JP2023095795A - Pigment composition used in optical lens for infrared sensor or infrared communication device, or optical waveguide for infrared sensor of infrared communication device, film, optical lens, and optical waveguide - Google Patents

Abstract

To provide a pigment composition having a high refractive index and excellent transparency, heat resistance and light resistance, in applications of a high refractive index material used in an optical lens or an optical waveguide for an infrared sensor or an infrared communication device.SOLUTION: A pigment composition that is used 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, contains an isoindoline-based pigment and a resin, wherein a percentage content of the isoindoline-based pigment is 40 mass% or more based on the total mass of a solid content in the pigment composition, when a film with a film thickness of 1.0 μm is formed, a refractive index at 23°C and a wavelength of 850 nm is 1.65 or more.SELECTED DRAWING: None

Description

The present invention relates to an optical lens for an infrared sensor or an infrared communication device, or a pigment composition used for an optical waveguide for an infrared sensor or an infrared communication device, and a film, an optical lens, and an optical waveguide containing the pigment composition.

2. Description of the Related Art Conventionally, a surface protective layer made of an inorganic substance or an organic substance is provided on the surfaces of glasses, films and sheets used for sensor elements such as CCD and CMOS and display elements such as displays. In recent years, a coating layer or the like in which a high refractive index layer and a low refractive index layer are alternately laminated is used for the purpose of imparting functions such as antireflection and optical waveguiding to the surface protective layer. For the high refractive index layer, a high refractive index inorganic film formed by vapor deposition of ceramics such as titania, zirconia, alumina, etc., or a high refractive index organic film made of an aromatic-containing resin is used depending on the purpose. there is However, when a high refractive index inorganic film is used, there are problems such as insufficient adhesion to the substrate and brittleness of the film. Therefore, in recent years, high refractive index organic films have been widely used.

In addition, organic electroluminescence (hereinafter referred to as organic EL) panels, which are attracting attention as next-generation displays, use silicon oxide, silicon nitride, It has a laminated structure of an inorganic layer made of alumina or the like and an organic layer made of an organic sealing material containing acrylic resin or epoxy resin as a main component. These inorganic layers and organic layers are alternately laminated. Here, the smaller the difference in refractive index between the inorganic layer and the organic layer, the higher the light extraction efficiency. Therefore, the higher the refractive index of the organic layer, the better. Therefore, an organic encapsulant with a high refractive index is desired.

Furthermore, in recent years, molded articles using three-dimensional modeling apparatuses have been widely used in the medical field, the optical field, and the like. Photocurable resins are used as modeling resins used for three-dimensional modeling (Patent Documents 1 and 2). In particular, for molded lenses used in medical equipment, microscopes, various cameras, and the like, stereolithography resins with a high refractive index are desired in order to make the lenses thinner.

As the above-mentioned high refractive index organic materials for surface protective layers, organic sealants for organic EL panels, and stereolithography resins, sulfur-containing resins and fluorenes having a structure in which aromatic rings are conjugated can be used. resins are known (Patent Documents 2, 3, 4).

In recent years, sensing and communication using near-infrared rays have become widespread, such as solid-state imaging devices for photographing subjects at night, infrared sensors such as Lidar for distance measurement, and infrared communication devices that propagate light through optical waveguides. Widespread. It is important to use an optical material having a high refractive index in the near-infrared region for lenses and the like for condensing these rays.

Patent Document 5 discloses a composition used for manufacturing an infrared transmission filter or the like, which blocks visible light and transmits near infrared rays, and a film obtained by using the composition, and the film has a wavelength of 800 nm or more. It is described that the refractive index becomes high in the range of However, the material described in Patent Document 5 has absorption in the wavelength region longer than 800 nm, and is not preferable for use in sensing or communication using near-infrared rays of 800 to 1600 nm. In addition, since the dispersibility of the dye used is not sufficient, there remains a problem in terms of the transparency of the film obtained from the composition.

Patent Document 6 discloses a film-like material for optical members containing an organic dye that exhibits a high refractive index and a high transmittance in the near-infrared region. No refractive index was obtained.

Patent Document 7 discloses a resin composition containing a thermoplastic resin and a coloring material that exhibits a high refractive index and a high transmittance in the near-infrared region. There was a problem in terms of practicality.

JP 2011-157543 A JP 2019-019245 A JP-A-2000-281787 JP 2011-168721 A WO2019/065475 WO2020/085499 WO2020/138050

Among sensing and communication using near-infrared rays, in sensing and communication using light rays of 800 to 1600 nm, which have become particularly widespread in recent years, optical lenses for condensing these light rays and propagating these light rays It is important to use an optical material with a high refractive index, high transparency and durability for the optical waveguide.
At present, however, no progress has been made in the development of high refractive index materials having sufficient resistance.

In view of the above problems, the present invention provides a high refractive index material used for optical lenses or optical waveguides for infrared sensors using light rays of 800 to 1600 nm or for infrared communication equipment. To provide a pigment composition which is excellent in heat resistance and light resistance.

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,
containing an isoindoline pigment and a resin,
The content of the isoindoline pigment is 40% by mass or more based on the total mass of solids in the pigment composition,
The present invention relates to a pigment composition having a refractive index of 1.65 or more at 23° C. and a wavelength of 850 nm when formed into a film having a thickness of 1.0 μm.

（Ｘ_１、Ｘ_２は、各々独立して、下記一般式（２）、（３）又は（４）を表す。Ｙ_１～Ｙ_４は、各々独立して、水素原子、ヒドロキシ基、カルボキシ基、シアノ基、ニトロ基、スルホ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数２～４のアルコキシカルボニル基、炭素数２～４のアルキルカルボキシ基、ハロゲン原子、炭素数２～４のアルケニル基、炭素数２～４のアルケニロキシ基、炭素数３～１０のシクロアルキル基、炭素数６～１２のアリール基、－ＳＯ_２－Ｏ－Ｒ_１１１、又は－ＳＯ_２－ＮＨ－Ｒ_１１２を表し、これらのうち２つがそれぞれ水素原子を除いた形で環を形成してもよく、環を形成する際に間に２価の有機基が入ってもよい。Ｒ_１１１、Ｒ_１１２は各々独立して、水素原子又は炭素数１～４のアルキル基を表す。）

一般式（２）

（Ｙ_５、Ｙ_６は、各々独立して、水素原子、炭素数１～４のアルキル基、炭素数２～４のアルケニル基、炭素数２～４のアルケニロキシ基、炭素数３～１０のシクロアルキル基、又は炭素数６～１２のアリール基を表し、＊は結合手を表す。）

一般式（３）

（Ｙ_７は、各々独立して、水素原子、炭素数１～４のアルキル基、炭素数２～４のアルケニル基、炭素数２～４のアルケニロキシ基、炭素数３～１０のシクロアルキル基、又は炭素数６～１２のアリール基を表し、＊は結合手を表す。）

一般式（４）

The present invention also relates to the above pigment composition, wherein the isoindoline pigment has a structure represented by general formula (1).
General formula (1)

(X ₁ and X ₂ each independently represent the following general formula (2), (3) or (4); Y ₁ to Y ₄ each independently represent a hydrogen atom, a hydroxy group, a carboxy group , cyano group, nitro group, sulfo group, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, alkoxycarbonyl group having 2 to 4 carbon atoms, alkylcarboxy group having 2 to 4 carbon atoms, halogen atom , an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, —SO ₂ —OR ₁₁₁ , or —SO represents ₂ -NH-R ₁₁₂ , two of which may form a ring in the form of removing a hydrogen atom, respectively, and a divalent organic group may be inserted between them when forming the ring. ₁₁₁ and R ₁₁₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

general formula (2)

(Y ₅ and Y ₆ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cyclo represents an alkyl group or an aryl group having 6 to 12 carbon atoms, and * represents a bond.)

General formula (3)

(Y ₇ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, Or represents an aryl group having 6 to 12 carbon atoms, * represents a bond.)

general formula (4)

The present invention also relates to the above pigment composition comprising a curing agent and a solvent.

The present invention also relates to the above pigment composition used as a high refractive index material in the range of 800 nm to 1600 nm.

The present invention also relates to a film containing the above pigment composition.

The present invention also relates to an optical material containing the above pigment composition.

The present invention also relates to an optical lens containing the above pigment composition.

The present invention also relates to an optical waveguide containing the above pigment composition.

