JP2022097226A - Coloring composition, colored film, and method for forming colored film - Google Patents

Abstract

To provide a coloring composition capable of forming a colored film excellent in low reflectivity and heat resistance, a colored film which can be formed using the coloring composition, and a method for forming a colored film using the coloring composition.SOLUTION: In the coloring composition containing a pigment dispersion and hollow silica, the pigment dispersion used contains a pigment, a polyamic acid, and an aprotic polar solvent. In the pigment dispersion, it is preferable that the pigment is dispersed in the aprotic polar solvent by using the polyamic acid containing at least one of a partial skeleton derived from an aromatic diamine of a specific structure and a partial skeleton derived from an alicyclic tetracarboxylic acid dianhydride of a specific structure.SELECTED DRAWING: None

Description

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 above-mentioned coloring composition.

Conventionally, liquid compositions such as inks and pigment dispersions containing various pigments have been used to color various resin compositions. Typical pigments include, for example, carbon black. The composition colored with the carbon black dispersion is used not only for printing and paint applications, but also as a material for forming a light-shielding material such as a black matrix or a black column spacer in various display panels. ..

For example, a colored film such as a black matrix may be required to have low reflection characteristics. In order to impart low reflection characteristics to the colored film, it is proposed to use a composition containing (A) a coloring material, (B) an organic binder, and (C) fine particles such as silica particles for forming the colored film. (See Patent Document 1).

In addition, the liquid coloring composition is typically prepared using a pigment dispersion. A pigment dispersion such as a carbon black dispersion is often produced by dispersing a pigment in a solvent such as an organic solvent using a dispersant. Regarding the method for producing such a pigment dispersion, for example, as a method for producing a carbon black dispersion, a low molecular weight compound such as an organic dye derivative or a triazine derivative is used as a dispersant, and an alcohol, a glycol solvent, a ketone, or a non-form is used. A method of dispersing carbon black in an organic solvent such as a protonic polar organic solvent is known (see Patent Document 2).

Japanese Unexamined Patent Publication No. 2014-067028 Japanese Unexamined Patent Publication No. 2005-21405

However, when the carbon black dispersion obtained by the method described in Patent Document 2 is used for coloring various compositions, the obtained black composition also has heat resistance due to the use of a dispersant having inferior heat resistance. There is an inferior problem.

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

The present inventors have solved the above problems by using a pigment dispersion containing a pigment, a polyamic acid, and an aprotic polar solvent in a coloring composition containing the pigment dispersion and hollow silica. We have found what we can do and have completed the present invention.

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

A second aspect of the present invention is a colored film obtained by drying, drying and curing a film comprising the coloring composition according to the first aspect.

A third aspect of the present invention is to apply the coloring composition according to the first aspect on a substrate to form a coating film.
Drying or drying and curing the coating film,
It is a method of forming a colored film containing.

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

≪Coloring composition≫
The coloring composition contains a pigment dispersion and hollow silica. The pigment dispersion contains a pigment, a polyamic acid, and an aprotic polar solvent.
When the coloring composition contains the above pigment dispersion liquid in combination with hollow silica, the coloring composition can be used to form a coloring film having excellent low reflectivity and heat resistance.

<Pigment dispersion>
The pigment dispersion contains a polyamic acid and an aprotic polar organic solvent. The pigment dispersion is usually prepared by dispersing the pigment in the presence of a polyamic acid in an aprotic polar organic solvent. In the pigment dispersion prepared by such a method, the polyamic acid acts as a dispersant to quickly and stably disperse the pigment. Further, when the coloring composition contains a pigment dispersion liquid containing a polyamic acid, a cured film having excellent heat resistance can be formed by using the coloring composition.
Hereinafter, the components that the pigment dispersion liquid contains indispensably or arbitrarily will be described in order.

[Pigment]
The pigment is not particularly limited, and various pigments can be used. The pigment may be an inorganic pigment or an organic pigment.

The pigment is not particularly limited, but for example, a compound classified as Pigment in the Color Index (CI; The Society of Dyers and Colorists), specifically, the following. It is preferable to use one with a color index (CI) number.

Examples of suitable yellow pigments include C.I. I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only the number is 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 preferably usable orange pigments include C.I. I. Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same and only the number is 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 suitably usable purple pigments include C.I. I. Pigment Violet 1 (hereinafter, "CI Pigment Violet" is the same and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50. Can be mentioned.

Examples of preferably usable red pigments include C.I. I. Pigment Red 1 (hereinafter, "CI Pigment Red" is the same and only the number is 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. I. Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 28, 60. , 64, and 66.

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

Further, the pigment may be a light-shielding agent having a black color or a hue close to black color. The pigment dispersion liquid containing a light-shielding agent is suitably used for preparing a photosensitive resin composition used for forming a black matrix or a black column spacer in a liquid crystal display panel and forming a bank for partitioning a light emitting layer in an organic EL device. Be done.

As the light-shielding agent as the pigment, it is preferable to use a black pigment or a purple pigment. As the black pigment or the purple pigment, various pigments can be used regardless of whether they are organic substances or inorganic substances. Examples of black pigments and purple pigments include carbon blacks, perylene pigments, lactam pigments, titanium blacks such as titanium oxynitrides and titanium nitrides, metal oxides, composite oxides, metal sulfides, metal sulfates or metal carbonates. Salt and the like can be mentioned. Examples of the metal constituting the metal oxide, metal composite oxide, metal sulfide, metal sulfate, or metal carbonate include copper, iron, manganese, cobalt, tungsten, chromium, nickel, zinc, calcium, and silver. Can be mentioned.

Among these light-shielding agents, carbon black is preferable because it is easily available and has 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. Further, resin-coated carbon black may be used.

As the carbon black, carbon black that has been treated to introduce an acidic group is also preferable. The acidic group introduced into carbon black is a functional group that exhibits acidity as defined by Bronsted. Specific examples of the acidic group include a carboxy group, a sulfonic acid group, a phosphoric acid group and the like. The acidic group introduced into the carbon black may form a salt. The cation forming the salt with the acidic group is not particularly limited as long as it does not impair the object of the present invention. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions and the like, and alkali metal ions such as sodium ion, potassium ion and lithium ion, and ammonium ions are preferable.

Among the carbon blacks that have been treated to introduce the acidic groups described above, carboxylic acid groups and carboxylic acids are used from the viewpoint of achieving high resistance of the light-shielding cured film formed by using the photosensitive resin composition. Carbon black having one or more functional groups selected from the group consisting of a base, a sulfonic acid group, and a sulfonic acid base is preferable.

The method for introducing an acidic group into carbon black is not particularly limited. Examples of the method for introducing an acidic group include the following methods.
1) A method of introducing a sulfonic acid group into carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, etc., or an indirect substitution method using sulfite, hydrogen sulfite, etc.
2) A method of diazo-coupling an organic compound having an amino group and an acidic group with carbon black.
3) A method in which an organic compound having a halogen atom and an acidic group and carbon black having a hydroxyl group are reacted by Williamson's etherification method.
4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group.
5) A method of subjecting a Friedel-Crafts reaction to carbon black using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group, and then deprotecting the carbon black.

Among these methods, method 2) is preferable because the process of introducing an acidic group is easy and safe. As the organic compound having an amino group and an acidic group used in the method 2), a compound in which an amino group and an acidic group are bonded to an aromatic group is preferable. Examples of such compounds include aminobenzenesulfonic acid such as sulfanilic acid and aminobenzoic acid such as 4-aminobenzoic acid.

The number of moles of acidic groups introduced into carbon black is not particularly limited as long as it does not impair the object of the present invention. The number of moles of the acidic group introduced into the carbon black is preferably 1 mmol or more and 200 mmol or less, and more preferably 5 mmol or more and 100 mmol or less with respect to 100 g of carbon black.

The carbon black may be coated with a resin. The coating treatment with the resin may be applied to the carbon black into which an acidic group has been introduced. When a coloring composition containing a colorant dispersion liquid containing carbon black coated with a resin is used, it is easy to form a light-shielding coating film or a cured product having excellent light-shielding property and insulating property and low surface reflectance.
It should be noted that the coating treatment with the resin does not cause any adverse effect on the dielectric constant of the light-shielding coating film or the cured product formed by using the coloring composition. Examples of resins that can be used for coating carbon black include thermocurable resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, and alkylbenzene resin, and polystyrene, polycarbonate, polyethylene terephthalate, and poly. Examples thereof include thermoplastic resins such as butylene terephthalate, modified polyphenylene oxide, polysulphon, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulphon, polyphenylensulphon, polyarylate, and polyether ether ketone. The coating amount of the resin on the carbon black is preferably 1% by mass or more and 30% by mass with respect to the total of the mass of the carbon black and the mass of the resin.

Further, the carbon black may be treated with a silane coupling agent for the purpose of improving the adhesion of the colored molded product formed by using the coloring composition containing carbon black to various substrates. The treatment with a silane coupling agent may be performed before or after the treatment for introducing an acidic group into carbon black, or may be performed before or after the dispersion treatment using a polyamic acid as a dispersant.

The silane coupling agent used for the treatment of carbon black can be appropriately selected from the conventionally known silane coupling agents. As the silane coupling agent used for the treatment of carbon black, the silane coupling agent represented by the following formula (I) is preferable.

R ^A1 _a R ^A2 _(3-a) Si-R ^A3 -NH-C (O) -Y-R ^A4 -X ... (I)
(In the formula (I), ^RA1 is an alkoxy group, ^RA2 is an alkyl group, a is an integer of 1 or more and 3 or less, ^RA3 is an alkylene group, and Y is -NH-, -O. -Or-S-, ^RA4 is a single bond or an alkylene group, and X is a nitrogen-containing heteroaryl group which may have a substituent and may be monocyclic or polycyclic, and is contained in X. The ring bonded to —Y—R ^A4- is a nitrogen-containing 6-membered aromatic ring, and —Y—R ^A4- is bonded to a carbon atom in the nitrogen-containing 6-membered aromatic ring.)

In formula (I), ^RA1 is an alkoxy group. Regarding ^RA1 , 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. Preferred specific examples of ^RA1 are methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, and n. -Hexyloxy group is mentioned. Among these alkoxy groups, a methoxy group and an ethoxy group are preferable.

The silanol group generated by hydrolysis of ^RA1 which is an alkoxy group reacts with a functional group containing active hydrogen atoms such as a hydroxyl group and a carboxyl group existing on the surface of carbon black, so that the silane coupling agent becomes carbon black. Bonds to the surface. Therefore, a is preferably 3 from the viewpoint that the silane coupling agent can be easily bonded to the surface of carbon black.

In formula (I), ^RA2 is an alkyl group. Regarding ^RA2 , 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. Preferred specific examples of ^RA2 are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group. , N-Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group.

In formula (I), ^RA3 is an alkylene group. Regarding ^RA3 , the number of carbon atoms of 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. Preferred specific examples of ^RA3 are methylene group, 1,2-ethylene group, 1,1-ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1-. Diyl Group, Propane-2,2-Diyl Group, Butane-1,4-Diyl Group, Butane-1,3-Diyl Group, Butane-1,2-Diyl Group, Butane-1,1-Diyl Group, Butane- 2,2-diyl group, butane-2,3-diyl group, pentane-1,5-diyl group, pentane-1,4-diyl group, and hexane-1,6-diyl group, heptane-1,7- Examples include diyl group, octane-1,8-diyl group, nonan-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, and dodecane-1,12-diyl group. Be done. Among these alkylene groups, 1,2-ethylene group, propane-1,3-diyl group, and butane-1,4-diyl group are preferable.

Y is —NH—, —O—, or —S—, preferably —NH—. This is because the bond represented by -CO-NH- is less susceptible to hydrolysis than the bond represented by -CO-O- or -CO-S-. In carbon black treated with a compound in which Y is -NH- as a silane coupling agent, the structure of the silane coupling agent is unlikely to change due to the action of acids, bases, etc., so it is desirable to use a silane coupling agent. It is easy to obtain the effect of

^RA4 is a single bond or an alkylene group, and is preferably a single bond. A preferred example when ^RA4 is an alkylene group is the same as ^RA3 .

X is a nitrogen-containing heteroaryl group which may have a substituent and may be monocyclic or polycyclic, and the ring bonded to —Y— ^RA4- in X is a nitrogen-containing 6-membered aromatic ring. -Y-RA4- ^bondes with a carbon atom in the nitrogen-containing 6-membered aromatic ring. Although the reason is unknown, when a coloring composition containing such a compound having X as a silane coupling agent is used, a colored molded product having excellent 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 in which a plurality of monocycles are condensed, or a group in which a plurality of monocycles are bonded via 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 fused or bonded to the nitrogen-containing 6-membered aromatic ring in X may or may not contain a hetero atom, and even if it is an aromatic ring, it is aromatic. It does not have to be a ring.

