JP2024092584A - Pigment composition, film, optical lens, and optical waveguide for use in an infrared sensor or an infrared communication device, or an optical lens for use in an infrared sensor or an infrared communication device - Google Patents

Abstract

The present invention provides a pigment composition for nanoimprints that has a high refractive index, and is excellent in transparency, heat resistance, light resistance, and suitability for nanoimprinting.
SOLUTION
A pigment composition for nanoimprints used in an optical lens used in an infrared sensor or an infrared communication device, or in an optical waveguide used in an infrared sensor or an infrared communication device, the pigment composition comprising at least one pigment selected from the group consisting of a phthalocyanine pigment, a naphthalocyanine pigment, a squarylium pigment, and an indigo pigment, a resin-type dispersant, and a photopolymerizable monomer, the pigment composition having a refractive index of 1.70 or more at 23°C and a wavelength of 940 nm, and having a maximum absorbance of 1.0 or more in the range of 700 to 1200 nm when a film having a thickness of 1.0 μm is formed.
[Selected Figure] Figure 1

Description

The present invention relates to a pigment composition for use in an optical lens for an infrared sensor or an infrared communication device, or an optical waveguide for an infrared sensor or an infrared communication device, as well as a film, an optical lens, and an optical waveguide that contain the pigment composition.

Conventionally, a surface protective layer made of an inorganic or organic material is provided on the surface of glass, film, and sheet used in sensor elements such as CCD and CMOS, and display elements such as displays. In recent years, coating layers in which high and low refractive index layers are alternately laminated have been used for the surface protective layer in order to impart functions such as anti-reflection and optical waveguide. For the high refractive index layer, a high refractive index inorganic film formed by deposition of ceramics such as titania, zirconia, and alumina, or a high refractive index organic film made of aromatic resin is used according to the purpose. However, when a high refractive index inorganic film is used, there are problems such as insufficient adhesion to the substrate and fragility of the film. Therefore, in recent years, a high refractive index organic film has been widely used.

Organic electroluminescence (hereinafter referred to as organic EL) panels, which are attracting attention as next-generation displays, have a laminated structure of inorganic layers made of silicon oxide, silicon nitride, alumina, etc., and organic layers made of organic sealing materials whose main components are acrylic resin and epoxy resin, in order to prevent deterioration of the organic EL elements due to the penetration of moisture and gas from the outside. These inorganic and organic layers are laminated alternately. Here, the smaller the difference in refractive index between the inorganic layer and the organic layer, the higher the refractive index of the organic layer, as this improves the light extraction efficiency. Therefore, there is a demand for organic sealing materials with a high refractive index.

Furthermore, in recent years, molded bodies produced using three-dimensional modeling devices have been widely used in the medical and optical fields. Photocurable resins are used as the molding resins used in three-dimensional modeling (Patent Documents 1 and 2). In particular, for molded bodies of lenses used in medical equipment, microscopes, various cameras, and the like, photo-molding resins with high refractive index are required to make the lenses thinner.

As high refractive index organic materials for the above-mentioned surface protection layers, organic sealants for organic EL panels, and resins for photolithography, resins containing sulfur and resins such as fluorene having a structure in which aromatic rings are conjugated are known (Patent Documents 2, 3, and 4).

Nowadays, sensing and communication using near-infrared rays are becoming widespread, such as in solid-state imaging devices for photographing subjects at night, infrared sensors such as Lidar used for distance measurement, and infrared communication devices that use light propagated through optical waveguides. For lenses and other devices used to focus these rays, it is important to use optical materials with a high refractive index in the near-infrared region.

Patent Document 5 discloses a composition used in the manufacture of infrared transmission filters that block visible light and transmit near-infrared light, and a film obtained using the composition, and describes that the film has a high refractive index in the wavelength range of 800 nm or more. However, the material described in Patent Document 5 does not have sufficient dispersibility of the pigment used, so there remains an issue with the transparency of the film obtained from the composition.

Patent Document 6 discloses a film-like material for optical components that contains an organic dye and shows a high refractive index and high transmittance in the near-infrared region, but the amount of dye added is very small, and a sufficiently high refractive index is not obtained.

Patent Document 7 discloses a resin composition containing a thermoplastic resin and a coloring material that exhibits a high refractive index and high transmittance in the near-infrared region, but the light resistance and heat resistance are insufficient, posing problems in terms of practical use.

JP 2011-157543 A JP 2019-019245 A JP 2000-281787 A JP 2011-168721 A International Publication No. 2019/065475 International Publication No. 2020/085499 WO 2020/138050

Among sensing and communication using near-infrared rays, sensing and communication using light rays of 800 to 1600 nm have become particularly widespread in recent years. In these sensing and communication methods, it is important to use optical materials with a high refractive index, high transparency and high durability for optical lenses for concentrating these light rays and for optical waveguides for propagating these light rays.
However, at present, there has been little progress in the development of high refractive index materials with sufficient durability.

Furthermore, for use in optical lenses for infrared sensors or infrared communication devices, or optical waveguides for infrared sensors or infrared communication devices, it is very useful if the material has suitability for nanoimprinting. Today's infrared sensors are finely processed, and the optical lenses used for these sensors must be very small, such as microlenses. In addition, optical waveguides for infrared communication devices also require fine processing.

Nanoimprinting is known as a method for forming fine patterns on the nanometer order. Nanoimprinting is a method for producing fine patterns such as dome-shaped or stripe-shaped patterns by pressing a mold with a fine pattern onto a pigment composition, curing the pigment composition, and removing the mold. Compared to other microfabrication techniques such as photolithography, the required devices and equipment are simple and inexpensive. Furthermore, the simple process allows products to be manufactured with a high throughput.

Nanoimprinting is broadly divided into photo-nanoimprinting and thermal nanoimprinting, depending on the curing method. Pigment compositions used in nanoimprinting must have high thermosetting or photosetting properties, as well as suitability for transferability, etc.

In view of the above problems, the present invention aims to provide a pigment composition for nanoimprinting that has a high refractive index and is excellent in transparency, heat resistance, light resistance, and suitability for nanoimprinting, for use as a high refractive index material in optical lenses or optical waveguides for infrared sensors or infrared communication devices that use light rays of 800 to 1600 nm.

That is, the present invention provides a pigment composition for use in an optical lens used in an infrared sensor or an infrared communication device, or an optical waveguide used in an infrared sensor or an infrared communication device, the pigment composition comprising at least one pigment selected from the group consisting of a phthalocyanine pigment, a naphthalocyanine pigment, a squarylium pigment, and an indigo pigment, a resin-type dispersant, and a photopolymerizable monomer,
The refractive index at 23° C. and a wavelength of 940 nm is 1.70 or more,
The pigment composition for nanoimprints has a maximum absorbance of 1.0 or more in the range of 700 to 1200 nm when a film having a thickness of 1.0 μm is formed.

The present invention provides a pigment composition that has a high refractive index in the wavelength range of 800 to 1600 nm and is excellent in transparency, heat resistance, light resistance, and suitability for nanoimprinting, for use as a high refractive index material in optical lenses or optical waveguides for infrared sensors or infrared communication devices.

Such a pigment composition of the present invention can be used as an optical material for infrared sensors or infrared communication devices that require a high refractive index in the wavelength region of 800 to 1600 nm, and is particularly suitable for use as an optical material for optical lenses, optical waveguides, etc.

FIG. 1 shows an infrared absorption spectrum of one embodiment of the present invention. FIG. 2 shows an infrared absorption spectrum of one embodiment of the present invention. FIG. 3 shows an infrared absorption spectrum of one embodiment of the present invention. FIG. 4 shows an infrared absorption spectrum of one embodiment of the present invention. FIG. 5 shows an infrared absorption spectrum of one embodiment of the present invention. FIG. 6 shows an infrared absorption spectrum of one embodiment of the present invention. FIG. 7 shows an infrared absorption spectrum of one embodiment of the present invention.

<Regarding the pigment composition of the present invention>
The pigment composition of the present invention contains at least one pigment selected from the group consisting of a phthalocyanine pigment, a naphthalocyanine pigment, a squarylium pigment, and an indigo pigment, a resin-type dispersant, and a photopolymerizable monomer,
The refractive index at 23° C. and a wavelength of 940 nm is 1.70 or more,
The pigment composition for nanoimprints has a maximum absorbance of 1.0 or more in the range of 700 to 1200 nm when a film having a thickness of 1.0 μm is formed.

<Optical Properties of Pigment Composition>
The optical properties of the pigment composition of the present invention will now be described.

First, the pigment composition of the present invention is characterized in that when a film having a thickness of 1 μm is formed, the maximum absorbance in the absorption spectrum from 700 to 1200 nm is 1.0 or more.
After extensive research, the present inventors have found that when a film formed from a pigment composition has very high absorption in the 700-1200 nm wavelength range, it has a high refractive index in the 800-1600 nm wavelength range. This makes it possible to obtain a film with a high refractive index even without containing sulfur atoms or iodine atoms, which are known to contribute to a high refractive index. As for the degree of absorption, in the absorption spectrum of a film with a thickness of 1 μm, the maximum absorbance in the 700-1200 nm range must be 1.0 or more, preferably 2.0 or more, more preferably 3.0 or more, and even more preferably 4.0 or more.

The pigment composition of the present invention has a refractive index at 23°C and a wavelength of 940 nm of 1.70 or more, preferably 1.8 or more, more preferably 1.9 or more, and most preferably 2.0 or more. There is no particular upper limit to the refractive index, but it is preferably 2.5 or less, and more preferably 2.4 or less.

<Nanoimprint method>
Furthermore, the pigment composition of the present invention is suitably used for nanoimprinting and has suitability for nanoimprinting.

In the thermal nanoimprinting method, a curable composition or the like is heated to a temperature equal to or higher than its glass transition temperature or crystalline melting temperature, and then a mold engraved with a concave-convex pattern is pressed against the composition at a pressure of several MPa, followed by release and further cooling to form a patterned substrate.
However, because the mold is heated to high temperatures, there is a concern that distortion may occur in the molded part, causing the position of the fine patterns to shift slightly.

On the other hand, in the photo-nanoimprinting method, a three-dimensional concave-convex pattern engraved on a light-transmitting mold is brought into contact with a liquid curable composition applied onto a substrate, and active energy rays such as ultraviolet rays are irradiated through the mold to photo-cure the curable composition, and finally the mold is released, thereby transferring the mold pattern and forming a fine pattern.
Photo-nanoimprinting is characterized by the ability to create fine patterns with greater precision because a mold is pressed and exposed at or near room temperature.

In addition, etching may be performed as a further process in nanoimprinting. If the above process alone is not sufficient to finely process the pattern, the precision of the fine pattern can be further improved by etching the pattern with chlorine gas or boron trichloride gas.

Pigment compositions used for nanoimprinting are generally in a liquid state at room temperature. In some cases, they are dissolved in a solvent, in which case the solvent is evaporated by spin coating or the like before use. When used for photo-nanoimprinting, the mold needs to be pressed at room temperature or close to it, so if the non-volatile components of the pigment composition are not flexible to a certain extent, they will not penetrate sufficiently into the pattern inside the mold when the mold is pressed, and transferability will tend to be poor. For this reason, it is important that the non-volatile components of the pigment composition have a certain degree of flexibility at room temperature.

<Pigments>
The pigment composition of the present invention contains a pigment in order to have the above optical properties. Pigments have higher heat resistance, light resistance, and chemical resistance than dyes. Light resistance is essential for optical materials used in optical lenses that collect near-infrared rays and optical waveguides that propagate near-infrared rays. In addition, since they are incorporated into various devices and used, it is important that they can withstand high-temperature processes and solvent immersion processes in the manufacturing process, and heat resistance and chemical resistance are required. Since pigments have excellent heat resistance and light resistance, the pigment composition of the present invention can be used as a high refractive index material in infrared sensors or infrared communication devices.

In the pigment composition of the present invention, the pigment content is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 65% by mass or more, based on the total mass of the solid content in the pigment composition.
By making the pigment content 40 mass % or more based on the total mass of the solids in the pigment composition, it is possible to obtain a film that has high absorption in the 700 to 1200 nm range and a high refractive index in the wavelength range of 800 to 1600 nm.
The upper limit of the pigment content is not particularly limited, but is preferably less than 95% by mass in that it provides excellent pigment dispersibility, gives a highly transparent film, and provides excellent stability as a pigment composition.
In this specification, the solid content means all components of the pigment composition excluding volatile components such as organic solvents.

The use of pigments is also important from the viewpoint of content. Dyes are usually dissolved in solvents before use, but when the ratio of the dye to the total mass becomes high, it is prone to crystallization, making it difficult to use after dissolving. When a composition consisting of dye, resin, and solvent contains dye at 40 mass% or more of the total mass of solids, a very large amount of solvent is required relative to the dye and resin in order to dissolve the dye, and it is often difficult to use it as an optical material. In addition, the film becomes fragile and often has poor resistance to chemicals, etc.

The pigment composition of the present invention also contains at least one pigment selected from the group consisting of phthalocyanine pigments, naphthalocyanine pigments, squarylium pigments, and indigo pigments. These pigments are characterized by having strong absorption in the range of 700 to 1200 nm.

<Phthalocyanine pigment or naphthalocyanine pigment>
Examples of the phthalocyanine pigment include a compound represented by the following general formula (1-1) and a compound represented by the following general formula (1-2), and the compound represented by formula (1-1) is preferred.

In formula (1-1) and formula (1-2), X ¹ to X ¹⁶ each independently represent a hydrogen atom or a substituent, and in formula (1-1), M ¹ represents a metal atom or an inorganic compound.
Examples of the substituent represented by X ¹ to X ¹⁶ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an amino group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a heteroarylthio group, an alkylsulfonyl group, an arylsulfonyl group, a heteroarylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a heteroarylsulfinyl group, a ureido group, a phosphoric acid amide group, a hydroxyl group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, etc. Examples include a halogen atom, an alkoxy group, an arylalkoxy group, a heteroarylalkoxy group, an amino group, an alkylthio group, an arylthio group, and a heteroarylthio group. From the viewpoint of increasing the refractive index for near infrared rays, a higher polarization is preferable. As the substituent, an electron-withdrawing group is preferable, and halogens such as F, Cl, Br, and I, a nitro group, a cyano group, etc. are preferable.

Examples of metal atoms represented by ^M1 include Li, Na, Mg, Mn, Fe, Co, Ni, Cu, Zn, Sn, Pb, and Pt. Examples of inorganic compounds include VO, TiO, AlCl, _SiCl2 , and _SnCl2 . In addition, the density of the phthalocyanine compound can be increased as ^M1 coordinated to the phthalocyanine ring moves toward the lower right of the periodic table.

From the viewpoint of increasing the refractive index for near-infrared rays, it is preferable that the phthalocyanine pigment has a high polarization. From this viewpoint, it is preferable that at least one of X ¹ to X ¹⁶ in formula (1-1) and formula (1-2) is a substituent. In addition, the substituent is preferably an electron-withdrawing group, and more preferably a halogen atom such as F, Cl, Br, or I, a nitro group, or a cyano group.

In the present invention, examples of the naphthalocyanine pigment include a compound represented by formula (2-1) and a compound represented by formula (2-2), with the compound represented by formula (2-1) being preferred.

In formula (2-1) and formula (2-2), X ¹ to X ²⁴ each independently represent a hydrogen atom or a substituent. In formula (2-1), M ¹ represents a metal atom or an inorganic compound. Examples of the substituents in X ¹ to X ²⁴ in formula (2-1) and formula (2-2) include the substituents described for X ¹ to X ¹⁶ in formula (2-1). Examples of the metal atom and inorganic compound in M ¹ in formula (2-1) include the metal atom and inorganic compound described for M ¹ in formula (1-1). The density of the naphthalocyanine compound can be increased as M ¹ coordinated to the naphthalocyanine ring moves toward the lower right of the periodic table.
From the viewpoint of increasing the refractive index for near-infrared rays, it is preferable that the naphthalocyanine pigment has a high polarization. From this viewpoint, it is preferable that at least one of X ¹ to X ²⁴ in formula (2-1) and formula (2-2) is a substituent. In addition, the substituent is preferably an electron-withdrawing group, and more preferably a halogen atom such as F, Cl, Br, or I, a nitro group, or a cyano group.

Specific examples of the above phthalocyanine pigments or naphthalocyanine pigments include phthalocyanine, lithium phthalocyanine, sodium phthalocyanine, magnesium phthalocyanine, chloroaluminum phthalocyanine, silicon dichloride phthalocyanine, titanium phthalocyanine, vanadium oxide phthalocyanine, manganese phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, α-type copper phthalocyanine, β-type copper phthalocyanine, ε-type copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, tin dichloride phthalocyanine, lead phthalocyanine, platinum phthalocyanine, nitrile phthalocyanine, and other phthalocyanine compounds, and naphthalocyanine and other naphthalocyanine compounds. Phthalocyanine pigments include C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, C.I. Pigment Green 7, 36, 58, 59, etc. can also be used.

As the phthalocyanine pigment or naphthalocyanine pigment, a phthalocyanine compound or naphthalocyanine compound having a structure represented by the following general formula (3) is also preferred.

<Pigment represented by formula (3)>
General formula (3)

General formula (4)

In the general formula (3), X ₄₀₁ to X ₄₀₈ and Y ₄₀₁ to Y ₄₀₈ each independently represent a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. X ₄₀₁ to X ₄₀₈ may be bonded to each other to form an aromatic ring, and the aromatic ring may have a substituent.
M represents an aluminum atom.
Z ₂ represents -OP(=O)R ₄₀₁ R ₄₀₂ or a polymer moiety containing a monomer unit represented by general formula (4). Here, R ₄₀₁ and R ₄₀₂ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent. In addition, in general formula (4), X is -CONH-R ₃₁₁ -, -COO-R ₃₁₂ -, -CONH-R ₃₁₃ -O-, or -COO-R ₃₁₄ -O-, and R ₃₁₁ to R ₃₁₄ represent an alkylene group, an arylene group, or an alkylene group or arylene group in which the carbon atoms are linked by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. Y represents hydrogen or a methyl group.

The pigment having the structure represented by the general formula (3) is preferably made from a compound represented by the following general formula (3-1) as a raw material.
General formula (3-1)

In the general formula (3-1), for X ₄₀₁ to X ₄₀₈ , Y ₄₀₁ to Y ₄₀₈ , and M, the descriptions for X ₄₀₁ to X ₄₀₈ , Y ₄₀₁ to Y ₄₀₈ , and M in the general formula (3) can be cited.