The present invention also relates to an infrared sensor or an infrared communication device comprising the film, the optical material, the optical lens, or the optical waveguide.

According to the present invention, in the application of a high refractive index material used for optical lenses or optical waveguides for infrared sensors or infrared communication devices, it has a high refractive index in the wavelength region of 800 to 1600 nm, transparency, and heat resistance. , and a pigment composition having excellent light resistance can be provided.

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

<About the pigment composition of the present invention>
The pigment composition of the present invention contains an isoindoline-based pigment and a resin, the content of the isoindoline-based pigment is 40% by mass or more based on the total mass of solids in the pigment composition, and the film thickness is 1 When a film having a thickness of 0.0 μm is formed, the refractive index at 23° C. and a wavelength of 850 nm is 1.65 or more.

<About the optical properties of the pigment composition>
Containing an isoindoline pigment and a resin is a feature of the pigment composition of the present invention.
After intensive studies, the present inventors have found that when a pigment composition contains a certain amount or more of an isoindoline pigment, the refractive index becomes high in the wavelength region of 800 to 1600 nm. This makes it possible to obtain a high refractive index film without containing sulfur atoms and iodine atoms, which are known to contribute to a high refractive index.

The pigment composition of the present invention has a refractive index at 23° C. and a wavelength of 850 nm of 1.65 or more, preferably 1.7 or more, more preferably 1.75 or more, and still more preferably 1.8 or more. is. Although the upper limit of the refractive index is not particularly limited, it is preferably 2.5 or less, more preferably 2.4 or less.
It should be noted that this is the refractive index when the pigment composition of the present invention forms a film having a thickness of 1.0 μm. It corresponds to the refractive index of the film after exposure.

<Pigment>
The pigment composition of the present invention contains a pigment 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 for optical lenses that collect near-infrared rays and optical waveguides that propagate near-infrared rays. In addition, since it is incorporated in various devices and used, it is important that it can withstand high-temperature processes and solvent immersion processes in the manufacturing process, and heat resistance and chemical resistance are required. Since the pigment has 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 isoindoline pigment content is 40% by mass or more based on the total mass of solids in the pigment composition. More preferably 50% by mass or more, still more preferably 60% by mass or more, and particularly preferably 70% or more.
A film having a high refractive index in the wavelength region of 800 to 1600 nm can be obtained when the content of the pigment is 40% by mass or more based on the total mass of solids in the pigment composition. The upper limit of the content of the pigment is not particularly limited, but when it is less than 95% by mass, the dispersibility of the pigment is excellent, a highly transparent film can be obtained, and the stability as a pigment composition is excellent. .
In this specification, the solid content means all components of the pigment composition excluding volatile components such as organic solvents.

<Isoindoline pigment>
Examples of isoindoline pigments include Pigment Yellow 185, 139, Pigment Red 260, and Pigment Orange 61, 66, 69.

（Ｘ_１、Ｘ_２は、各々独立して、下記一般式（２）、（３）又は（４）を表す。Ｙ_１～Ｙ_４は、各々独立して、水素原子、ヒドロキシ基、カルボキシ基、シアノ基、ニトロ基、スルホ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数２～４のアルコキシカルボニル基、炭素数２～４のアルキルカルボキシ基、ハロゲン原子、炭素数２～４のアルケニル基、炭素数２～４のアルケニロキシ基、炭素数３～１０のシクロアルキル基、炭素数６～１２のアリール基、－ＳＯ_２－Ｏ－Ｒ_１１１、又は－ＳＯ_２－ＮＨ－Ｒ_１１２を表し、これらのうち２つがそれぞれ水素原子を除いた形で環を形成してもよく、環を形成する際に間に２価の有機基が入ってもよい。Ｒ_１１１、Ｒ_１１２は各々独立して、水素原子又は炭素数１～４のアルキル基を表す。）
一般式（２）

（Ｙ_５、Ｙ_６は、各々独立して、水素原子、炭素数１～４のアルキル基、炭素数２～４のアルケニル基、炭素数２～４のアルケニロキシ基、炭素数３～１０のシクロアルキル基、又は炭素数６～１２のアリール基を表し、＊は結合手を表す。）
一般式（３）

（Ｙ_７は、各々独立して、水素原子、炭素数１～４のアルキル基、炭素数２～４のアルケニル基、炭素数２～４のアルケニロキシ基、炭素数３～１０のシクロアルキル基、又は炭素数６～１２のアリール基を表し、＊は結合手を表す。）
一般式（４）

The isoindoline pigment preferably has a structure represented by general formula (1).
General formula (1)

(X ₁ and X ₂ each independently represent the following general formula (2), (3) or (4); Y ₁ to Y ₄ each independently represent a hydrogen atom, a hydroxy group, a carboxy group , cyano group, nitro group, sulfo group, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, alkoxycarbonyl group having 2 to 4 carbon atoms, alkylcarboxy group having 2 to 4 carbon atoms, halogen atom , an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, —SO ₂ —OR ₁₁₁ , or —SO ₂ -NH-R ₁₁₂ , two of which may form a ring in the form of removing a hydrogen atom, respectively, and a divalent organic group may be inserted between them when forming the ring. ₁₁₁ and R ₁₁₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
general formula (2)

(Y ₅ and Y ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cyclo represents an alkyl group or an aryl group having 6 to 12 carbon atoms, and * represents a bond.)
General formula (3)

(Y ₇ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, Or represents an aryl group having 6 to 12 carbon atoms, * represents a bond.)
general formula (4)

Examples of alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group and tertiary butyl group. Examples of alkoxy groups having 1 to 4 carbon atoms include methoxy group. , ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, t-butyloxy group and the like. The alkenyl group having 2 to 4 carbon atoms includes ethylenyl group, propenyl group, butylenyl group and the like. The cycloalkyl group having 3 to 10 carbon atoms includes cyclopentyl substrate, cyclohexyl group and the like, and the aryl group having 6 to 12 carbon atoms includes phenyl group, benzyl group, naphthyl group and the like.

Y ₁ to Y ₄ may form a ring by removing a hydrogen atom from each of two of the above groups. For example, Y ₁ and Y ₂ may combine to form a phenyl group.

The isoindoline pigments represented by formula (1) can be used alone or in combination of two or more. It may also be a mixture containing isomers.

As the isoindoline pigment, for example, those exhibiting a yellow hue such as Pigment Yellow 185 and 139 transmit light in the vicinity of 555 nm, which is the wavelength region with the highest relative luminosity, so that the visibility of the pigment composition is improved. very high. As a result, when used industrially as a high refractive index material for near infrared rays of 800 to 1600 nm, it becomes easy to visually confirm scratches and stains inside the high refractive index material, and the high refractive index material can be visually confirmed. The other side can also be confirmed, and can be preferably used as a high refractive index material.

Examples of isoindoline pigments having a structure represented by general formula (1) include the following compounds.

The pigment composition of the present invention may also contain pigments other than isoindoline pigments.
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, 221.

Examples of red pigments include C.I. 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, 208, 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, 287.
Examples of orange pigments include C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 71, 73.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 1:3, 2, 2:1, 2:2, 3, 8, 9, 10, 10:1, 11, 12, 15, 15:1, 15:2, 15: 3, 15:4, 15:6, 16, 18, 19, 22, 24, 24:1, 53, 56, 56:1, 57, 58, 59, 60, 61, 62, 64.

Examples of green pigments include C.I. I. Pigment Green 7, 10, 36, 37, 58, 62, 63.
It is also preferable to use an aluminum phthalocyanine pigment. For example, the aluminum phthalocyanine pigments described in JP-A-2004-333817, Japanese Patent No. 4893859, etc. can also be used.

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

(Inorganic pigment)
In addition, an inorganic pigment can be used in combination. Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, amber, synthetic iron black and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good applicability, sensitivity, developability, etc. while balancing chroma and lightness.

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

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

Furthermore, an ultraviolet absorber can also be used together. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers, all of which can be used in combination.