The substituent that X, which is a nitrogen-containing heteroaryl group, may have is an alkyl group having 1 or more and 6 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, and 2 or more and 6 or less carbon atoms. Alkenyl group, alkenyloxy group with 2 or more and 6 or less carbon atoms, aliphatic acyl group with 2 or more and 6 or less carbon atoms, benzoyl group, nitro group, nitroso group, amino group, hydroxy group, mercapto group, cyano group, sulfone Examples thereof include an acid group, a carboxyl group, and a halogen atom. The number of substituents of X is not particularly limited as long as it does not impair the object of the present invention. The number of substituents of X is preferably 5 or less, and more preferably 3 or less. When X has a plurality of substituents, the plurality of substituents may be the same or different.

Preferred examples of X include a group of the following formula.

Among the above groups, the group of the following formula is more preferable as X.

Preferable specific examples of the compound represented by the formula (I) described above include the following compounds 1 to 8.

The method for treating carbon black with a silane coupling agent is not particularly limited, and the treatment with a silane coupling agent is performed according to a well-known method. Typically, a method of reacting the carbon black with the silane coupling agent in the presence of water in an organic solvent in which the silane coupling agent is soluble is preferable.

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, and more preferably 3 parts by mass or more and 7 parts by mass or less with respect 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 the silane coupling agent, but it is not always necessary to add water to the treatment liquid. When the treatment with the silane coupling agent is performed in an air atmosphere containing a sufficient amount of water, the water in the air hydrolyzes the alkoxy group contained in the silane coupling agent to generate a silanol group.

The temperature at which 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 carried out at a temperature of 25 ° C. or higher and 100 ° C. or lower.

Further, as the pigment, a perylene-based 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). Examples include perylene-based pigments. As commercial products, product names K0084 and K0083 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used as perylene-based pigments.

式（Ａ－１）中、Ｒ^Ａ１１及びＲ^Ａ１２は、それぞれ独立に炭素原子数１以上３以下のアルキレン基を表し、Ｒ^Ａ１３及びＲ^Ａ１４は、それぞれ独立に、水素原子、水酸基、メトキシ基、又はアセチル基を表す。

In the formula (A-1), ^RA11 and ^RA12 each independently represent an alkylene group having 1 or more and 3 or less carbon atoms, and ^RA13 and ^RA14 independently represent a hydrogen atom, a hydroxyl group, and a methoxy group, respectively. Or represents an acetyl group.

式（Ａ－２）中、Ｒ^Ａ１５及びＲ^Ａ１６は、それぞれ独立に、炭素原子数１以上７以下のアルキレン基を表す。

In the formula (A-2), ^{RA15 and RA16 each} independently represent an alkylene group having 1 or more carbon atoms and 7 or less carbon atoms.

式（Ａ－３）中、Ｒ^Ａ１７及びＲ^Ａ１８は、それぞれ独立に、水素原子、炭素原子数１～２２のアルキル基であり、Ｎ，Ｏ、Ｓ、又はＰのヘテロ原子を含んでいてもよい。Ｒ^Ａ１７及びＲ^Ａ１８がアルキル基である場合、当該アルキル基は、直鎖状であっても、分岐鎖状であってもよい。

In formula (A-3), ^{RA17 and RA18 are} each independently a hydrogen atom and an alkyl group having 1 to 22 carbon atoms, even if they contain a heteroatom of N, O, S, or P. good. When ^{RA17 and RA18 are} alkyl groups, the alkyl groups may be linear or branched.

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) are, for example, Japanese Patent Application Laid-Open No. 62-1753. , No. 63-26784 can be synthesized by using the method described in Japanese Patent Publication No. 63-26784. That is, a heating reaction is carried out in water or an organic solvent using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride or amines as raw materials. Then, the desired product can be obtained by reprecipitating the obtained crude product in sulfuric acid or recrystallizing it in water, an organic solvent or a mixed solvent thereof.

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

Further, the light-shielding agent may contain a lactam pigment. Examples of the lactam pigment include compounds represented by the following formula (A-4).

In formula (A-4), X ^A1 shows a double bond and is an E-form or a Z-form independently as geometric isomers, and ^RA19 is independently a hydrogen atom, a methyl group, a nitro group, and a methoxy. A group, a bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfo group, ^RA20 independently indicates a hydrogen atom, a methyl group, or a phenyl group, and ^RA21 independently indicates a hydrogen atom. , Methyl group, or chlorine atom.
The compound represented by the formula (A-4) can be used alone or in combination of two or more.
^RA19 is preferably bonded to the 6-position of the dihydroindron ring, and ^RA21 is bonded to the 4-position of the dihydroindron ring because the compound represented by the formula (A-4) can be easily produced. It is preferable to do. From the same viewpoint, ^RA19 , ^RA20 , and ^RA21 are preferably hydrogen atoms.
The compound represented by the formula (A-4) has an EE form, a ZZ form, and an EZ form as geometric isomers, but may be a single compound of any one of these, or these geometric isomers may be used. May be a mixture of.
The compound represented by the formula (A-4) can be produced, for example, by the method described in International Publication No. 2000/24736 and International Publication No. 2010/0816224.

In order to satisfactorily disperse the lactam pigment in the colorant dispersion, the average particle size of the lactam pigment is preferably 10 nm or more and 1000 nm or less.

Further, as the pigment, metal particles can also be used. Such metal particles are preferably formed of a metal or a metal and a metal compound, and particularly preferably formed of a metal. The metal particles may contain two or more kinds of metals or metal compounds in combination.
In particular, it is preferable that the metal particles 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, it is preferable that the metal particles contain a metal selected from the group consisting of groups 2 to 14 as a main component, and group 2 and 8 and 9 and 10 and groups 11 and 12 are preferable. , 13th group, and 14th group are more preferably contained as a main component of a metal selected from the group. As the metal particles, the metal of the 4th period, the 5th period, or the 6th period, and the metal particles of the 2nd group, the 10th group, the 11th group, the 12th group, or the 14th group are more preferable. ..

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

Among the metal particles listed above, an inorganic pigment composed of fine particles containing silver-tin (AgSn) alloy as a main component (hereinafter referred to as "AgSn alloy fine particles") is also preferably used as a light-shielding agent. The AgSn alloy fine particles may contain AgSn alloy as a main component, and may contain, for example, Ni, Pd, Au, etc. 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 in which a chemically stable AgSn alloy can be obtained is 1 ≦ x ≦ 10, and the range of x in which chemical stability and blackness can be obtained at the same time is. 3 ≦ x ≦ 4.
Here, when the mass ratio of Ag in the AgSn alloy is obtained in the range of x above,
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
Will be.
Therefore, this AgSn alloy becomes chemically stable when it contains 47.6 to 90% by mass of Ag, and is effective with respect to the amount of Ag when it contains 73.17 to 78.43% by weight of Ag. Chemical stability and blackness can be obtained.

The AgSn alloy fine particles can be produced by using a usual fine particle synthesis method. Examples of the fine particle synthesis method include a gas phase reaction method, a spray pyrolysis method, an atomizing method, a liquid phase reaction method, a freeze-drying method, and a hydrothermal synthesis method.

The AgSn alloy fine particles have high insulating properties, but depending on the use of the coloring composition prepared by using the pigment dispersion liquid, the surface may be covered with an insulating film in order to further improve the insulating properties. As the material of such an insulating film, a metal oxide or an organic polymer compound is suitable.
As the metal oxide, a metal oxide having an insulating property, for example, silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), ittrium oxide (itria), titanium oxide (titania) and the like is preferably used. Be done.
Further, as the organic polymer compound, a resin having an insulating property, for example, a polyimide, a polyether, a polyacrylate, a polyamine compound or the like is preferably used.

When the insulating film is formed using the coloring composition described later, the film 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 in order to sufficiently enhance the insulating property on the surface of the AgSn alloy fine particles. It is as follows.
The insulating film can be easily formed by a surface modification technique or a surface coating technique. In particular, it is preferable to use an alkoxide such as tetraethoxysilane or aluminum triethoxyde because an insulating film having a uniform film thickness can be formed at a relatively low temperature.

As the light-shielding agent, the above-mentioned perylene-based pigment, lactam-based pigment, or AgSn alloy fine particles may be used alone, or these may be used in combination.
In addition, the light-shielding agent may contain a pigment having a hue such as red, blue, green, or yellow in addition to the above-mentioned black pigment or purple pigment for the purpose of adjusting the color tone. The pigments having other hues of the black pigment and the purple pigment can be appropriately selected from known pigments. For example, as the pigments having other hues of black pigments and purple pigments, the above-mentioned various pigments can be used. The amount of the pigment having a hue 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 light-shielding agent.

Further, the inorganic pigment and the organic pigment may be used alone or in combination of two or more, but when they are used in combination, the organic pigment is added in an amount of 10 parts by mass or more and 80 parts by mass based on 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. It is preferably used in the range of 20 parts by mass or less, and more preferably 20 parts by mass or more and 40 parts by mass or less.

The pigment described above is a pigment dispersion liquid together with a dispersion medium containing a polyamic acid described later and 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 is 40% by mass or more and 99% by mass because it is easy to disperse the pigment well and it is easy to prepare a coloring composition containing the pigment at a desired concentration. % Or less is preferable, 40% by mass or more and 90% by mass or less is more preferable, and 40% by mass or more and 80% by mass or less is further preferable.

By dispersing the pigment in a dispersion medium containing an aprotonic polar organic solvent in the presence of a polyamic acid having a specific structure described later, the pigment does not aggregate and is stable in the pigment dispersion in a short time. Distributed in. The smaller the dispersed particle size, the better the dispersibility without agglomeration of the pigment. For example, the dispersed particle size is 90 nm or less.

[Polyamic acid]
Polyamic acids are used as dispersants to disperse pigments. The molecular chains of polyamic acids are thought to be point-bonded to the surface of the primary particles of the pigment by hydrogen bonds and interactions such as intramolecular forces with the surface of the pigment. Therefore, it is considered that the molecular chain of the polyamic acid acts as a spacer on the surface of the primary particles of the pigment to promote the dispersion of the pigment and stabilize the dispersion.

The pigment dispersion liquid preferably does not contain a resin component other than the polyamic acid. When the pigment dispersion liquid contains a resin component other than the polyamic acid, the aggregates of the primary particles of the pigment are coated with the resin, so that the aggregates are less likely to collapse or the molecules of the polyamic acid on the surface of the primary particles of the pigment. It may be difficult to disperse the pigment due to the inhibition of the adsorption of the pigment.

The molecular weight of the polyamic acid is preferably 5,000 or more and 30,000 or less, and more preferably 10,000 or more and 20,000 or less, as a mass average molecular weight. When the molecular weight of the polyamic acid is within such a range, the pigment is dispersed well and stably by using an amount of the polyamic acid that does not significantly affect the characteristics of various compositions to which the pigment dispersion liquid is blended. Can be done.

The amount of polyamic acid used is not particularly limited. From the viewpoint of ease of dispersion of the pigment, the polyamic acid is preferably used in an amount of 20 parts by mass or more and 80 parts by mass or less, and 30 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the pigment. Is more preferable.

As the polyamic acid, a conventionally known polyamic acid can be used without particular limitation. The polyamic acid is usually a polymer in which a diamine component and a tetracarboxylic acid dianhydride component are polycondensed.
The diamine component is not particularly limited. The diamine component may be an aliphatic diamine compound or a diamine compound having an aromatic group in its structure.
The tetracarboxylic acid dianhydride component is not particularly limited. The tetracarboxylic acid dianhydride component may be an aliphatic tetracarboxylic acid dianhydride or a tetracarboxylic acid dianhydride having an aromatic group in its structure.
For example, as the diamine component and the tetracarboxylic acid dianhydride component, the compounds described below can be used without particular limitation.