The "alkyl group" of the alkyl group which may have a substituent includes, for example, a straight-chain or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a n-hexyl group, a n-octyl group, a stearyl group, and a 2-ethylhexyl group. The "alkyl group having a substituent" includes, for example, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, and a 2,4-dichlorobenzyl group.

Examples of the "aryl group" of the aryl group which may have a substituent include a phenyl group, a naphthyl group, and anthryl group.
Examples of the "substituted aryl group" include a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-aminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-hydroxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group.

The "cycloalkyl group" of the cycloalkyl group which may have a substituent is, for example, a cyclopentyl group, a cyclohexyl group, or an adamantyl group.
Examples of the "substituted cycloalkyl group" include a 2,5-dimethylcyclopentyl group and a 4-tert-butylcyclohexyl group.

The "heterocyclic group" of the heterocyclic group which may have a substituent includes a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, and an acridinyl group, and the "heterocyclic group having a substituent" includes a 3-methylpyridyl group, an N-methylpiperidyl group, and an N-methylpyrrolyl group.

Examples of the "alkoxyl group" of the alkoxyl group which may have a substituent include straight-chain or branched alkoxyl groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, a 2,3-dimethyl-3-pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group.
Examples of the "substituted alkoxyl group" include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, and an anthryloxy group.
Examples of the "substituted aryloxy group" include a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, and a 2-methyl-4-chlorophenoxy group.

Examples of the "alkylthio group" of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group.
Examples of the "substituted alkylthio group" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

Examples of the "arylthio group" of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group.
Examples of the "substituted arylthio group" include a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, and a 2-hydroxyphenylthio group.

Examples of the substituent of the aromatic ring which may have a substituent include a halogen atom, a nitro group, a nitrile group, a carboxy group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, and an arylthio group which may have a substituent.

<Phosphorus Compound and Polymer Moiety>
One form of the phthalocyanine represented by general formula (3) is a salt formed between a phosphate group in the phosphorus compound moiety represented by HO-P(=O _{) R401R402} and an aluminum cation in the phthalocyanine moiety, or a salt formed between a phosphate group in the polymer moiety containing the monomer unit represented by general formula (4) and an aluminum cation in the naphthalocyanine moiety.
The raw material of the phosphorus compound portion is, for example, a phosphorus compound represented by the general formula (3-2).
In general formula (3-2), R ₄₂₉ and R ₄₃₀ each independently represent a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent, and R ₄₂₉ and R ₄₃₀ may be bonded to each other to form a ring.

General formula (3-2)

Representative examples of phosphorus compounds include the structures shown below.

Next, the polymer segment containing the monomer unit represented by formula (4) will be described.
The polymer segment is formed by vinyl polymerization of the raw material monomer represented by general formula (4-1). The polymer segment may be formed by using a monomer represented by general formula (4-1) and a monomer other than the monomer represented by general formula (4-1).

General formula (4-1)

In general formula (4-1), X is -CONH-R ₃₁₁ -, -COO-R ₃₁₂ -, -CONH-R ₃₁₃ -O-, or -COO-R ₃₁₄ -O-, and R ₃₁₁ to R ₃₁₄ represent an alkylene group, an arylene group, or an alkylene group or arylene group in which carbon atoms are linked by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-.
Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, a terphenylene group, and an anthrylene group. Examples of R ₃₁₁ to R ₃₁₄ include a methylene group, an ethylene group, a propylene group, and a butylene group. Y represents a hydrogen atom or a methyl group.

Examples of the monomer represented by general formula (4) include (2-(meth)acryloyloxyethyl) acid phosphate, (2-(meth)acryloyloxypropyl) acid phosphate, and (2-(meth)acryloyloxyisopropyl) acid phosphate.

Other monomers include, for example, (meth)acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth)acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth)acrylonitrile, acid group-containing monomers, and thermally crosslinkable group-containing monomers.

Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, t-octyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, acetoxyethyl (meth)acrylate, phenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, Examples of the acrylate include diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monoethyl ether (meth)acrylate, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tribromophenyl (meth)acrylate, and tribromophenyloxyethyl (meth)acrylate.

Examples of crotonate esters include butyl crotonate and hexyl crotonate.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, and vinyl benzoate.

Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of itaconate diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of (meth)acrylamides include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-n-butylacryl(meth)amide, N-t-butyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-benzyl(meth)acrylamide, (meth)acryloylmorpholine, and diacetone acrylamide.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (e.g., t-Boc, etc.), methyl vinylbenzoate, and α-methylstyrene.

Examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; trivalent or higher unsaturated polyvalent carboxylic acids or their anhydrides; mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate, mono(2-acryloyloxyethyl) phthalate, and mono(2-methacryloyloxyethyl) phthalate; and mono(meth)acrylates of polymers with carboxy terminals at both ends such as ω-carboxy-polycaprolactone monoacrylate and ω-carboxy-polycaprolactone monomethacrylate.

The thermally crosslinkable group in the thermally crosslinkable group-containing monomer becomes, for example, a crosslinking point of the dye, and contributes to improving the heat resistance of the dye. Examples of the thermally crosslinkable group include a hydroxyl group, a carboxylic acid anhydride, a primary or secondary amino group, an imino group, an oxetanyl group, a tert-butyl group, an epoxy group, a mercapto group, and an isocyanate group. Among these, in terms of storage stability and reactivity, a hydroxyl group, a carboxyl group, an oxetanyl group, a tert-butyl group, an isocyanate group, and a (meth)acryloyl group are preferred, and a hydroxyl group is more preferred.

Examples of hydroxyl group-containing monomers include, but are not limited to, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, and caprolactone adducts of these monomers (molar number 1 to 5). Among these, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred from the viewpoint of heat resistance.

Examples of oxetanyl group-containing monomers include 3-(acryloyloxymethyl) 3-methyloxetane, 3-(methacryloyloxymethyl) 3-methyloxetane, 3-(acryloyloxymethyl) 3-ethyloxetane, 3-(methacryloyloxymethyl) 3-ethyloxetane, 3-(acryloyloxymethyl) 3-butyloxetane, 3-(methacryloyloxymethyl) 3-butyloxetane, 3-(acryloyloxymethyl) 3-hexyloxetane, and 3-(methacryloyloxymethyl) 3-hexyloxetane.

Examples of tert-butyl group-containing monomers include tert-butyl acrylate and tert-butyl methacrylate.

Examples of isocyanate group-containing monomers include 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, and 4-isocyanate butyl acrylate. The isocyanate group includes, for example, a blocked isocyanate group. A blocked isocyanate group is a functional group that, under normal conditions, protects an isocyanate group with another functional group to suppress the reactivity of the isocyanate group, but can be deprotected by heating to regenerate an active isocyanate group.

Commercially available blocked isocyanate group-containing monomers include, for example, 2-[(3,5-dimethylpyrazolyl)carboxyamino]ethyl methacrylate (KarenzMOI-BP, manufactured by Showa Denko K.K.); 2-(O-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (KarenzMOI-BM, manufactured by Showa Denko K.K.); etc.

These monomers can be used alone or in combination of two or more.

The amount of the monomer represented by general formula (4-1) used in the synthesis of the polymer portion is preferably 1 to 50 mass% and more preferably 20 to 35 mass% of the total monomers (100 mass%). Using an appropriate amount improves the optical properties.

The amount of the thermocrosslinkable group-containing monomer used is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass, based on 100% by mass of the total monomers. Using an appropriate amount improves heat resistance.

Methods for synthesizing the polymer moiety include, for example, anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. Among these, free radical polymerization and living radical polymerization are preferred.

The free radical polymerization method uses a polymerization initiator, such as an azo compound or an organic peroxide.
Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of organic peroxides include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide.

Polymerization initiators can be used alone or in combination of two or more types.

The polymerization temperature is preferably 40 to 150°C, more preferably 50 to 110°C. The polymerization time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

Living radical polymerization suppresses side reactions that occur in general radical polymerization and allows the polymerization to grow uniformly, making it possible to synthesize block polymers and polymers with narrow molecular weight distributions.

Among the various living radical polymerization methods, the atom transfer radical polymerization method, which uses an organic halide or a sulfonyl halide compound as a polymerization initiator and a transition metal complex as a catalyst, is preferred. This method is preferred in that it can polymerize monomers with a variety of structures and can adopt a polymerization temperature that is compatible with existing equipment. The atom transfer radical polymerization method can be carried out by the methods described in References 1 to 8 below.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al., J. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science
ce, 1996, 272, 866
(Reference 5) WO96/030421 (Reference 6) WO97/018247 (Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

It is preferable to use an organic solvent for synthesizing the polymer portion. Examples of organic solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

The weight average molecular weight of the polymer portion is preferably 5,000 to 20,000, and more preferably 8,000 to 15,000. Having an appropriate molecular weight improves optical properties and heat resistance.

The glass transition temperature (Tg) of the polymer portion is preferably -50 to 150°C, and more preferably 20 to 80°C. A moderate Tg improves the optical properties.

Organic solvents can be used alone or in combination of two or more types.

The pigment having the structure represented by general formula (3) preferably contains a compound represented by the following general formula (3-3):

General formula (3-3)

In general formula (3-3), Y ₄₀₉ to Y ₄₁₆ and R ₄₀₈ to R ₄₂₁ each independently represent a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent.
M represents an aluminum atom.
_Z2 is represented by -OP(=O) _{R401R402 ,} or a polymer moiety containing a monomer unit represented by general formula (4), in which _R401 and _R402 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent.

The pigment having the structure represented by general formula (3-3) is composed of a phthalocyanine moiety, and OP(═O)R _R ( _a phosphorus compound moiety) or a polymer moiety containing a monomer unit represented by general formula (4). The phthalocyanine moiety is preferably made from phthalocyanine represented by the following general formula (3-4) as a raw material.

General formula (3-4)

In the general formula _{(3-4), the descriptions of Y 409 to Y 416 , R 408 to R 421 and M in the general formula (} 3-3) can be cited for these.

The descriptions in general formula (3-1) can be used for the alkyl group which may have a substituent, the aryl group which may have a substituent, the cycloalkyl group which may have a substituent, the heterocyclic group which may have a substituent, the alkoxyl group which may have a substituent, the aryloxy group which may have a substituent, the alkylthio group which may have a substituent, the arylthio group which may have a substituent, the phthalimidomethyl group which may have a substituent, and the sulfamoyl group which may have a substituent.

In the pigment represented by formula (3-4), from the viewpoint of dispersibility and color characteristics, it is preferable that at least one of Y ₄₀₉ to Y ₄₁₆ and R ₄₀₈ to R ₄₂₁ is at least one selected from the group consisting of a hydrogen atom, a halogen atom, and an alkoxyl group which may have a substituent.

(Synthesis method of phthalocyanine moiety)
General industrial methods for producing the phthalocyanine represented by the general formula (3-4) are described below. When the methods (1) to (3) are used, the phthalocyanine represented by the general formula (3-4) contains a plurality of structures. When the pigment contains a plurality of structures, aggregation due to association of aromatic rings is alleviated, and a photosensitive composition with excellent dispersion stability can be obtained, so the methods (1) to (3) are preferred.
(1) Wyler method: A method in which substituted or unsubstituted phthalic anhydride and naphthalenedicarboxylic anhydride, or substituted or unsubstituted phthalimide anhydride and naphthalenedicarboxylic anhydride are reacted with urea in the presence of a metal salt at high temperature. By using phthalic anhydride and naphthalenedicarboxylic anhydride in combination, or phthalimide anhydride and naphthalenedicarboxylic anhydride in combination, a phthalocyanine represented by the general formula (3-4) can be obtained.
(2) Phthalodinitrile Method: A method in which substituted or unsubstituted phthalodinitrile and 2,3-dicyanonaphthalene are reacted with a metal salt in an alcoholic solvent such as n-amyl alcohol, n-hexyl alcohol, 1-methoxyethanol, or 1-ethoxyethanol in the presence of a strong base such as DBU (1,8-diazabicyclo[5,4,0]undecene-7), DBN (1,5-diazabicyclo[4,3,0]nonene-5), or a (metal) alkoxide. By using phthalodinitrile and 2,3-dicyanonaphthalene in combination, a phthalocyanine represented by the general formula (3-4) can be obtained.
(3) Diiminoisoindoline method: A method in which substituted or unsubstituted 1,3-diiminoisoindoline and 1,3-diiminobenzo[f]isoindoline are reacted with a metal salt in the presence of a strong base such as 2-dimethylaminoethanol, quinoline, or DBU (1,8-diazabicyclo[5,4,0]undecene-7). By using 1,3-diiminoisoindoline and 1,3-diiminobenzo[f]isoindoline in combination, a phthalocyanine represented by the general formula (3-4) can be obtained.
(4) Subphthalocyanine ring-opening method (method of synthesizing asymmetric phthalocyanine from subphthalocyanine)
A method in which a compound represented by the general formula (3-5) is synthesized from boron SUB-2,3-naphthalocyanine chloride and substituted or unsubstituted 1,3-diiminoisoindoline, and then the compound is reacted with a metal salt.

General formula (3-5)

In the general formula (3-5), for Y ₄₀₉ to Y ₄₁₆ and R ₄₀₈ to R ₄₂₁ , the descriptions for Y ₄₀₉ to Y ₄₁₆ and R ₄₀₈ to R ₄₂₁ in the general formula (3-3) can be cited.

Examples of the phthalocyanine compound represented by the general formula (3-1) include, but are not limited to, the following compounds:

(Method for synthesizing a pigment having a structure represented by formula (3))
The phthalocyanine compound represented by the general formula (3) or (3-3) can be synthesized, for example, by reacting a phthalocyanine compound represented by the general formula (3-1) or (3-4) with a phosphorus compound represented by the general formula (3-2).
The phthalocyanine compound may be reacted with both the phosphorus compound and the polymer simultaneously or successively.

The compound represented by general formula (3) can be synthesized, for example, by adding a phthalocyanine moiety, a phosphorus compound, or a polymer to an organic solvent, heating and stirring for several hours, pouring the reaction solution into water, filtering the precipitated product, washing it with water, and drying it.

Regarding the ratio of the phthalocyanine moiety and the phosphorus compound moiety, from the viewpoint of dispersibility and color characteristics, the amount of the phosphorus compound represented by general formula (3-2) added is preferably 0.8 to 2.0 molar equivalents relative to the phthalocyanine moiety, and more preferably 1.0 to 1.5 molar equivalents.

<Squarylium pigment>
Examples of squarylium pigments include compounds represented by the following general formula (5) and compounds represented by the following general formula (6).
(Compound represented by general formula (5))
First, a squarylium pigment having a structure represented by the following general formula (5) will be described.

General formula (5)

In the general formula (5), X ₁₀₁ to X ₁₁₀ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, a sulfo group, -SO ₂ NR ₁₀₁ R ₁₀₂ , -COOR ₁₀₁ , -CONR ₁₀₁ R ₁₀₂ , a nitro group, a cyano group, or a halogen atom. R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or an alkyl group which may have a substituent. X ₁₀₁ to X ₁₁₀ may be bonded to each other to form a ring.

In X ₁₀₁ to X ₁₁₀ , examples of the "alkyl group which may have a substituent" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a tert-amyl group, a 2-ethylhexyl group, a stearyl group, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a 2-chloroethyl group, a 2-nitroethyl group, a cyclopentyl group, a cyclohexyl group, and a dimethylcyclohexyl group. Among these, the methyl group, the ethyl group, and the n-propyl group are preferred from the viewpoints of imparting durability and ease of synthesis, and the methyl group is particularly preferred.

In X ₁₀₁ to X ₁₁₀ , examples of the "alkenyl group which may have a substituent" include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, and a 5-hexenyl group. Among these, the vinyl group and the 2-propenyl group are preferred from the viewpoints of imparting durability and ease of synthesis.

In X ₁₀₁ to X ₁₁₀ , examples of the "aryl group which may have a substituent" include a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, a 4-bromophenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, and a 4-cyanophenyl group. Among these, the phenyl group and the 4-methylphenyl group are preferred from the viewpoints of imparting durability and ease of synthesis.

In X ₁₀₁ to X ₁₁₀ , the "aralkyl group which may have a substituent" is, for example, a benzyl group, a phenethyl group, a phenylpropyl group, or a naphthylmethyl group. Among these, a benzyl group is preferred from the viewpoints of imparting durability and ease of synthesis.

In X ₁₀₁ to X ₁₁₀ , the "alkoxy group which may have a substituent" is, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, a 2-ethylhexyloxy group, a trifluoromethoxy group, a cyclohexyloxy group, and a stearyloxy group. Among these, a methoxy group, an ethoxy group, and a trifluoromethoxy group are preferable from the viewpoint of imparting durability and the ease of synthesis.

In X ₁₀₁ to X ₁₁₀ , examples of the "aryloxy group which may have a substituent" include a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group, a 4-chloro-2-methylphenyloxy group, a 4-tert-butylphenyloxy group, a 4-methoxyphenyloxy group, a 4-diethylaminophenyloxy group, and a 4-nitrophenyloxy group. Among these, the phenoxy group and the naphthyloxy group are preferred from the viewpoints of imparting durability and ease of synthesis.

In X ₁₀₁ to X ₁₁₀ , examples of the "substituted amino group" include a methylamino group, an ethylamino group, an isopropylamino group, an n-butylamino group, a cyclohexylamino group, a stearylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, an N,N-di(2-hydroxyethyl)amino group, a phenylamino group, a naphthylamino group, a 4-tert-butylphenylamino group, a diphenylamino group, and an N-phenyl-N-ethylamino group. Among these, the dimethylamino group and the diethylamino group are preferred from the viewpoints of imparting durability and ease of synthesis.

In X ₁₀₁ to X ₁₁₀ , the "halogen atom" is, for example, fluorine, bromine, chlorine, or iodine.

X ₁₀₁ to X ₁₁₀ may be bonded to each other to form a ring. Examples of the ring include, but are not limited to, the following structures.

For the "alkyl group which may have a substituent" in R ₁₀₁ and R ₁₀₂ , for example, the description in X ₁ to X ₁₀ can be cited.

At least one of X ₁₀₁ to X ₁₁₀ is preferably an unsubstituted alkyl group, more preferably at least one of X ₁₀₃ , X ₁₀₄ , X ₁₀₇ and X ₁₀₈ is an unsubstituted alkyl group, and further preferably X ₁₀₃ and X ₁₀₇ are unsubstituted alkyl groups. The unsubstituted alkyl group is preferably, for example, a methyl group.

