. The number of carbon atoms of the carbon atom-containing group is not particularly limited, but is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less. As a suitable example when R ^b8 is a monovalent organic group, the same group as a suitable example as a monovalent organic group of R ^b5 in formula (b3) can be mentioned.

In formula (b4), R ^b6 and R ^b7 are each an optionally substituted chain alkyl group, an optionally substituted chain alkoxy group, an optionally substituted cyclic organic group, or a hydrogen atom. R ^b6 and R ^b7 may be bonded to each other to form a ring. Among these groups, R ^b6 and R ^b7 are preferably chain alkyl groups which may have a substituent. When R ^b6 and R ^b7 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^b6 and R ^b7 are unsubstituted chain alkyl groups, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. Specific examples when R ^b6 and R ^b7 are chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. , n-pentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl base, n-decyl, and isodecyl, etc. Moreover, when R ^b6 and R ^b7 are an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxy Ethoxyethyl, and methoxypropyl, etc.

When R ^b6 and R ^b7 are a substituted chain alkyl group, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. In this case, the carbon number of the substituent is not included in the carbon number of the chain alkyl group. The chain alkyl group having a substituent is preferably a straight chain.

The substitution which the alkyl group may have is not particularly limited within a range that does not inhibit the object of the present invention. Preferable examples of the substituent include an alkoxy group, a cyano group, a halogen atom, a haloalkyl group, a cyclic organic group, and an alkoxycarbonyl group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. The cyclic organic group may, for example, be a cycloalkyl group, an aromatic hydrocarbon group, or a heterocyclic group. Specific examples of the cycloalkyl group are the same as the suitable examples when R ^b8 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group. Specific examples of the heterocyclic group are the same as the suitable examples when R ^b8 is a heterocyclic group. When R ^b8 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, but preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.

When the chain alkyl group has a substituent, the number of the substituents is not particularly limited. The number of preferable substituents varies depending on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

When R ^b6 and R ^b7 are an unsubstituted chain alkoxy group, the number of carbon atoms of the chain alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. . Specific examples when R ^b6 and R ^b7 are chain alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, th Dibutoxy, tert-butoxy, n-pentyloxy, isopentyloxy, second-pentyloxy, third-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy group, the second octyloxy group, the third octyloxy group, the n-nonyloxy group, the isononyloxy group, the n-decyloxy group, the isodecyloxy group, and the like. Moreover, when R ^b6 and R ^b7 are an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy , propoxyethoxyethoxy, and methoxypropoxy, etc.

When R ^b6 and R ^b7 are chain alkoxy groups having a substituent, the substituents that the alkoxy group may have are the same as when R ^b6 and R ^b7 are chain alkyl groups.

When R ^b6 and R ^b7 are a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. The cyclic organic group may, for example, be an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group. When R ^b6 and R ^b7 are cyclic organic groups, the substituents that the cyclic organic groups may have are the same as when R ^b6 and R ^b7 are chain alkyl groups.

When R ^b6 and R ^b7 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding a plurality of benzene rings through carbon-carbon bonds, or a group formed by condensing a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, Excellent is 1. Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group.

When R ^b6 and R ^b7 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 10 or less. Examples of the monocyclic cyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norxyl, isoxyl, tricyclononyl, Tricyclodecyl, tetracyclododecyl, and adamantyl, etc.

When R ^b6 and R ^b7 are heterocyclic groups, the same groups as those used as the heterocyclic groups for R ^b5 in the formula (b3) can be exemplified.

R ^b6 and R ^b7 may be bonded to each other to form a ring. The group comprising the ring formed by R ^b6 and R ^b7 is preferably a cycloalkylene group. When R ^b6 and R ^b7 are bonded to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a five-membered to six-membered ring, more preferably a five-membered ring.

When R ^b7 and the benzene ring of the pyrene skeleton form a ring, the ring may be an aromatic ring or an aliphatic ring.

When the group formed by bonding R ^b6 and R ^b7 is a cycloalkylene group, the cycloalkylene group may be condensed with one or more other rings. Examples of the ring which can be condensed with a cycloalkylene ring include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, and a furan ring. , thiophene ring, pyrrole ring, pyridine ring, pyridine ring, and pyrimidine ring, etc.