（式（ａ１）中、Ａ^１は４価の有機基であり、Ａ^２は２価の有機基である。）
で表される構成単位を含み、
Ａ^１が、下記式（ａ２）：

（式（ａ２）中、Ｒ^ａ１１、Ｒ^ａ１２、及びＲ^ａ１３は、それぞれ独立に、水素原子、炭素原子数１以上５以下のアルキル基及びフッ素原子からなる群より選択される１種であり、ａは０以上１２以下の整数である。）
で表される基であるか、
Ａ^２が、下記式（ａ３）：
－Ａｒ^１－Ｘ－Ａｒ^２－・・・（ａ３）
（式（ａ３）中、Ａｒ^１、及びＡｒ^２は、それぞれ独立に、置換基を有してもよいフェニレン基又はナフチレン基であり、Ｘは－ＣＯ－ＮＨ－である。） The polyamic acid includes a structural unit represented by the following formula (a1) from the viewpoint that the dispersibility of the pigment is particularly good and it is particularly easy to obtain a coloring composition capable of forming a colored film having excellent heat resistance. Polyamic acids are preferably used.

(In the formula (a1), A ¹ is a tetravalent organic group and A ² is a divalent organic group.)
Including the building blocks represented by
A ¹ is the following formula (a2):

(In the formula (a2), R ^a11 , R ^a12 , and R ^a13 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, and a fluorine atom. a is an integer of 0 or more and 12 or less.)
Is it a group represented by?
A ² is the following formula (a3):
-Ar ¹ -X-Ar ² -... (a3)
(In the formula (a3), Ar ¹ and Ar ² are each independently a phenylene group or a naphthylene group which may have a substituent, and X is -CO-NH-.)

In the formula (a1), A1 is ^a tetravalent organic group, and the number of carbon atoms thereof is preferably 2 or more and 50 or less, and more preferably 2 or more and 30 or less. A ¹ may be an aliphatic group, an aromatic group, or a group combining these structures.
Generally, A ¹ is a residue obtained by removing two acid anhydride groups from the tetracarboxylic acid dianhydride used in the production of polyamic acid.
However, in the formula (a1), when A ² is a group other than the group represented by the above formula (a3), A ¹ in the formula (a1) is always a group represented by the formula (a2). Is.
A ¹ may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to the carbon atom and the hydrogen atom. When A ¹ contains an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, the nitrogen atom, or the sulfur atom is a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N = N-, -CH =. It may be contained in A ¹ as a group selected from N-, -COO-, -O-, -CO-, -SO-, -SO _2- , -S-, and -S-S-. It is more preferably contained in A1 as ^a group selected from —O—, —CO—, —SO—, _—SO2- , —S—, and —SS—.

A1 in the formula (a1) is described above because the dispersion stability of the pigment in the pigment dispersion liquid and the heat resistance of the colored molded product formed by using the coloring composition prepared by using the pigment dispersion liquid are good. It is preferable that the group is represented by the formula (a2) of.

The alkyl group that can be selected as ^{Ra 11} in the formula (a2) is an alkyl group having 1 or more and 5 or less carbon atoms. Since the number of carbon atoms of the alkyl group as R ^a11 is within such a range, it is easy to form a colored molded product having excellent heat resistance by using a coloring composition containing a pigment dispersion. The number of carbon atoms of the alkyl group is more 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.

The R ^a11 in the formula (a2) includes a hydrogen atom, a methyl group, and an ethyl because it is easy to obtain and purify a tetracarboxylic acid dianhydride having a tetravalent organic group represented by the formula (a2). A group, an n-propyl group or an isopropyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferable.
The plurality of Ra ^11s in the formula (a2) are preferably the same group because it is easy to purify the tetracarboxylic acid dianhydride giving a tetravalent organic group represented by the formula (a2). ..

In the equation (a2), a represents an integer of 0 or more and 12 or less. When the value of a is more than 12, it is difficult to purify the tetracarboxylic acid dianhydride giving a tetravalent organic group represented by the formula (a2).
The upper limit of a is preferably 5 and more preferably 3 because it is easy to purify the tetracarboxylic acid dianhydride giving a tetravalent organic group represented by the formula (a2).
From the viewpoint of the chemical stability of the tetracarboxylic acid dianhydride giving a tetravalent organic group represented by the formula (a2), the lower limit of a is preferably 1 and more preferably 2.
2 or 3 is particularly preferable for a in the formula (a2).

The alkyl group having 1 or more and 5 or less carbon atoms that can be selected as Ra 12 and Ra ¹³ in the formula (a2) is the ^{same as the alkyl group having 1 or more and 5 or less carbon atoms that can be selected as R a11 .}
R ^a12 and R ^a13 have hydrogen atoms or carbon atoms of 1 or more and 5 or less because it is easy to purify a tetracarboxylic acid dianhydride having a tetravalent organic group represented by the formula (a2). An alkyl group is preferable, and a hydrogen atom or a methyl group is particularly preferable.

Examples of the tetracarboxylic acid dianhydride having a tetravalent organic group represented by the formula (a2) include norbornan-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornan-5. , 5'', 6,6''-tetracarboxylic acid dianhydride (also known as "norbornan-2-spiri-2'-cyclopentanone-5'-spiro-2"-norbornan-5,5 ", 6,6''-tetracarboxylic acid dianhydride "), methylnorbornan-2-spiro-α-cyclopentanone-α'-spiro-2''- (methylnorbornan) -5,5'', 6, 6''-tetracarboxylic acid dianhydride, norbornan-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid dianhydride (Also known as "norbornan-2-spiri-2'-cyclohexanone-6'-spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid dianhydride"), methylnorbornan-2 -Spiro-α-cyclohexanone-α'-Spiro-2''-(methylnorbornan) -5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornan-2-spiro-α-cyclopropa Non-α'-spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornan-2-spiro-α-cyclobutanone-α'-spiro-2'' -Norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornan-2-spiro-α-cycloheptanone-α'-spiro-2''-norbornan-5,5'' , 6,6''-tetracarboxylic acid dianhydride, norbornan-2-spiro-α-cyclooctanone-α'-spiro-2''-norbornan-5,5'', 6,6''-tetra Carboxylic acid dianhydride, norbornan-2-spiro-α-cyclononanon-α'-spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornan-2- Spiro-α-cyclodecanone-α'-spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornan-2-spiro-α-cycloundecanone-α' -Spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornan-2-spiro-α-cyclododecanone-α'-spiro-2''-norbornan -5,5'', 6,6''-tetracarboxylic acid Norbornane-2-spiro-α-cyclotridecanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2- Spiro-α-cyclotetradecanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α-cyclopentadeca Non-α'-Spyro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α- (methylcyclopentanone) -α'- Spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride, norbornane-2-spiro-α- (methylcyclohexanone) -α'-spiro-2''-norbornane -5,5'', 6,6''-tetracarboxylic acid dianhydride and the like can be mentioned.

（式（ａ２－１）中、Ｒ^ａ１１、Ｒ^ａ１２、Ｒ^ａ１３、ａは、式（ａ２）中のＲ^ａ１１、Ｒ^ａ１２、Ｒ^ａ１３、ａと同義である。）
で表される化合物（Ａ２－１）及び下記式（ａ２－２）：

（式（ａ２－２）中、Ｒ^ａ１１、Ｒ^ａ１２、Ｒ^ａ１３、ａは、式（ａ２）中のＲ^ａ１１、Ｒ^ａ１２、Ｒ^ａ１３、ａと同義である。）
で表される化合物（Ａ２－２）のうちの少なくとも１種を含有し、且つ、化合物（Ａ２－１）及び化合物（Ａ２－２）の総量が３０モル％以上であるものが好ましい。 Further, as the tetracarboxylic acid dianhydride having a tetravalent organic group represented by the formula (a2), the polyimide resin from which the polyamic acid is purified has good thermal, mechanical, optical and electrical characteristics. From the point, the following equation (a2-1):

(In the formula (a2-1), R ^a11 , R ^a12 , R ^a13 , a are synonymous with R ^a11 , R ^a12 , R ^a13 , a in the formula (a2).)
The compound represented by (A2-1) and the following formula (a2-2):

(In the formula (a2-2), R ^a11 , R ^a12 , R ^a13 , a are synonymous with R ^a11 , R ^a12 , R ^a13 , a in the formula (a2).)
It is preferable that the compound (A2-2) containing at least one of the compounds represented by (A2-2) is contained and the total amount of the compound (A2-1) and the compound (A2-2) is 30 mol% or more.

In the compound (A2-1) represented by the formula (a2-1), two norbornan groups are trans-arranged, and the carbonyl group of cycloalkanol is an end configuration for each of the two norbornan groups. It is an isomer of a tetracarboxylic acid dianhydride that gives a tetravalent organic group represented by the formula (a2).
In the compound (A2-2) represented by the formula (a2-2), two norbornan groups are cis-arranged, and the carbonyl group of cycloalkanol is an end configuration for each of the two norbornan groups. It is an isomer of a tetracarboxylic acid dianhydride that gives a tetravalent organic group represented by the formula (a2).
The method for producing a tetracarboxylic acid dianhydride containing such an isomer in the above ratio is not particularly limited, and a known method can be appropriately adopted, and is described in, for example, International Publication No. 2014/034760. The method of the above may be appropriately adopted.

As the tetracarboxylic acid dianhydride giving A1 which is a tetravalent organic group, aromatic tetracarboxylic acid dianhydride is also preferable.
Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 3,3', 4,4'-oxy. Biphenylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4, Examples thereof include 4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride and the like.

The aromatic tetracarboxylic acid dianhydride may also be, for example, a compound represented by the following general formulas (a2a) to (a2c).

In the above formulas (a2a) and (a2b), Ra ¹ , Ra ² and Ra ³ each contain an aliphatic group, an oxygen atom, a sulfur atom or one or more divalent elements which may be substituted with halogen. Indicates a divalent group that is either an interstitial aromatic group or is composed of a combination thereof. R ^a2 and R ^a3 may be the same or different.
That is, Ra ¹ , Ra ² and Ra ³ may contain a carbon-carbon single bond, a carbon-oxygen-carbon ether bond or a halogen element (fluorine, chlorine, bromine, iodine). Examples of the compound represented by the formula (a2a) include 2,2-bis (3,4-dicarboxyphenoxy) propane dianhydride and 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride. And so on.

Further, in the above formula (a2c), R ^a4 and R ^a5 are either an aliphatic group that may be substituted with a halogen, an aromatic group via one or more divalent elements, or a halogen. The monovalent substituent composed of the combination thereof is shown. R ^a4 and R ^a5 may be the same or different from each other. As the compound represented by the formula (a2c), difluoropyromellitic acid dianhydride, dichloropyromellitic acid dianhydride and the like can also be used.

Examples of the tetracarboxylic acid benzene chloride containing fluorine in the molecule include (trifluoromethyl) pyromellitic acid benzene, di (trifluoromethyl) pyromellitic acid benzene, and di (heptafluoropropyl) pyro. Merit Acid Benzene, Pentafluoroethyl Pyromeric Acid Benzene, Bis {3,5-di (Trifluoromethyl) Phenoxy} Pyromeritic Acid Benzene, 2,2-Bis (3,4-dicarboxyphenyl) ) Hexafluoropropane dianhydride, 5,5'-bis (trifluoromethyl) -3,3', 4,4'-tetracarboxybiphenyl dianhydride, 2,2', 5,5'-tetrakis (tri) Fluoromethyl) -3,3', 4,4'-tetracarboxybiphenyl dianhydride, 5,5'-bis (trifluoromethyl) -3,3', 4,4'-tetracarboxydiphenyl ether dianhydride, 5,5'-bis (trifluoromethyl) -3,3', 4,4'-tetracarboxybenzophenone dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} benzene dianhydride, bis {(trifluoromethyl) Methyl) dicarboxyphenoxy} (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) benzene dianhydride, bis (Dicarboxyphenoxy) Tetrax (trifluoromethyl) benzene dianhydride, 2,2-bis {4- (3,4-dicarboxyphenoxy) phenyl} hexafluoropropane dianhydride, bis {(trifluoromethyl) dianoxide Carboxyphenoxy} biphenyl dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} bis (trifluoromethyl) biphenyl dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} diphenyl ether dianhydride, bis (dicarboxy) Phenoxy) bis (trifluoromethyl) biphenyl dianhydride, difluoropyromellit acid dianhydride, 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride, 1,4-bis ( 3,4-Dicarboxytrifluorophenoxy) Octafluorobiphenyl benzene and the like can be mentioned.

In the 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, and more preferably 6 or more and 30 or less. A ² may be an aliphatic group, an aromatic group, or a group combining these structures.
Generally, A ² is a residue obtained by removing two amino groups from the diamine used in the production of polyamic acid.
However, in the formula (a1), when A1 is ^a group other than the group represented by the above formula (a2), ^A2 in the formula (a1) is always a group represented by the formula (a3). Is.