When it is desired to control the transmission and absorption of a specific wavelength region as well as the performance as a high refractive index material, the above dyes and UV absorbers are preferably used.
For example, when sensing near-infrared rays, if you want to cut off a region with a shorter wavelength than the light, you can add a yellow pigment or an ultraviolet absorber to a blue, red, or purple pigment to function as an IR pass material. can let

(Refinement of pigment)
In the pigment composition of the present invention, from the viewpoint of obtaining high transmittance, it is preferable that the organic pigment is finely divided by salt milling treatment or the like. The primary particle size of the pigment is preferably 10 nm or more because it is well dispersed in the colorant carrier. Moreover, it is preferably 80 nm or less because a coating film with little scattering can be formed. A particularly preferred range is from 20 to 60 nm.

(Salt milling treatment)
The salt milling process involves milling a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent while heating using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, and sand mill. This is a treatment in which water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water after kneading. The water-soluble inorganic salt functions as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2,000% by mass, most preferably 300 to 1,000% by mass, based on the total mass of the pigment (100% by mass), from both processing efficiency and production efficiency.

The water-soluble organic solvent has the function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible in) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint 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, more preferably 50 to 500% by mass, based on the total mass of the pigment (100% by mass).

When salt milling the pigment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resins used are preferably solid at room temperature, water-insoluble, 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).

<Resin>
The pigment composition of the invention contains a resin. Examples of resins include those that act as binder resins and those that act as dispersants. The binder resin disperses the pigment in the resin, and examples thereof include thermoplastic resins and thermosetting resins. A resin-type dispersant that functions as a dispersant will be described later.

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, and 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.

Examples of thermosetting resins include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenolic resins.

The spectral transmittance of the binder resin in the entire wavelength region of 400 to 700 nm in the visible light region is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more. Also, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic group.

Alkali-soluble resins obtained by copolymerizing ethylenically unsaturated monomers containing acidic groups include, for example, resins having acidic groups such as carboxy groups and sulfone groups. Specific examples of alkali-soluble resins include acrylic resins having acidic groups, α-olefin/(anhydride) maleic acid copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, or isobutylene/(anhydrous) maleic acid copolymer and the like. Among them, at least one resin selected from the group consisting of an acrylic resin having an acidic group and a styrene/styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group has high heat resistance and transparency, and is therefore preferable. Used.

An energy ray-curable resin having an ethylenically unsaturated active double bond can also be used in order to improve the photosensitivity of an alkali-soluble resin obtained by copolymerizing an ethylenic unmonomer containing an acidic group. Moreover, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain from the viewpoint of various resistances.

Examples of active energy ray-curable resins having ethylenically unsaturated double bonds include resins into which unsaturated ethylenic double bonds are introduced by methods (a) and (b) shown below.

[Method (a)]
As the method (a), an unsaturated ethylenic monomer having an epoxy group and a side chain epoxy group of a copolymer obtained by copolymerizing one or more other monomers are unsaturated. The carboxyl group of an unsaturated monobasic acid having an ethylenic double bond is subjected to an addition reaction, and the resulting hydroxy group is reacted with a polybasic acid anhydride to introduce an unsaturated ethylenic double bond and a carboxyl group. There is a way.

Examples of unsaturated ethylenic monomers having an epoxy group include glycidyl (meth)acrylate, methylglycidyl (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 (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid. Monocarboxylic acids and the like can be mentioned, and 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, and maleic anhydride. These may be used alone or in combination of two or more. good. In order to increase the number of carboxy groups, if necessary, use a tricarboxylic anhydride such as trimellitic anhydride, or use a tetracarboxylic dianhydride such as pyromellitic dianhydride to remove the remaining anhydride. It is also possible to hydrolyze the group. Further, when etrahydrophthalic anhydride or maleic anhydride having unsaturated ethylenic double bonds is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be further increased.

As a method analogous to method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxy group and one or more other monomers There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of the carboxy group to introduce an unsaturated ethylenic double bond and a carboxy group.

[Method (b)]
As the method (b), by using an unsaturated ethylenic monomer having a hydroxy group and copolymerizing it with another unsaturated monobasic acid monomer having a carboxy group or another monomer There is a method of reacting the side chain hydroxy groups of the resulting copolymer with the isocyanate groups of an unsaturated ethylenic monomer having an isocyanate group.

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

The unsaturated ethylenic monomer having an isocyanate group includes 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but is limited to these. Alternatively, two or more types can be used in combination.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000, in order to disperse the colorant preferably. 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 dispersibility, permeability, and heat resistance of the pigment, the binder resin has a carboxy group that functions as a colorant adsorption group and an alkali-soluble group during development, and a colorant carrier other than the binder resin and an affinity group for the solvent. The balance of working aliphatic groups and aromatic groups is important for the dispersibility, permeability and durability of pigments and salt-forming compounds, and it is preferable to use a resin having an acid value of 20-300 mgKOH/g. If the acid value is less than 20 mgKOH/g, the solubility in a developer is poor, making it difficult to form a fine pattern. If it exceeds 300 mgKOH/g, no fine pattern remains.
Here, the colorant carrier is a resin or other low-molecular-weight component that supports the colorant by affinity, adsorption, or the like.

The binder resin is preferably used in an amount of 30% by mass or more based on the total mass of the colorant (100% by mass) from the viewpoint of film-forming properties and various resistances. From the viewpoint of expressing properties, it is preferably used in an amount of 500% by mass or less.

<Organic solvent>
The pigment composition of the present invention may contain an organic solvent in order to sufficiently disperse and permeate the colorant into the colorant carrier and 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, ethyl 3-ethoxypropionate, 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-butyl alcohol, 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 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, 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, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters.

Among them, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc., and benzyl It is preferable to use aromatic alcohols such as alcohol and ketones such as cyclohexanone. In particular, propylene glycol monomethyl ether acetate is more preferable from the viewpoint of safety and hygiene and low viscosity.

These organic solvents can be used singly or in combination of two or more. When a mixed solvent of two or more kinds is used, it preferably contains 65 to 95% by mass of the above preferred organic solvent.

The organic solvent is used in an amount of 800 to 4000% by mass based on the total mass of the colorant (100% by mass) from the viewpoint of adjusting the viscosity of the pigment composition to an appropriate level and improving the formability of the high refractive index material. It is preferable to use in

<Dispersion>
The pigment composition of the present invention is dispersed in a colorant carrier comprising a pigment, optionally containing a resin and a solvent, preferably together with a dispersing aid such as a pigment derivative, in a three-roll mill, a two-roll mill, or a sand mill. , a kneader, an attritor, or other dispersing means. The pigment composition of the present invention can also be produced by mixing pigments, dyes, other coloring agents, etc. separately dispersed in a coloring agent carrier.

(dispersion aid)
When dispersing the colorant in the colorant carrier, a dispersing aid such as a pigment derivative, a resin-type dispersant, or a surfactant can be used as appropriate. The dispersing aid is excellent in dispersing the colorant and has a great effect of preventing reaggregation of the colorant after dispersion. When used, a film with high spectral transmittance is obtained.

《Dye derivative》
Examples of dye derivatives include compounds obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group optionally having a substituent into an organic pigment, anthraquinone, acridone or triazine. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-9469, etc. can be used, and these are It can be used alone or in combination of two or more.

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

《Resin type dispersant》
The resin-type dispersant has a pigment-affinity site that has the property of adsorbing to the pigment and a site that is compatible with the colorant carrier, and acts to adsorb to the added pigment to stabilize dispersion on the colorant carrier. It is intended to Specific examples of resin-type dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, and salts thereof Oily dispersants such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble such as polyvinylpyrrolidone Resins, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide addition compounds, phosphoric acid esters, etc. are used, and these can be used alone or in combination of two or more. It is 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, and 170 manufactured by BYK-Chemie Japan. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21 manufactured by Nippon Lubrizol, such as P104, P104S, 220S, 6919, Lactimon, Lactimon-WS or Bykumen 000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA manufactured by BASF Japan -46, 47, 48, 452, 4008, 4009, 4015, 4015, 4020, 4050, 4050, 4060, 4060, 40600, 4401, 4402, 4403, 4403, 4403, 4408, 4310, 4330, 4330, 451, 451, 451, 451, 451, 451, 451. 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajinomoto Fine-Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824 etc.

《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. A 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 having no basic group. .

When the block acrylic basic dispersant is an AB type block, a more preferable mode is as described above. It is more preferable that the B block is a polymer of ethylenically unsaturated monomers having no basic group.

By using a block acrylic basic dispersant as the resin type dispersant, the block having a basic group adsorbs to the surface of the pigment, while the other block having no basic group maintains affinity with the solvent. It is considered that the steric hindrance works to develop good dispersibility.