Examples of suitable groups in R ^b6 and R ^b7 described above include groups represented by formula -A ¹ -A ² . In the formula, A ¹ is a straight-chain extended alkyl group, and A ² is exemplified by an alkoxy group, a cyano group, a halogen atom, a haloalkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms of the linear alkyl group of A1 is preferably ¹ or more and 10 or less, more preferably 1 or more and 6 or less. When A ² is an alkoxy group, the alkoxy group may be linear or branched, but preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When ^A2 is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom. When A ² is a haloalkyl group, the halogen atom contained in the haloalkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom. The haloalkyl group may be straight-chain or branched, but straight-chain is preferred. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups R ^b6 and R ^b7 have as substituents. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups R ^b6 and R ^b7 have as substituents.

Suitable specific examples of R ^b6 and R ^b7 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; 2-methoxyethyl, 3 -Methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n-octyl base, 2-ethoxyethyl, 3-ethoxyn-propyl, 4-ethoxyn-butyl, 5-ethoxyn-pentyl, 6-ethoxyn-hexyl, 7-ethoxy n-heptyl, and alkoxyalkyl groups such as 8-ethoxyn-octyl; 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl , 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl cyanoalkyl groups; 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-octyl Butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl and other phenylalkyl groups; 2-cyclohexylethyl, 3-cyclohexyl Hexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl , 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl Cycloalkylalkyl such as pentyl-n-octyl; 2-methoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl , 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4 - Ethoxycarbonyl-n-butyl, 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl, and 8-ethoxycarbonyl-n-octyl alkanes Oxycarbonylalkyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-butyl Octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, Halogenated alkyl groups such as 3,3,3-trifluoropropyl and 3,3,4,4,5,5,5-heptafluoro-n-pentyl.

As R ^b6 and R ^b7 , preferred groups among the above are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5, 5,5-heptafluoro-n-pentyl.

In the formula (b5), A is particularly preferably S from the viewpoint of easily obtaining a photopolymerization initiator excellent in sensitivity.

In formula (b5), R ^b9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group. When R ^b9 in the formula (b5) is a monovalent organic group, it can be selected from various organic groups within a range that does not inhibit the purpose of the present invention. The organic group is preferably a group containing a carbon atom, more preferably one or more carbon atoms, and a group selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms group of one or more atoms. The number of carbon atoms of the carbon atom-containing group is not particularly limited, but is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less. As a suitable example when R ^b9 in formula (b5) is an organic group, the same group as that used as a valent organic group of R ^b5 in formula (b3) can be mentioned.

Among R ^b9 , preferably benzalyl; naphthoyl; selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperidine-1-yl, and phenyl benzalyl group substituted by the group in the group; nitro group; benzofuranyl carbonyl group which may have substituents, more preferably benzyl group; naphthoyl group; 2-methylphenylcarbonyl; 4-( Piper-1-yl)phenylcarbonyl; 4-(phenyl)phenylcarbonyl.

Moreover, in Formula (b5), n4 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. When n4 is 1, the bonding position of R ^b9 is preferably the para position with respect to the bonding bond between the phenyl group bonded to R ^b9 and the oxygen atom or sulfur atom.

In the formulae (b1) and (b2), as a valent organic compound of R ^b2 , it is not particularly limited within a range that does not inhibit the object of the present invention. The organic group is preferably a group containing a carbon atom, more preferably one or more carbon atoms, and a group selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms group of one or more atoms. The number of carbon atoms of the carbon atom-containing group is not particularly limited, but is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less. Suitable examples of the monovalent organic group for R ^b2 include the same groups as those for the monovalent organic group for R ^b5 in the formula (b3). Specific examples of these groups are the same as those described with respect to R ^b5 in the formula (b3). Moreover, as R ^b2 , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents when the phenyl group, naphthyl group, and heterocyclic group contained in R ^b5 in the formula (b3) have further substituents.

Among the organic groups, R ^b2 is preferably a substituent containing a group represented by the above-mentioned HX ₂ C- or H ₂ XC-, an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, or a cycloalkylalkyl group , A phenylthioalkyl group which may have a substituent on the aromatic ring. Regarding the alkyl group, the phenyl group which may have a substituent, the number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group, the number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group, the cycloalkylalkyl group, The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring, or the phenylthioalkyl group which may have a substituent on the aromatic ring, is the same as R ^b5 of the formula (b3). same.