A ² in the formula (a1) has good heat resistance of the colored molded product formed by using the coloring composition prepared by using the pigment dispersion liquid and the dispersion stability of the pigment in the pigment dispersion liquid. It is preferably a group represented by the following formula (a3).
-Ar ¹ -X-Ar ² -... (a3)
(In the formula (a3), Ar ¹ and Ar ² are each independently a phenylene group or a naphthylene group which may have a substituent, 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. Preferable examples of the phenylene group and the substituent which the naphthylene group may have are an alkyl group having 1 or more and 4 or less carbon atoms, an alkyl halide group having 1 or more and 4 or less carbon atoms, and 1 or more carbon atoms. Examples thereof include an alkoxy group having 4 or less, a halogenated alkoxy group having 1 or more and 4 or less carbon atoms, an acyl group having 2 or more and 4 or less carbon atoms, an acyloxy group having 2 or more and 4 or less carbon atoms, a halogen atom, and a cyano group. Be done.

The number of substituents that the phenylene group or naphthylene group as Ar ¹ and Ar ² may have is not particularly limited as long as the object of the present invention is not impaired. The number of substituents is preferably 0 or more and 4 or less, more preferably 0 or more and 2 or less, and even more preferably 0 or 1.

The phenylene group which may have a substituent as Ar ¹ and Ar ² may be any of an o-phenylene group, an m-phenylene group, and a p-phenylene group, and the m-phenylene group and the p-phenylene group. Is preferable, and a p-phenylene group is more preferable.
The positions of the two bonds of the naphthylene group which may have a substituent as Ar ¹ and Ar ² are not particularly limited as long as they do not impair the object of the present invention. Examples of the naphthylene group include naphthalene-1,4-diyl group, naphthalene-1,3-diyl group, naphthalene-1,2-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, and the like. And naphthalene-2,7-diyl group are preferable, and naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, and naphthalene-2,7-diyl group are more preferable.

As the groups represented by the formula (a3), Ar ¹ and Ar ² are independently p-phenylene group, m-phenylene group, naphthalene-1,4-diyl group and naphthalene-2,6-diyl, respectively. A group or a group which is a naphthalene-2,7-diyl group is preferable, and a group in which Ar ¹ and Ar ² are independently p-phenylene groups or m-phenylene groups is more preferable, and Ar ¹ and Ar 2 are more preferable. A group in which both Ar ² are p-phenylene groups is particularly preferable.
That is, the unit represented by the formula (a3) is 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, or a residue obtained by removing two amino groups from 4,3'-diaminobenzanilide. It is preferable that it is a residue obtained by removing two amino groups from 4,4'-diaminobenzanilide.

When A ² is an organic group containing 1 or more aromatic rings, the organic group may be 1 aromatic group itself, and 2 or more aromatic groups are an aliphatic hydrocarbon group and a halogenated fat. It may be a group hydrocarbon group or a group bonded via a bond containing a hetero atom such as an oxygen atom, a sulfur atom and a nitrogen atom. Bonds containing heteroatoms such as oxygen atom, sulfur atom, and nitrogen atom contained in A ² include -CONH-, -NH-, -N = N-, -CH = N-, -COO-,-. O-, -CO-, -SO-, -SO _2- , -S-, -S-S-, etc. are mentioned, and -O-, -CO-, -SO-, -SO _2- , -S, etc. are mentioned. -, And-S-S- are preferable.

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 A ² is a fused ring containing two or more rings, the ring bonded to the amino group in the condensed ring is preferably a benzene ring.
Further, the aromatic ring contained in A ² may be an aromatic heterocycle.

（式（２１）～（２４）中、Ｒ^１１１は、水素原子、フッ素原子、水酸基、炭素原子数１以上４以下のアルキル基、及び炭素原子数１以上４以下のハロゲン化アルキル基よりなる群から選択される１種を示す。式（２４）中、Ｑは、９，９’－フルオレニリデン基、又は、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－、及び－Ｏ－Ｃ_６Ｈ_４－Ｏ－で表される基よりなる群から選択される１種を示す。
Ｑの例示における、－Ｃ_６Ｈ_４－はフェニレン基であり、ｍ－フェニレン基、及びｐ－フェニレン基が好ましく、ｐ－フェニレン基がより好ましい。また、－Ｃ_１０Ｈ_６－は、ナフタレンジイル基であり、ナフタレン－１，２－ジイル基、ナフタレン－１，４－ジイル基、ナフタレン－２，３－ジイル基、ナフタレン－２，６－ジイル基、及びナフタレン－２，７－ジイル基が好ましく、ナフタレン－１，４－ジイル基、及びナフタレン－２，６－ジイル基がより好ましい。） When A ² is an organic group containing an aromatic ring, the organic group is a group represented by the following formulas (21) to (24) from the viewpoint of heat resistance of the cured product formed by using the resin composition. It is preferably at least one of them.

(In formulas (21) to (24), R ¹¹¹ is a group consisting of a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group having 1 or more and 4 or less carbon atoms, and an alkyl halide group having 1 or more and 4 or less carbon atoms. In formula (24), Q is a 9,9'-fluorenylidene group, or formulas: -C ₆ H _4- , -CONH-C ₆ H ₄ -NHCO-, -NHCO. -C ₆ H ₄ -CONH-, -O-C 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- , -O -C 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 -O _- C ₆ H4 Shows one selected from the group consisting of groups represented by -O-.
In the example of Q, -C ₆ H _4- is a phenylene group, preferably an m-phenylene group and a p-phenylene group, and more preferably a p-phenylene group. Further, -C _{10H 6-} is a naphthalene diyl group, which is a naphthalene-1,2-diyl group, a naphthalene-1,4-diyl group, a naphthalene-2,3-diyl group, and a naphthalene-2,6-diyl group. Groups and naphthalene-2,7-diyl groups are preferred, and naphthalene-1,4-diyl groups and naphthalene-2,6-diyl groups are more preferred. )

The R ¹¹¹ in the formulas (21) to (24) includes a hydrogen atom, a hydroxyl group, a fluorine atom, a methyl group, and ethyl from the viewpoint of the heat resistance of the polyamic acid and the heat resistance of the polyimide resin provided by the polyamic acid. A group or a trifluoromethyl group is more preferable, and a hydrogen atom, a hydroxyl group, or a trifluoromethyl group is particularly preferable.

As Q in the formula (24), from the viewpoint of heat resistance of the polyimide resin to be formed, 9,9'-fluorenylidene group, -OC ₆ H ₄ -O-, -C (CF ₃ ) _2- , -O-, -C (CH ₃ ) _2- , or -CH _2- is preferable.

When an aromatic diamine is used as the diamine compound that gives A ² other than the group represented by the formula (a3), for example, the aromatic diamine shown below can be preferably 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'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,4' -Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminobenzanilide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3 -Bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene , 9,9-Bis (4-amino-3-methylphenyl) fluorene, and 4,4'-[1,4-phenylenebis (1-methylethane-1,1-diyl)] dianiline and the like. Among these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenyl ether, and 4,4'-diaminobenzanilide are preferable from the viewpoint of price, availability, and the like.

Further, as A ² , a silicon atom-containing group which may have a chain-like aliphatic group and / or an aromatic ring can be adopted. As such a silicon atom-containing group, typically, a group shown below can be used.

（式（Ｓｉ－１）中、Ｒ^１１２及びＲ^１１３は、それぞれ独立に、単結合又はメチレン基、炭素原子数２以上２０以下のアルキレン基、炭素原子数３以上２０以下のシクロアルキレン基、又は炭素原子数６以上２０以下のアリーレン基等であり、Ｒ^１１４、Ｒ^１１５、Ｒ^１１６、及びＲ^１１７は、それぞれ独立に、炭素原子数１以上２０以下のアルキル基、炭素原子数３以上２０以下のシクロアルキル基、炭素原子数６以上２０以下のアリール基、炭素原子数２０以下のアミノ基を含む基、－Ｏ－Ｒ^１１８で表される基（Ｒ^１１８は炭素原子数１以上２０以下の炭化水素基）、炭素原子数２以上２０以下の１以上のエポキシ基を含む有機基であり、ｌは、３以上５０以下の整数である。） Further, as A ² , a group represented by the following formula (Si-1) can also be preferably used.

(In the formula (Si-1), R ¹¹² and R ¹¹³ are each independently a single bond or a methylene group, an alkylene group having 2 or more and 20 or less carbon atoms, a cycloalkylene group having 3 or more and 20 or less carbon atoms, or a cycloalkylene group. It is an arylene group having 6 or more and 20 or less carbon atoms, and R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , and R ¹¹⁷ are independently an alkyl group having 1 or more and 20 or less carbon atoms and 3 or more and 20 or less carbon atoms. Cycloalkyl group, an aryl group having 6 to 20 carbon atoms, a group containing an amino group having 20 or less carbon atoms, and a group represented by -OR ^{118 (R 118 has} 1 to 20 carbon atoms). Hydrocarbon group), an organic group containing 1 or more epoxy groups having 2 or more and 20 or less carbon atoms, and l is an integer of 3 or more and 50 or less.)

As the alkylene group having 2 or more and 20 or less carbon atoms in R ¹¹² and R ¹¹³ in the formula (Si-1), an alkylene group having 2 or more and 10 or less carbon atoms is preferable from the viewpoint of heat resistance, and a dimethylene group and trimethylene are used. Examples thereof include a group, a tetramethylene group, a pentamethylene group, a hexamethylene group and the like.

As the cycloalkylene group having 3 or more and 20 or less carbon atoms in R ¹¹² and R ¹¹³ in the formula (Si-1), a cycloalkylene group having 3 or more and 10 or less carbon atoms is preferable from the viewpoint of heat resistance, and cyclobutylene. Examples thereof include a group, a cyclopentylene group, a cyclohexylene group, a cycloheptyrene group and the like.
As the arylene group having 6 or more and 20 or less carbon atoms in R ¹¹² and R ¹¹³ in the formula (Si-1), an aromatic group having 6 or more and 20 or less carbon atoms is preferable from the viewpoint of heat resistance. Examples include a naphthylene group.

As the alkyl group having 1 or more and 20 or less carbon atoms in R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , and R ¹¹⁷ in the formula (Si-1), an alkyl group having 1 or more and 10 or less carbon atoms is used from the viewpoint of heat resistance. Preferably, specific examples thereof include 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 and the like.
The cycloalkyl groups having 3 or more and 20 or less carbon atoms in R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , and R ¹¹⁷ in the formula (Si-1) are cycloalkyls having 3 or more and 10 or less carbon atoms from the viewpoint of heat resistance. A group is preferable, and specific examples thereof include a cyclopentyl group and a cyclohexyl group.
As the aryl group having 6 or more and 20 or less carbon atoms in R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , and R ¹¹⁷ in the formula (Si-1), an aryl group having 6 or more and 12 or less carbon atoms is used from the viewpoint of heat resistance. Preferably, specific examples thereof include a phenyl group, a tolyl group, a naphthyl group and the like.
Examples of the group containing an amino group having 20 or less carbon atoms in R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , and R ¹¹⁷ in the formula (Si-1) include an amino group and a substituted amino group (for example, bis (trialkylsilyl)). ) Amino group) and the like.
The groups represented by —OR ¹¹⁸ in R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , and R ¹¹⁷ in the formula (Si-1) include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, and a butoxy group. Examples thereof include a phenoxy group, a triloxy group, a naphthyloxy group, a propenyloxy group (for example, an allyloxy group), a cyclohexyloxy group and the like.
Among them, R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , and R ¹¹⁷ are preferably a methyl group, an ethyl group, a propyl group, and a phenyl group.

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

（式（ａ４）中、Ａ^３は、前述の式（ａ２）で表される基以外の４価の有機基であり、Ａ^４は、前述の式（ａ３）で表される基以外の２価の有機基である。） The polyamic acid may contain a structural unit represented by the following formula (a4).

( ^In the formula (a4), A3 is a ^tetravalent organic group other than the group represented by the above formula (a2), and A4 is 2 other than the group represented by the above formula (a3). It is an organic group of valence.)

As A3 ^, a tetravalent organic group other than the group represented by the formula (a2) described in the formula (a1) can be appropriately adopted. As A4, a ^divalent organic group other than the group represented by the formula (a3) described in the formula (a1) can be appropriately adopted.

The ratio of the constituent units represented by the above formula (a1) in the polyamic acid is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, based on the molar amount of all the constituent units. Preferably, 90 mol% or more is even more preferable, and 100 mol% is particularly preferable.