In general, resin-type dispersants tend to obtain good dispersibility when used in combination with dye derivatives. Good dispersibility is often obtained. Since the pigment derivative often has a spectrum different from that of the pigment used in the present invention, the pigment composition can exhibit a higher refractive index when the pigment derivative is not used.

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 these may be used in combination. is particularly preferred.

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 methacrylate chloride, dimethylaminoethylbenzyl methacrylate, dimethylaminoethylpropyl methacrylate, dimethylaminoethylbutyl methacrylate, diethylaminoethylmethyl methacrylate, diethylaminoethylbenzyl methacrylate salt, dimethylaminoethylpropyl methacrylate, diethylaminoethylbutyl methacrylate, dimethylaminoethylmethyl acrylate, dimethylaminoethylbenzyl acrylate, dimethylaminoethylpropyl chloride, dimethyl acrylate Aminoethylbutyl chloride salt and the like can be mentioned.

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 the ethylenically unsaturated monomer having a basic group, a block acrylic base There are two typical methods for synthesizing a polydispersant.

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

In the second method, a block having a basic group is polymerized using an ethylenically unsaturated monomer having a tertiary amino group, and the other block having no basic group is also polymerized to perform block polymerization. After completing the above, a part of the tertiary amino group is converted to a quaternary ammonium salt by reacting with a quaternizing agent such as benzyl chloride. Examples of quaternizing agents include alkyl halides such as benzyl chloride, iodobutane, iodopropane, iodoethane, bromobutane, bromopropane, bromoethane, and chlorobutane.
If the ethylenically unsaturated monomer having a tertiary amino group and the ethylenically unsaturated monomer having a quaternary ammonium salt have an amide bond in the molecule, they easily adsorb to the surface of the organic pigment, It is preferable because higher dispersibility can be obtained.

In the synthesis of a block polymer, for example, an AB block polymer can be produced by first synthesizing the A block and then synthesizing the B block. Alternatively, a BAB block polymer can be produced by first synthesizing the B block, then synthesizing the A block, and further synthesizing the B block. Note that the order in which the A block and the B block are combined is arbitrary.

Radical polymerization initiators used for living radical polymerization are preferably azo compounds and peroxides.

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), or 2,2′- azobis[2-(2-imidazolin-2-yl)propane].

Examples of peroxides include benzoyl peroxide, t-butylperbenzoate, cumene hydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, carbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionylperoxide, or diacetylperoxide. A polymerization initiator may be used independently or may use two or more types together.

The reaction temperature for polymerization 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 a known polymerization method, and 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, and it is easy to control the molecular weight and molecular weight distribution of the polymer.

The RAFT agent is a compound having a chain transfer effect and a polymerization initiation effect, and includes, for example, dithiobenzoate type, trithiocarbonate type, dithiocarbamate type, xantheto type, and disulfide type which are precursors thereof.

Dithiobenzoate types include, for example, 2-cyano-2-propyl dithiobenzoate, 4-cyano-4-(thiobenzoylthio)pentanoic acid, and 2-phenyl-2-propyl benzodithioate.

Trithiocarbonate types include, for example, 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]methyl pentanoate, 2-methyl-2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, S,S-dibenzyltrithiocarbonate, 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}, trithiocarbonate = bis[4-(2-hydroxyethoxycarbonyl)benzyl].

Examples of the dithiocarbamate type include 2'-cyanobutane-2'-yl 4-chloro-3,5-dimethylpyrazole-1-carbodithioate and 2'-cyanobutane 3,5-dimethylpyrazole-1-carbodithioate. -2′-yl, cyanomethyl 3,5-dimethylpyrazol-1-carbodithioate, cyanomethyl N-methyl-N-phenyldithiocarbamate.

Disulfide types include, for example, bis(dodecylsulfanylthiocarbonyl)disulfide and bis(thiobenzoyl)disulfide. These are preferred for making AB block polymers.

Among these, trithiocarbonate-type compounds are preferred for easy reaction control during synthesis, 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), bis(dodecylsulfanylthiocarbonyl ) disulfides are more preferred.

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

It is preferable to use an organic solvent in the synthesis of the block acrylic basic dispersant. 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, or diethylene glycol monobutyl ether acetate may be mentioned. An organic solvent may be used independently and may use two or more types together.

(Resin Dispersant Having Carboxy Group)
Further, the resin-type dispersant used in the present invention preferably contains (S1) or (S2) below as a resin-type dispersant having a carboxy group, for example.
(S1) A resin type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride.
(S2) 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 anhydride and/or a tetracarboxylic dianhydride; A resin-type dispersant that is a coalesce.

[Resin Dispersant (S1)]
The resin-type dispersant (S1) can be produced by known methods such as those disclosed in WO2008/007776, JP-A-2008-029901, JP-A-2009-155406, and the like. The polymer (p) having a hydroxyl group is preferably a polymer having a terminal hydroxyl group. For example, an ethylenically unsaturated monomer (r) is polymerized in the presence of a compound (q) having a hydroxyl group. It can be obtained as a polymer. 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 has a plurality of hydroxyl groups, the compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, is obtained by adding a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (p1) by polymerizing the ethylenically unsaturated monomer (r) contained. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of the tricarboxylic anhydride and/or the tetracarboxylic dianhydride to form an ester bond, while the anhydride ring is opened to form a carboxylic acid. produces

[Resin Dispersant (S2)]
The resin-type dispersant (S2) can be produced by known methods such as JP-A-2009-155406, JP-A-2010-185934, and JP-A-2011-157416. By polymerizing an ethylenically unsaturated monomer (r) in the presence of a reaction product between a hydroxyl group of (q) and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride. can get. Among them, in the presence of a reaction product of 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 anhydride and/or a tetracarboxylic dianhydride. Furthermore, it is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing a monomer (r1).

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

The resin-type dispersants may be used alone or in combination of two or more.

《Surfactant》
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate. , monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; They can be mixed and used.

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

<Photopolymerizable monomer>
The pigment composition of the present invention can be used as a photosensitive pigment composition by further adding a photopolymerizable monomer and/or a photopolymerization initiator. The photopolymerizable monomers of the present invention include monomers or oligomers that form transparent resins by curing with ultraviolet light, heat, or the like, and these can be used alone or in combination of two or more. The amount of the monomer compounded is preferably 5 to 150% by mass based on the total mass of the colorant (100% by mass), and more preferably 10 to 100% by mass from the viewpoint of photocurability and developability. preferable.

Examples of monomers and oligomers that form transparent resins by curing with ultraviolet light or heat include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 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, polypropylene glycol di(meth)acrylate ) acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethyleneglycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth) Acrylates, isocyanurate EO-modified di(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6 - hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate ) acrylates, tricyclodecanyl (meth)acrylates, methylolated melamine (meth)acrylates, epoxy (meth)acrylates, various acrylic esters and methacrylic esters such as urethane acrylates,
Styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc., but not necessarily limited to these. not something.

These commercially available products include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO- 303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, and Aronix M-303, M manufactured by Toagosei Co., Ltd. -305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403 , M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, #335HP, #700, #295 manufactured by Osaka Organic Co., Ltd. , #330, #360, #GPT, #400, #405, NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and the like can be preferably used.

(Polymerizable compound having acid group)
The photopolymerizable monomer in the invention may contain a polymerizable compound having an acid group. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups.
Since a polymerizable compound having an acid group is highly soluble in alkali, it is preferable to contain a polymerizable compound having an acid group, particularly in order to form a fine pattern.

Examples of the polymerizable compound having an acid group include, for example, poly(meth)acrylates containing free hydroxyl groups of polyhydric alcohol and (meth)acrylic acid, and esters of dicarboxylic acids; Esterified products with (meth)acrylates and the like can be mentioned. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. and free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 - Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2- Monohydroxy monoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, etc., but the effects of the present invention are limited to these. not to be

As these commercially available products, Viscoat #2500P manufactured by Osaka Organic Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toa Gosei Co., Ltd. can be preferably used. .

(Polymerizable compound having urethane bond)
The photopolymerizable monomer in the invention may contain a polymerizable compound containing at least one ethylenically unsaturated bond and at least one urethane bond. For example, a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, or a polyfunctional polyfunctional obtained by reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth)acrylate having a hydroxyl group. urethane acrylate and the like.

(Meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri( meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate Examples include methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylates.

Polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate and the like.

These commercial products include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., Shin-Nakamura Chemical Co., Ltd. UA-160TM, manufactured by Osaka Organic Chemical Industry Co., Ltd., UV-4108F, UV-4117F, etc. can be preferably used.
In addition, since a polymerizable compound having a hydroxyl group has a high affinity with an alkaline developer, it is preferable to contain a compound having a hydroxyl group in order to form a fine pattern.

The above photopolymerizable monomers may be used singly or as a mixture of two or more at any ratio as required.

The amount of the photopolymerizable monomer is based on the total non-volatile matter of the photosensitive coloring composition (100 parts by mass), preferably 1 to 50 parts by mass, from the viewpoint of photocurability and developability 2 More preferably, it is up to 40 parts by mass.

<Photoinitiator>
The pigment composition of the present invention can be cured by UV irradiation. The amount of the photopolymerization initiator used is preferably 1 to 200% by mass based on the total amount of the colorant, and is preferably 2 to 150% by mass from the viewpoint of photocurability and developability. more preferred.

Examples of photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl] -1-[4-(4-morpholinyl)phenyl]-1-butanone, or acetophenone compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin , benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide or 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone compounds such as ,4-diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 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, Triazine compounds such as 4-trichloromethyl-(4′-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine and other oxime ester compounds; bis(2,4,6-trimethylbenzoyl)phenyl phosphine compounds such as phosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole compounds; imidazole -based compounds; Alternatively, titanocene-based compounds are used.
In particular, an oxime ester compound has high sensitivity and exhibits photocurability even in a small amount. Therefore, it is preferable to use an oxime ester compound for forming a fine pattern.

<Sensitizer>
Furthermore, the pigment composition of the present invention can contain a sensitizer. Sensitizers include, for example, chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl 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, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolines derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyr Radine 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 ketone derivatives, α-a siloxyester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4 '-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone.

More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al. Special Functional Materials" (1986, CMC), but are not limited to these. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be included.

Two or more kinds of sensitizers may be used in an arbitrary ratio as necessary. The blending amount when using a sensitizer is preferably 1 to 60% by mass based on the total mass of the photopolymerization initiator contained in the pigment composition (100% by mass). From the viewpoint of developability, it is more preferably 2 to 50% by mass.

<Amine compound>
In addition, the pigment composition of the present invention may contain an amine-based compound that acts to reduce dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylamino benzoate. ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl p-toluidine and the like.

<Leveling agent>
A leveling agent is preferably added to the pigment composition of the present invention in order to improve the leveling properties of the composition. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. 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. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. A dimethylsiloxane having a polyether structure in its main chain and a dimethylsiloxane having a polyester structure in its main chain can be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by mass based on the total mass of the pigment composition (100% by mass).

A particularly preferred leveling agent is a type of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule. It is useful to have a low surface tension-reducing ability and good wettability to a glass plate despite the low surface tension-reducing ability, and the addition amount is sufficient so that film defects due to bubbling do not occur. A material capable of suppressing charging property can be preferably used. Dimethylpolysiloxane having polyalkylene oxide units can be preferably used as a leveling agent having such preferred properties. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

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

Anionic, cationic, nonionic, or amphoteric surfactants can be added to the leveling agent as auxiliaries. Two or more kinds of surfactants may be mixed and used.

Examples of anionic surfactants to be added to the leveling agent include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, and alkyldiphenyl ethers. Sodium disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether Phosphate esters are mentioned.

Cationic surfactants added to the leveling agent include, for example, alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of nonionic surfactants added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan mono Examples include stearates, polyethylene glycol monolaurate, alkylbetaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the pigment composition of the present invention may optionally contain a curing agent, a curing accelerator, and the like in order to assist curing of the thermosetting resin. Phenol-based resins, amine-based compounds, acid anhydrides, active esters, carboxylic acid-based compounds, sulfonic acid-based compounds and the like are effective as curing agents, but are not particularly limited to these. Any curing agent can be used as long as it can react with the . Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. Examples of the curing accelerator include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl -N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2- ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6 -methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.) can be used. These may be used individually by 1 type, and may use 2 or more types together. The content of the curing accelerator is preferably 0.01 to 15% by mass with respect to the total amount of the thermosetting resin.

<Curing agent, curing accelerator>
Further, the pigment composition of the present invention may optionally contain a curing agent, a curing accelerator, and the like in order to assist curing of the thermosetting resin. Phenol-based resins, amine-based compounds, acid anhydrides, active esters, carboxylic acid-based compounds, sulfonic acid-based compounds and the like are effective as curing agents, but are not particularly limited to these. Any curing agent can be used as long as it can react with the . Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. Examples of the curing accelerator include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl -N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2- ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6 -methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.) can be used. These may be used individually by 1 type, and may use 2 or more types together. The content of the curing accelerator is preferably 0.01 to 15% by mass with respect to the total amount of the thermosetting resin.

<Other additive components>
The pigment composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. In addition, an adhesion improver such as a silane coupling agent may be contained in order to improve the adhesion to the substrate.

Storage stabilizers include, for example, benzyltrimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. organic phosphines 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 coloring agent (100% by mass).

Examples of adhesion improvers include vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane and vinyltrimethoxysilane, (meth)acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β-( 3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxy Epoxysilanes such as cyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ silane coupling agents such as aminosilanes such as -aminopropyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane; and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. be done. 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 colorants in the pigment composition (100% by mass).

<Removal of coarse particles>
The pigment composition of the present invention is mixed with coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more by means of centrifugal separation, sintered filters, membrane filters, etc. Dust removal is preferred. Thus, the pigment composition preferably does not substantially contain particles of 0.5 μm or larger. More preferably, it is 0.3 μm or less.

<Membrane Containing Pigment Composition and Its Use>
A film containing the pigment composition of the present invention can be obtained by curing the pigment composition of the present invention, for example, by solvent volatilization, exposure (photocuring) or heating (thermal curing). The film formation method is not limited to the above.
Light rays for exposure in photocuring include ultraviolet rays, electron beams, X-rays, and the like. Sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, UV-LEDs, and the like can be used as light sources for ultraviolet irradiation. After exposure, post-baking may be applied to stabilize the physical properties of the cured product. The method of post-baking is not particularly limited, but is usually carried out at 50 to 260° C. for 1 to 120 minutes using a hot plate, oven, or the like.
The heating conditions for thermosetting are not particularly limited, but are usually appropriately selected from the range of 50 to 300° C. for 1 to 120 minutes. Moreover, the heating means is not particularly limited, but includes, for example, a hot plate, an oven, and the like.

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

The pigment composition of the present invention can be molded into any shape such as a dome shape, a sheet shape, or the like to form a film.

For example, it can be molded as follows. The pigment composition of the present invention containing a photopolymerization initiator and a photopolymerizable monomer is potted on a transparent substrate such as glass, and a desired molding die is pressed thereon to obtain the molding die. It can be cured by filling the inside with the pigment composition and irradiating it with light. After that, by removing the molding tool, a cured product of the pigment composition integrated on the transparent substrate can be obtained. Alternatively, it is also possible to fill the pigment composition into a transparent mold that transmits light and then photo-cure it. A hybrid lens, for example, can be produced by such a production method. Also, the pigment composition of the present invention can be cured by itself in a mold to form an optical component such as an optical lens.
It can also be molded as a microlens. An etch-back method is known as one of the microlens manufacturing methods. A resist pattern is formed on the coating film of the pigment composition of the present invention, and the resist pattern is reflowed by heat treatment to form a lens pattern. Using the lens pattern formed by reflowing this resist pattern as an etching mask, the lower coating film of the pigment composition of the present invention is etched back, and the shape of the lens pattern is transferred to the film of the pigment composition of the present invention. Make a lens. As another method for producing microlenses, the pigment composition of the present invention containing a photopolymerization initiator and an alkali-soluble resin is exposed and developed to form a resist pattern, and heat-treated to reflow the microlenses. There is also a way to make them.
In the case of molding as an optical waveguide, for example, the pigment composition of the present invention containing a photopolymerization initiator and an alkali-soluble resin is exposed and developed to form a resist pattern, and the photopolymerization initiator and the alkali-soluble resin are formed. By exposing and developing another resin composition or pigment composition having a different refractive index to form adjacent resist patterns, a core and a clad are formed, and an optical waveguide can be produced.