Moreover, R ^b2 is also preferably a group represented by -A ³ -CO-OA ⁴ . A ³ is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. A ⁴ is a monovalent organic group, preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched, preferably linear. When A ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.

Suitable examples of A4 include an alkyl group having ¹ to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Suitable specific examples of A4 include methyl, ethyl, n ^- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, Phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl, etc.

Suitable specific examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, 2-n-propoxycarbonylethyl, -n-Butoxycarbonylethyl, 2-n-pentoxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methoxy n-propyl carbonyl, 3-ethoxycarbonyl-n-propyl, 3-n-propoxycarbonyl-n-propyl, 3-n-butoxycarbonyl-n-propyl, 3-n-pentoxycarbonyl-n-propyl, 3 -n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, and 3-phenoxycarbonyl-n-propyl, etc.

(式(b7)及(b8)中，R ^b10及R ^b11各自獨立地為一價有機基， n5為0以上4以下之整數， 當R ^b10及R ^b11存在於苯環上之相鄰位置上時，R ^b10與R ^b11可以彼此鍵結而形成環， R ^b12為一價有機基， n6為1以下8以下之整數， n7為1以上5以下之整數， n8為0以上且(n7＋3)以下之整數) Moreover, R ^b2 is also preferably a group represented by the following formula (b7) or (b8). [Chemical 26]

(In formulae (b7) and (b8), R ^b10 and R ^b11 are each independently a monovalent organic group, n5 is an integer of 0 or more and 4 or less, when R ^b10 and R ^b11 are present at adjacent positions on the benzene ring , R ^b10 and R ^b11 may be bonded to each other to form a ring, R ^b12 is a monovalent organic group, n6 is an integer of 1 or less than 8, n7 is an integer of 1 or more and 5 or less, and n8 is 0 or more and (n7+3) or less integer)

The organic groups used as R ^b10 and R ^b11 in formula (b7) are the same as R ^b8 in formula (b4). R ^b10 is preferably a haloalkoxy group containing a group represented by HX ₂ C- or H ₂ XC-, a haloalkyl group containing a group represented by HX ₂ C- or H ₂ XC-, an alkyl group or a phenyl group. When R ^b10 and R ^b11 are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Suitable examples of the group represented by the formula (b7) and wherein R ^b10 and R ^b11 form a ring include naphthalene-1-yl, 1,2,3,4-tetrahydronaphthalene-5-yl, and the like. In the above formula (b7), n7 is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.

In the above formula (b8), R ^b12 is an organic group. As an organic group, the same group as the organic group demonstrated about R ^b8 in formula (b4) is mentioned. Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. As R ^b12 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like can be preferably exemplified, and among them, a methyl group is more preferred.

In the above formula (b8), n7 is an integer of 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably 1 or 2. In the above formula (b8), n8 is 0 or more and (n7+3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0. In the above formula (b8), n8 is an integer of 1 or more and 8 or less, preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, and particularly preferably 1 or 2.

In formula (b2), R ^b3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group. As a substituent which R ^b3 may have when it is an aliphatic hydrocarbon group, a phenyl group, a naphthyl group and the like can be preferably exemplified.

In formulas (b1) and (b2), as R ^b3 , hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-cyclopentylethyl group, 2- Cyclobutylethyl, cyclohexylmethyl, phenyl, benzyl, methylphenyl, naphthyl, etc., among which methyl or phenyl is more preferred.

As a suitable specific example of the compound represented by formula (b2) and having a group represented by formula (b3) as R ^b1 , the following compounds may be mentioned. [Chemical 27]

[Chemical 28]

[Chemical 29]

[Chemical 30]

As a suitable specific example of the compound represented by formula (b2) and having a group represented by formula (b4) as R ^b1 , the following compounds can be mentioned. [Chemical 31]

[Chemical 32]

[Chemical 33]

[Chemical 34]

[Chemical 35]

As a preferable specific example of the compound represented by formula (b2) and having a group represented by formula (b5) as R ^b1 , the following compounds can be mentioned. [Chemical 36]

When the initiator (B) is used, the content of the initiator (B) in the solid content of the coloring composition may be appropriately adjusted, for example, 0.1 mass % or more and 30 mass % or less, preferably 1 mass % or more and 25 mass % %the following.