(Manufacturing method of polyamic acid)
The polyamic acid is usually prepared by reacting a tetracarboxylic acid dianhydride component with a diamine component.
Typically, a polyamic acid is obtained by reacting a tetracarboxylic acid dianhydride component and a diamine component in a solvent capable of dissolving both. The amount of the tetracarboxylic acid dianhydride component and the diamine component used in synthesizing the polyamic acid is not particularly limited, but the diamine component is 0.50 mol or more per 1 mol of the tetracarboxylic acid dianhydride component. It is preferable to use 50 mol or less, 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.

Solvents that can be used for the synthesis of polyamic acids include, for example, N, N, N', N'-tetramethylurea, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide. , Hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, and aprotonic polar organic solvents such as γ-butyrolactone, diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, Examples thereof include glycol ethers such as propylene glycol monoalkyl ether acetate and propylene glycol monoalkyl ether propionate. These solvents can be used in combination of two or more. Among these, it is preferable to use N, N, N', N'-tetramethylurea.

The amount of the solvent used for synthesizing the polyamic acid is not particularly limited as long as the polyamic acid having a desired molecular weight can be synthesized. Typically, the amount of the solvent used is preferably 100 parts by mass or more and 4000 parts by mass or less, preferably 150 parts by mass or more, with respect to 100 parts by mass in total of the amount of the tetracarboxylic acid dianhydride component and the amount of the diamine component. More preferably, it is 2000 parts by mass or less.

The temperature at which the tetracarboxylic acid dianhydride component and the diamine component are reacted is not particularly limited as long as the reaction proceeds well. Typically, the reaction temperature between the tetracarboxylic acid 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. preferable. The time for reacting the tetracarboxylic acid dianhydride component with the diamine component varies depending on the reaction temperature, but is typically preferably 1 hour or more and 50 hours or less, and more preferably 2 hours or more and 40 hours or less. 5 hours or more and 30 hours or less are particularly preferable.

[Aprotic polar organic solvent]
The pigment dispersion contains an aprotic polar organic solvent. By dispersing the pigment using the above-mentioned polyamic acid in a dispersion medium containing an aprotic polar organic solvent, the pigment is 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 can be kept good. 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 type of the aprotic polar organic solvent is not particularly limited as long as it does not impair the object of the present invention. Examples of suitable aprotonic polar organic solvents are N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N, N-dimethylisobutylamide, N, N-diethylacetamide, N. , N-Dimethylformamide (DMF), N, N-diethylformamide, N-methylcaprolactone, 1,3-dimethyl-2-imidazolidinone (DMI), pyridine, and N, N, N', N'-tetra Nitrogen-containing polar solvents such as methylurea (TMU); lactone-based polar solvents such as β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone; dimethylsulfoxide; Hexamethylphosphoric triamides; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; ketones such as cyclopentanone and cyclohexanone.

（式（Ｓ１）中、Ｒ^Ｓ１及びＲ^Ｓ２は、それぞれ独立に炭素原子数１以上３以下のアルキル基であり、Ｒ^Ｓ３は下記式（Ｓ１－１）又は下記式（Ｓ１－２）：

で表される基である。式（Ｓ１－１）中、Ｒ^Ｓ４は、水素原子又は水酸基であり、Ｒ^Ｓ５及びＲ^Ｓ６は、それぞれ独立に炭素原子数１以上３以下のアルキル基である。式（Ｓ１－２）中、Ｒ^Ｓ７及びＲ^Ｓ８は、それぞれ独立に水素原子、又は炭素原子数１以上３以下のアルキル基である。） The aprotic polar solvent is preferably a nitrogen-containing polar organic solvent represented by the following formula (S1) because it has good solubility of the polyamic acid and is easy to disperse the pigment in a good and stable manner.

(In the formula ( ^S1 ), RS1 and ^RS2 are each independently an alkyl group having 1 or more and 3 or less carbon atoms, and ^RS3 is the following formula (S1-1) or the following formula (S1-2):

It is a group represented by. In the formula (S1-1), ^{RS4 is a hydrogen atom or a hydroxyl group, and RS5 and RS6 are independently} alkyl groups having 1 or more and 3 or less carbon atoms. In the formula (S1-2), ^RS7 and ^RS8 are independently hydrogen atoms or alkyl groups having 1 or more and 3 or less carbon atoms. )

Among the nitrogen-containing polar organic solvents represented by the formula (S1), specific examples of the case where ^RS3 is a group represented by the formula (S1-1) include N, N, 2-trimethylpropionamide and N. -Ethyl, N, 2-dimethylpropionamide, N, N-diethyl-2-methylpropionamide, N, N, 2-trimethyl-2-hydroxypropionamide, N-ethyl-N,2-dimethyl-2-hydroxy Examples thereof include propionamide and N, N-diethyl-2-hydroxy-2-methylpropionamide.

Among the nitrogen-containing polar organic solvents represented by the formula (S1), specific examples of the case where ^RS3 is a group represented by the formula (S1-2) are N, N, N', N'-tetra. Examples thereof include methylurea, N, N, N', N'-tetraethylurea and the like.

Among the nitrogen-containing polar organic solvents represented by the above-described formula (S1), the polyamic acid has good solubility and the pigment is easily and stably dispersed. Therefore, N, N, N', N'-tetramethylurea and N, N, N', N'-tetraethylurea are preferable, and N, N, N', N'-tetramethylurea are particularly preferable.

When the dispersion medium contains a dispersion medium other than the aprotic polar organic solvent such as an aprotic polar organic solvent or a non-polar solvent, suitable examples of the other solvent include water; ethylene glycol, diethylene glycol, and the like. Triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propylene glycol, isopropylene glycol, polypropylene glycol, pentamethylene glycol, trimethylene glycol, butylene glycol, isobutylene glycol, Thiodiglycol, 1,2-hexanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4 -Polyhydric alcohols such as pentandiol, 1,3-propanediol, 1,4-butanediol, 1,7-heptanediol, 1,8-octanediol, and 2-butene-1,4-diol and glycerin. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-tert-butyl 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 Mono-tert-Butyl Ether, Triethylene Glycol Monoethyl Ether, Triethylene 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, Di Propylene glycol monopropyl ether and dipropylene glycol Examples thereof include polyhydric alcohol ethers such as colemonoisopropyl ether.

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

[Other ingredients]
The pigment dispersion liquid may contain various additives conventionally blended in the pigment dispersion liquid. Examples of such additives include viscosity regulators, surfactants, antioxidants, UV absorbers, pH regulators, antifoaming agents and the like. These additives are conventionally used in the same amount as those conventionally blended in the pigment dispersion liquid, as long as they do not adversely affect the properties of the pigment dispersion liquid and the coloring composition.

The pigment dispersion liquid described above contains a pigment that is well and stably dispersed, and is blended with the hollow silica described later in the coloring composition to form a colored film having excellent low reflectivity and heat resistance. Gives a possible coloring composition.

[Pigment dispersion method]
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 or more and 99% by mass or less, and then the pigment is added in the dispersion medium. Disperse.

As the dispersion device used for the pigment dispersion treatment, various dispersion devices conventionally used for pigment dispersion can be used. Specific examples of suitable dispersers include kneaders, salt milling kneaders, roll mills, planetary mixers, paint shakers, ball mills, sand mills, attritors, pearl mills, coball mills, homomixers, homogenizers, wet jet mills, high pressure homogenizers, and ultrasonic waves. A homogenizer or the like can be used. When the disperser uses media, glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads and the like can be used as the media.

When performing dispersion treatment with an ultrasonic homogenizer, a pigment pre-dispersed using the above-mentioned kneader, salt milling kneader, roll mill, planetary mixer, homomixer, homogenizer, wet jet mill, high-pressure homogenizer, bead mill, or the like in advance. It is preferable to use.

When dispersing the pigment, the dispersion medium containing the pigment, the polyamic acid, and the aprotic polar organic solvent is used in an amount in the above range, respectively.

By dispersing the pigment by the method described above, a carbon black dispersion liquid that can disperse the pigment well and stably in a short time and gives a coating film having excellent heat resistance and a coloring composition that gives a molded product is prepared. can.

<Hollow silica>
The coloring composition comprises hollow silica. The refractive index of hollow silica is significantly lower than the refractive index of 1.46 of ordinary silica. This is because hollow silica contains air having a low refractive index of 1.0.
Therefore, by using a coloring composition containing hollow silica, a colored film having excellent low reflectivity can be formed.
The refractive index of the hollow silica is typically 1.2 or more and 1.3 or less.

Conventionally known hollow silica can be blended into the coloring composition without particular limitation. The hollow silica may be a commercially available product or a synthetic product.
The hollow silica is preferably selected from known hollow silica in consideration of the particle size and the refractive index.

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

The content of hollow silica in the coloring composition is not particularly limited as long as it does not impair the object of the present invention. The content of hollow silica in the coloring composition is preferably 0.5% by mass or more and 25% by mass or less with respect to the total solid content in the coloring composition from the viewpoint that it is easy to form a coloring film having excellent low reflectivity. It is more preferably 1% by mass or more and 15% by mass or less, and particularly preferably 2% by mass or more and 8% by mass or less.

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

The base material component is a component that imparts shapeability to the coloring composition so that the coloring composition can be formed into a film shape or various three-dimensional three-dimensional shapes. The base material component is not particularly limited as long as it is a material capable of imparting the desired excipient property to the coloring composition. As the base material component, a resin material made of a polymer compound is typically used, or a reactive low molecular weight compound that is crosslinked by heating to form a polymer compound is used.

As the base material component contained in the coloring composition, precursors used for forming cured products of various thermosetting resins can be used. By heating the coloring composition containing the precursor of the cured product of the thermosetting resin and the pigment dispersion liquid described above, the colored cured product is formed as a colored molded product. Specific examples of the precursor of the cured product of the thermosetting resin that can be blended in the coloring composition or the resin material composed of the polymer compound include epoxy resin, phenol resin, polyimide resin, polybenzoxazole resin, urea resin, and melamine. Precursors of thermosetting resins such as resins, alkyd resins, and polyurethane resins; polyacetal resin, polyamide resin, polycarbonate resin, polyester resin (polybutylene terephthalate, polyethylene terephthalate, polyarylate, etc.), FR-AS resin, FR-ABS. Resin, AS resin, ABS resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, fluororesin, polyimide resin, polyamideimide resin, polyamide bismaleimide resin, polyetherimide resin , Polybenzoxazole resin, polybenzothiazole resin, polybenzoimidazole resin, silicone resin, BT resin, polymethylpentene, ultrahigh molecular weight polyethylene, FR-polypropylene, (meth) acrylic resin (polymethylmethacrylate, etc.), polystyrene, etc. Resin material; The precursor or resin material used to form such a cured product is blended into the coloring composition together with a curing agent, a cross-linking agent, a curing catalyst and the like, if necessary. The curing agent may be a heat-sensitive curing agent or a photosensitive curing agent. When a heat-sensitive curing agent is used, a colored film is formed by heating a coating film made of a colored composition. When a photosensitive curing agent is used, a colored film is formed by exposing a coating film made of a colored composition.

For example, when the cured product is an epoxy resin, the colored composition contains an epoxy compound as a base material component and a curing agent. When the cured product is a phenol resin, the coloring composition contains phenols such as phenol and cresol as a base material component, aldehydes such as formaldehyde as a cross-linking agent, hexamethylenetetramine and the like. When the cured product is a polyimide resin, a polyamic acid is blended as a base material component in the coloring composition.

From the viewpoint of mechanical properties, solvent resistance, chemical resistance and the like of the colored molded product to be formed, the colored composition preferably contains an epoxy compound or a polyamic acid as a base material component. Further, a coloring composition containing a polyamic acid as a base material component is more preferable from the viewpoint of dispersibility of the pigment in the coloring film. The content of the polyamic acid is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more and 100% by mass with respect to the entire base material component (precursor or resin material) contained in the coloring composition. % Or less is more preferable. As the polyamic acid used as the base material component, the same polyamic acid as the polyamic acid contained in the pigment dispersion can be used.

When performing lithography patterning or the like using the coloring composition, the coloring composition preferably contains, for example, a polymerizable compound (A) having a radically polymerizable group as a base material component. Further, the coloring composition preferably contains a 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 is 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, and the polyfunctional compound is preferable.
As the polymerizable compound (A) having a radically polymerizable group, a compound having one or more (meth) acryloyl groups such as a (meth) acrylate compound and a (meth) acrylamide compound is preferable, and one or more (meth) acryloyl groups. The (meth) acrylate compound having the above is more preferable.