(Method for producing a compound represented by formula (5))
The compound represented by the general formula (5) can be synthesized, for example, as shown in the following formula (5-1), by heating and refluxing 1,8-diaminonaphthalene and cyclohexanones together with a catalyst in a solvent to cause condensation, and then adding 3,4-dihydroxy-3-cyclobutene-1,2-dione shown below and further heating and refluxing to cause condensation.

Formula (5-1)

(Compound represented by general formula (6))
Next, a squarylium pigment having a structure represented by the following general formula (6) will be described.

General formula (6)

In formula 6, Q ₁ , Q ₄ , Q ₅ and Q ₈ each independently represent a carbon atom or a nitrogen atom. When Q ₁ , Q ₄ , Q ₅ or Q ₈ is a nitrogen atom, there is no X ₂₀₁ , X ₂₀₄ , X ₂₀₅ or X ₂₀₈ bonded to the nitrogen atom.
R ₂₀₁ to R ₂₀₅ each independently represent a hydrogen atom, a sulfo group, —SO ₃ ⁻ M ⁺ or a halogen atom, where M ⁺ represents an inorganic or organic cation.
X ₂₀₁ to X ₂₀₈ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxy group, an amino group, -NR ₂₀₆ R ₂₀₇ , a sulfo group, -SO ₂ NR ₂₀₈ R ₂₀₉ , -COOR ₂₁₀ , -CONR ₂₁₁ R ₂₁₂ , a nitro group, a cyano group, or a halogen atom. X ₂₀₁ to X ₂₀₈ may be bonded to each other to form a ring.
R ₂₀₆ to R ₂₁₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, or a pyridinyl group which may have a substituent. R ₂₀₆ and R ₂₀₇ , R ₂₀₈ and R _{209, and} R ₂₁₁ and R ₂₁₂ may be bonded to each other to form a ring.

From the viewpoint of spectral shape, Q ₁ , Q ₄ , Q ₅ and Q ₈ are preferably carbon atoms.

In R ₂₀₁ to R ₂₀₅ , examples of the "halogen atom" include fluorine, bromine, chlorine and iodine.

In R ₂₀₁ to R ₂₀₅ , the "inorganic or organic cation" of M ⁺ can be, for example, any known cation without limitation, and in the case of an organic cation, it may be either a low molecular weight type or a high molecular weight type. Specific examples include metal atoms, ammonium compounds, pyridinium compounds, imidazolium compounds, phosphonium compounds, sulfonium compounds, etc. In the case of a high molecular weight type, for example, a "resin having a quaternary ammonium base" can be mentioned. Among these, trivalent metal atoms, ammonium compounds, and resins having a quaternary ammonium base are preferred from the viewpoint of heat resistance.

From the viewpoint of imparting resistance, it is preferred that R ₂₀₁ to R ₂₀₅ are all hydrogen atoms, or that four of R ₂₀₁ to R ₂₀₅ are hydrogen atoms and one is a sulfo group, -SO ₃ ^- M ⁺ or a halogen atom. Of these, it is more preferred that all are hydrogen atoms, or that four of R ₂₀₁ to R ₂₀₅ are hydrogen atoms and one is a sulfo group or a halogen atom.

In X ₂₀₁ to X ₂₀₈ , examples of the "alkyl group which may have a substituent" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an isobutyl group, a tert-amyl group, a 2-ethylhexyl group, a stearyl group, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a 2-chloroethyl group, a 2-nitroethyl group, a cyclopentyl group, a cyclohexyl group, and a dimethylcyclohexyl group. Among these, a methyl group and an ethyl group are preferred from the viewpoint of the difficulty of synthesis.

In X ₂₀₁ to X ₂₀₈ , examples of the "alkenyl group which may have a substituent" include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, and a 5-hexenyl group. Among these, the vinyl group and the 2-propenyl group are preferred from the viewpoint of the difficulty of synthesis.

In X ₂₀₁ to X ₂₀₈ , examples of the "aryl group which may have a substituent" include a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, a 4-bromophenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, and a 4-cyanophenyl group. Among these, a phenyl group and a 4-methylphenyl group are preferred from the viewpoint of the ease of synthesis.

In X ₂₀₁ to X ₂₀₈ , the "aralkyl group which may have a substituent" is, for example, a benzyl group, a phenethyl group, a phenylpropyl group, or a naphthylmethyl group. Among these, the benzyl group is preferable from the viewpoint of the ease of synthesis.

In X ₂₀₁ to X ₂₀₈ , examples of the "alkoxy group even if it has a substituent" include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, a 2-ethylhexyloxy group, a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group, and a 2-(diethylamino)ethoxy group. Among these, a methoxy group, an ethoxy group, a trifluoromethoxy group, and a 2-(diethylamino)ethoxy group are preferable from the viewpoint of the difficulty of synthesis.

In X ₂₀₁ to X ₂₀₈ , examples of the "aryloxy group which may have a substituent" include a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group, a 4-chloro-2-methylphenyloxy group, a 4-tert-butylphenyloxy group, a 4-methoxyphenyloxy group, a 4-diethylaminophenyloxy group, and a 4-nitrophenyloxy group. Among these, the phenoxy group and the naphthyloxy group are preferred from the viewpoint of the ease of synthesis.

In X ₂₀₁ to X ₂₀₈ , the "halogen atom" is, for example, fluorine, bromine, chlorine, or iodine.

X ₂₀₁ to X ₂₀₈ may combine with each other to form a ring. Preferred examples of the ring are shown below, but are not limited thereto.

From the viewpoints of dispersibility, storage stability and ease of synthesis, it is particularly preferable that X ₂₀₁ to X ₂₀₈ are all hydrogen atoms.

In R ₂₀₆ to R ₂₁₂ , examples of the "alkyl group which may have a substituent" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an isobutyl group, a sec-butyl group, a tert-amyl group, a 2-ethylhexyl group, a stearyl group, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a 2-chloroethyl group, a 2-nitroethyl group, a cyclopentyl group, a cyclohexyl group, and a dimethylcyclohexyl group. Of these, a methyl group and an ethyl group are preferred from the viewpoint of the difficulty of synthesis.

In R ₂₀₆ to R ₂₁₂ , examples of the "aryl group which may have a substituent" include a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, a 4-bromophenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, and a 4-cyanophenyl group. Of these, the phenyl group and the 4-methylphenyl group are preferred from the viewpoint of ease of synthesis.

In R ₂₀₆ to R ₂₁₂ , examples of the "acyl group which may have a substituent" include an acetyl group, a propioyl group, a benzoyl group, an acrylyl group, and a trifluoroacetyl group. Among these, the acetyl group is preferred from the viewpoint of the ease of synthesis.

In R ₂₀₆ to R ₂₁₂ , examples of the "pyridinyl group which may have a substituent" include a 2-pyridinyl group, a 3-pyridinyl group, a 4-pyridinyl group, and a 2-methyl-4-pyridinyl group. Among these, the 4-pyridinyl group is preferred from the viewpoint of ease of synthesis.

R ₂₀₆ and R ₂₀₇ , R ₂₀₈ and R _{209 , and} R ₂₁₁ and R ₂₁₂ may each be bonded to each other to form a ring.

(Method for producing a compound represented by formula (6))
The compound represented by general formula (6) can be synthesized, for example, by the method shown in formula (6-1) below. First, 1,8-diaminonaphthalenes and fluorenones are condensed together with a catalyst by heating under reflux in a solvent, and then 3,4-dihydroxy-3-cyclobutene-1,2-dione is added and the mixture is further condensed by heating under reflux. When at least one of R ₁ to R ₅ is SO ₃ ^- M ⁺ , a dye substituted with SO ₃ ^- M ⁺ is obtained by counter ion exchange between the hydrogen ion of the sulfo group of the dye substituted with a sulfo group and a compound having the desired cation.

Formula (6-1)

<Indigo pigment>
Examples of indigo pigments include a compound represented by the following general formula (7), a compound represented by the following general formula (8), and a compound represented by the following general formula (9).

<Pigment having a structure represented by general formula (7)>
The indigo pigment having a structure represented by general formula (7) will be described.

General formula (7)


General formula (10)


(** represents the bond to the nitrogen atom)

In formula (7), R ₅₀₁ and R ₅₀₂ each independently represent a hydrogen atom, a group represented by formula (10), or a metal atom having a ligand, provided that R ₅₀₁ and R ₅₀₂ are not hydrogen at the same time.
X ₅₀₁ to X ₅₁₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an arylalkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an amino group, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, a cyano group, a halogen atom, a nitro group, a hydroxyl group, or -SO ₃ H, -COOH, a monovalent to trivalent metal salt or an alkylammonium salt of these acidic groups. Two adjacent groups among the groups represented by X ₅₀₁ to X ₅₁₂ may be linked to form a 5-membered or 6-membered ring together with the carbon atoms to which they are bonded.

The "alkyl group" of the alkyl group which may have a substituent includes, for example, a straight-chain or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a n-hexyl group, a n-octyl group, a stearyl group, and a 2-ethylhexyl group. The "alkyl group having a substituent" includes, for example, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, and a 2,4-dichlorobenzyl group.

Examples of the "aryl group" of the aryl group which may have a substituent include a phenyl group, a naphthyl group, an anthryl group (anthracenyl group), and the like.
Examples of the "substituted aryl group" include a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-aminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-hydroxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group.

Examples of the "alkoxyl group" of the alkoxyl group which may have a substituent include straight-chain or branched alkoxyl groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, a 2,3-dimethyl-3-pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group.
Examples of the "substituted alkoxyl group" include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

The "aryloxy group" of the aryloxy group which may have a substituent includes, for example, a phenoxy group, a naphthoxy group, an anthryloxy group, etc., and the "aryloxy group having a substituent" includes, for example, a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, a 2-methyl-4-chlorophenoxy group, etc.

"Optionally substituted arylalkyl groups" include, for example, benzyl groups, 2-phenylpropane-yl groups, styryl groups, diphenylmethyl groups, triphenylmethyl groups, etc.

Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group, etc. Examples of the "cycloalkyl group having a substituent" include a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, etc.

Examples of the "alkylthio group" of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group.
Examples of the "substituted alkylthio group" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

Examples of the "arylthio group" of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group.
Examples of the "substituted arylthio group" include a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, and a 2-hydroxyphenylthio group.

Examples of the "alkylamino group" of the alkylamino group which may have a substituent include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, a decylamino group, a dodecylamino group, an octadecylamino group, an isopropylamino group, an isobutylamino group, an isopentylamino group, a sec-butylamino group, a tert-butylamino group, a sec-pentylamino group, a tert-pentylamino group, a tert-octylamino group, a neopentylamino group, a cyclopropylamino group, a cyclobutylamino group, a cyclopentylamino group, a cyclohexylamino group, a cycloheptylamino group, a cyclooctylamino group, a cyclododecylamino group, a 1-adamantamino group, a 2-adamantamino group, and the like.

The "arylamino group" of the arylamino group which may have a substituent includes, for example, an anilino group, a 1-naphthylamino group, a 2-naphthylamino group, an o-toluidino group, a m-toluidino group, a p-toluidino group, a 2-biphenylamino group, a 3-biphenylamino group, a 4-biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, etc.

Halogen atoms include fluorine, chlorine, bromine, and iodine.

Examples of the acidic group include _-SO3H and -COOH, and examples of the monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, aluminum salts, etc. Examples of the alkyl ammonium salts of acidic groups include ammonium salts of long-chain monoalkyl amines such as octylamine, laurylamine, stearylamine, etc., and quaternary alkyl ammonium salts such as palmityl trimethyl ammonium, lauryl trimethyl ammonium, dilauryl dimethyl ammonium, distearyl dimethyl ammonium salts, etc.

Of the above substituents, preferred substituents for X ₅₀₁ to X ₅₁₂ include a hydrogen atom, a methoxy group, a fluorine atom, a chlorine atom and a bromine atom.

Among the groups represented by X ₅₀₁ to X ₅₁₂ , two adjacent groups may be linked to form a 5-membered or 6-membered ring together with the carbon atoms to which they are bonded. The 5-membered or 6-membered ring may have a substituent. Examples of such 5-membered rings include a cyclopentene ring, a cyclopentadiene ring, an imidazole ring, a thiazole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiophene ring, a furan ring, and a pyrrole ring, and examples of the 6-membered ring include a cyclohexane ring, a cyclohexene ring, a cyclohexadiene ring, a benzene ring, a pyridine ring, a piperazine ring, a piperidine ring, a morpholine ring, a pyrazine ring, a pyrone ring, and a pyrrolidine ring.

<Pigment having a structure represented by general formula (8) or general formula (9)>
The indigo pigment having a structure represented by general formula (8) or general formula (9) of the present invention will be described.


[In the formula, X ₁ to X ₄₀ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an arylalkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an amino group, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, a cyano group, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ H, -COOH, or a monovalent to trivalent metal salt or alkylammonium salt of these acidic groups. Two adjacent groups among the groups represented by _{X 1} to X ₄₀ may be linked to form a 5- or 6-membered ring together with the carbon atoms to which they are bonded.
M represents a metal atom.

The "alkyl group" of the alkyl group which may have a substituent includes, for example, a straight-chain or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a n-hexyl group, a n-octyl group, a stearyl group, and a 2-ethylhexyl group. The "alkyl group having a substituent" includes, for example, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, and a 2,4-dichlorobenzyl group.

Examples of the "aryl group" of the aryl group which may have a substituent include a phenyl group, a naphthyl group, and anthryl group.
Examples of the "substituted aryl group" include a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-aminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-hydroxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group.

Examples of the "alkoxyl group" of the alkoxyl group which may have a substituent include straight-chain or branched alkoxyl groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, a 2,3-dimethyl-3-pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group.
Examples of the "substituted alkoxyl group" include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

The "aryloxy group" of the aryloxy group which may have a substituent includes, for example, a phenoxy group, a naphthoxy group, an anthryloxy group, etc., and the "aryloxy group having a substituent" includes, for example, a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, a 2-methyl-4-chlorophenoxy group, etc.

"Optionally substituted arylalkyl groups" include, for example, benzyl groups, 2-phenylpropane-yl groups, styryl groups, diphenylmethyl groups, triphenylmethyl groups, etc.

Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group, etc. Examples of the "cycloalkyl group having a substituent" include a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, etc.

Examples of the "alkylthio group" of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group.
Examples of the "substituted alkylthio group" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

Examples of the "arylthio group" of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group.
Examples of the "substituted arylthio group" include a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, and a 2-hydroxyphenylthio group.

Examples of the "alkylamino group" of the alkylamino group which may have a substituent include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, a decylamino group, a dodecylamino group, an octadecylamino group, an isopropylamino group, an isobutylamino group, an isopentylamino group, a sec-butylamino group, a tert-butylamino group, a sec-pentylamino group, a tert-pentylamino group, a tert-octylamino group, a neopentylamino group, a cyclopropylamino group, a cyclobutylamino group, a cyclopentylamino group, a cyclohexylamino group, a cycloheptylamino group, a cyclooctylamino group, a cyclododecylamino group, a 1-adamantamino group, a 2-adamantamino group, and the like.

The "arylamino group" of the arylamino group which may have a substituent includes, for example, an anilino group, a 1-naphthylamino group, a 2-naphthylamino group, an o-toluidino group, a m-toluidino group, a p-toluidino group, a 2-biphenylamino group, a 3-biphenylamino group, a 4-biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, etc.

Halogen atoms include fluorine, chlorine, bromine, and iodine.

Examples of the acidic group include _-SO3H and -COOH, and examples of the monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, aluminum salts, etc. Examples of the alkyl ammonium salts of acidic groups include ammonium salts of long-chain monoalkyl amines such as octylamine, laurylamine, stearylamine, etc., and quaternary alkyl ammonium salts such as palmityl trimethyl ammonium, lauryl trimethyl ammonium, dilauryl dimethyl ammonium, distearyl dimethyl ammonium salts, etc.

Among the groups represented by X ₁ to X ₄₀ , two adjacent groups may be linked to form a 5-membered or 6-membered ring together with the carbon atoms to which they are bonded. The 5-membered or 6-membered ring may have a substituent. Examples of such 5-membered rings include a cyclopentene ring, a cyclopentadiene ring, an imidazole ring, a thiazole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiophene ring, a furan ring, and a pyrrole ring, and examples of the 6-membered rings include a cyclohexane ring, a cyclohexene ring, a cyclohexadiene ring, a benzene ring, a pyridine ring, a piperazine ring, a piperidine ring, a morpholine ring, a pyrazine ring, a pyrone ring, and a pyrrolidine ring.

Of the above substituents, preferred substituents for X ₁ to X ₄₀ include a hydrogen atom, a methyl group, a methoxy group, a fluorine atom, a chlorine atom, a bromine atom and --SO ₃ H.

M represents a metal atom. Examples of metal atoms include Zn, Co, Ni, Ru, Pt, Mn, Sn, and Ti. Among these, divalent metal atoms are preferred, and Zn, Co, and Ni are more preferred. By forming a dimer represented by general formula (8) or a trimer represented by general formula (9), a compound with good heat resistance is obtained.

(Method of synthesizing pigments having structures represented by general formulas (7) to (9))
Methods for synthesizing pigments having structures represented by general formulas (7) to (9) are described below.
The pigments having the structures represented by the general formulas (7) to (9) use as a raw material a compound represented by the general formula (11). The compound represented by the general formula (11) can be obtained according to the synthesis method described in JP-A-2012-224593.

General formula (11)

[In the formula, X ₆₀₁ to X ₆₀₈ have the same meaning as X ₁ to X ₄₀ and X ₅₀₁ to X _512. ]

The compound represented by the general formula (7) can be obtained by reacting the compound represented by the general formula (11) with a boron compound or a metal complex. If necessary, a Lewis acid such as titanium tetrachloride or aluminum chloride is added.

The reaction temperature is not particularly limited, but is preferably in the range of 40 to 170°C, and more preferably 50 to 130°C.

The reaction solvent is not particularly limited, but is preferably one in which the intermediate and the boron compound or metal complex are soluble. Specific examples include tetrahydrofuran, toluene, xylene, bromobenzene, etc.

When a boron compound is used, boric acid esters are preferred, with 2-aminoethyl diphenylborinate being particularly preferred.

The reaction time is not particularly limited, but the progress of the reaction can be confirmed by MALDI TOF-MS spectroscopy or a spectrophotometer to confirm the disappearance of the raw materials.