In this specification, the term "optical lens for an infrared sensor or an infrared communication device" refers to a lens for condensing infrared rays. Lenses for pickups, lenses for vehicle-mounted cameras, lenses for mobile cameras, lenses for digital cameras, lenses for OHPs, and microlenses can be mentioned.

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

Although the present invention will be described in more detail below, it is not limited to these examples as long as it does not deviate from the technical idea of the present invention. In the following description, "parts by mass" is simply described as "parts", and "% by mass" is simply described as "%".

<Production of isoindoline pigment>

(Synthesis Example 1-1)
700 parts of water, 344.5 mmol of 1,3-diiminoisoindoline, and 100 parts of 28% aqueous ammonia were sequentially added to a 3 L four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, followed by stirring. A solution prepared by dissolving 361.7 mmol of 2-cyano-N-methylacetamide in 100 parts of water was added dropwise thereto over 30 minutes using a dropping funnel. The mixture was heated and stirred at 30° C. until 1,3-diiminoisoindoline as a starting material disappeared. Disappearance of raw materials was confirmed by UPLC (ultra-high resolution liquid chromatography). This reaction slurry was filtered using a Buchner funnel to obtain a solid content. The entire amount of this solid content was used in the following reactions.
Into a 3 L four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, were added the entire amount of the solid content obtained in the previous preparation as raw materials, 1200 parts of water, and 400 parts of 80% acetic acid, followed by stirring. 396.1 mmol of barbituric acid was added thereto and stirred at 85°C. The heating and stirring was continued until the solid content used as the raw material disappeared. Disappearance of raw materials was confirmed by UPLC.
Thereafter, the reaction slurry was cooled to room temperature, filtered using a Buchner funnel, and washed three times with 2000 parts of water to obtain a solid content. The solid content was dried in a hot air dryer at 80° C. to obtain 105.7 parts of isoindoline pigment (a-1) (yield 91%).

(Synthesis Example 1-2)
800 parts of water and 800 parts of 80% acetic acid were added to a 3 L four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and stirred. 688.9 mmol of barbituric acid was added thereto and stirred at 85° C. to dissolve the barbituric acid. 344.5 mmol of 1,3-diiminoisoindoline was added thereto and stirred at 85°C. Stirring was continued until the starting material, 1,3-diiminoisoindoline, disappeared. Disappearance of raw materials was confirmed by UPLC. Thereafter, the reaction slurry was cooled to room temperature, filtered using a Buchner funnel, and washed three times with 2000 parts of water to obtain a solid content. The solid content was dried in a hot air dryer at 80° C. to obtain 121.5 parts of isoindoline compound (a-2) (yield 96%).

(Synthesis Example 1-3)
Reaction procedure in the same manner as in Synthesis Example 1-1, except that 2-cyano-N-methylacetamide in Synthesis Example 1-1 was changed to 2-(4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile 130.7% of isoindoline pigment (a-3) was obtained (yield 89%).

(Synthesis Example 1-4)
1200 parts of water, 344.5 mmol of 1,3-diiminoisoindoline and 200 parts of 28% aqueous ammonia were sequentially added to a 3 L four-necked flask equipped with a reflux condenser, a dropping funnel and a stirrer, followed by stirring. A solution prepared by dissolving 792.3 mmol of 2-cyano-N-(3,4-dichlorophenyl)acetamide in 200 parts of water was added dropwise thereto over 30 minutes using a dropping funnel. The mixture was heated and stirred at 30° C. until 1,3-diiminoisoindoline as a starting material disappeared. Disappearance of raw materials was confirmed by UPLC (ultra-high resolution liquid chromatography). This reaction slurry was filtered using a Buchner funnel to obtain a solid content.
Thereafter, this reaction slurry was filtered using a Buchner funnel and washed three times with 2000 parts of water to obtain a solid content. This solid content was dried in a hot air dryer at 80° C. to obtain 127.5 parts of isoindoline pigment (a-4) (yield 65%).

(Synthesis Example 1-5)
Except for changing 2-cyano-N-methylacetamide in Synthesis Example 1-1 to N-(4-chlorophenyl)-2-cyanoacetamide and barbituric acid to 1-(4-methylphenyl)barbituric acid, A reaction operation was carried out in the same manner as in Synthesis Example 1-1 to obtain 158.8 parts of an isoindoline pigment (a-5) (yield 88%).

(Synthesis Example 1-6)
Except for changing the barbituric acid in Synthesis Example 1-1 to 1,3-dimethylbarbituric acid, the reaction was carried out in the same manner as in Synthesis Example 1-1, and the isoindoline pigment (a-6) was converted to 115.8 part (yield 92%).

(Synthesis Example 1-7)
Except for changing the barbituric acid in Synthesis Example 1-2 to 1,3-dimethylbarbituric acid, the reaction was carried out in the same manner as in Synthesis Example 1-2, and the isoindoline pigment (a-7) was 138.6. part (yield 95%).

(Synthesis Example 1-8)
344.5 mmol of 1,3-diiminoisoindoline of Synthesis Example 1-1 to 256.1 mmol of 1,3-diiminobenzo[f]isoindoline, 361.7 mmol of 2-cyano-N-methylacetamide to 268.9 mmol, Except for changing 396.1 mmol of barbituric acid to 294.5 mmol, the reaction was carried out in the same manner as in Synthesis Example 1-1 to obtain 88.3 parts of isoindoline pigment (a-8) (yield 89%). rice field.

(Synthesis Example 1-9)
Synthesis except that 344.5 mmol of 1,3-diiminoisoindoline in Synthesis Example 1-2 was changed to 256.1 mmol of 1,3-diiminobenzo[f]isoindoline and 688.9 mmol of barbituric acid was changed to 537.9 mmol. The reaction was carried out in the same manner as in Example 1-2 to obtain 96.2 parts of isoindoline pigment (a-9) (yield 90%).

(Synthesis Example 1-10)
The reaction was carried out in the same manner as in Synthesis Example 1-4, except that 2-cyano-N-(3,4-dichlorophenyl)acetamide in Synthesis Example 1-4 was changed to 2-cyano-N-methylacetamide to obtain isoindoline. 54.0 parts of the system pigment (a-10) was obtained (yield 51%).

(Synthesis Example 1-11)
700 parts of water, 344.5 mmol of 1,3-diiminoisoindoline, and 100 parts of 28% aqueous ammonia were sequentially added to a 3 L four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, followed by stirring. A solution prepared by dissolving 396.1 mmol of 2-cyano-N-methylacetamide in 100 parts of water was added dropwise thereto over 30 minutes using a dropping funnel. The mixture was heated and stirred at 30° C. until 1,3-diiminoisoindoline as a starting material disappeared. Disappearance of raw materials was confirmed by UPLC (ultra-high resolution liquid chromatography). This reaction slurry was filtered using a Buchner funnel to obtain a solid content. The entire amount of this solid content was used in the following reactions.
Into a 3 L four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, the entire solid content obtained in the previous preparation as raw materials, 1200 parts of water, and 150 parts of 28% aqueous ammonia were added in this order and stirred. A solution prepared by dissolving 396.1 mmol of 2-cyano-N-(3,4-dichlorophenyl)acetamide in 100 parts of water was added dropwise thereto over 30 minutes using a dropping funnel. This was carried out at 30° C. until the solid content used as the raw material disappeared. Disappearance of raw materials was confirmed by UPLC.
Thereafter, this reaction slurry was filtered using a Buchner funnel and washed three times with 2000 parts of water to obtain a solid content. The solid content was dried in a hot air dryer at 80° C. to obtain 69.4 parts of isoindoline pigment (a-11) (yield 46%).

(Synthesis Example 1-12)
Synthesis Example 1- The reaction was carried out in the same manner as in 4 to obtain 73.6 parts of isoindoline pigment (a-12) (yield 44%).

(Synthesis Example 1-13)
Except for changing the barbituric acid in Synthesis Example 1-2 to 1-(4-methylphenyl)barbituric acid, the reaction operation was carried out in the same manner as in Synthesis Example 1-2 to give an isoindoline pigment (a-13). 160.3 parts (yield 85%) were obtained.