Examples of the monofunctional compound having a radically polymerizable group include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, and butoxymethoxymethyl ( Meta) acrylamide, N-methylol (meth) 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-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl ( Meta) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyl Oxy-2-hydroxypropylphthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, Examples thereof include 2,2,3,3-tetrafluoropropyl (meth) acrylate and half (meth) acrylate of phthalic acid derivative. These monofunctional compounds can be used alone or in combination of two or more.

Examples of the polyfunctional compound having a radically polymerizable group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polypropylene glycol di (meth). Acrylate, Butylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, Dimethyloltricyclodecanedi (meth) acrylate, Trimethylol propanthry (meth) acrylate , Glycerindi (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-Bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (Meta) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate. , Urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, poly. Examples thereof include polyfunctional compounds such as a condensate of a valent alcohol and N-methylol (meth) acrylamide, triacrylic formal and the like. These polyfunctional compounds can 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. It is preferably 1% by mass or more and 20% by mass or less.

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

Specific examples of the photoradical polymerization initiator useful as a radical polymerization initiator capable of polymerizing the polymerizable compound (A) having a radically polymerizable group include 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl. -1-Phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2 -Hydroxy-2-methylpropane-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one , Bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-) Morphorinophenyl) -butane-1-one, O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazole-3-yl] etanone oxime, (9-ethyl-6- Nitro-9H-carbazole-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl] Metanon O-acetyloxime, 2- (benzoyloxyimino) -1- [4- (phenylthio) ) Phenyl] -1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-dimethylamino Ethyl benzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamyl benzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethylketal, 1-phenyl- 1,2-Propandione-2- (O-ethoxycarbonyl) oxime, o-Methyl benzoyl benzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxy Thioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3- Diphenylanthraquinone, azobisi Sobutyronitrile, benzoylperoxide, cumenehydroperoxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolylni Phenyl, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, 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, thioxanthone, 2- Methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, pentyl-4-dimethylaminobenzoate, 9-phenylacridin, 1,7-bis- (9-acrydinyl) heptane, 1,5-bis- (9-acrydinyl) pentane , 1,3-bis- (9-acrydinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s -Triazine, 2- [2- (5-methylfuran-2-yl) ether] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (fran-2-yl) ether]- 4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ether] -4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(3,4-Dimethoxyphenyl) ether] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-ethoxystyryl) -4,6-bis (trick) Loromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-) Phenyl) Phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-) Examples thereof include 4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine and the like. These photoradical polymerization initiators can be used alone or in combination of two or more.

Among the photoradical polymerization initiators, the oxime ester compound is preferable in terms of the sensitivity of the curable composition.
As the oxime ester compound, a compound having a partial structure represented by the following formula (b1) is preferable.

（式（ｂ１）中、
ｎ１は、０、又は１であり、
Ｒ^ｂ２は、一価の有機基であり、
Ｒ^ｂ３は、水素原子、置換基を有してもよい炭素原子数１以上２０以下の脂肪族炭化水素基、又は置換基を有してもよいアリール基であり、
＊は結合手である。）

(In equation (b1),
n1 is 0 or 1,
R ^b2 is a monovalent organic group and
R ^b3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.
* Is a bond. )

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

Examples of the compound having a partial structure represented by the formula (b1) include a compound represented by the following formula (b2).

（式（ｂ２）中、Ｒ^ｂ１は、下記式（ｂ３）、（ｂ４）、又は（ｂ５）で表される基であり、
ｎ１は、０、又は１であり、
Ｒ^ｂ２は、一価の有機基であり、
Ｒ^ｂ３は、水素原子、置換基を有してもよい炭素原子数１以上２０以下の脂肪族炭化水素基、又は置換基を有してもよいアリール基である。）

(In the 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 and
R ^b3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. )

（式（ｂ３）中、Ｒ^ｂ４及びＲ^ｂ５は、それぞれ独立に、１価の有機基であり、
ｎ２は、０以上３以下の整数であり、
ｎ２が２又は３の場合、複数のＲ^ｂ５は同一でも異なっていてもよく、複数のＲ^ｂ５は互いに結合して環を形成してもよい。
＊は結合手である。）

(In the formula (b3), R ^b4 and R ^b5 are independently monovalent organic groups, respectively.
n2 is an integer of 0 or more and 3 or less,
When n2 is 2 or 3, the plurality of R ^b5s may be the same or different, and the plurality of R ^b5s may be combined with each other to form a ring.
* Is a bond. )

（式（ｂ４）中、Ｒ^ｂ６及びＲ^ｂ７は、それぞれ独立に、置換基を有してもよい鎖状アルキル基、置換基を有してもよい鎖状アルコキシ基、置換基を有してもよい環状有機基、又は水素原子であり、
Ｒ^ｂ６とＲ^ｂ７とは互いに結合して環を形成してもよく、
Ｒ^ｂ７とフルオレン骨格中のベンゼン環とが互いに結合して環を形成してもよく、
Ｒ^ｂ８は、ニトロ基、又は１価の有機基、であり、
ｎ３は、０以上４以下の整数であり、
＊は結合手である。）

(In the formula (b4), R ^b6 and R ^b7 each independently have a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, and a substituent. May be a cyclic organic group, or a hydrogen atom,
R ^b6 and R ^b7 may be combined with each other to form a ring.
R ^b7 and the benzene ring in the fluorene skeleton may be bonded to each other to form a ring.
R ^b8 is a nitro group or a monovalent organic group.
n3 is an integer of 0 or more and 4 or less.
* Is a bond. )

（式（ｂ５）中、Ｒ^ｂ９は、１価の有機基、ハロゲン原子、ニトロ基、又はシアノ基であり、
Ａは、Ｓ又はＯであり、
ｎ４は、０以上４以下の整数であり、
＊は結合手である。）

(In the 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.
* Is a bond. )

In formula (b3), R ^b4 is a monovalent organic group. R ^b4 can be selected from various organic groups as long as it does not impair the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms are selected. Is more preferred. The number of carbon atoms of the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less.
Preferable examples of R ^b4 are an alkyl group which may have a substituent having 1 or more and 20 or less carbon atoms, a cycloalkyl group which may have a substituent having 3 or more and 20 or less carbon atoms, and a carbon atom. A saturated aliphatic acyl group which may have a substituent of 2 or more and 20 or less, an alkoxycarbonyl group which may have a substituent of 2 or more and 20 or less of carbon atoms, and a phenyl group which may have a substituent. , A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group which may have a substituent and has 7 or more and 20 or less carbon atoms, and a substituent. A naphthyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group which may have a substituent and has 11 or more and 20 or less carbon atoms, a substituent. Examples thereof include a heterocyclyl group which may have a group and a heterocyclylcarbonyl group which may have a substituent.

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

When R ^b4 has a substituent, suitable examples of the substituent include a hydroxyl group, an alkyl group having 1 or more and 20 or less carbon atoms, an alkoxy group having 1 or more and 20 or less carbon atoms, and 2 or more and 20 or less carbon atoms. An aliphatic acyl group, an aliphatic acyloxy group having 2 or more and 20 or less carbon atoms, a phenoxy group, a benzoyl group, a benzoyloxy group, and a group represented by -PO (OR) ₂ (R has 1 or more and 6 or less carbon atoms). Alkyl group), halogen atom, cyano group, heterocyclyl group and the like.

When R ^b4 is a heterocyclyl group, the heterocyclyl group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. When R ^b4 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or fused between such monocycles, or between such monocycles and a benzene ring. It is a heterocyclyl group. When the heterocyclyl group is a fused ring, the number of rings is up to 3. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isooxazole, thiazole, thiaziazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene and indole. Isoindole, indole, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxalin, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. Will be.
When R ^b4 is a heterocyclyl group, examples of the substituent that the heterocyclyl group may have include a hydroxyl group, an alkoxy group having 1 or more and 6 or less carbon atoms, a halogen atom, a cyano group, a nitro group and the like.

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

In formula (b3), R ^b5 is a monovalent organic group. R ^b5 can be selected from various organic groups as long as it does not impair the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms are selected. Is more preferred. The number of carbon atoms of the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less.
Examples of a monovalent organic group suitable for R ^b5 include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a benzoyloxy which may have a substituent. A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, and a substituent. It has a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent. It may be a heterocyclylcarbonyl group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, a cyano group, an HX ₂ C- or H ₂ . Examples thereof include a substituent containing a group represented by XC- (where X is 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, and more preferably 1 or more and 6 or less. When R ^b5 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ^b5 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, Examples thereof include an n-decyl group and an isodecyl group. Further, 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 a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

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, and more preferably 1 or more and 6 or less. When R ^b5 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^b5 is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group and n. -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , Trt-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. 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 group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.

When R ^b5 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. Specific examples of the case where 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. Specific examples of the case where R ^b5 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group and the like.

When R ^b5 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, and more preferably 2 or more and 7 or less. Specific examples of the case where R ^b5 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanol group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group and n. -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadeca Examples thereof include a noyl group and an n-hexadecanoyl group. Specific examples of the case where R ^b5 is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoloxy group, an n-pentanoyloxy group, and 2, 2-Dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like can be mentioned.

When R ^b5 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less. Specific examples of the case where R ^b5 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group and sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples thereof include an isodecyloxycarbonyl group.

When R ^b5 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. When R ^b5 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. Specific examples of the case where 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 of the case where R ^b5 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group, and 2- (β-naphthyl) ethyl group. .. 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 heterocyclyl group, the heterocyclyl group is the same as when R ^b4 in the formula (b3) is a heterocyclyl group, and the heterocyclyl group may further have a substituent.
When R ^b5 is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ^b5 is a heterocyclyl group.

When R ^b5 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and the like. Saturated aliphatic acyl group having 2 or more and 21 or less carbon atoms, phenyl group which may have a substituent, benzoyl group which may have a substituent, and 7 or more and 20 carbon atoms which may have a substituent. The following phenylalkyl group, naphthyl group which may have a substituent, naphthoyl group which may have a substituent, naphthylalkyl group which may have a substituent and has 11 or more and 20 or less carbon atoms, and heterocyclyl. The group etc. can be mentioned. Specific examples of these suitable organic groups are the same as for R ^b5 . Specific examples of the amino group substituted with the organic group 1 or 2 include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group and n-. Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naftylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples thereof include a decanoyylamino group, a benzoylamino group, an α-naphthoylamino group, a β-naphthoylamino group and the like.

When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^b5 further have a substituent, the substituent includes a substituent represented by HX ₂ C- or H ₂ XC- (for example, HX). ₂ A halide alkoxy group containing a group represented by C- or H ₂ XC-, an alkyl halide group containing a group represented by HX ₂ C- or H ₂ XC-), having 1 or more and 6 or less carbon atoms. Alkyl group, alkoxy group with 1 to 6 carbon atoms, saturated aliphatic acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated fat with 2 to 7 carbon atoms Group acyloxy group, monoalkylamino group having an alkyl group with 1 to 6 carbon atoms, dialkylamino group having an alkyl group with 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group , Benzoyl group, halogen, nitro group, cyano group and the like. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^b5 further have a substituent, the number of the substituents is not limited as long as the object of the present invention is not impaired, and is preferably 1 or more and 4 or less. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^b5 have a plurality of substituents, the plurality of substituents may be the same or different.

When the benzoyl group contained in R ^b5 further has a substituent, the substituent includes an alkyl group having 1 or more and 6 or less carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, and a 2-tenoyl group. (Thiophen-2-ylcarbonyl group), furan-3-ylcarbonyl group, phenyl group and the like can be mentioned.

Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom and the like, and a fluorine atom is preferable.

Substituents containing the group represented by HX ₂ C- or H ₂ XC- include halogenated alkoxy groups containing the group represented by HX ₂ C- or H ₂ XC-, HX ₂ C- or H ₂ XC. A group having a halogenated alkoxy group including a group represented by-, an alkyl halide group containing a group represented by HX ₂ C- or H ₂ XC-, and represented by HX ₂ C- or H ₂ XC-. Examples thereof include a group having an alkyl halide group including a group, and an alkoxy halide group containing a group represented by HX ₂ C- or H ₂ XC-, or a group represented by HX ₂ C- or H ₂ XC-. It is more preferable that the group has a halogenated alkoxy group including a group.