Pigments having structures represented by general formulas (7) to (9) can be obtained by reacting a compound represented by general formula (11) with a metal salt in a solvent.

Examples of metal salt raw materials include acetates, acetylacetone complexes, metal halides, etc.

The reaction temperature is not particularly limited, but is preferably in the range of 20 to 120°C, and more preferably 20 to 50°C.

The reaction solvent is not particularly limited, but is preferably one in which the intermediate and metal salt are soluble. Specific examples include tetrahydrofuran, toluene, and N-methylpyrrolidone.

The amount of metal salt used is 0.5 moles or more, and preferably 1.0 to 3.0 moles, per mole of the compound represented by general formula (11).

The reaction time is not particularly limited, but the progress of the reaction can be confirmed by MALDI TOF-MS spectroscopy or a spectrophotometer to confirm the disappearance of the raw materials.

In the production of pigments having a structure represented by general formula (8) or general formula (9), it can be confirmed by TOF-MS spectrum that compounds represented by general formula (8) (hereinafter referred to as dimer) and general formula (9) (hereinafter referred to as trimer) are produced as a mixture, and compounds represented by general formula (12) (hereinafter referred to as tetramer) are produced as a minor component. The production ratio of dimer, trimer, and tetramer was calculated by calculating the peak intensity (relative intensity) of each molecular ion relative to the sum of all molecular ion peak intensities in the TOF-MS spectrum, and the relative intensity ratio was regarded as the molar ratio.

General formula (12)

[In the formula, X ₄₉ to X ₈₀ have the same meaning as X ₁ to X _40. ]

During synthesis, if the molar ratio of the metal salt to the compound represented by general formula (12) is high, the ratio of trimers produced will be high. The molar ratio of tetramers is preferably 30.0 mass% or less based on the total molecules of the compound produced.

Pigments having a structure represented by general formula (8) or general formula (9) have absorption in a specific near-infrared region (700 nm to 800 nm) and little absorption in the visible light region (480 nm to 650 nm), and therefore function well as near-infrared absorbents when used as near-infrared absorbing dyes.

In the present invention, examples of the pigment having a structure represented by general formula (7) include the following compounds, but the present invention is not limited to these.

In the present invention, examples of pigments having a structure represented by general formula (8) include the following compounds, but the present invention is not limited to these.

In the present invention, examples of pigments having a structure represented by general formula (9) include the following compounds, but the present invention is not limited to these.

The photosensitive composition of the present invention may contain a pigment other than the phthalocyanine pigment or the naphthalocyanine pigment.
Examples of yellow pigments include Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119 , 120, 123, 126, 127, 128, 129, 138, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, and 221.

Examples of red pigments include C.I. Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 97, 122, 123, 146, 149, 150, 168, 169, 170, 176, 177, 178, 180, 184, 185, 187, 192, 200, 202, 20 8, 209, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 268, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, and 287.
Examples of orange pigments include C.I. Pigment Orange 36, 38, 43, 51, 55, 59, 71, and 73.

Examples of blue pigments include C.I. Pigment Blue 1, 1:2, 1:3, 2, 2:1, 2:2, 3, 8, 9, 10, 10:1, 11, 12, 18, 19, 22, 24, 24:1, 53, 56, 56:1, 57, 58, 59, 60, 61, 62, and 64.

Examples of green pigments include C.I. Pigment Green 10, 37, 62, and 63.

Examples of purple pigments include C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50.

(Inorganic pigments)
In addition, inorganic pigments can be used in combination. Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, and synthetic iron black. Inorganic pigments are used in combination with organic pigments to ensure good coatability, sensitivity, developability, and the like while maintaining a balance between saturation and brightness.

Dyes can also be used in combination. Examples of dyes include oil-soluble dyes, acid dyes, and basic dyes, all of which can be used in combination. Examples of dyes include anthraquinone dyes, monoazo dyes, disazo dyes, oxazine dyes, aminoketone dyes, xanthene dyes, quinoline dyes, triphenylmethane dyes, cyanine dyes, and squarylium dyes, all of which can be used in combination.

Hereinafter, the above pigments and dyes will be collectively referred to as colorants.

Furthermore, an ultraviolet absorbing agent can be used in combination. Examples of ultraviolet absorbing agents include benzotriazole-based ultraviolet absorbing agents, triazine-based ultraviolet absorbing agents, benzophenone-based ultraviolet absorbing agents, benzoate-based ultraviolet absorbing agents, and cyanoacrylate-based ultraviolet absorbing agents, and any of these can be used in combination.

Furthermore, an ultraviolet absorbing agent can be used in combination. Examples of ultraviolet absorbing agents include benzotriazole-based ultraviolet absorbing agents, triazine-based ultraviolet absorbing agents, benzophenone-based ultraviolet absorbing agents, benzoate-based ultraviolet absorbing agents, and cyanoacrylate-based ultraviolet absorbing agents, and any of these can be used in combination.

When it is desired to control the transmission and absorption of a specific wavelength region in addition to the performance as a high refractive index material, the above-mentioned dyes and ultraviolet absorbents are preferably used.
For example, when sensing near-infrared rays, if it is desired to cut off wavelengths shorter than that of the light, a yellow pigment or an ultraviolet absorber can be added to a blue pigment, a red pigment, or a purple pigment to give it the function of an IR-passing material.

(Micronization of pigments)
In the pigment composition of the present invention, from the viewpoint of obtaining a high transmittance, it is preferable that the organic pigment is micronized by a salt milling process or the like. The primary particle size of the pigment is preferably 10 nm or more because it is easily dispersed in the colorant carrier. In addition, it is preferable that it is 400 nm or less, and more preferably 200 nm or less, because it is possible to form a coating film with little scattering. The particularly preferable range is 20 to 60 nm.

(Salt milling process)
The salt milling process is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while being heated using a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or other kneading machine, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed during the salt milling process by utilizing the high hardness of the inorganic salt. By optimizing the conditions for the salt milling process of the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

Sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used as the water-soluble inorganic salt, but sodium chloride (table salt) is preferred from the viewpoint of cost. From the viewpoints of both processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, and most preferably 300 to 1000% by mass, based on the total mass of the pigment (100% by mass).

The water-soluble organic solvent is a solvent that moistens the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (is miscible with) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporate, a high-boiling solvent with a boiling point of 120°C or higher is preferred from the standpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by mass, and more preferably 50 to 500% by mass, based on the total mass of the pigment (100% by mass).

When the pigment is subjected to salt milling, a resin may be added as necessary. There are no particular limitations on the type of resin used, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. may be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the above organic solvents. The amount of resin used is preferably in the range of 5 to 200% by mass, based on the total mass of the pigment (100% by mass).

<Binder resin>
The pigment composition of the present invention may contain a binder resin. The binder resin is preferably one capable of binding substances such as pigments together, and examples of the binder resin include thermosetting resins, photocurable resins, and thermoplastic resins. From the viewpoint of curability, thermosetting resins or photocurable resins are preferred.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.
The photocurable resin may be an acrylic resin having an ethylenically unsaturated double bond introduced therein.

Examples of active energy ray-curable resins having ethylenically unsaturated double bonds include resins into which unsaturated ethylenically double bonds have been introduced by the following methods (a) and (b).

[Method (a)]
Method (a) includes a method in which an unsaturated ethylenic monomer having an epoxy group is copolymerized with one or more other monomers to obtain a copolymer, and a carboxy group of an unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction with the side-chain epoxy group of the copolymer, and further, a polybasic acid anhydride is reacted with the resulting hydroxy group to introduce an unsaturated ethylenic double bond and a carboxy group.

Examples of unsaturated ethylenic monomers having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4 epoxybutyl (meth)acrylate, and 3,4 epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

Examples of unsaturated monobasic acids include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position. These may be used alone or in combination of two or more.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., which may be used alone or in combination of two or more. In order to increase the number of carboxyl groups, if necessary, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups. In addition, if tetrahydrophthalic anhydride or maleic anhydride, which has an unsaturated ethylenic double bond, is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be further increased.

A method similar to method (a) is, for example, a method in which an unsaturated ethylenic monomer having an epoxy group is added to some of the side chain carboxy groups of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxy group with one or more other monomers, thereby introducing an unsaturated ethylenic double bond and a carboxy group.

[Method (b)]
Method (b) includes a method in which an unsaturated ethylenic monomer having a hydroxy group is used and copolymerized with another monomer of an unsaturated monobasic acid having a carboxy group or with another monomer, and the side chain hydroxy group of the copolymer obtained is reacted with an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group.

Examples of the unsaturated ethylenic monomer having a hydroxy group include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. These may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to the above hydroxyalkyl (meth)acrylates, and (poly)ester mono(meth)acrylates obtained by addition of (poly)γ-valerolactone, (poly)ε-caprolactone, and/or (poly)12-hydroxystearic acid, etc., may also be used. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferred.

Examples of unsaturated ethylenic monomers having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but are not limited to these and two or more types can be used in combination.

Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

The binder resin should preferably have a spectral transmittance of 80% or more, and more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light region.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000, in order to disperse the colorant favorably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less.

From the viewpoint of film-forming properties and various resistances, it is preferable to use the binder resin in an amount of 30% by mass or more, based on the total mass of the colorant (100% by mass), and from the viewpoint of increasing the colorant concentration and achieving good color characteristics, it is preferable to use the binder resin in an amount of 500% by mass or less.

(Dispersant)
The dispersant functions to disperse and stabilize the pigment in the pigment composition and to prevent re-aggregation after dispersion, and thus a film with high spectral transmittance can be obtained. The dispersant includes a resin-type dispersant, and may optionally include a dye derivative, a surfactant, etc.

Resin-type dispersant
The resin-type dispersant has a pigment-affinity portion that has the property of being adsorbed to the pigment, and a portion that is compatible with the colorant carrier, and functions to adsorb to the added pigment and stabilize the dispersion in the colorant carrier. Specifically, as the resin type dispersant, polyurethane, polycarboxylate esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylate esters, and modified products thereof, poly (lower alkylene imine) and free carboxyl group-containing polyesters formed by reaction with amides and their salts, oil-based dispersants such as amides and their salts, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, water-soluble resins such as polyvinylpyrrolidone and water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, phosphate esters, and the like are used, which can be used alone or in a mixture of two or more, but are not necessarily limited to these.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, and Anti-Terra-U, 203, 204, BYK-P104, P104S, 220S, 6919, Lactimon, Lactimon-WS, Bykumen, etc. manufactured by Lubrizol Japan Co., Ltd. SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 29000, 30000, 31000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39000, 40000, 41000, 42000, 43000, 44000, 45000, 46000, 47000, 48000, 49000, 5000, 51000, 52000, 53000, 54000, 5500, 56000, 57000, 58000, 59000, 60000, 61000, 6200, 6300, 6400, 6500, 66000, 67000, 6800, 69000, 7000, 71000, 7200, 7300, 7400, 7500, 76000, 7700 000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402 manufactured by BASF Japan Ltd. , 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd.

<Block acrylic basic dispersant>
In the pigment composition of the present invention, it is preferable to use a block acrylic basic dispersant as the resin type dispersant. The block acrylic basic dispersant is a block type acrylic polymer having a basic group. Among them, it is more preferable that one block is a polymer of an ethylenically unsaturated monomer having a basic group and the other block is a polymer of an ethylenically unsaturated monomer not having a basic group.

When the block acrylic basic dispersant is an AB type block, the more preferred embodiment is as described above, but when it is a BAB type block, it is more preferred that the A block is a polymer of an ethylenically unsaturated monomer having a basic group, and the B block is a polymer of an ethylenically unsaturated monomer not having a basic group.

By using a block acrylic basic dispersant as a resin-type dispersant, it is believed that the block with the basic group is adsorbed to the pigment surface, and the other block without the basic group acts as a steric hindrance while maintaining affinity with the solvent, resulting in good dispersibility.

Generally, resin-type dispersants tend to provide good dispersibility when used in combination with dye derivatives, but when block acrylic-type basic dispersants are used, good dispersibility is often obtained even without dye derivatives due to the above mechanism. Furthermore, dye derivatives often have a different spectrum from the pigments used in the present invention, so a pigment composition can exhibit a higher refractive index without using dye derivatives.

As the ethylenically unsaturated monomer having a basic group, an ethylenically unsaturated monomer having a tertiary amino group and an ethylenically unsaturated monomer having a quaternary ammonium salt are preferred, and it is particularly preferred to use these in combination.

Examples of ethylenically unsaturated monomers having a tertiary amino group include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and dipropylaminoethyl methacrylate. Examples of ethylenically unsaturated monomers having a quaternary ammonium base include dimethylaminoethyl methyl chloride salt of methacrylate, dimethylaminoethyl benzyl chloride salt of methacrylate, dimethylaminoethyl propyl chloride salt of methacrylate, dimethylaminoethyl butyl chloride salt of methacrylate, diethylaminoethyl methyl chloride salt of methacrylate, diethylaminoethyl benzyl chloride salt of methacrylate, diethylaminoethyl propyl chloride salt of methacrylate, diethylaminoethyl butyl chloride salt of methacrylate, dimethylaminoethyl methyl chloride salt of acrylate, dimethylaminoethyl benzyl chloride salt of acrylate, dimethylaminoethyl propyl chloride salt of acrylate, and dimethylaminoethyl butyl chloride salt of acrylate.

When an ethylenically unsaturated monomer having a tertiary amino group and an ethylenically unsaturated monomer having a quaternary ammonium salt are used in combination as an ethylenically unsaturated monomer having a basic group, there are two typical methods for synthesizing a block acrylic basic dispersant.

The first method is to synthesize these ethylenically unsaturated monomers separately and then mix them together when polymerizing the block having a basic group.

The second method is to polymerize a block having a basic group using an ethylenically unsaturated monomer having a tertiary amino group, polymerize the other block having no basic group, and after completing the block polymerization, react with a quaternizing agent such as benzyl chloride to convert a part of the tertiary amino group into a quaternary ammonium salt. Examples of the quaternizing agent include alkyl halides such as benzyl chloride, iodobutane, iodopropane, iodoethane, bromobutane, bromopropane, bromoethane, and chlorobutane.
The ethylenically unsaturated monomer having a tertiary amino group and the ethylenically unsaturated monomer having a quaternary ammonium salt are preferably those having an amide bond in the molecule, since they are easily adsorbed to the surface of the organic pigment and can provide higher dispersibility.

When synthesizing a block polymer, for example, an A-B block polymer can be produced by first synthesizing the A block and then the B block. Alternatively, a B-A-B block polymer can be produced by first synthesizing the B block, then the A block, and then the B block. The order in which the A block and the B block are synthesized is arbitrary.

The radical polymerization initiator used in living radical polymerization is preferably an azo compound or a peroxide.

Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(methyl isobutyrate), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane].

Examples of peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide. The polymerization initiators may be used alone or in combination of two or more kinds.

The polymerization reaction temperature is preferably 40 to 150°C, more preferably 50 to 110°C. The reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

Living radical polymerization can be carried out by known polymerization methods, but RAFT polymerization (reversible addition-fragmentation chain transfer polymerization) is preferred. RAFT polymerization is a method of radically polymerizing a monomer in the presence of a RAFT agent, which makes it easy to control the molecular weight and molecular weight distribution of the polymer.

RAFT agents are compounds that have a chain transfer effect and a polymerization initiation effect, and examples of these include dithiobenzoate type, trithiocarbonate type, dithiocarbamate type, xanthate type, and disulfide type, which are precursors of these.

Examples of dithiobenzoate include 2-cyano-2-propyl dithiobenzoate, 4-cyano-4-(thiobenzoylthio)pentanoic acid, and 2-phenyl-2-propyl benzodithioate.

Examples of trithiocarbonate types include 4-[(2-carboxyethylsulfanylthiocarbonyl)sulfanyl]-4-cyanopentanoic acid, 2-{[(2-carboxyethyl)sulfanylthiocarbonyl]sulfanyl}propanoic acid, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, 2-cyano-2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propane, 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pe These include methyl trithiocarbonate, 2-methyl-2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, S,S-dibenzyl trithiocarbonate, trithiocarbonate = bis[4-(allyloxycarbonyl)benzyl], trithiocarbonate = bis[4-(2,3-dihydroxypropoxycarbonyl)benzyl], trithiocarbonate = bis{4-[ethyl-(2-acetyloxyethyl)carbamoyl]benzyl}, trithiocarbonate bis{4-[ethyl-(2-hydroxyethyl)carbamoyl]benzyl}, and trithiocarbonate = bis[4-(2-hydroxyethoxycarbonyl)benzyl].

Examples of dithiocarbamate include 2'-cyanobutan-2'-yl 4-chloro-3,5-dimethylpyrazole-1-carbodithioate, 2'-cyanobutan-2'-yl 3,5-dimethylpyrazole-1-carbodithioate, cyanomethyl 3,5-dimethylpyrazole-1-carbodithioate, and cyanomethyl N-methyl-N-phenyldithiocarbamate.

Examples of disulfide types include bis(dodecylsulfanylthiocarbonyl) disulfide and bis(thiobenzoyl) disulfide. These are preferred for producing A-B block polymers.

Among these, trithiocarbonate type compounds are preferred because the reaction during synthesis can be easily controlled, and 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, 2-cyano-2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propane, methyl 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate, bis{4-[ethyl-(2-hydroxyethyl)carbamoyl]benzyl} trithiocarbonate, and bis(dodecylsulfanylthiocarbonyl)disulfide are more preferred.

The amount of RAFT agent used is preferably 0.1 to 10 parts by mass per 100 parts by mass of monomer.

In the synthesis of the block acrylic basic dispersant, it is preferable to use an organic solvent. Examples of organic solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. The organic solvents may be used alone or in combination of two or more.

(Carboxylic acid-containing resin-type dispersant)
The resin-type dispersant used in the present invention preferably contains, for example, the following (S1) or (S2) as a resin-type dispersant having a carboxy group.
(S1) A resin-type dispersant which is a reaction product between a hydroxyl group of a hydroxyl group-containing polymer and an acid anhydride group of a tricarboxylic acid anhydride and/or a tetracarboxylic acid dianhydride.
(S2) A resin-type dispersant which is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and/or a tetracarboxylic acid dianhydride.