(Synthesis Example 1-14)
Except for changing the barbituric acid in Synthesis Example 1-1 to 1-(4-methylphenyl)barbituric acid, the reaction operation was carried out in the same manner as in Synthesis Example 1-1 to give an isoindoline pigment (a-14). 123.7 parts (yield 84%) were obtained.

(Synthesis Example 1-15)
344.5 mmol of 1,3-diiminoisoindoline of Synthesis Example 1-1 was added to 285.4 mmol of 4-methoxy-1,3-diiminoisoindoline, and 361.7 mmol of 2-cyano-N-methylacetamide was added to 299.7 mmol. In addition, except that 396.1 mmol of barbituric acid was changed to 328.2 mmol, the reaction was carried out in the same manner as in Synthesis Example 1-1, and 81.8 parts of isoindoline pigment (a-15) was obtained (yield 78% )Obtained.

(Synthesis Example 1-16)
Except for changing the barbituric acid in Synthesis Example 1-15 to 1,3-dimethylbarbituric acid, the reaction was carried out in the same manner as in Synthesis Example 1-15, and the isoindoline pigment (a-16) was 86.9. part (yield 77%).

(Synthesis Example 1-17)
Except that 344.5 mmol of 1,3-diiminoisoindoline in Synthesis Example 1-2 was changed to 285.4 mmol of 4-methoxy-1,3-diiminoisoindoline, and 688.9 mmol of barbituric acid was changed to 570.8 mmol. , and the reaction operation was carried out in the same manner as in Synthesis Example 1-2 to obtain 93.0 parts of an isoindoline pigment (a-17) (yield 82%).

(Synthesis Example 1-18)
Except for changing the barbituric acid in Synthesis Example 1-17 to 1,3-dimethylbarbituric acid, the reaction was carried out in the same manner as in Synthesis Example 1-17, and the isoindoline pigment (a-18) was converted to 103.5 part (yield 80%).

(Synthesis Example 1-19)
Reaction procedure in the same manner as in Synthesis Example 1-15, except that 2-cyano-N-methylacetamide in Synthesis Example 1-15 was changed to 2-(4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile was carried out to obtain 96.4 parts of an isoindoline pigment (a-19) (yield 74%).

(Synthesis Example 1-20)
Except for changing the barbituric acid in Synthesis Example 1-17 to 1-(4-methylphenyl)barbituric acid, the reaction was carried out in the same manner as in Synthesis Example 1-17 to give an isoindoline pigment (a-20). 118.6 parts (yield 75%) were obtained.

(Synthesis Example 1-21)
344.5 mmol of 1,3-diiminoisoindoline of Synthesis Example 1-4 was added to 285.4 mmol of 4-methoxy-1,3-diiminoisoindoline and 792 mmol of 2-cyano-N-(3,4-dichlorophenyl)acetamide. The reaction was carried out in the same manner as in Synthesis Example 1-4 except that 0.3 mmol was changed to 656.4 mmol to obtain 71.8 parts of isoindoline pigment (a-21) (yield 42%).

(Synthesis Example 1-22)
344.5 mmol of 1,3-diiminoisoindoline of Synthesis Example 1-4 was added to 256.1 mmol of 1,3-diiminobenzo[f]isoindoline and 792.3 mmol of 2-cyano-N-(3,4-dichlorophenyl)acetamide. was changed to 589.1 mmol of 2-cyano-N-methylacetamide, the reaction was carried out in the same manner as in Synthesis Example 1-4, and 36.6 parts of the isoindoline pigment (a-22) was added (yield 40% )Obtained.

(Synthesis Example 1-23)
344.5 mmol of 1,3-diiminoisoindoline of Synthesis Example 1-11 to 256.1 mmol of 1,3-diiminobenzo[f]isoindoline, 396.1 mmol of 2-cyano-N-methylacetamide to 294.5 mmol, The reaction was carried out in the same manner as in Synthesis Example 1-11, except that 2-cyano-N-(3,4-dichlorophenyl)acetamide (396.1 mmol) was changed to 294.5 mmol to give an isoindoline pigment (a-23). 48.8 parts (yield 39%) were obtained.

(Synthesis Example 1-24)
Reaction procedure in the same manner as in Synthesis Example 1-22, except that 2-cyano-N-methylacetamide in Synthesis Example 1-22 was changed to 2-(4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile to obtain 53.5 parts of isoindoline pigment (a-24) (yield 39%).

(Synthesis Example 1-25)
344.5 mmol of 1,3-diiminoisoindoline of Synthesis Example 1-11 to 256.1 mmol of 1,3-diiminobenzo[f]isoindoline, 396.1 mmol of 2-cyano-N-methylacetamide to 294.5 mmol, Synthesis Example 1- 46.9 parts of isoindoline pigment (a-25) was obtained (yield: 41%).

(Synthesis Example 1-26)
Except for changing the barbituric acid in Synthesis Example 1-9 to 1-(4-methylphenyl)barbituric acid, the reaction was carried out in the same manner as in Synthesis Example 1-9 to give an isoindoline pigment (a-26). 105.6 parts (yield 69%) were obtained.

(Synthesis Example 1-27)
Except for changing the barbituric acid in Synthesis Example 1-8 to 1-(4-methylphenyl)barbituric acid, the reaction operation was carried out in the same manner as in Synthesis Example 1-8 to give an isoindoline pigment (a-27). 83.2 parts (yield 68%) were obtained.

Table 1 shows the structures of the isoindoline pigments obtained in Synthesis Examples 1-1 to 1-27. For example, when the relationship between Y ₁ and Y ₂ and Y ₃ and Y ₄ is asymmetrical as seen in the compound of Synthesis Example 1-15, the compound is obtained as a mixture of isomers.

The isoindoline compound was identified by comparing the mass spectrum molecular ion peak with the calculated mass number (theoretical value). Measurement of the molecular ion peak of the mass spectrum was performed using Waters ACQUITY UPLS H-Class (column used: ACQUITY UPLC BEH C18 Column 130 Å, 1.7 μm, 2.1 mm×50 mm)/Ms TAP XEVO TQD. Table 1 shows the theoretical molecular weights and the measured values of mass spectrometry for the isoindoline compounds (Synthesis Examples 1-1 to 1-27). Due to the nature of the measurement, the H (proton) of the compound is eliminated from the measured value, so if the value is the mass number of the theoretical molecular weight - (minus) 1, the compound will match.

In Table 1, Ph represents a phenyl group, for example Ph-Me represents a structure in which one hydrogen in a phenyl group is replaced with a methyl group. Np represents that Y ₁ and Y ₂ have the following structures in general formula (1).

<Production of micronized pigment>
(Refinement of isoindoline pigment (a-1))
10 parts of the isoindoline pigment (a-1), 100 parts of sodium chloride and 12.5 parts of ethylene glycol were placed in a gallon kneader made of stainless steel (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 12 hours. Next, the kneaded mixture is poured into warm water, stirred for 1 hour while heating to about 80°C to form a slurry, filtered and washed with water to remove salt and diethylene glycol, dried at 80°C for a day and night, and pulverized. Thus, 9.4 parts of isoindoline-based finely divided pigment (a-1K) was obtained.

(Refinement of isoindoline pigments (a-2) to (a-27))
The isoindoline-based pigments (a-2) to (a-27) are also subjected to the same refinement treatment as the isoindoline-based pigment (a-1), and isoindoline-based finely divided pigments (a-2K) to (a- 27K) was obtained.

(Production of yellow finely divided pigment (PY-1))
yellow pigment C.I. I. 200 parts of Pigment Yellow 74 (“LIONOGEN YELLOW 0390” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. . Next, this kneaded product was put into 8 liters of hot water and stirred for 2 hours while being heated to 80° C. to form a slurry. The slurry was filtered, washed repeatedly with water to remove sodium chloride and diethylene glycol, and dried at 85° C. for one day to obtain a fine yellow pigment (PY-1).

(Production of yellow finely divided pigment (PY-2))
yellow pigment C.I. I. Pigment Yellow 74 was mixed with yellow pigment C.I. I. Pigment Yellow 12 ("FINESS YELLOW G-20S-12" manufactured by Toyocolor Co., Ltd.), except that it was changed to yellow fine pigment (PY-1) in the same manner as the production of yellow fine pigment (PY-1), 97 parts of yellow fine pigment (PY- 2) was obtained.