Groups having an alkyl halide group including a group represented by HX ₂ C- or H ₂ XC- are substituted with an alkyl halide group containing a group represented by HX ₂ C- or H ₂ XC-. A cycloalkyl group substituted with an alkyl halide group (eg, cyclopentyl group, cyclohexyl) including an aromatic group (eg, phenyl group, naphthyl group, etc.), a group represented by HX ₂ C- or H ₂ XC-. Groups and the like) are mentioned, and it is preferable that it is an aromatic group substituted with an alkyl halide group containing a group represented by HX ₂ C- or H ₂ XC-.

The group having a halogenated alkoxy group including a group represented by HX ₂ C- or H ₂ XC- is substituted with a halogenated alkoxy group containing a group represented by HX ₂ C- or H ₂ XC-. Alkyl groups (eg, methyl groups, ethyl groups, etc.) substituted with halogenated alkoxy groups, including aromatic groups (eg, phenyl groups, naphthyl groups, etc.), groups represented by HX ₂ C- or H ₂ XC-. , N-propyl group, i-propyl group, etc.), cycloalkyl group substituted with halogenated alkoxy group including group represented by _HX2C- or _H2XC- (eg, cyclopentyl group, cyclohexyl group, etc.) ) And the like, and it is preferable that it is an aromatic group substituted with a halogenated alkoxy group containing a group represented by HX ₂ C- or H ₂ XC-.

Further, 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 may have an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, or a substituent on the aromatic ring. A good phenylthioalkyl group is preferred. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is the most preferable. preferable. Among the phenyl groups that may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. 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, a cyclopentylethyl group is preferable. 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 that may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

In the group represented by the formula (b3), when a plurality of R ^b5s are present and the plurality of R ^b5s are bonded to each other to form a ring, examples of the formed ring include a hydrocarbon ring and a heterocycle. Be done. Examples of the heteroatom contained in the heterocycle include N, O and S. As the ring formed by bonding a plurality of R ^b5 to each other, an aromatic ring is particularly preferable. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle. As such an aromatic ring, an aromatic hydrocarbon ring is preferable. Specific examples of the case where a plurality of R ^b5s are bonded to each other to form a benzene ring in the formula (b3) are shown below.

In the group represented by the formula (b4), R ^b8 is a nitro group or a monovalent organic group. R ^b8 is attached to a 6-membered aromatic ring on the fused ring in the formula (b4), which is different from the aromatic ring attached to the group represented by − (CO) _n1 −. In the formula (b4), the binding position of R ^b8 is not particularly limited. When the group represented by the formula (b4) has one or more R ^b8s , one of the one or more R ^b8s is fluorene because the compound represented by the formula (b4) can be easily synthesized. It is preferable to bind to the 7th position of the skeleton. That is, when the group represented by the formula (b4) has 1 or more R ^b8 , the group represented by the formula (b4) is preferably represented by the following formula (b6). When there are a plurality of R ^b8s , the plurality of R ^b8s may be the same or different.

（式（ｂ６）中、Ｒ^ｂ６、Ｒ^ｂ７、Ｒ^ｂ８、ｎ３は、それぞれ式（ｂ４）におけるＲ^ｂ６、Ｒ^ｂ７、Ｒ^ｂ８、ｎ３と同様である。）

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

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

In formula (b4), R ^b6 and R ^b7 have a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, and a cyclic group which may have a substituent, respectively. It is an organic group or a hydrogen atom. R ^b6 and R ^b7 may be coupled to each other to form a ring. Among these groups, as R ^b6 and R ^b7 , a chain alkyl group which may have a substituent is preferable. When R ^b6 and R ^b7 are chain alkyl groups which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched chain alkyl group.

When R ^b6 and R ^b7 are chain alkyl groups having no substituent, 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. preferable. Specific examples of cases where R ^b6 and R ^b7 are chain alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , N-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl Examples thereof include a group, an isononyl group, an n-decyl group, and an isodecyl group. Further, when R ^b6 and R ^b7 are alkyl groups, 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 a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When R ^b6 and R ^b7 are chain alkyl groups having a substituent, 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 number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.

The substituent that the alkyl group may have is not particularly limited as long as it does not impair the object of the present invention. Preferable examples of the substituent include an alkoxy group, a cyano group, a halogen atom, an alkyl halide group, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as in the preferred example when R ^b8 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like. Specific examples of the heterocyclyl group are the same as in the preferred example when R ^b8 is a heterocyclyl group. When R ^b8 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, 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, and more preferably 1 or more and 6 or less.

When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The number of preferred substituents depends on the number of carbon atoms of 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 chain alkoxy groups having no substituent, 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. preferable. Specific examples of cases where R ^b6 and R ^b7 are chain alkoxy groups include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group and a tert. -Butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, Examples thereof include sec-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. When R ^b6 and R ^b7 are alkoxy groups, 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 group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.

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 cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^b6 and R ^b7 are cyclic organic groups, the substituents that the cyclic organic group 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, is the aromatic hydrocarbon group a phenyl group or a group formed by bonding a plurality of benzene rings via a carbon-carbon bond? , It is preferable that the group is 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 rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited. 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like.

When R ^b6 and R ^b7 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group 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, and more preferably 3 or more and 10 or less. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, Examples thereof include a tetracyclododecyl group and an adamantyl group.

When R ^b6 and R ^b7 are heterocyclyl groups, the same group as the heterocyclyl group as R ^b5 in the formula (b3) can be mentioned.

R ^b6 and R ^b7 may be coupled to each other to form a ring. The group consisting of the rings formed by R ^b6 and R ^b7 is preferably a cycloalkylidene group. When R ^b6 and R ^b7 are bonded to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring.

When forming a ring with R ^b7 and a benzene ring having a fluorene skeleton, the ring may be an aromatic ring or an aliphatic ring.

When the group formed by binding R ^b6 and R ^b7 is a cycloalkylidene group, the cycloalkrylidene group may be condensed with one or more other rings. Examples of rings that may be fused with a cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, and a pyridine. Rings, pyrazine rings, pyrimidine rings and the like can be mentioned.

Among the R ^b6 and R ^b7 described above, examples of suitable groups include groups represented by the formulas ^{−A1 −A2} . In the formula, A ¹ is a linear alkylene group, and A ² is an alkoxy group, a cyano group, a halogen atom, an alkyl halide group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms of the linear alkylene group of A ¹ is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ² is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable. When A ² is an alkyl halide group, the halogen atom contained in the alkyl halide group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom or a bromine atom. The alkyl halide group may be linear or branched, preferably linear. When A ² is a cyclic organic group, the example of the cyclic organic group is the same as that of the cyclic organic group that R ^b6 and R ^b7 have as a substituent. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are similar to the alkoxycarbonyl group that R ^b6 and R ^b7 have as substituents.

Suitable specific examples of R ^b6 and R ^b7 are alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl. Group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -N-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkyl alkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n -Cyanoalkyl groups such as pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl Phyls such as groups, 4-phenyl-n-butyl groups, 5-phenyl-n-pentyl groups, 6-phenyl-n-hexyl groups, 7-phenyl-n-heptyl groups, and 8-phenyl-n-octyl groups. Alkyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -Heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl- Cycloalkylalkyl groups such as n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxy Carbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxy Carbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-etoki An alkoxycarbonylalkyl group such as a sicarbonyl-n-heptyl group and an 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5- Chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4- Bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-tri Examples thereof include a fluoropropyl group and an alkyl halide group such as a 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Among the above-mentioned suitable groups as R ^b6 and R ^b7 are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group and 2-phenylethyl group. 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5-hepta It is a fluoro-n-pentyl group.

In the formula (b5), A is particularly preferably S because it is easy to obtain a photopolymerization initiator having excellent 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 as long as the object of the present invention is not impaired. As the organic group, a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms are selected. Is more preferred. The number of carbon atoms of the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less.
A preferred example of the case where R ^b9 is an organic group in the formula (b5) is a group similar to the monovalent organic group as R ^b5 in the formula (b3).

In R ^b9 , it is substituted with a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, and a phenyl group. Benzoyl group; nitro group; benzofuranylcarbonyl group which may have a substituent is preferable, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazine-1-yl) phenylcarbonyl group. A 4- (phenyl) phenylcarbonyl group is more preferred.

Further, in the 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 a para position with respect to the bond where the phenyl group to which R ^b9 is bonded is bonded to an oxygen atom or a sulfur atom.

In the formulas (b1) and (b2), the monovalent organic group as R ^b2 is not particularly limited as long as it does not impair the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms are selected. Is more preferred. The number of carbon atoms of the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less.
A preferred example of the monovalent organic group as R ^b2 is a group similar to the monovalent organic group as R ^b5 in the formula (b3). Specific examples of these groups are the same as those described for R ^b5 in the formula (b3).
Further, 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 substituent which the phenoxyalkyl group and the phenylthioalkyl group may have is the substitution when the phenyl group, the naphthyl group and the heterocyclyl group contained in R ^b5 in the formula (b3) further have a substituent. Same as the group.

Among the organic groups, as R ^b2 , a substituent including the group represented by HX ₂ C- or H ₂ XC-, an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a substituent, or Cycloalkylalkyl groups and phenylthioalkyl groups which may have a substituent on the aromatic ring are preferable. An alkyl group, a phenyl group which may have a substituent, the number of carbon atoms of a cycloalkyl group contained in a cycloalkylalkyl group, the number of carbon atoms of an alkylene group contained in a cycloalkylalkyl group, a cycloalkylalkyl group, and an aromatic group. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the ring, or the phenylthioalkyl group which may have a substituent on the aromatic ring is described in the formula (b3). ) Is the same as R ^b5 .

Further, as R ^b2 , a group represented by ^{−A3 -} CO—O—A4 is also preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. ^A4 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.

Preferable 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 are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl. Examples thereof include a group, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, a β-naphthylmethyl group and the like.

Preferable specific examples of the group represented by -A ³ -CO-O-A ⁴ are 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n. -Butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl Group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, 3-phenoxycarbonyl-n-propyl group and the like.

（式（ｂ７）及び（ｂ８）中、Ｒ^ｂ１０及びＲ^ｂ１１は、それぞれ独立に、１価の有機基であり、
ｎ５は０以上４以下の整数であり、
Ｒ^ｂ１０及びＲ^ｂ１１がベンゼン環上の隣接する位置に存在する場合、Ｒ^ｂ１０とＲ^ｂ１１とが互いに結合して環を形成してもよく、
Ｒ^ｂ１２は、１価の有機基であり、
ｎ６は１以下８以下の整数であり、
ｎ７は１以上５以下の整数であり、
ｎ８は０以上（ｎ７＋３）以下の整数である。） Further, as R ^b2 , a group represented by the following formula (b7) or (b8) is also preferable.

(In the formulas (b7) and (b8), R ^b10 and R ^b11 are independently monovalent organic groups, respectively.
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 and
n6 is an integer of 1 or less and 8 or less.
n7 is an integer of 1 or more and 5 or less,
n8 is an integer of 0 or more (n7 + 3) or less. )

The organic groups as R ^b10 and R ^b11 in the formula (b7) are the same as those of R ^b8 in the formula (b4). R ^b10 includes a halogenated alkoxy group containing a group represented by HX ₂ C- or H ₂ XC-, an alkyl halide group containing a group represented by HX ₂ C- or H ₂ XC-, an alkyl group or an alkyl group. A phenyl group is preferred. When R ^b10 and R ^b11 are combined 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) in which R ^b10 and R ^b11 form a ring include a naphthalene-1-yl group and 1,2,3,4-. Examples thereof include tetrahydronaphthalene-5-yl groups.
In the above formula (b7), n7 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

In the above formula (b8), R ^b12 is an organic group. Examples of the organic group include groups similar to the organic group described for R ^b8 in the formula (b4). Among the organic groups, an alkyl group is preferable. 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 are preferably exemplified, and among these, a methyl group is more preferable.

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

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

In the formulas (b1) and (b2), R ^b3 includes a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-cyclopentylethyl group and a 2-cyclobutylethyl group. Cyclohexylmethyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group and the like are preferably exemplified, and among these, methyl group or phenyl group is more preferable.

Preferable specific examples of the compound represented by the formula (b2) and having a group represented by the formula (b3) as R ^b1 include the following compounds.

Preferable specific examples of the compound represented by the formula (b2) and having a group represented by the formula (b4) as R ^b1 include the following compounds.

Preferable specific examples of the compound represented by the formula (b2) and having a group represented by the formula (b5) as R ^b1 include the following compounds.

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% by mass or more and 30% by mass or less, and 1% by mass. % Or more and 25% by mass or less are preferable.