[Resin-type dispersant (S1)]
The resin-type dispersant (S1) can be produced by known methods such as those described in International Publication No. 2008/007776, JP 2008-029901 A, and JP 2009-155406 A. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the end, and can be obtained, for example, as a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) in the presence of a compound (q) having a hydroxyl group. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since it is preferable that the terminal hydroxyl group is a plurality of hydroxyl groups, among them, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a more preferred example of a polymer having two hydroxyl groups at one end can be obtained as a polymer (p1) by polymerizing an ethylenically unsaturated monomer (r) including a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. The hydroxyl groups of the polymer (p) having hydroxyl groups react with the acid anhydride groups of the tricarboxylic acid anhydride and/or tetracarboxylic acid dianhydride to form ester bonds, while the anhydride ring opens to produce a carboxylic acid.

[Resin-type dispersant (S2)]
The resin-type dispersant (S2) can be produced by known methods such as those described in JP-A-2009-155406, JP-A-2010-185934, and JP-A-2011-157416, and is obtained, for example, by polymerizing an ethylenically unsaturated monomer (r) in the presence of a reaction product between a hydroxyl group of a compound (q) having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and/or a tetracarboxylic acid dianhydride. Among them, a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing a monomer (r1) in the presence of a reaction product between a hydroxyl group of a compound (q1) having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of a tricarboxylic acid anhydride and/or a tetracarboxylic acid dianhydride is preferred.

The difference between (S1) and (S2) is whether the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (r) is introduced first or later. The molecular weight and other factors may differ slightly depending on various conditions, but in theory, the same product can be produced if the raw materials and reaction conditions are the same.

The resin-type dispersant is preferably thermosetting or photosetting. In addition, when used for photo-nanoimprinting, it is preferable that the resin-type dispersant is also more flexible from the viewpoint of transferability.

Resin-type dispersants may be used alone or in combination of two or more types.

When a resin-type dispersant or surfactant is added, the amount is preferably 0.1 to 200% by weight, and more preferably 0.1 to 150% by weight, based on the total amount of pigment (100% by weight). By keeping the amount of the resin-type dispersant or surfactant within the above range, favorable dispersibility can be achieved.

《Dye derivatives》
Examples of the dye derivative include compounds in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent has been introduced into an organic pigment, an anthraquinone, an acridone, or a triazine. For example, those described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-53-9469, and the like can be used, and these can be used alone or in combination of two or more kinds.

From the viewpoint of improving the dispersibility of the pigment, the amount of the dye derivative is preferably 0.5% by mass or more, more preferably 1% by mass or more, and most preferably 3% by mass or more, based on the total amount of the pigment (100% by mass). Also, from the viewpoint of heat resistance and light fastness, the amount is preferably 40% by mass or less, more preferably 35% by mass or less, based on the total amount of the added pigment (100% by mass).

Surfactants
Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphate esters; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyl dimethylaminoacetate betaine, and amphoteric surfactants such as alkyl imidazolines. These can be used alone or in combination of two or more.

When a resin-type dispersant or surfactant is added, the blending amount is preferably 0.1 to 200% by mass, and more preferably 0.1 to 150% by mass, based on the total amount of pigment (100% by mass). By blending the resin-type dispersant or surfactant in the above range, favorable dispersibility can be achieved.

<Organic Solvent>
The photosensitive composition of the present invention may contain an organic solvent in order to thoroughly disperse and penetrate the pigment and to facilitate molding of the high refractive index material.

Examples of organic solvents include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxyethyl propionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butylalcohol, ethanol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol glycerol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether Examples of the diethyl ether include diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

Among these, it is preferable to use glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone, because they have good pigment dispersibility and solubility. In particular, propylene glycol monomethyl ether acetate is more preferable from the viewpoints of safety and hygiene and low viscosity.

These organic solvents can be used alone or in combination of two or more. When using a mixed solvent of two or more, it is preferable that the above preferred organic solvents are contained in an amount of 65 to 95% by mass.

In addition, from the viewpoint of adjusting the viscosity of the photosensitive composition to an appropriate level and improving the formability of the high refractive index material, it is preferable to use the organic solvent in an amount of 800 to 4,000% by mass, based on the total mass of the colorant (100% by mass).

<Dispersion>
The pigment composition of the present invention can be produced by finely dispersing a pigment in a colorant carrier comprising a pigment and, if necessary, a resin and a solvent, preferably together with a dispersing aid such as a dye derivative, using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, an attritor, etc. The pigment composition of the present invention can also be produced by mixing pigments, dyes, other colorants, etc., which are separately dispersed in colorant carriers.

<Photopolymerizable Monomer>
The pigment composition of the present invention contains a photopolymerizable monomer. The photopolymerizable monomer has both heat curing and photocuring properties, and therefore can be suitably used in the nanoimprint method.
Furthermore, when used in photo-nanoimprinting, it is required to contain a photopolymerizable monomer that is flexible and photocurable from the viewpoint of transferability, and therefore the photopolymerizable monomer is preferably liquid at room temperature (25° C.).
The photopolymerizable monomer of the present invention includes a monomer or oligomer that is cured by ultraviolet light or heat to produce a transparent resin, and these can be used alone or in combination of two or more. In consideration of photocurability and flexibility, the blending amount of the photopolymerizable monomer is preferably 10 to 50 mass% of the solid content, and more preferably 15 to 30 mass%. If it is less than 10 mass%, the photocurability and flexibility tend to be insufficient, and if it is more than 50 wt%, the ratio of the pigment in the solid content tends to be low, making it difficult to achieve a high refractive index.

Examples of monomers and oligomers that harden when exposed to ultraviolet light or heat to produce a transparent resin include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A (meth)acrylate, tert-butyl ether ... Examples include phenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, (meth)acrylic acid ester of methylol melamine, epoxy (meth)acrylate, urethane acrylate, and other various acrylic acid esters and methacrylic acid esters, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

<Photopolymerization initiator>
The pigment composition of the present invention can be suitably used for photo-nanoimprinting, in which the pigment composition is cured by irradiation with ultraviolet light, as a photosensitive pigment composition containing a photopolymerization initiator (hereinafter, may be simply referred to as a photosensitive composition).
When a photopolymerization initiator is used, the amount of the photopolymerization initiator is preferably 0.2 to 20% by mass based on the solid content, and more preferably 0.5 to 10% by mass from the viewpoint of photocurability.

Examples of the photopolymerization initiator include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin, benzoin methyl ether, benzoin ether, and the like. Benzoin compounds such as benzoyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal; benzophenone compounds such as benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazanthone; 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl) )-6-triazine; oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.
In particular, oxime ester compounds have high sensitivity and exhibit photocurability even in small amounts, so that it is preferable to use oxime ester compounds in forming fine patterns.

These photopolymerization initiators can be used alone or in a mixture of two or more in any ratio as needed.

<Sensitizer>
Furthermore, the pigment composition of the present invention may contain a sensitizer. Examples of the sensitizer include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrin derivatives, and the like. Examples of the compound include aryl ether derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 4,4'-diethylaminobenzophenone.

More specifically, examples of sensitizers include those described in "Dye Handbook" edited by Okawara Makoto et al. (Kodansha, 1986), "Chemistry of Functional Dyes" edited by Okawara Makoto et al. (CMC, 1981), "Tokushu No Futon Zairyo" edited by Ikemori Chuzaburo et al., and "Tokushu No Futon Zairyo" (CMC, 1986), but are not limited to these. In addition, sensitizers that absorb light from the ultraviolet to near infrared regions can also be included.

Two or more types of sensitizers may be used in any ratio as necessary. When using a sensitizer, the amount is preferably 3 to 60% by mass, based on the total mass of the photopolymerization initiator contained in the pigment composition (100% by mass), and more preferably 5 to 50% by mass from the viewpoint of photocurability.

<Amine compounds>
The pigment composition of the present invention may contain an amine compound that has the function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

<Leveling Agent>
In order to improve the leveling properties of the composition, it is preferable to add a leveling agent to the pigment composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK-Chemie Co., Ltd. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie Co., Ltd. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5 mass% based on the total mass of the pigment composition (100 mass%).

Particularly preferred leveling agents are those that have hydrophobic and hydrophilic groups in the molecule, and are characterized by low solubility in water despite having hydrophilic groups, and low surface tension reducing ability when added to a pigment composition. Furthermore, those that have good wettability to glass plates despite their low surface tension reducing ability are useful, and those that can sufficiently suppress electrostatic charging at an amount added that does not cause film defects due to bubbling are preferably used. Dimethylpolysiloxanes having polyalkylene oxide units are preferably used as leveling agents having such preferred properties. Examples of polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxanes may have both polyethylene oxide units and polypropylene oxide units.

The bonding form of the polyalkylene oxide unit with the dimethylpolysiloxane may be any of a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane, a terminal modified type in which the polyalkylene oxide unit is bonded to the terminal of the dimethylpolysiloxane, and a linear block copolymer type in which the polyalkylene oxide unit is bonded alternately and repeatedly to the dimethylpolysiloxane. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray Co., Ltd., and examples thereof include, but are not limited to, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207.

The leveling agent may be supplemented with an anionic, cationic, nonionic, or amphoteric surfactant. Two or more types of surfactants may be mixed together.

Examples of anionic surfactants that can be added to the leveling agent as an auxiliary include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.

Examples of cationic surfactants that can be added to the leveling agent as supplementary agents include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of nonionic surfactants that can be added to the leveling agent as supplementary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, alkyl betaines such as alkyl dimethylaminoacetate betaine, amphoteric surfactants such as alkyl imidazolines, and fluorine-based and silicone-based surfactants.

<Other additives>
The pigment composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time, and may also contain an adhesion improver such as a silane coupling agent to improve adhesion to a substrate.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, organic phosphines such as tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the colorant (100% by mass).

Examples of adhesion enhancers include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth)acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of the silane coupling agents include epoxy silanes such as silane, amino silanes such as N-β (aminoethyl) γ-aminopropyl trimethoxy silane, N-β (aminoethyl) γ-aminopropyl triethoxy silane, N-β (aminoethyl) γ-aminopropyl methyl diethoxy silane, γ-aminopropyl triethoxy silane, γ-aminopropyl trimethoxy silane, N-phenyl-γ-aminopropyl trimethoxy silane, and N-phenyl-γ-aminopropyl triethoxy silane, and thio silanes such as γ-mercaptopropyl trimethoxy silane and γ-mercaptopropyl triethoxy silane. The adhesion improver can be used in an amount of 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the total amount of the colorant in the photosensitive composition (100% by mass).

<Removal of coarse particles>
The pigment composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation, a sintered filter, a membrane filter, etc. In this way, it is preferable that the photosensitive composition does not substantially contain particles of 0.5 μm or more, and more preferably particles of 0.3 μm or less.

<Membrane>
The present invention also covers a film obtained by curing the pigment composition of the present invention by solvent evaporation or exposure (photocuring) or heating (thermocuring) using a nanoimprint method, and a film having any fine shape can be formed. Examples of light rays for exposure include ultraviolet rays, electron beams, and X-rays. Examples of light sources that can be used for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs. After exposure, post-baking may be performed to stabilize the physical properties of the cured product. The method of post-baking is not particularly limited, but is usually performed using a hot plate, oven, or the like at 50 to 260° C. for 1 to 120 minutes.
The heating conditions for thermal curing are not particularly limited, but are usually appropriately selected from the ranges of 50 to 300° C. and 1 to 120 minutes. The heating means is not particularly limited, but examples thereof include a hot plate and an oven.

The film formed from the pigment composition of the present invention has a high refractive index in the wavelength region of 800 to 1600 nm, and is suitable as a material for forming optical lenses for infrared sensors or infrared communication devices, or optical waveguides for infrared sensors or infrared communication devices.

The photosensitive composition of the present invention can be molded into any minute shape, such as a dome or stripe shape, by nanoimprinting. For example, it can be molded into a microlens or an optical waveguide.

In this specification, an optical lens for an infrared sensor or infrared communication device refers to a lens for concentrating infrared light, and examples of such lenses include eyeglass lenses, lenses for optical devices, lenses for optoelectronics, lenses for lasers, lenses for pickups, lenses for in-vehicle cameras, lenses for mobile phones, lenses for digital cameras, lenses for overhead projectors, and microlenses.

In this specification, an optical waveguide for an infrared sensor or infrared communication device refers to a waveguide for propagating infrared rays, and its shape is not limited to a sheet or plate. Examples of uses include cables used for optical communication in computers and sensor devices, optical interconnections used for optical communication inside devices, and materials used on the optical path when an infrared sensor or the like senses infrared rays.

The present invention will be described in more detail below, but is not limited to these examples as long as they do not deviate from the technical concept of the present invention. In the following, "parts by mass" will simply be written as "parts" and "% by mass" will simply be written as "%".

<Production of Phthalocyanine or Naphthalocyanine Pigments>
<Production of copper phthalocyanine pigment>

(Production of Phthalocyanine Pigment (PC-1))
100 parts of a phthalocyanine blue pigment C.I. Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70° C. This mixture was added to 3,000 parts of warm water, heated to about 70° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly with water to remove salt and the solvent, and then dried at 80° C. for 24 hours to obtain 98 parts of a phthalocyanine pigment (PC-1).

(Production of Phthalocyanine Pigment (PC-2))
A phthalocyanine pigment (PC-2) was obtained in the same manner as in the production of the phthalocyanine pigment (PC-1), except that C.I. Pigment Blue 15:2 was used instead of the phthalocyanine blue pigment C.I. Pigment Blue 15:6.

(Production of Phthalocyanine Pigment (PC-3))
A phthalocyanine pigment (PC-3) was obtained in the same manner as in the production of the phthalocyanine pigment (PC-1), except that C.I. Pigment Blue 15:3 was used instead of the phthalocyanine blue pigment C.I. Pigment Blue 15:6.

(Production of Phthalocyanine Pigment (PC-4))
Phthalocyanine pigment (PC-4) was obtained in the same manner as in the production of phthalocyanine pigment (PC-1), except that CI Pigment Blue 15:1 was used instead of the phthalocyanine blue pigment CI Pigment Blue 15:6.

The following phthalocyanine pigments (PC-5) to (PC-12) were obtained by a known method.
Phthalocyanine pigment (PC-5): C.I. Pigment Green 36
Phthalocyanine pigment (PC-6): C.I. Pigment Green 58
Phthalocyanine pigment (PC-7): C.I. Pigment Green 7
Phthalocyanine pigment (PC-8): Lithium phthalocyanine phthalocyanine pigment (PC-9): Magnesium phthalocyanine phthalocyanine pigment (PC-10): Chloroaluminum phthalocyanine phthalocyanine pigment (PC-11): Dichlorosilicon phthalocyanine phthalocyanine pigment (PC-12): Titanium phthalocyanine phthalocyanine pigment (PC-13): Manganese phthalocyanine phthalocyanine pigment (PC-14): Iron phthalocyanine phthalocyanine pigment (PC-15): Cobalt phthalocyanine phthalocyanine pigment (PC-16): Nickel phthalocyanine phthalocyanine pigment (PC-17): Tin phthalocyanine phthalocyanine pigment (PC-18): Lead phthalocyanine phthalocyanine pigment (PC-19): Platinum phthalocyanine

<Production of Aluminum Phthalocyanine Pigment>
The following aluminum phthalocyanine was produced with reference to JP2012-155231A.

<Production of halogenated aluminum phthalocyanine>
With reference to JP2016-153481A, the following halogenated aluminum phthalocyanine pigment was produced.

<Production of aluminum naphthalocyanine pigment>

Aluminum naphthalocyanine pigments (Cpr-1) to (Cpr-21)

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-1))
In a reaction vessel, 1135 parts of quinoline, 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol, and 40 parts of anhydrous aluminum chloride were mixed and stirred, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water while stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 159 parts of chloroaluminum naphthalocyanine represented by the following structural formula (1-1). As a result of mass analysis and elemental analysis by TOF-MS, the obtained compound was identified by the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

Chloroaluminum Naphthalocyanine (1-1)

Next, in a reaction vessel, 100 parts of concentrated sulfuric acid was added with 10 parts of the above chloroaluminum naphthalocyanine (1-1) in an ice bath, and the mixture was stirred for 1 hour. Subsequently, this sulfuric acid solution was poured into 1,000 parts of cold water at 3°C, and the resulting precipitate was filtered, washed with water, washed with a 2.5% aqueous sodium hydroxide solution, and washed with water, and then dried to obtain 8 parts of naphthalocyanine pigment (Cpr-1). As a result of mass analysis and elemental analysis using TOF-MS, the compound obtained was identified by the agreement between the molecular ion peak in the obtained mass spectrum and the mass number obtained by calculation. The molecular weight was 884.74.

Synthesis of aluminum naphthalocyanine pigment (Cpr-2) Instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol and 1135 parts of quinoline used in the synthesis of aluminum naphthalocyanine pigment (Cpr-1), 178 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, and 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) were used, respectively, and the same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was performed to obtain 125 parts of naphthalocyanine pigment (Cpr-2). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation were matched, and the obtained compound was identified. The molecular weight was 756.75.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-3))
100 parts of the above naphthalocyanine pigment (Cpr-2) was added to 1500 parts of concentrated sulfuric acid under ice bath. Then, 151 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25°C for 6 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3°C, and the resulting precipitate was filtered, washed with water, washed with a 1% aqueous sodium hydroxide solution, and washed with water, and then dried to obtain 170 parts of naphthalocyanine pigment (Cpr-3). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. When the number of bromine substitutions was calculated for the obtained naphthalocyanine pigment (Cpr-3), it was found to be 8.4 on average, and a peak corresponding to the same molecular weight was also confirmed from the mass spectrum, and the target compound was identified. The molecular weight was 1419.51.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-4))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 339 parts of 4,9-dibutoxy-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 237 parts of naphthalocyanine pigment (Cpr-4). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1333.59.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-5))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 264 parts of 4,9-dichloro-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 185 parts of naphthalocyanine pigment (Cpr-5). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1032.31.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-6))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 232 parts of 5-nitro-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 162 parts of naphthalocyanine pigment (Cpr-6). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 905.08.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-7))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 245 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-6,7-dicarbonitrile was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 171 parts of naphthalocyanine pigment (Cpr-7). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 956.82.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-8))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 239 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-5-carboxylic acid was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 167 parts of naphthalocyanine pigment (Cpr-8). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 932.79.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-9))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 275 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-5-sulfonic acid was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 192 parts of naphthalocyanine pigment (Cpr-9). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1077.0.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-10))
Except for using 271 parts of 4-phenyl-1H-benzo[f]isoindole-1,3(2H)-diimine instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), the same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was performed to obtain 190 parts of naphthalocyanine pigment (Cpr-10). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1061.13.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-11))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 223 parts of 6,7-dimethyl-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 156 parts of naphthalocyanine pigment (Cpr-11). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 868.96.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-12))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 281 parts of 5-(neopentyloxy)-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 197 parts of naphthalocyanine pigment (Cpr-12). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1101.28.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-13))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 287 parts of 6-phenoxy-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 201 parts of naphthalocyanine pigment (Cpr-13). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1125.13.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-14))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 269 parts of 6-(isopropylthio)-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 188 parts of naphthalocyanine pigment (Cpr-14). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1053.33.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-15))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 303 parts of 6-(phenylthio)-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 212 parts of naphthalocyanine pigment (Cpr-15). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1189.39.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-16))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 266 parts of N-tert-butyl-1,3-diimino-2,3-dihydro-1H-benzo[f]isoindol-6-amine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindol-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 186 parts of naphthalocyanine pigment (Cpr-16). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1041.23.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-17))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 300 parts of 1,3-diimino-N-p-tolyl-2,3-dihydro-1H-benzo[f]isoindol-6-amine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindol-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 210 parts of naphthalocyanine pigment (Cpr-17). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1177.3.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-18))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 277 parts of 6-cyclohexyl-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 194 parts of naphthalocyanine pigment (Cpr-18). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1085.32.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-19))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 302 parts of 1,3-diimino-N,N-dimethyl-2,3-dihydro-1H-benzo[f]isoindole-6-sulfonamide was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 211 parts of naphthalocyanine pigment (Cpr-19). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1185.27.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-20))
Except for using 324 parts of 6,7-dichloro-4,9-dimethoxy-1H-benzo[f]isoindole-1,3(2H)-diimine instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), the same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was performed to obtain 227 parts of naphthalocyanine pigment (Cpr-20). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1272.52.