When the base material contained in the coloring composition is a thermosetting material, the coloring composition is heated to a temperature corresponding to the type of the base material to provide a heat-cured colored molded body. When the coloring composition is a composition containing a polyimide resin as a base component and providing a polyimide resin, the coloring composition is heated to, for example, 120°C or higher and 350°C or lower, preferably 150°C or higher and 350°C or lower.

Since the coloring composition demonstrated above contains the said pigment dispersion liquid, the coloring film formed using this coloring composition is hard to change color even if it heats to the high temperature of 120 degreeC or more and 350 degreeC or less, for example. Moreover, the cured film formed using the coloring composition demonstrated above showed the low reflectance of less than 6%.

＜Organic solvent＞ The coloring composition contains the above-mentioned pigment dispersion liquid. Therefore, the coloring composition must contain an organic solvent as a dispersion medium from the pigment dispersion liquid. In the coloring composition, only the organic solvent as a component of the pigment dispersion liquid may be formulated, or an organic solvent may be formulated in addition to the organic solvent formulated as a component of the pigment dispersion liquid. The kind of the organic solvent which the coloring composition can contain is not specifically limited in the range which does not inhibit the desired effect. As the organic solvent which the coloring composition can contain, the same solvent as the organic solvent which the pigment dispersion liquid can contain is preferable.

The content of the organic solvent in the coloring composition is appropriately determined in consideration of the solid content concentration of the coloring composition. The solid content concentration of the coloring composition is, for example, preferably 1 mass % or more and 40 mass % or less, more preferably 2 mass % or more and 30 mass % or less, and still more preferably 3 mass % or more and 20 mass % or less.

A coloring composition can be obtained by uniformly mixing each component demonstrated above in a desired ratio.

≪Formation method of colored film≫ A colored film can be formed by drying the film containing the said coloring composition, or drying and hardening. As a preferred method for forming the colored film, the following methods can be exemplified, including: coating the above-mentioned coloring composition on a substrate to form a coating film; and The coating film is dried, or dried and cured.

The method of applying the coloring composition is not particularly limited. For example, contact transfer type coating apparatuses such as roll coaters, reverse coaters, bar coaters, and slot coaters, and non-contact types such as spinners (rotary coaters) and curtain coaters are used. The coating apparatus can form a coating film by coating a coloring composition on a substrate so that it may become a desired film thickness. The film thickness of the coating film is not particularly limited. The film thickness of the coating film is appropriately set, for example, so as to form a colored film having a thickness of preferably 50 nm or more and 20 μm or less, more preferably 500 nm or more and 10 μm or less.

The coating film formed in this way is then dried, or dried and cured. The drying method is not particularly limited. The coating film is dried, for example, by baking the coating film or placing the coating film under reduced pressure. The baking temperature is appropriately determined in consideration of the boiling point and the like of the solvent (S). Baking can be carried out at low temperature under reduced pressure.

The method of baking is not particularly limited, but for example, a method of drying at a temperature of 80° C. or higher and 150° C. or lower, preferably 85° C. or higher and 120° C. or lower using a hot plate, for 60 seconds or more and 500 seconds or less, may be mentioned. time.

When the coloring composition contains a photosensitive curing agent and a base material component cured by the curing agent, a cured colored film can be obtained by exposing the coating film to light after forming the coating film by the above-mentioned method. .

The conditions for exposing the coating film to light are not particularly limited, as long as curing proceeds well. Exposure is performed by, for example, irradiating with active energy rays such as ultraviolet rays and excimer laser light. The dose of energy ray to be irradiated is not particularly limited, for example, 30 mJ/cm ² or more and 5000 mJ/cm ² or less can be mentioned. After exposure, the exposed coating film can be baked by the same method as the heating after coating. It does not specifically limit as a baking method after exposure, For example, a method of drying at a temperature of 80°C or more and 160°C or less, preferably 85°C or more and 150°C or less using a hot plate for 60 seconds or more and 500 seconds or less may be mentioned. time.

When the coloring composition contains a thermosetting substrate component such as polyamide, or a combination of a heat-sensitive curing agent and a substrate component cured by the curing agent, after forming a coating film by using the above method, The coating film is heated to obtain a cured film. The heating temperature is appropriately determined in consideration of the type of base material components and the type of curing agent. The heating conditions are, for example, 120°C or higher and 350°C or lower, preferably 150°C or higher and 350°C or lower. The heating time is, for example, preferably 5 minutes or more and 12 hours or less, more preferably 10 minutes or more and 6 hours or less, and particularly preferably 30 minutes or more and 1 hour or more.