When the base material component 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 component to give a thermosetting colored molded body. When the coloring composition is a composition for giving a polyimide resin containing a polyamic acid as a base material component, 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. To.

Since the coloring composition described above contains the pigment dispersion liquid described above, the coloring film formed by using the coloring composition is heated to a high temperature such as 120 ° C. or higher and 350 ° C. or lower. Is also hard to discolor. Further, the cured film formed by using the coloring composition described above exhibits a low reflectance of less than 6%.

<Organic solvent>
The coloring composition contains the above-mentioned pigment dispersion liquid. Therefore, the coloring composition indispensably contains an organic solvent as a dispersion medium derived from the pigment dispersion liquid. The coloring composition may contain only an organic solvent as a component of the pigment dispersion liquid, or may further contain an organic solvent in addition to the organic solvent blended as a component of the pigment dispersion liquid.
The type of organic solvent that can be contained in the coloring composition is not particularly limited as long as the desired effect is not impaired. As the organic solvent that can be contained in the coloring composition, a solvent similar to the organic solvent that can be contained in the pigment dispersion 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% by mass or more and 40% by mass or less, more preferably 2% by mass or more and 30% by mass or less, and further preferably 3% by mass or more and 20% by mass or less.

A colored composition can be obtained by uniformly mixing each of the components described above in a desired ratio.

≪How to form a colored film≫
A colored film can be formed by drying, or drying and curing the film made of the above-mentioned coloring composition.
As a preferable method for forming the colored film, the above-mentioned coloring composition is applied onto a substrate to form a coating film.
Drying or drying and curing the coating film,
The method including is mentioned.

The method of applying the coloring composition is not particularly limited. For example, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or a slit coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater is used to apply a coloring composition onto a substrate. A coating film can be formed by applying the coating to 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 so that, for example, a colored film having a film thickness of preferably 50 nm or more and 20 μm or less, more preferably 500 nm or more and 10 μm or less is formed.

The coating film thus formed is then dried or dried and cured.
The method of drying is not particularly limited. For example, the coating film is dried by baking the coating film or placing the coating film under reduced pressure conditions.
The bake temperature is appropriately determined in consideration of the boiling point of the solvent (S) and the like. Baking may be performed at a low temperature under reduced pressure conditions.

The baking method is not particularly limited, and examples thereof include 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 for 60 seconds or longer and 500 seconds or lower using a hot plate.

When the coloring composition contains a photosensitive curing agent and a substrate component that is cured by the curing agent, the coating film is formed by the above method and then cured by exposing the coating film. A colored film can be obtained.

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

When the coloring composition contains a thermosetting base material component such as polyamic acid, or contains a heat-sensitive curing agent and a base material component cured by the curing agent in combination, the above-mentioned A cured film can be obtained by heating the coating film after forming the coating film by the method.
The heating temperature is appropriately determined in consideration of the type of the base material component and the type of the curing agent. As the heating conditions, for example, 120 ° C. or higher and 350 ° C. or lower, preferably 150 ° C. or higher and 350 ° C. or lower are preferable. 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.

According to the above method, a colored film having low reflectivity and excellent heat resistance can be formed.

Hereinafter, the present invention will be described in detail with reference to Examples, but the scope of the present invention is not limited to these Examples.

[Preparation Example 1: Preparation of carbon black into which an acidic group has been introduced]
Add 550 g of untreated carbon black (P1, Regal 250R, Cabot), 31.5 g of sulfanilic acid, and 1000 g of ion-exchanged water to a reaction vessel with a jacket and a stirrer set to a jacket temperature of 60 ° C. rice field. A solution prepared by dissolving 12.6 g of sodium nitrite in 100 g of deionized water is added to a Brow mixer, and then the mixture in the mixer is stirred at 60 ° C. and 50 rpm for 2 hours to carry out a diazo coupling reaction. rice field. 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 the diafiltration method using deionized water. Benzenesulfonic acids derived from sulfanilic acid were not detected in the wash water, and it was found that a benzenesulfonic acid group was introduced into carbon black by the diazo coupling reaction. The purified carbon black was dried at 75 ° C. overnight and then pulverized to obtain carbon black (P2) into which a benzenesulfonic acid group was introduced.

[Preparation Example 2: Preparation of carbon black treated with silane coupling agent]
50 g of untreated carbon black (P1) and 200 g of an isopropyl alcohol solution of a silane coupling agent having a concentration of 1.25% by mass were mixed and stirred at 60 ° C. for 3 hours. The suspension containing carbon black after stirring was heated to 100 ° C. to volatilize isopropyl alcohol and by-product methanol to obtain a powder of carbon black (P3) treated with a silane coupling agent. As the silane coupling agent, the silane coupling agent SC-A having the following structure was used.

[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 the acidic group obtained in Preparation Example 1 was introduced P3: Carbon black treated with the silane coupling agent obtained in Preparation Example 2 P4: Titanium nitride (Titanium black)
P5: Tungsten oxide (IV) (WO ₂ )
P6: Copper oxide (II) (CuO)
P7: Manganese dioxide (MnO ₂ )
P8: Iron oxide (Fe ₃ O ₄ )
P9: Perylene pigment P10: Lactam pigment P11: Titanium white (titanium oxide (TIO ₂ ))
P12: Cobalt blue (CoAl ₂ O ₄ )
P13: Bengara (Fe ₂ O ₃ )
P14: C.I. I. Pigment White 7 (ZnS)

In Examples and Comparative Examples, polyamic acids PAA1 to PAA4 having the following constituent units and a commercially available dispersant D1 (DISPERBYK-167 (manufactured by Big Chemie Japan Co., Ltd.)) were used as dispersants. PAA1 and PAA2 correspond to polyamic acids having a structural unit represented by the above formula (a1). PAA3 and PAA4 correspond to polyamic acids having no structural unit represented by the above-mentioned formula (a1).
The polystyrene-equivalent mass average molecular weight of PAA1 is 12000. The polystyrene-equivalent mass average molecular weight of PAA2 is 11000. The polystyrene-equivalent mass average molecular weight of PAA3 is 12000. The polystyrene-equivalent mass average molecular weight of PAA4 is 11000.

In Examples and Comparative Examples, N, N, N', N'-tetramethylurea (TMU), or N-methyl-2-pyrrolidone (NMP), which are aprotic polar organic solvents, are used as the dispersion medium. board.

In the examples and comparative examples, hollow silica particles having an average particle diameter of 60 nm were used.

First, 15 g of the pigment of the type shown in Table 1, 7.5 g of the dispersant of the type shown in Table 1 and 50 g of the organic solvent of the type shown in Table 1 are mixed, and the pigment content in the solid content is increased. A mixed solution having an amount of 67% by mass was obtained. And said. In Comparative Example 2, the pigment dispersion was not used. Then, the obtained mixture was stirred to disperse the pigment. The obtained high-concentration pigment dispersion was diluted with a dispersion medium of the type shown in Table 1 to a solid content concentration of 30% by mass to obtain a pigment dispersion.

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

The heat resistance and reflectance of the cured film formed by using the obtained coloring composition were evaluated according to the following methods. The evaluation results are shown in Table 1.

<Heat resistance evaluation>
The coloring composition was applied onto a wafer substrate by 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 having a film thickness of about 1.0 μm. From the colored film formed by heating to 300 ° C., 5 μg of each sample for heat resistance evaluation was scraped off. Using a sample for heat resistance evaluation, measure with a differential thermal / thermogravimetric measuring device (TG / DTA-6200, manufactured by Seiko Instruments Inc.) under the condition of a temperature rise rate of 10 ° C / min in an air stream. This was done to obtain a TG curve. From the obtained TG curve, the 5% weight loss temperature of the sample was determined. When the 5% weight loss temperature is over 400 ° C, it is judged as 〇, when the 5% weight loss temperature is over 350 ° C and 400 ° C or less, it is judged as Δ, and when the 5% weight loss temperature is 350 ° C or less, it is ×. It was judged as.

<Reflectance evaluation>
The coloring composition was applied onto a wafer substrate by 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 having a film thickness of about 1.0 μm. The reflectance of the formed colored film was determined by a reflectance measuring device (MCPD3700, manufactured by Otsuka Electronics Co., Ltd.) according to the following criteria.
⊚: The reflectance is less than 5%.
〇: The reflectance is 5% or more and less than 6%.
Δ: The reflectance is 6% or more and less than 8%.
X: The reflectance is 8% or more.

According to Examples 1 to 18, a pigment dispersion obtained by dispersing a pigment in an aprotic polar organic solvent using a polyamic acid is further mixed with the polyamic acid as a base material component and hollow silica. In addition, it can be seen that the obtained coloring composition provides a coloring film having low reflectivity and excellent heat resistance. Further, it can be seen from Examples 18 to 36 that further patterning characteristics can be imparted.
On the other hand, according to Comparative Examples 1 and 2, when a commercially available dispersant other than a polyamic acid is used as the dispersant, or when the coloring composition does not contain hollow silica, excellent low reflectivity and excellent properties are obtained. It can be seen that it is difficult to form a colored film that also has heat resistance.

[Examples 19 to 36]
<Patterning evaluation>
Colored compositions of Examples 19 to 36 were prepared by combining the initiators having the following structures and dipentaerythritol hexaacrylates (polymerizable compounds) with respect to the components used in Examples 1 to 18, respectively. The solid content ratio is 45% by mass of the pigment, 30% by mass of the polyamic acid, 1% by mass of the hollow silica, 15% by mass of the initiator, and 9% by mass of the polymerizable compound. The ratio of the polyamic acid is the sum of the dispersant and the base material, and the mass ratio of the pigment and the polyamic acid in the pigment dispersion is 2: 1. The solid content ratio was 10% by mass.

The obtained coloring composition of each example is applied onto a wafer substrate by a spin coater (manufactured by Mikasa, 1H-360S) and then heated at 100 ° C. for 2 minutes to form a cured film having a film thickness of 1 μm. A thick coating film was obtained. The obtained coating film was exposed at 100 mJ / cm ² using an exposure apparatus (TME150RTO manufactured by Topcon). After exposure, it was developed with an aqueous potassium hydroxide solution having a concentration of 0.05% by mass to form a line-and-space pattern. In each composition, a line pattern having a width of 6 μm was obtained. By performing post-baking at 300 ° C. for 1 hour, a good coloring pattern with good heat resistance and low reflectivity could be obtained.

Claims (9)

A coloring composition containing a pigment dispersion and hollow silica.
A coloring composition in which the pigment dispersion liquid contains a pigment, a polyamic acid, and an aprotic polar organic solvent. The polyamic acid has the following formula (a1):

(In the formula (a1), A ¹ is a tetravalent organic group and A ² is a divalent organic group.)
Including the building blocks represented by
The A ¹ is the following formula (a2):

(In the formula (a2), R ^a11 , R ^a12 , and R ^a13 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, and a fluorine atom. a is an integer of 0 or more and 12 or less.)
Is it a group represented by?
The A ² is the following formula (a3):
-Ar ¹ -X-Ar ² -... (a3)
(In the formula (a3), Ar ¹ and Ar ² are each independently a phenyl group or a naphthyl group which may have a substituent, and X is -CO-NH-.)
The coloring composition according to claim 1, which is a group represented by. The coloring composition according to claim 1 or 2, wherein in the polyamic acid, the ratio of the structural units represented by the formula (a1) to all the structural units of the polyamic acid is 30 mol% or more. The aprotic polar organic solvent has the following formula (S1):

(In the formula ( ^S1 ), RS1 and ^RS2 are each independently an alkyl group having 1 or more and 3 or less carbon atoms, and ^RS3 is a hydrogen atom, or the following formula (S1-1) or the following formula (S1). -2):

RS4 is a hydrogen atom or a hydroxyl group, and ^RS5 and ^RS6 are independently hydrogen atoms and alkyl groups having 1 or more and 3 or less carbon atoms, respectively, and ^RS7 and ^R are ^S8 is an independently hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms, and when ^RS3 is a group represented by the formula (S1-1), ^RS2 and ^RS3 are bonded to each other. May form a ring. )
The coloring composition according to any one of claims 1 to 3, which is a nitrogen-containing polar organic solvent represented by. 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, further comprising a base material component. The coloring composition according to claim 6, which contains a polyamic acid as the base material component. A colored film obtained by drying, drying and curing a film made of the coloring composition according to any one of claims 1 to 7. The coloring composition according to any one of claims 1 to 7 is applied onto a substrate to form a coating film.
The coating film may be dried or dried and cured.
A method for forming a colored film including.