(Synthesis of Aluminum Naphthalocyanine Pigment (Cpr-21))
The same operation as in the synthesis of naphthalocyanine pigment (Cpr-1) was carried out, except that 397 parts of 4,9-dibromo-6-ethoxy-1H-benzo[f]isoindole-1,3(2H)-diimine was used instead of 227 parts of 1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-4,9-diol used in the synthesis of naphthalocyanine pigment (Cpr-1), to obtain 278 parts of naphthalocyanine pigment (Cpr-21). As a result of mass analysis and elemental analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum coincided with the mass number obtained by calculation, and the obtained compound was identified. The molecular weight was 1564.13.

(Synthesis of Aluminum Naphthalocyanine Pigment (C-1))
A naphthalocyanine pigment (C-1) consisting of a naphthalocyanine pigment (Cpr-2) and a phosphorus compound was produced by the following procedure. 5 parts of diphenyl phosphoric acid was added to 200 parts of N-methylpyrrolidone, and the mixture was thoroughly stirred and mixed, and then heated to 50°C. 10 parts of the naphthalocyanine pigment (Cpr-2) was gradually added to this solution, and the mixture was stirred at 90°C for 120 minutes. The end point of the reaction was confirmed, for example, by dropping the reaction solution onto a filter paper and determining that no bleeding had occurred. Subsequently, the reaction solution was poured into 2000 parts of water, and the resulting precipitate was filtered, washed with water, and dried to obtain 12 parts of the following naphthalocyanine pigment (C-1).

Aluminum naphthalocyanine pigment (C-1)

Aluminum naphthalocyanine pigments (C-2) to (C-34)

Aluminaphthalocyanine pigments (C-2) to (C-34) were synthesized in the same manner as aluminum naphthalocyanine pigment (C-1), except that the composition was changed to that shown in Table 1-1.

<Production of Aluminum Phthalocyanine/Naphthalocyanine Co-Synthetic Pigment>
(Synthesis of Aluminum Phthalocyanine/Naphthalocyanine Co-Synthetic Pigment (a-1))
In a reaction vessel, 64 parts of phthalonitrile, 89 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) and 34 parts of aluminum trichloride were mixed and stirred, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water while stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 140 parts of phthalocyanine pigment (apr-1) (a mixture of compounds represented by the following structural formula). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation were matched, and the obtained compound was identified.

Aluminum phthalocyanine/naphthalocyanine co-synthetic pigment (apr-1)

Next, in a reaction vessel, 140 parts of the above phthalocyanine pigment (apr-1) was added to 1,500 parts of concentrated sulfuric acid in an ice bath, and the mixture was stirred for 1 hour. Subsequently, this sulfuric acid solution was poured into 1,000 parts of cold water at 3°C, and the resulting precipitate was filtered, washed with water, washed with a 2.5% aqueous sodium hydroxide solution, and washed with water, and then dried to obtain 120 parts of phthalocyanine pigment (a-1). As a result of mass analysis using TOF-MS, the molecular ion peak of the obtained mass spectrum matched with the mass number obtained by calculation, and the obtained compound was identified. Phthalocyanine pigment (a-1) was a mixture of compounds represented by the following structural formula, and the main component was the n2 form.

(Synthesis of Aluminum Phthalocyanine/Naphthalocyanine Co-Synthetic Pigment (a-2))
The same operations as in the synthesis of phthalocyanine pigment (a-1) were carried out, except that 26 parts of phthalonitrile and 143 parts of 2,3-dicyanonaphthalene were used instead of 64 parts of phthalonitrile and 89 parts of 2,3-dicyanonaphthalene used in the synthesis of phthalocyanine pigment (a-1), respectively, to obtain 147 parts of phthalocyanine pigment (a-2). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched with the mass number obtained by calculation, and the obtained compound was identified. The main component of phthalocyanine pigment (a-2) was an n3 form having the following structure.

(Synthesis of Aluminum Phthalocyanine/Naphthalocyanine Co-Synthetic Pigment (a-3))
The same operations as in the synthesis of phthalocyanine pigment (a-1) were carried out, except that 13 parts of phthalonitrile and 160 parts of 2,3-dicyanonaphthalene were used instead of 64 parts of phthalonitrile and 89 parts of 2,3-dicyanonaphthalene used in the synthesis of phthalocyanine pigment (a-1), respectively, to obtain 147 parts of phthalocyanine pigment (a-3). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched with the mass number obtained by calculation, and the obtained compound was identified. The main component of phthalocyanine pigment (a-3) was an n3 form having the following structure.

(Synthesis of Aluminum Phthalocyanine/Naphthalocyanine Co-Synthetic Pigment (a-4))
The same operations as in the synthesis of phthalocyanine pigment (a-1) were carried out, except that 102 parts of phthalonitrile and 36 parts of 2,3-dicyanonaphthalene were used instead of 64 parts of phthalonitrile and 89 parts of 2,3-dicyanonaphthalene used in the synthesis of phthalocyanine pigment (a-1), respectively, to obtain 147 parts of phthalocyanine pigment (a-4). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched with the mass number obtained by calculation, and the obtained compound was identified. The main component of phthalocyanine pigment (a-4) was the n1 form having the following structure.

(Synthesis of Aluminum Phthalocyanine/Naphthalocyanine Co-Synthetic Pigment (a-5))
In a reaction vessel, 900 parts of quinoline, 30 parts of 3-tetrafluoropropyloxy-1,3-diiminoisoindoline, 86 parts of 1,3-diiminobenzo[f]isoindoline, and 50 parts of anhydrous aluminum chloride were mixed and stirred. The mixture was heated and stirred at 140°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into a mixed solvent consisting of 5,000 parts of methanol and 10,000 parts of water while stirring, to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2,000 parts of methanol and 4,000 parts of water, and dried to obtain 108 parts of phthalocyanine pigment (apr-5).

Then, in a reaction vessel, 114 parts of the above phthalocyanine pigment (apr-5) was added to 1,500 parts of concentrated sulfuric acid in an ice bath, and the mixture was stirred for 1 hour. Subsequently, this sulfuric acid solution was poured into 15,000 parts of cold water at 3°C, and the resulting precipitate was filtered, washed with water, washed with a 2.5% aqueous sodium hydroxide solution, and washed with water, and then dried to obtain 100 parts of phthalocyanine pigment (a-5). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched with the mass number obtained by calculation, and the obtained compound was identified. The main component of the phthalocyanine pigment (a-5) was the n3 form of the following structure.

The composition of the resulting aluminum phthalocyanine/naphthalocyanine co-synthetic pigment is shown in Table 1-2. The n3 form corresponds to the phthalocyanine pigment represented by the general formula (3-3) above.

(Production of Aluminum Phthalocyanine/Naphthalocyanine Co-Synthetic Pigment (A-1))
5 parts of diphenyl phosphoric acid was added to 200 parts of N-methylpyrrolidone, and the mixture was thoroughly stirred and mixed, and then heated to 50°C. 10 parts of phthalocyanine pigment (a-1) was gradually added to this solution, and the mixture was stirred at 90°C for 120 minutes. The end point of the reaction was confirmed, for example, by dropping the reaction solution onto filter paper and determining that the end point was when no bleeding occurred. Subsequently, this reaction solution was poured into 2000 parts of water, and the resulting precipitate was filtered, washed with water, and dried to obtain 12 parts of phthalocyanine pigment (A-1).

(Production of Aluminum Phthalocyanine/Naphthalocyanine Co-Synthetic Pigments (A-2) to (A-5))
The same procedure as for the production of the aluminum phthalocyanine/naphthalocyanine co-synthetic pigment (A-1) was carried out for the phthalocyanine pigments (a-2) to (a-5) to obtain the phthalocyanine pigments (A-2) to (A-5).

<Measurement of the average primary particle size of pigment>
The average primary particle size of the pigment was measured by a method of directly measuring the size of the primary particles from an electron microscope photograph. Specifically, the minor axis diameter and major axis diameter of each primary particle of the pigment were measured, and the average was taken as the particle size of the pigment particle. Next, for 100 or more pigment particles, the volume (weight) of each particle was calculated by approximating it to a cube of the calculated particle size, and the volume average particle size was taken as the average primary particle size. Note that a transmission electron microscope (TEM) was used.
As a result of measurement by this method, the average primary particle diameter of the phthalocyanine pigment (PC-1) was 28 nm.
The average primary particle diameters of the pigment and finely divided pigment measured by the above method are shown in Table 2.

<Production of squarylium pigments>

Squarylium pigments (S-1) to (S-12)

(Production of squarylium pigment (S-1))
400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 25.1 parts of cyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 3 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 8 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation.
After completion of the reaction, the solvent was distilled, and 200 parts of hexane was added to the resulting reaction mixture while stirring. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain 61.9 parts of squarylium pigment (S-1) (yield: 92%). As a result of mass analysis using a TOF-MS (time-of-flight mass spectrometer), the resulting product was identified as the squarylium pigment (S-1).

(Production of squarylium pigment (S-2))
The same procedure as in the production of squarylium pigment (S-1) was carried out, except that 32.2 parts of 2,6-dimethylcyclohexanone was used instead of the 25.1 parts of cyclohexanone used in the production of squarylium pigment (S-1), to obtain 71.9 parts of squarylium pigment (S-2) (yield: 97%). As a result of mass analysis by TOF-MS, the resulting product was identified as the squarylium pigment (S-2).

(Production of squarylium pigment (S-3))
The same procedure as in the production of squarylium pigment (S-1) was carried out, except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of the 25.1 parts of cyclohexanone used in the production of squarylium pigment (S-1), to obtain 72.6 parts of squarylium pigment (S-3) (yield: 98%). As a result of mass analysis by TOF-MS, the resulting product was identified as the squarylium pigment (AS-3).

(Production of squarylium pigment (S-4))
The same procedure as in the production of squarylium pigment (S-1) was carried out, except that 28.6 parts of 4-methylcyclohexanone was used instead of the 25.1 parts of cyclohexanone used in the production of squarylium pigment (S-1), to obtain 67.2 parts of squarylium pigment (S-4) (yield: 95%). As a result of mass analysis by TOF-MS, the resulting product was identified as the squarylium pigment (S-4).

(Production of squarylium pigment (S-5))
The same procedure as in the production of squarylium pigment (S-1) was carried out, except that 39.4 parts of 3,5-diethylcyclohexanone was used instead of the 25.1 parts of cyclohexanone used in the production of squarylium pigment (S-1), to obtain 76.9 parts of squarylium pigment (S-5) (yield: 95%). As a result of mass analysis by TOF-MS, the resulting product was identified as the squarylium pigment (S-5).

(Production of squarylium pigment (S-6))
The same procedure as in the production of squarylium pigment (S-1) was carried out, except that 28.1 parts of 2-norbornanone was used instead of the 25.1 parts of cyclohexanone used in the production of squarylium pigment (S-1), to obtain 64.6 parts of squarylium pigment (S-6) (yield: 92%). As a result of mass analysis by TOF-MS, the resulting product was identified as the squarylium pigment (S-6).

(Production of squarylium pigment (S-7))
400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 46.0 parts of 9-fluorenone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 3 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 8 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the solvent was distilled, and 200 parts of hexane was added while stirring the resulting reaction mixture. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain 84.6 parts (yield: 97%) of a squarylium pigment (S-7). As a result of mass spectrometry and elemental analysis by TOF-MS, the squarylium pigment (S-7) was identified as the squarylium pigment (S-7).

(Production of squarylium pigment (S-8))
The same operations as in the production of squarylium pigment (S-7) were carried out, except that 49.6 parts of 2-methyl-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of squarylium pigment (S-7), to obtain 86.7 parts of squarylium pigment (S-8) (yield: 96%). As a result of mass spectrometry and elemental analysis by TOF-MS, the product was identified as the squarylium pigment (S-8).

(Production of squarylium pigment (S-9))
The same operations as in the production of squarylium pigment (S-7) were carried out, except that 60.3 parts of 3,6-diethyl-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of squarylium pigment (S-7), to obtain 95.0 parts of squarylium pigment (S-9) (yield: 94%). As a result of mass spectrometry and elemental analysis by TOF-MS, the product was identified as the squarylium pigment (S-9).

(Production of squarylium pigment (S-10))
The same operations as in the production of squarylium pigment (S-7) were carried out, except that 80.7 parts of 2,7-bis(trifluoromethyl)-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of squarylium pigment (S-7), to obtain 109.8 parts of squarylium pigment (S-10) (yield: 91%). As a result of mass analysis and elemental analysis by TOF-MS, the product was identified as the squarylium pigment (S-10).

(Production of squarylium pigment (S-11))
The same operations as in the production of squarylium pigment (S-7) were carried out, except that 50.1 parts of 2-hydroxy-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of squarylium pigment (S-7), to obtain 83.9 parts of squarylium pigment (S-11) (yield: 92%). As a result of mass spectrometry and elemental analysis by TOF-MS, the squarylium pigment was identified as the squarylium pigment (S-11).

(Production of squarylium pigment (S-12))
The same operations as in the production of squarylium pigment (S-7) were carried out, except that 72.1 parts of 13H-benzo[g]indeno[2,1-b]quinoxalin-13-one was used instead of 46.0 parts of 9-fluorenone used in the production of squarylium pigment (S-7), to obtain 107.1 parts of squarylium pigment (S-12) (yield: 96%). As a result of mass spectrometry and elemental analysis by TOF-MS, the product was identified as the squarylium pigment (S-12).

(Micronization of squarylium pigment (S-1))
10 parts of the squarylium pigment (S-1), 100 parts of sodium chloride, and 12.5 parts of ethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 12 hours at 60° C. Next, the kneaded mixture was poured into warm water and stirred for 1 hour while heating to about 80° C. to form a slurry, which was then filtered and washed with water to remove the salt and diethylene glycol, and then dried overnight at 80° C. and pulverized to obtain 9.4 parts of squarylium pigment (S-1K).

(Micronization of squarylium pigments (S-2) to (S-12))
Squaryllium pigments (S-2) to (S-12) were also subjected to the same micronization treatment as squarylium pigment (S-1), to obtain squarylium pigments (S-2K) to (S-12K).

<Production of indigo pigment>
(Production of Pigment (aa-1))
In a reaction vessel, 10.7 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. Then, 95.2 parts of a 1 mol/l toluene solution of titanium tetrachloride was added dropwise. After the dropwise addition, 10.0 parts of indigo were added and refluxed for 10 hours. After the reaction was completed, methanol was added and filtered to obtain a green powder. This was separated with dichloromethane and water, and the organic layer was concentrated to obtain 14.6 parts of compound (1).

[Compound (1)]

In a reaction vessel, 13.5 parts of compound (1), 9.0 parts of bis(2,4-pentanedionato)zinc(II), and 120 parts of tetrahydrofuran were mixed and stirred, and the mixture was heated and stirred at 40°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into 500 parts of methanol while stirring to obtain a blue slurry. This slurry was filtered, washed with 500 parts of methanol, washed with 500 parts of water, and dried to obtain 12.2 parts of pigment (aa-1). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-1) was compound (aa-1-1), and the formation of compound (aa-1-2) (hereinafter referred to as trimer) and compound (aa-1-3) (hereinafter referred to as tetramer) was also confirmed by TOF-MS. The infrared absorption spectrum of pigment (aa-1) is shown in Figure 1.

(Production of Pigment (aa-2))
The same procedure as in the synthesis of pigment (aa-1) was carried out, except that the 9.0 parts of bis(2,4-pentanedionato)zinc(II) used in the synthesis of pigment (aa-1) was changed to 25.0 parts, to obtain 11.7 parts of pigment (aa-2). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-2) was compound (aa-1-2). The infrared absorption spectrum of pigment (aa-2) is shown in FIG. 2.

(Production of Pigment (aa-3))
The same procedure as in the synthesis of pigment (aa-1) was carried out, except that 9.0 parts of bis(2,4-pentanedionato)zinc(II) used in the synthesis of pigment (aa-1) was replaced with 15.0 parts of zinc acetate dihydrate, to obtain 12.3 parts of pigment (aa-3). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched with the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-3) was compound (aa-1-1). The infrared absorption spectrum of pigment (aa-3) is shown in FIG. 3.

(Production of Pigment (aa-4))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 18.5 parts of 2,3-dichloroaniline, to obtain 17.8 parts of compound (2).

[Compound (2)]

Except for changing the 13.5 parts of compound (1) used in the synthesis of pigment (aa-2) to 15.8 parts of compound (2), the same procedure as in the synthesis of pigment (aa-2) was carried out to obtain 14.6 parts of pigment (aa-4). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-4) was compound (aa-4-1). The infrared absorption spectrum of pigment (aa-4) is shown in Figure 4.

Compound (aa-4-1)

(Production of Pigment (aa-5))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 14.6 parts of 3,4-difluoroaniline, to obtain 16.2 parts of compound (3).