By the above-mentioned method, a colored film excellent in low reflectivity and heat resistance can be formed. Example

Hereinafter, the present invention will be described in detail by way of examples, but the scope of the present invention is not limited to these examples.

[Preparation Example 1: Preparation of Carbon Black Introduced with Acidic Groups] 550 g of untreated carbon black (P1, Regal 250R, manufactured by Cabot Co., Ltd.), 31.5 g of p-aminobenzenesulfonic acid, and 1000 g of ion-exchanged water were put into a jacket with a jacket temperature set at 60°C and stirred. in the reaction vessel of the device. A solution prepared by dissolving 12.6 g of sodium nitrite in 100 g of deionized water was added to a Braun mixer, and the mixture in the mixer was stirred at 60°C and 50 rpm for 2 hours, the diazo coupling reaction was carried out. After stirring, the contents of the mixer were cooled to room temperature. Next, the carbon black contained in the contents of the mixer was purified by diafiltration using deionized water. The benzenesulfonic acid derived from p-aminobenzenesulfonic acid was not detected from the washing water, and it was found that the benzenesulfonic acid group was introduced into the carbon black by the diazo coupling reaction. The purified carbon black was dried at 75°C overnight, and then pulverized to obtain a carbon black (P2) into which a benzenesulfonic acid group was introduced.

[Preparation Example 2: Preparation of Silane Coupling Agent Treated Carbon Black] 50 g of untreated carbon black (P1) was mixed with 200 g of an isopropanol solution of a silane coupling agent having a concentration of 1.25% by mass, and stirred at 60°C for 3 Hour. The stirred suspension containing carbon black was heated to 100° C. to volatilize isopropanol and methanol produced as a by-product to obtain a powder of carbon black (P3) treated with a silane coupling agent. As the silane coupling agent, silane coupling agent SC-A of the following structure was used. [Chemical 37]

[Examples 1 to 18, Comparative Example 1, and Comparative Example 2] In Examples and Comparative Examples, the following P1 to P14 were used as pigments. P1: Untreated carbon black used in Preparation Example 1 P2: Carbon black into which an acid group was introduced obtained in Preparation Example 1 P3: Carbon black treated with a silane coupling agent obtained in Preparation Example 2 P4: Titanium nitride (titanium Black) P5: Tungsten (IV) oxide (WO ₂ ) P6: Copper (II) oxide (CuO) P7: Manganese dioxide (MnO ₂ ) P8: Iron oxide (Fe ₃ O ₄ ) P9: Perylene pigment P10: Endohydrin Amine Pigment P11: Titanium White (Titanium Oxide (TiO ₂ )) P12: Cobalt Blue (CoAl ₂ O ₄ ) P13: Iron Dan (Fe ₂ O ₃ ) P14: CI Pigment White 7 (ZnS)

In Examples and Comparative Examples, the polyamic acids PAA1 to PAA4 containing the following structural units and D1 (DISPERBYK-167 (manufactured by BYK-Chemie Japan Co., Ltd.)), which is a commercially available dispersant, were used as dispersants, respectively. . PAA1 and PAA2 belong to the polyamic acid having the structural unit represented by the above formula (a1). PAA3 and PAA4 belong to polyamides which do not have the structural unit represented by the above formula (a1). The mass average molecular weight of PAA1 in terms of polystyrene was 12,000. The mass average molecular weight of PAA2 in terms of polystyrene was 11,000. The mass average molecular weight of PAA3 in terms of polystyrene is 12,000. The mass average molecular weight of PAA4 in terms of polystyrene is 11,000. [Chemical 38]

In the examples and comparative examples, N,N,N',N'-tetramethylurea (TMU) or N-methyl-2-pyrrolidone (NMP), which is an aprotic polar organic solvent, was used as the dispersion. medium.

In Examples and Comparative Examples, hollow silica particles having an average particle diameter of 60 nm were used.

First, 15 g of pigments of the type described in Table 1, 7.5 g of the dispersant of the type described in Table 1, and 50 g of the organic solvent of the type described in Table 1 were mixed to obtain a pigment content of 67 g in the solid content. mass % of the mixture. In addition, in the comparative example 2, the pigment dispersion liquid was not used. Next, the obtained mixed solution is stirred to disperse the pigment. Using the dispersion medium of the kind described in Table 1, the obtained high-concentration pigment dispersion liquid was diluted to a solid content concentration of 30% by mass to obtain a pigment dispersion liquid.

5.7 parts by mass of the obtained pigment dispersion liquid and 5 parts by mass of the base resin solution of the type described in Table 1, and 0.9 parts by mass of propylene glycol monomethyl ether and 0.2 parts by mass of hollow silica as a dispersion medium. After the silicon dispersion liquid was mixed, the obtained mixed liquid was diluted with the organic solvent of the kind described in Table 1 to a solid content concentration of 11% by mass to obtain a coloring composition.

About the cured film formed using the obtained coloring composition, the heat resistance and reflectance were evaluated according to the following method. The evaluation results are described in Table 1.

<Evaluation of Heat Resistance> The coloring composition was applied on the wafer substrate using a spin coater (manufactured by Mikasa, 1H-360S). The coating film on the wafer substrate was heated at 300°C for 1 hour to form a colored film with a thickness of about 1.0 μm. 5 μg of samples for heat resistance evaluation were cut out from the colored film formed by heating to 300°C. Using a sample for heat resistance evaluation, using a differential calorimetry/thermogravimetric measuring apparatus (TG/DTA-6200, manufactured by Seiko Instruments Co., Ltd.), in an air flow, the temperature was increased at a rate of 10°C/min. TG curve. From the obtained TG curve, the 5% weight loss temperature of the sample was determined. The case where the 5% weight loss temperature exceeds 400°C is judged as 0, the case where the 5% weight loss temperature exceeds 350°C and is 400°C or less is judged as △, and the case where the 5% weight loss temperature is 350°C or less is judged as × .

<Reflectivity evaluation> The coloring composition was applied on the wafer substrate using a spin coater (manufactured by Mikasa, 1H-360S). The coating film on the wafer substrate was heated at 300° C. for 1 hour to form a colored film with a film thickness of about 1.0 μm. Using a reflectance measuring device (MCPD3700, manufactured by Otsuka Electronics Co., Ltd.), the reflectance of the formed colored film was determined according to the following criteria. ◎: The reflectance is less than 5%. ○: The reflectance is 5% or more and less than 6%. △: The reflectance is 6% or more and less than 8%. ×: The reflectance is 8% or more.

[Table 1] coloring composition Pigment dispersion hollow silica Base resin Organic solvents Heat resistance evaluation Reflectivity evaluation pigment Dispersions dispersion medium Example 1 P1 PAA1 TMU Have PAA1 TMU 〇 〇 Example 2 P2 PAA1 TMU Have PAA1 TMU 〇 〇 Example 3 P3 PAA1 TMU Have PAA1 TMU 〇 〇 Example 4 P4 PAA1 TMU Have PAA1 TMU 〇 ◎ Example 5 P5 PAA1 TMU Have PAA1 TMU 〇 〇 Example 6 P6 PAA1 TMU Have PAA1 TMU 〇 〇 Example 7 P7 PAA1 TMU Have PAA1 TMU 〇 〇 Example 8 P8 PAA1 TMU Have PAA1 TMU 〇 〇 Example 9 P9 PAA1 TMU Have PAA1 TMU 〇 〇 Example 10 P10 PAA1 TMU Have PAA1 TMU 〇 〇 Example 11 P11 PAA1 TMU Have PAA1 TMU 〇 〇 Example 12 P12 PAA1 TMU Have PAA1 TMU 〇 〇 Example 13 P13 PAA1 TMU Have PAA1 TMU 〇 〇 Example 14 P14 PAA1 TMU Have PAA1 TMU 〇 〇 Example 15 P3 PAA1 NMP Have PAA1 NMP 〇 〇 Example 16 P3 PAA2 TMU Have PAA2 TMU 〇 〇 Example 17 P3 PAA3 TMU Have PAA3 TMU 〇 〇 Example 18 P3 PAA4 TMU Have PAA4 TMU 〇 〇 Comparative Example 1 P3 D1 TMU Have PAA1 TMU × 〇 Comparative Example 2 P3 PAA1 TMU none PAA1 TMU 〇 ×

From Examples 1 to 18, it can be seen that in the pigment dispersion liquid obtained by dispersing the pigment in an aprotic polar organic solvent using polyamic acid, polyamic acid and hollow silica are added as base components. The resulting coloring composition provides a coloring film excellent in low reflectivity and heat resistance. In addition, as can be seen from Examples 18 to 36, patterning properties can also be imparted. On the other hand, according to Comparative Example 1 and Comparative Example 2, when a commercially available dispersant other than polyamic acid is used as the dispersant, or when the coloring composition does not contain hollow silica, it is difficult to form both excellent Colored film with excellent low reflectivity and excellent heat resistance.