[Compound (3)]

Except for changing the 13.5 parts of compound (1) used in the synthesis of pigment (aa-2) to 14.7 parts of compound (3), the same procedure as in the synthesis of pigment (aa-2) was carried out to obtain 13.4 parts of pigment (aa-5). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-5) was compound (aa-5-1). The infrared absorption spectrum of pigment (aa-5) is shown in Figure 5.

Compound (aa-5-1)

(Production of Pigment (aa-6))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 19.8 parts of 4-bromoaniline, to obtain 20.0 parts of compound (4).

[Compound (4)]

Except for changing the 13.5 parts of compound (1) used in the synthesis of pigment (aa-2) to 19.7 parts of compound (4), the same procedure as in the synthesis of pigment (aa-2) was carried out to obtain 15.0 parts of pigment (aa-6). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-6) was compound (aa-6-1).

Compound (aa-6-1)

(Production of Pigment (aa-7))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 12.3 parts of p-toluidine, to obtain 14.9 parts of compound (5).

[Compound (5)]

Except for changing the 13.5 parts of compound (1) used in the synthesis of pigment (aa-2) to 14.0 parts of compound (5), the same procedure as in the synthesis of compound (aa-2) was carried out to obtain 13.2 parts of pigment (aa-7). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-7) was compound (aa-7-1).

Compound (aa-7-1)

(Production of Pigment (aa-8))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 16.0 parts of 4-(methylthio)aniline, to obtain 16.4 parts of compound (6).

[Compound (6)]

Except for changing the 13.5 parts of compound (1) used in the synthesis of pigment (aa-2) to 15.0 parts of compound (6), the same procedure as in the synthesis of compound (aa-2) was carried out to obtain 14.2 parts of pigment (aa-8). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-8) was compound (aa-8-1).

Compound (aa-8-1)

(Production of Pigment (aa-9))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 20.0 parts of sulfanilic acid, to obtain 17.5 parts of compound (7).

[Compound (7)]

Except for changing the 13.5 parts of compound (1) used in the synthesis of pigment (aa-2) to 16.0 parts of compound (6), the same procedure as in the synthesis of compound (aa-2) was carried out to obtain 15.2 parts of compound (aa-9). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (aa-9) was compound (aa-9-1).

Compound (aa-9-1)

(Production of Pigment (aa-10))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 14.2 parts of 4-amino-2-methylphenol, to obtain 17.5 parts of compound (8).

[Compound (8)]

Except for changing the 13.5 parts of compound (1) used in the synthesis of pigment (aa-2) to 14.5 parts of compound (8), the same procedure as in the synthesis of compound (aa-2) was carried out to obtain 13.1 parts of pigment (aa-10). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-10) was compound (aa-10-1).

Compound (aa-10-1)

(Production of Pigment (aa-11))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 14.2 parts of 3-methoxyaniline, to obtain 17.3 parts of compound (9).

[Compound (9)]

Except for changing the 13.5 parts of compound (1) used in the synthesis of pigment (aa-2) to 14.5 parts of compound (9), the same procedure as in the synthesis of pigment (aa-2) was carried out to obtain 12.8 parts of pigment (aa-11). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-11) was compound (aa-11-1).

Compound (aa-11-1)

(Production of Pigment (aa-12))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 21.3 parts of 4-phenoxyaniline, to obtain 18.8 parts of compound (10).

[Compound (10)]

Except for changing the 13.5 parts of compound (1) used in the synthesis of pigment (aa-2) to 16.5 parts of compound (10), the same procedure as in the synthesis of compound (aa-2) was carried out to obtain 15.3 parts of pigment (aa-12). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-12) was compound (aa-12-1).

Compound (aa-12-1)

(Production of Pigment (aa-13))
The same procedure as in the synthesis of compound (1) was carried out except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 18.8 parts of N,N-diethyl-1,4-phenylenediamine, to obtain 18.8 parts of compound (11).

[Compound (11)]

Except for changing the 13.5 parts of compound (1) used in the synthesis of pigment (aa-2) to 15.7 parts of compound (11), the same procedure as in the synthesis of pigment (aa-2) was carried out to obtain 14.2 parts of pigment (aa-13). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-13) was compound (aa-13-1).

Compound (aa-13-1)

(Production of compound (aa-14))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 13.7 parts of 4-cyanoaniline, to obtain 16.0 parts of compound (12).

[Compound (12)]

The same procedure as in the synthesis of pigment (aa-2) was carried out, except that 13.5 parts of compound (1) used in the synthesis of pigment (aa-2) was replaced with 15.2 parts of compound (12), to obtain 14.6 parts of pigment (aa-14). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched with the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-14) was compound (aa-14-1).

Compound (aa-14-1)

(Production of compound (aa-15))
The same procedure as in the synthesis of compound (1) was carried out except that 10.0 parts of indigo used in the synthesis of compound (1) was changed to 16.0 parts of Bat Blue 35, to obtain 19.5 parts of compound (13).

[Compound (13)]

Except for changing the 13.5 parts of compound (1) used in the synthesis of pigment (aa-2) to 18.7 parts of compound (13), the same procedure as in the synthesis of pigment (aa-2) was carried out to obtain 17.5 parts of pigment (aa-15). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-15) was compound (aa-15-1).

Compound (aa-15-1)

(Production of Pigment (aa-16))
The same procedure as in the synthesis of compound (1) was carried out except that 10.0 parts of indigo used in the synthesis of compound (1) was changed to 22.0 parts of Bat Blue 5, to obtain 24.4 parts of compound (14).

[Compound (14)]

Except for changing the 13.5 parts of compound (1) used in the synthesis of pigment (aa-2) to 23.9 parts of compound (14), the same procedure as in the synthesis of pigment (aa-2) was carried out to obtain 21.5 parts of pigment (aa-16). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-16) was compound (aa-16-1).

Compound (aa-16-1)

(Production of pigment (aa-17))

Except for changing the 9.0 parts of bis(2,4-pentanedionato)zinc(II) used in the synthesis of pigment (aa-1) to 8.8 parts of bis(2,4-pentanedionato)nickel(II) hydrate, the same procedure as in the synthesis of pigment (aa-1) was carried out to obtain 11.5 parts of pigment (aa-17). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-17) was compound (aa-17-1). The infrared absorption spectrum of pigment (aa-17) is shown in Figure 6.

Compound (aa-17-1)

(Production of pigment (aa-18))

The same procedure as in the synthesis of pigment (aa-3) was carried out, except that 15.0 parts of zinc acetate dihydrate used in the synthesis of pigment (aa-3) was replaced with 17.0 parts of nickel (II) acetate tetrahydrate, to obtain 10.1 parts of pigment (aa-18). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched with the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-18) was compound (aa-18-2).
Compound (aa-18-2)

(Production of Pigment (aa-19))
The same operations as in the synthesis of pigment (aa-1) were carried out, except that 9.0 parts of bis(2,4-pentanedionato)zinc(II) used in the synthesis of pigment (aa-1) was changed to 12.6 parts of bis(2,4-pentanedionato)cobalt(II), to obtain 12.7 parts of pigment (aa-19). As a result of mass analysis by TOF-MS, the molecular ion peak of the obtained mass spectrum matched with the mass number obtained by calculation, and the obtained compound was identified. The main component of pigment (aa-19) was compound (aa-19-1). The infrared absorption spectrum of pigment (aa-19) is shown in FIG. 7.

Compound (aa-19-1)

(Synthesis of Pigment (aa-20))
According to JP 2012-224593 A, a pigment (aa-20) having the following structure was obtained.

Pigment (aa-20)

＜Production of fine pigments＞

(Production of Yellow Micronized Pigment (PY-1))
200 parts of isoindoline-based yellow pigment C.I. Pigment Yellow 139 (BASF "Paliotol Yellow L 2146HD"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water and stirred for 2 hours while heating to 80 ° C. to form a slurry. This slurry was filtered and repeatedly washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for one day to obtain a yellow fine pigment (PY-1).

(Production of Purple Micronized Pigment (PV-1))
120 parts of dioxazine-based purple pigment C.I. Pigment Violet 23 (Clariant's "FastViolet RL"), 1600 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded at 90 ° C for 18 hours. This mixture was added to 5000 parts of hot water, heated to about 70 ° C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C for 24 hours to obtain 118 parts of purple fine pigment (PV-1). The average primary particle diameter of the obtained pigment was 26 nm.

<Method of preparing binder resin solution>
(Binder resin solution 1)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer to prepare a reaction vessel. 70.0 parts of cyclohexanone were charged, and the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. A mixture of 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 0.4 parts of 2,2'-azobisisobutyronitrile was dripped over 2 hours from the drip tube. After dripping was completed, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin with a weight average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the resin solution synthesized earlier so that the nonvolatile content was 20% by weight to prepare binder resin solution 1. Here, the weight average molecular weight (Mw) of the binder resin was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

(Binder resin solution 2)
A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 370 parts of cyclohexanone, heated to 80°C, and the atmosphere in the flask was replaced with nitrogen. From the dropping tube, a mixture of 18 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate and 2.0 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours. After the dropping, the mixture was further reacted at 100°C for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 100°C for 1 hour. Next, the inside of the vessel was replaced with air, and 9.3 parts of acrylic acid (100% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the vessel, and the reaction was continued for 6 hours at 120° C., and the reaction was terminated when the solid acid value reached 0.5, to obtain a copolymer solution. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added, and the reaction was continued for 3.5 hours at 120° C., to obtain a copolymer solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content became 20% by weight, to prepare binder resin solution 2. The weight average molecular weight (Mw) was 19,000.
The binder resin solution 2 has a methacryloyl group and is therefore thermosetting and photosetting.

<Method for preparing a resin-type dispersant solution>
(Resin-type dispersant solution 1): Block acrylic-type basic dispersant [Synthesis of monomer (b-1)]
In a reaction vessel equipped with a stirrer and a thermometer, 60 parts of 2-isocyanatoethyl methacrylate, 29 parts of 3-(dimethylamino)propylamine, and 120 parts of THF were charged and stirred at room temperature for 5 hours. After confirming the completion of the reaction by FT-IR, the solvent was distilled off with a rotary evaporator to obtain 73 parts of the following monomer (b-1) as a pale yellow transparent liquid (yield 82%). The obtained compound was identified by ¹ H-NMR.

Monomer (b-1)

[Synthesis of Monomer (b-2)]
In a reaction vessel equipped with a stirrer and a thermometer, 6.6 parts of monomer (b-1) obtained by the synthesis of monomer (b-1) and 5 parts of ion-exchanged water were charged and stirred at room temperature, and then 8 parts of 35% aqueous hydrochloric acid solution was added dropwise. The completion of the reaction was confirmed by amine value measurement, and 20 parts of an aqueous solution of monomer (b-2) was obtained as a pale yellow transparent liquid. The obtained compound was identified by ¹ H-NMR.

Monomer (b-2)

A reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 17.7 parts of methyl methacrylate, 53.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 20 parts of PGMAc, 21.2 parts of monomer (b-1) as a second block monomer, and 27 parts of an aqueous solution of monomer (b-2) (non-volatile content 38%) were added to this reaction tank, and the reaction was continued by stirring while maintaining a nitrogen atmosphere at 110° C. After 2 hours, a sample of the polymerization solution was taken to measure the non-volatile content, and it was confirmed that the polymerization conversion rate of the second block was 98% or more calculated from the non-volatile content, and the reaction solution was cooled to room temperature to terminate the polymerization.
PGMAc was added to the block copolymer solution synthesized above so that the non-volatile content was 40% by weight. In this way, a resin-type dispersant solution 1 was obtained, which had an amine value per non-volatile content of 50 mg KOH/g, a quaternary ammonium salt value of 20 mg KOH/g, and a weight average molecular weight (Mw) of 9,800.

(Resin-type dispersant solution 2): Block acrylic-type basic dispersant A reaction apparatus equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine, and stirred at 50 ° C. for 1 hour while flowing nitrogen, and the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were added to this reaction apparatus, and the reaction was continued by stirring while maintaining a nitrogen atmosphere at 110° C. Two hours after the addition of dimethylaminoethyl methacrylate, a sample was taken from the polymerization solution and the nonvolatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more calculated from the nonvolatile content, and the reaction solution was cooled to room temperature to terminate the polymerization.
PGMAc was added to the block copolymer solution synthesized above so that the non-volatile content was 40% by weight. In this way, a resin-type dispersant solution 2 having a poly(meth)acrylate skeleton and a tertiary amino group and an amine value per non-volatile content of 71.4 mg KOH/g and a weight average molecular weight of 9900 (Mw) was obtained.

(Resin type dispersant solution 3): Block acrylic type basic dispersant A reaction apparatus equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine, and stirred at 50 ° C. for 1 hour while flowing nitrogen, and the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to start polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 61 parts of PGMAc and 25.6 parts of an aqueous solution of methacryloyloxyethyl trimethyl ammonium chloride ("Acryester DMC78" manufactured by Mitsubishi Rayon Co., Ltd.) as a second block monomer were added to the reactor, and the reaction was continued by stirring while maintaining 110° C. and a nitrogen atmosphere. Two hours after the addition of methacryloyloxyethyl trimethyl ammonium chloride, the polymerization solution was sampled and the nonvolatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more calculated from the nonvolatile content, and the reaction solution was cooled to room temperature to stop the polymerization.
PGMAc was added to the block copolymer solution synthesized above so that the non-volatile content was 40% by weight. In this way, a resin-type dispersant solution 3 having a poly(meth)acrylate skeleton and a quaternary ammonium salt group, an amine value per non-volatile content of 29.4 mgKOH/g and a weight average molecular weight of 9800 (Mw), was obtained.

(Resin-type dispersant solution 4): Block acrylic-type basic dispersant
In a reaction vessel equipped with a stirrer and a thermometer, 55 parts of 4-dimethylamino-1,2-epoxybutane and 120 parts of tetrahydrofuran (THF) were charged, and the mixture was heated and stirred at 70° C., and 35 parts of methacrylic acid was added dropwise over 60 minutes. After completion of the dropwise addition, the mixture was heated and stirred at 70° C. for another 2 hours, and the reaction was confirmed to be complete by ¹ H-NMR, and then the mixture was allowed to cool to room temperature. The reaction solution was washed successively with 300 parts of ion-exchanged water, 200 parts of saturated sodium bicarbonate, and 200 parts of saturated saline, and then 20 g of magnesium sulfate was added to the organic layer, and the mixture was stirred and filtered. The solvent of the obtained solution was distilled off with a rotary evaporator, and 31 parts of the following monomer (b-3) was obtained as a pale yellow transparent liquid (yield 42%). The obtained compound was identified by ¹ H-NMR.

Monomer (b-3)

In a reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 17.6 parts of methyl methacrylate, 52.8 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of propylene glycol monomethyl ether acetate were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content.
Next, 25 parts of PGMAc and 25.1 parts of ethylenically unsaturated monomer (b-3) as a second block monomer were added to this reaction tank, and the reaction was continued by stirring while maintaining a nitrogen atmosphere at 110° C. Two hours after the addition of the ethylenically unsaturated monomer (b-3), a sample was taken from the polymerization solution and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate of the second block was 98% or more based on the nonvolatile content.
Further, 4.5 parts of benzyl chloride was added to the reaction vessel, and the mixture was stirred for 3 hours while maintaining the temperature at 110° C. under a nitrogen atmosphere, and then cooled.
PGMAc was added to the block copolymer solution synthesized above so that the nonvolatile content was 40% by weight. In this way, a resin-type dispersant solution 4 was obtained, which had an amine value per nonvolatile content of 50 mgKOH/g, a quaternary ammonium salt value of 20 mgKOH/g, a weight average molecular weight (Mw) of 9,800, and a nonvolatile content of 40% by weight.

(Resin-type dispersant solution 5)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate, and 45.4 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 70 ° C., 6 parts of 3-mercapto-1,2-propanediol were added, and 0.12 parts of AIBN (azobisisobutyronitrile) were further added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and the reaction was carried out at 120 ° C. for 7 hours. It was confirmed by measuring the acid value that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%. In this manner, a resin-type dispersant solution 5 having an acid value of 43, a weight average molecular weight of 9000, a poly(meth)acrylate skeleton, and an aromatic carboxy group was obtained.

(Resin-type dispersant solution 6)
A resin-type dispersant having the following structure was obtained by a known method (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Mw = 26,000). PGMAc was added so that the non-volatile content became 40% by weight, and resin-type dispersant solution 6 was obtained.

(Resin-type dispersant solution 7)
A resin-type dispersant having the following structure was obtained by a known method (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Mw = 21000). PGMAc was added so that the non-volatile content became 40% by weight, and resin-type dispersant solution 7 was obtained.

(Resin-type dispersant solution 8)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 45 parts of methyl methacrylate, 5 parts of methacrylic acid, 50 parts of n-butyl methacrylate, and 45.4 parts of PGMAc, and substituted with nitrogen gas. The reaction vessel was heated to 70°C, 6 parts of 3-mercapto-1,2-propanediol was added, and 0.12 parts of AIBN (azobisisobutyronitrile) were further added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and the reaction was carried out at 120°C for 7 hours. It was confirmed that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%. In this way, a resin-type dispersant solution 8 having an acid value of 75, a weight average molecular weight of 9000, a poly(meth)acrylate skeleton, and an aromatic carboxy group was obtained.

(Resin-type dispersant solution 9)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate, and 45.4 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 70 ° C., 6 parts of 3-mercapto-1,2-propanediol were added, and 0.12 parts of AIBN (azobisisobutyronitrile) were further added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and the reaction was carried out at 120 ° C. for 7 hours. It was confirmed by measuring the acid value that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%. In this manner, a resin-type dispersant solution 9 having an acid value of 43, a weight average molecular weight of 9000, a poly(meth)acrylate skeleton, and an aromatic carboxy group was obtained.

(Resin-type dispersant solution 10)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate, and 45.4 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 70 ° C., 6 parts of 3-mercapto-1,2-propanediol were added, and 0.12 parts of AIBN (azobisisobutyronitrile) were further added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. Next, 19.2 parts of trimellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and the reaction was carried out at 120 ° C. for 7 hours. It was confirmed by measuring the acid value that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%. In this manner, a resin-type dispersant solution 10 having an acid value of 90, a weight average molecular weight of 9,000, a poly(meth)acrylate skeleton, and an aromatic carboxy group was obtained.