[Examples 19 to 36] <Patterning evaluation> Example 19 was prepared by combining the components used in Examples 1 to 18 with an initiator having the following structure and dipentaerythritol hexaacrylate (polymerizable compound), respectively. Coloring composition of ~36. The solid content ratio was 45 mass % of pigment, 30 mass % of polyamic acid, 1 mass % of hollow silica, 15 mass % of initiator, and 9 mass % of polymerizable compound. Furthermore, the ratio of the polyamic acid is the sum of the dispersant and the base material, and the mass ratio of the pigment in the pigment dispersion to the polyamic acid is 2:1. The solid content ratio was 10% by mass. [Chemical 39]

Using a spin coater (manufactured by Mikasa, 1H-360S), the obtained coloring compositions of each example were coated on a wafer substrate, and then heated at 100° C. for 2 minutes to obtain a cured film with a film thickness of 1 μm. the thickness of the coating film. The obtained coating film was exposed to light at 100 mJ/cm ² using an exposure apparatus (manufactured by Topcon, TME150RTO). After exposure, development was performed with a potassium hydroxide aqueous solution having a concentration of 0.05 mass % to form a line and space pattern. A line pattern with a width of 6 μm was obtained for any composition. By post-baking at 300 degreeC for 1 hour, the coloring pattern favorable in heat resistance and low reflectivity can be obtained.

Claims (9)

A coloring composition comprising a pigment dispersion, and hollow silica, and The said pigment dispersion liquid contains a pigment, a polyamic acid, and an aprotic polar organic solvent. The coloring composition of claim 1, wherein the above-mentioned polyamic acid comprises a structural unit represented by the following formula (a1),

(In formula (a1), A ¹ is a tetravalent organic group, and A ² is a divalent organic group), and the above-mentioned A ¹ is a group represented by the following formula (a2), [Chemical 2]

(In formula (a2), R ^a11 , R ^a12 , and R ^a13 are each independently one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a fluorine atom, and a is An integer of 0 or more and 12 or less) Alternatively, the above-mentioned A ² is a group represented by the following formula (a3), -Ar ¹ -X-Ar ² -・・・(a3) (in the formula (a3), Ar ¹ , and Ar ² is each independently an optionally substituted phenyl or naphthyl group, and X is -CO-NH-). The coloring composition according to claim 1 or 2, wherein in the above-mentioned polyamic acid, the ratio of the structural unit represented by the above-mentioned formula (a1) to all the structural units of the above-mentioned polyamic acid is 30 mol% or more. The coloring composition according to any one of claims 1 to 3, wherein the aprotic polar organic solvent is a nitrogen-containing polar organic solvent represented by the following formula (S1),

(In formula (S1), R ^S1 and R ^S2 are each independently an alkyl group having 1 to 3 carbon atoms, and R ^S3 is a hydrogen atom, or the following formula (S1-1) or the following formula (S1- 2) The base of the representation, [化4]

R ^S4 is a hydrogen atom or a hydroxyl group, R ^S5 and R ^S6 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and R ^S7 and R ^S8 are each independently a hydrogen atom or 1 or more carbon atoms In addition, in the alkyl group of 3 or less, when R ^S3 is a group represented by the formula (S1-1), R ^S2 and R ^S3 may be bonded to each other to form a ring). The coloring composition according to claim 4, wherein the nitrogen-containing polar organic solvent is N,N,N',N'-tetramethylurea. The coloring composition according to any one of claims 1 to 5, which further comprises a base material component. The coloring composition according to claim 6, which comprises polyamic acid as the above-mentioned base material component. A colored film obtained by drying, or drying and curing a film containing the coloring composition according to any one of claims 1 to 7. A method for forming a colored film, comprising: Applying the coloring composition according to any one of claims 1 to 7 on a substrate to form a coating film; and The above-mentioned coating film is dried, or dried and cured.