(Resin-type dispersant solution 11)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 45 parts of methyl methacrylate, 5 parts of methacrylic acid, 50 parts of n-butyl methacrylate, and 45.4 parts of PGMAc, and replaced with nitrogen gas. The reaction vessel was heated to 70 ° C., 2 parts of 3-mercapto-1,2-propanediol was added, and 0.12 parts of AIBN (azobisisobutyronitrile) were further added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. Next, 3.2 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and the reaction was carried out at 120 ° C. for 7 hours. It was confirmed that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%. In this manner, a resin-type dispersant solution 11 having an acid value of 47, a weight average molecular weight of 18,000, a poly(meth)acrylate skeleton, and an aromatic carboxy group was obtained.

(Acidic resin type dispersant solution 12)
A gas inlet tube, a thermometer, a condenser, and a reaction vessel equipped with a stirrer were charged with 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc (methoxypropyl acetate), and 0.2 parts of monobutyltin oxide as a catalyst, and then substituted with nitrogen gas, and reacted at 120 ° C. for 5 hours (first step). It was confirmed that 95% or more of the acid anhydride was half-esterified by measuring the acid value. Next, the compound obtained in the first step was charged in terms of solid content of 160 parts, 2-hydroxypropyl methacrylate 200 parts, ethyl acrylate 200 parts, t-butyl acrylate 150 parts, 2-methoxyethyl acrylate 200 parts, methyl acrylate 200 parts, methacrylic acid 50 parts, and PGMAc 663 parts, and the inside of the reaction vessel was heated to 80 ° C., and 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) were added, and the reaction was carried out for 12 hours (second step). It was confirmed that 95% had reacted by solid content measurement. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and the reaction was carried out until the disappearance of the peak at 2270 cm ⁻¹ due to the isocyanate group was confirmed by IR (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the solid content was adjusted with PGMAc to obtain a resin-type dispersant solution 12 with a non-volatile content of 40%. The acid value of the obtained dispersant was 68, the unsaturated double bond equivalent was 1593, and the weight average molecular weight was 13,000.
The resin-type dispersant solution 12 has a methacryloyl group and is therefore thermosetting and photosetting.

(Resin-type dispersant solution 13)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 50.0 parts of tert-butyl acrylate, 50.0 parts of methyl methacrylate, and 25.0 parts of propylene glycol monomethyl ether acetate, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 50°C, and 6.0 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 45.7 parts of propylene glycol monomethyl ether acetate was added, and the reaction was carried out for 10 hours. It was confirmed that 95% had reacted by measuring the nonvolatile content.
Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 38.0 parts of PGMAc, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 120 ° C. for 5 hours. Then, 12.1 g of 3-methoxybutanol was added and reacted at 120 ° C. for 3 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After the reaction was completed, propylene glycol monomethyl ether acetate was added to prepare a non-volatile content of 40% by mass, and a solution of resin-type dispersant solution 13 having an acid value of 95 mg KOH / g and a weight average molecular weight of 9500 was obtained.

(Resin-type dispersant solution 14)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 14.5 parts of PMA, and 70.8 parts of propylene glycol monomethyl ether acetate were charged, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 100°C and reacted for 5 hours. Then, 12.1 g of 3-methoxybutanol was added, and the reaction was carried out at 120°C for 3 hours. After confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, the temperature in the system was cooled to 70°C, 50.0 parts of t-butyl acrylate and 50.0 parts of methyl methacrylate were charged, and 38.0 parts of propylene glycol monomethyl ether acetate in which 0.1 parts of 2,2'-azobisisobutyronitrile had been dissolved was added, and the reaction was carried out for 10 hours. It was confirmed that the polymerization had progressed to 95% by measuring the non-volatile content, and the reaction was terminated. After the reaction was completed, propylene glycol monomethyl ether acetate was added so that the nonvolatile content became 40% by mass, and a resin type dispersant solution 14 having an acid value of 93 mgKOH/g and a weight average molecular weight of 10,800 was obtained.

(Resin-type dispersant solution 15)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 35 parts of OXE-30 ((3-ethyloxetan-3-yl) methyl methacrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd., 5 parts of methacrylic acid, 60 parts of t-butyl methacrylate, and 45.4 parts of PGMAc were charged and replaced with nitrogen gas. The reaction vessel was heated to 70 ° C., 6 parts of 3-mercapto-1,2-propanediol were added, and 0.12 parts of AIBN (azobisisobutyronitrile) were further added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and the reaction was carried out at 120 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. PGMAc was added to adjust the non-volatile content to 40%. In this way, a resin-type dispersant solution 15 having an acid value of 75, a weight average molecular weight of 9000, a poly(meth)acrylate skeleton, and an aromatic carboxy group was obtained.

(Resin-type dispersant solution 16)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 12 parts of 3-mercapto-1,2-propanediol, 12 parts of PMA, 11 parts of trimellitic anhydride, and 35 parts of PGMAc were charged and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., 80 parts of methyl methacrylate, 80 parts of butyl acrylate, 20 parts of hydroxyethyl methacrylate, and 20 parts of 2-hydroxypropyl methacrylate were charged, and 200 parts of PGMAc solution in which 0.5 parts of 2,2'-azobisisobutyronitrile were dissolved was added, and the reaction was continued for 10 hours. It was confirmed that the polymerization had progressed to 95% by measuring the solid content, and the reaction was terminated. PGMAc was added to adjust the nonvolatile content to 40%, and a resin-type dispersant solution 16 having an acid value of 53 and a weight average molecular weight of 10,000 was obtained.

(Resin-type dispersant solution 17)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 12 parts of 3-mercapto-1,2-propanediol, 15 parts of PMA, 11 parts of neopentyl glycol, 14 parts of trimellitic anhydride, and 52 parts of PGMAc were charged and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., 80 parts of methyl methacrylate, 100 parts of butyl acrylate, and 20 parts of 2-hydroxypropyl methacrylate were charged, and 200 parts of PGMAc solution in which 0.5 parts of 2,2'-azobisisobutyronitrile were dissolved was added, and the reaction was continued for 10 hours. It was confirmed that the polymerization had progressed to 95% by measuring the solid content, and the reaction was terminated. PGMAc was added to adjust the nonvolatile content to 40%, and a resin-type dispersant solution 17 having an acid value of 63 and a weight average molecular weight of 9,000 was obtained.

<Production of Comparative High Refractive Index Resin>
(Comparative high refractive index resin solution 1)
As the high refractive index resin, a comparative high refractive index resin 1, which is a fluorene-based polyester, was synthesized.
In a 1L separable flask, 45 g of 9-fluorenone (0.25 mol, manufactured by Osaka Gas Chemicals Co., Ltd.), 188 g (1 mol) of ethylene glycol mono(2-naphthyl)ether, and 1 g of 3-mercaptopropionic acid were added, and then heated to 60°C to completely dissolve. Thereafter, 54 g of sulfuric acid was gradually added, and the mixture was stirred for 5 hours while maintaining the temperature at 60°C. It was confirmed by HPLC (high performance liquid chromatography) that the conversion rate of 9-fluorenone was 99% or more. After neutralizing the reaction liquid obtained by adding a 48% by mass aqueous solution of sodium hydroxide, 400 g of xylene was added, and the mixture was washed several times with distilled water and cooled to precipitate crystals. Furthermore, after filtering and drying, 87 g (yield 67%) of the target 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF) was obtained as crystals. The HPLC purity of the obtained crystals was measured to be 98.3%. The obtained sample was confirmed to be 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF) by 1H-NMR and mass spectrometry.

The above BNEF (0.80 mol), ethylene glycol (hereinafter referred to as EG) (0.20 mol), dimethyl 2,6-naphthalenedicarboxylate (hereinafter referred to as DMN) (0.30 mol), 9,9-di(2-methoxycarbonylethyl)fluorene (9,9-di(carboxyethyl)fluorene or dimethyl ester of fluorene-9,9-dipropionic acid, hereinafter referred to as FDPM) 0.70 mol, and 2 x 10-4 mol of manganese acetate tetrahydrate and 8 x 10-4 mol of calcium acetate monohydrate as ester exchange catalysts were added to the reactor and gradually heated and melted while stirring. After heating to 250°C, the pressure was reduced stepwise to 10,000 Pa. The ethylene glycol was removed while gradually heating and reducing the pressure until it reached 270°C and 0.13 kPa or less. After reaching the predetermined stirring torque, the contents were removed from the reactor and polyester resin pellets were obtained.

FDPM was synthesized by replacing t-butyl acrylate with methyl acrylate in Example 1 of JP 2005-89422 A.

The pellets obtained were analyzed by NMR, and it was found that 80 mol% of the diol components introduced into the polyester resin were derived from BNEF and 20 mol% were derived from EG, and 30 mol% of the dicarboxylic acid components introduced into the polyester resin were derived from DMN and 70 mol% were derived from FDPM.

The weight average molecular weight Mw of the resulting polyester resin was 31,300, and the refractive index at 589 nm was 1.66.

The obtained polyester resin was dissolved in cyclohexanone to a non-volatile content of 20%, to give comparative high refractive index resin solution 1.

<Production of Pigment Composition>
(Production of Pigment Composition (D-1))
The mixture having the following composition was stirred and mixed uniformly, dispersed in an Eiger mill using zirconia beads having a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a pigment composition (D-1).
Squarylium-based fine pigment (S-1K): 12.0
Acidic resin type dispersant 1 solution: 15.0 parts Binder resin solution 2: 10.0 parts PGMAc (methoxypropyl acetate): 63.0 parts

(Production of Pigment Compositions (D-2) to (D-173))
Pigment compositions (D-2) to (D-173) were prepared in the same manner as in (D-1), except that the compositions were changed as shown in Tables 3-1 to 3-6.
The structures of dye derivatives 1 and 2 are shown below.

(Dye Derivative 1)

(Dye derivative 2)

(Production of dye compositions (DD-1) to (DD-3))
Dye compositions (DD-1) to (DD-3) were prepared in the same manner as (D-1), except that the compositions were changed as shown in Table 3-6.
The following dye (H-1) was used to prepare (DD-1), the following dye (H-2) was used to prepare (DD-2), and the following dye (H-3) was used to prepare (DD-3).

(Production of Pigment Compositions (Y-1) to (Y-5))
84 parts of the pigment composition (D-33), 8 parts of (D-172), and 8 parts of (D-173) were mixed to prepare a pigment composition (Y-1).
Pigment compositions (Y-2) to (Y-5) were prepared as shown in Table 4 in the same manner as for the pigment composition (Y-1).

<Preparation of Photosensitive Composition>
[Example 1]
(Preparation of Photosensitive Composition (XR-1))
The following composition was mixed and stirred until homogeneous to prepare a photosensitive composition (XR-1).
Pigment composition (D-1): 100.0 parts Photopolymerizable monomer ("Aronix M-402" manufactured by Toagosei Co., Ltd., liquid at room temperature): 3.52 parts Photopolymerization initiator ("Irgacure OXE02" manufactured by BASF Corporation): 0.48 parts PGMAc: 56.0 parts

[Examples 2 to 184, Comparative Examples 1 to 9]
(Production of Photosensitive Compositions (XR-2) to (XR-184), (XXR-1) to (XXR-9))
Photosensitive compositions (XR-2) to (XR-184), (XXR-1) to (XXR-9) were prepared in the same manner as photosensitive composition (XR-1), except that the compositions were changed as shown in Tables 5-1 to 5-6.
The materials used are shown below.
Viscoat #295: trimethylolpropane, manufactured by Osaka Organic Chemical Industry Co., Ltd., a photopolymerizable monomer that is liquid at room temperature EBECRYL 8701: manufactured by Daicel Allnex Co., Ltd., a photopolymerizable monomer that is solid at room temperature Irgacure 907: manufactured by IGM Resins B.V., a photopolymerization initiator

<Preparation of a film for evaluation of a photosensitive composition>

The photosensitive compositions (XR-1) to (XR-184) and (XXR-1) to (XXR-9) were each applied onto a glass substrate having a size of 100 mm×100 mm and a thickness of 1.1 mm using a spin coater, and then dried at 70° C. for 20 minutes.
In the above procedure, the rotation speed of the spin coater was adjusted to obtain a substrate on which a film having a thickness of 1.0 μm was formed.

<Evaluation of Photosensitive Composition>
The following evaluations were carried out using the above evaluation membrane. The results are shown in Table 6.

[Maximum absorbance at 700 to 1200 nm]
◯++: 3.0 or more ◯+: 2.0 or more and less than 3.0 ◯: 1.0 or more and less than 2.0 ×: less than 1.0

[Refractive index]
The substrate on which the above-mentioned film was formed was subjected to spectroscopic ellipsometry measurement to determine the refractive indexes at 850 nm, 940 nm, and 1550 nm.
Incidentally, since the transmittance at 850 nm of (XR-1) to (XR-28), (XR-157) to (XR-179), and (XXR-1) to (XXR-2) was low, the refractive index at 850 nm was not measured.

[Light resistance]
The substrate on which the above-mentioned film was formed was subjected to a light resistance test by exposing it to an illuminance of 60 W/ ^m2 at 300 to 400 nm for 20 hours using a xenon weather meter.
The change in absorbance at the maximum absorption wavelength in the range of 400 to 700 nm was evaluated according to the following criteria.
◯: The rate of decrease in absorbance at the maximum absorption wavelength is less than 5%. △: The rate of decrease in absorbance at the maximum absorption wavelength is 5% or more but less than 30%. ×: The rate of decrease in absorbance at the maximum absorption wavelength is 30% or more.

[Heat-resistant]
The substrate on which the above-mentioned film was formed was heated at 250° C. for 1 hour to carry out a heat resistance test.
The change in absorbance at the maximum absorption wavelength in the range of 400 to 700 nm was evaluated according to the following criteria.
◯: The rate of decrease in absorbance at the maximum absorption wavelength is less than 5%. △: The rate of decrease in absorbance at the maximum absorption wavelength is 5% or more but less than 30%. ×: The rate of decrease in absorbance at the maximum absorption wavelength is 30% or more.

[transparency]
The haze of the substrate on which the above film was formed was measured with a haze meter, and the transparency was evaluated according to the following criteria.
◯: Haze is less than 0.5 △: Haze is 0.5 or more and less than 1.0 ×: Haze is 1.0 or more

[Curability]
Photosensitive compositions (XR-1) to (XR-184), (XXR-1) to (XXR-9) were each applied onto a silicon wafer having a size of 100 mm×100 mm and a thickness of 1.1 mm using a spin coater, and then dried at 70° C. for 20 minutes.
In the above procedure, the rotation speed of the spin coater was adjusted to obtain a substrate on which a film having a thickness of 1.0 μm was formed.
A pattern forming mold (made of polydimethylsiloxane, aspect ratio = 2/1) was prepared. This mold was brought into contact with the coating film at a pressing force of 200 Pa for a pressing time of 1 minute, while being irradiated with ultraviolet light at 1 j/ ^cm2 to harden it. The mold was then released to obtain a fine pattern in which the mold pattern was transferred. This was then immersed in acetone at a temperature of 25°C for 5 seconds, and the hardening property was evaluated visually according to the following three-level scale.
◯+: The fine pattern was not dissolved in acetone at all, and the shape of the pattern was maintained.
◯: The fine pattern was hardly dissolved in acetone, and the shape of the pattern was mostly maintained.
Δ: A part of the fine pattern was dissolved in acetone, and a part of the pattern shape was lost.
×: The fine pattern was dissolved in acetone, and the pattern shape did not remain.

[Transferability evaluation]
The aspect ratio (AR=height/width) of the fine pattern that had been subjected to the curing property evaluation was measured, and the transferability was evaluated according to the following four-level scale.
◯+: 1.9≦AR≦2.
◯: 1.6≦AR<1.9.
Δ: 1.3≦AR<1.6.
x: AR<1.3, or at least a part of the pattern shape was lost.

<Evaluation of Comparative High Refractive Index Resin Solution 1>
Comparative high refractive index resin solution 1 was applied onto a glass substrate of 100 mm×100 mm and 1.1 mm thick using a spin coater, and then dried at 70° C. for 20 minutes and then heat-treated at 230° C. for 30 minutes.
In the above manner, the rotation speed of the spin coater was adjusted to obtain a substrate on which a film having a thickness of 1.0 μm was formed. Spectroscopic ellipsometry measurement was performed to determine the refractive indexes at 850 nm, 940 nm, and 1550 nm. The refractive index at 850 nm was 1.63, the refractive index at 940 nm was 1.62, and the refractive index at 1550 nm was 1.60.

As described above, the pigment composition of the present invention has a particularly high refractive index in the wavelength region of 800 to 1600 nm, and can form a film that is excellent in transparency, heat resistance, light resistance, curing property, and transferability. Therefore, the pigment composition of the present invention can be suitably used in a nanoimprint method, and is useful for applications such as optical lenses for infrared sensors or infrared communication devices, or optical waveguides for infrared sensors or infrared communication devices.

Claims (11)

A pigment composition for use in an optical lens used in an infrared sensor or an infrared communication device, or an optical waveguide used in an infrared sensor or an infrared communication device, comprising:
The ink composition contains at least one pigment selected from the group consisting of a phthalocyanine pigment, a naphthalocyanine pigment, a squarylium pigment, and an indigo pigment, a resin-type dispersant, and a photopolymerizable monomer,
The refractive index at 23° C. and a wavelength of 940 nm is 1.70 or more,
A pigment composition for nanoimprints, which when a film having a thickness of 1.0 μm is formed, has a maximum absorbance of 1.0 or more in the range of 700 to 1200 nm. The pigment composition for nanoimprinting according to claim 1, wherein the pigment content is 40 mass% or more based on the total mass of the solid content in the pigment composition. The nanoimprint pigment composition according to claim 1 or 2, further comprising a photopolymerization initiator. The pigment composition for nanoimprints according to claim 1 or 2, wherein the photopolymerization initiator is an oxime ester compound. The nanoimprint pigment composition according to claim 1 or 2, used as a high refractive index material in the range of 800 nm to 1600 nm. A film comprising the nanoimprint pigment composition according to claim 1. An optical material comprising the nanoimprint pigment composition according to claim 1. An optical lens comprising the nanoimprint pigment composition according to claim 1. An optical waveguide comprising the nanoimprint pigment composition according to claim 1. An infrared sensor comprising the film according to claim 6, the optical material according to claim 7, the optical lens according to claim 8, or the optical waveguide according to claim 9. An infrared communication device comprising the film according to claim 6, the optical material according to claim 7, the optical lens according to claim 8, or the optical waveguide according to claim 9.