(Production of red finely divided pigment (PR-1))
Commercially available C.I. I. 100 parts of Pigment Red 242 (PR242) (“Sandorin Scarlet 4RF” manufactured by Clariant), 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60°C for 6 hours. , salt milled. The resulting kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70°C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for a day and night. , 98 parts of red finely divided pigment (PR-1) were obtained.

(Production of red finely divided pigment (PR-2))
C. I. Pigment Red 242 (PR242) ("Sandorin Scarlet 4RF" manufactured by Clariant) was added to C.I. I. Pigment Red 269 (PR269) ("Permanent Carmine 3810" manufactured by Sanyo Color Co., Ltd.) in the same manner as in the production of red fine pigment (PR-1), 97 parts of red fine pigment (PR-2 ).

(Production of red finely divided pigment (PR-3))
C. I. Pigment Red 242 (PR242) ("Sandorin Scarlet 4RF" manufactured by Clariant) was added to C.I. I. Pigment Red 57:1 ("LIONOL RED TT-5701G" manufactured by Toyocolor Co.) was used in the same manner as in the production of red finely divided pigment (PR-1), except that 96 parts of red finely divided pigment (PR- 3) was obtained.

(Production of red finely divided pigment (PR-4))
C. I. Pigment Red 242 (PR242) (“Sandorin Scarlet 4RF” manufactured by Clariant) was added to C.I. I. Pigment Red 48:3 ("LIONOL RED TT-4803" manufactured by Toyocolor Co.) was used in the same manner as in the production of red finely divided pigment (PR-1), except that 99 parts of red finely divided pigment (PR- 4) was obtained.

(Production of red finely divided pigment (PR-5))
C. I. Pigment Red 242 (PR242) ("Sandorin Scarlet 4RF" manufactured by Clariant) was added to C.I. I. Pigment Red 146 ("LIONOL RED 5620" manufactured by Toyocolor Co., Ltd.) was used in the same manner as the production of red fine pigment (PR-1) to obtain 97 parts of red fine pigment (PR-5). rice field.

(Production of blue finely divided pigment (PB-1))
phthalocyanine blue pigment C.I. I. Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyocolor Co., Ltd.) 100 parts, pulverized salt 800 parts, and diethylene glycol 100 parts were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 12 hours. Kneaded. This mixture is poured into 3000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, and then heated to 80°C for 24 hours. It was dried to obtain 98 parts of blue fine pigment (PB-1).

(Production of purple fine pigment (PV-1))
dioxazine-based purple pigment C.I. I. 120 parts of Pigment Violet 23 (“FastViolet RL” manufactured by Clariant), 1600 parts of pulverized salt, and 100 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 90° C. for 18 hours. This mixture is poured into 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, which is repeatedly filtered and washed with water to remove salt and solvent, then heated to 80°C for 24 hours. After drying, 118 parts of purple fine pigment (P-2) were obtained.

<Measurement of 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 primary particles from an electron micrograph. Specifically, the short axis diameter and long axis diameter of the primary particles of each pigment were measured, and the average was used as the particle size of the pigment particles. Next, for 100 or more pigment particles, the volume (mass) of each particle was obtained by approximating a cube of the obtained particle size, and the volume average particle size was taken as the average primary particle size.
A transmission type (TEM) electron microscope was used.
As a result of measurement by this method, the average primary particle size of the isoindoline pigment (a-1) was 460 nm.
Table 2-1 shows the average primary particle size of the pigment and the finely divided pigment measured by the above method. Incidentally, (a-1) and (a-2) are crude pigments before being subjected to the above-described fine-refining treatment.

<Measurement of Metal Atom Content of Pigment>
Pigments generally contain trace amounts of metal atoms.
When the metal atom content of pigments (a-1K), (a-2K), and (a-6K) was measured by high-frequency inductively coupled plasma emission spectrometry, Li, Na, K, Cs, Mg, Ca , Ti, Fe, Co, Ni, Pd, Cu, Zn, Si and Al were all contained in trace amounts. Contents of these metal atoms are shown in Table 2-2.

<Dye production>
(Production of red dye (DR-1))
red acid dye C.I. I. 39.2 parts of Basic Red 12, 392 parts of water and 39.2 parts of methanol were mixed, and a solution of 36.2 parts of didecyldimethylammonium chloride dissolved in 362 parts of water was added little by little. Since powder was gradually deposited, it was filtered on a Nutsche and washed by sprinkling 200 parts of water twice. After that, the powder was taken out and dried at 80° C. for 8 hours. I. 70.1 parts of a red dye (DR-1), which is a salt product of Basic Red 12 and didecyldimethylammonium chloride, was obtained.

(Production of red dye (DR-2))
red acid dye C.I. I. 58.0 parts of Acid Red 52, 580 parts of water and 58.0 parts of methanol were mixed, and a solution of 36.2 parts of didecyldimethylammonium chloride dissolved in 362 parts of water was added little by little. Since powder was gradually deposited, it was filtered on a Nutsche and washed by sprinkling 200 parts of water twice. After that, the powder was taken out and dried at 80° C. for 8 hours. I. 90.6 parts of a red dye (DR-2), which is a salt product of Acid Red 52 and didecyldimethylammonium chloride, was obtained.

(Production of yellow dye (DY-1))
yellow acid dye C.I. I. 42.6 parts of Acid Yellow 49, 426 parts of water and 42.6 parts of methanol were mixed, and a solution of 36.2 parts of didecyldimethylammonium chloride dissolved in 362 parts of water was added little by little. Since powder was gradually deposited, it was filtered on a Nutsche and washed by sprinkling 200 parts of water twice. After that, the powder was taken out and dried at 80° C. for 8 hours. I. 90.6 parts of a yellow dye (DY-1), which is a salt product of Acid Red 52 and didecyldimethylammonium chloride, was obtained.

<Preparation of binder resin solution>
(Preparation of binder resin solution 1)
70.0 parts of cyclohexanone was charged into a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirring device, and the temperature was raised to 80°C. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) 7.4 parts, A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 hours to obtain a solution of an acrylic resin having a weight-average molecular weight of 26,000. 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. was added to prepare a 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.

(Preparation of binder resin solution 2)
A separable 4-necked flask equipped with a thermometer, a condenser tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device was charged with 370 parts of cyclohexanone, heated to 80°C, and after replacing the inside of the flask with nitrogen, parachlorate was added from the dropping tube. Millphenol ethylene oxide-modified acrylate (Toagosei Aronix M110) 18 parts, benzyl methacrylate 10 parts, glycidyl methacrylate 18.2 parts, methyl methacrylate 25 parts, and 2,2'-azobisisobutyronitrile 2.0 The mixture of parts was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was changed to air exchange, and 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl groups) in the container, and the mixture was heated at 120°C. The reaction was continued for 6 hours and terminated when the solid content acid value reached 0.5 to obtain a copolymer solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain carboxyl groups and 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. to prepare a binder resin solution 2. The weight average molecular weight (Mw) was 19,000.

<Preparation of resin type dispersant>
(Preparation of basic resin type dispersant 1 solution)
60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C for 1 hour while flowing nitrogen. After stirring, the inside of 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 non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile 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 the reactor, and the mixture was stirred while maintaining the temperature at 110° C. under a nitrogen atmosphere to continue the reaction. Two hours after the addition of dimethylaminoethyl methacrylate, the polymerization solution was sampled and the nonvolatile content was measured to confirm that the polymerization conversion rate of the second block was 98% or more in terms of the nonvolatile content. Polymerization was stopped by cooling.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by mass. In this way, the amine value per non-volatile content is 71.4 mg KOH / g, the weight average molecular weight is 9900 (Mw), the non-volatile content is a poly (meth) acrylate skeleton of 40% by mass, a basic having a tertiary amino group A resin type dispersant 1 solution was obtained.

(Adjustment of basic resin type dispersant solution 2)
60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C for 1 hour while flowing nitrogen. After stirring, the inside of 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 non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 25.6 parts of an aqueous solution of methacryloyloxyethyltrimethylammonium chloride as a second block monomer ("Acryester DMC78" manufactured by Mitsubishi Rayon Co., Ltd.) were added to the reactor, and the temperature was maintained at 110°C under a nitrogen atmosphere. The reaction was continued while stirring. Two hours after the addition of methacryloyloxyethyltrimethylammonium chloride, the polymerization solution was sampled and the nonvolatile content was measured. Polymerization was terminated by cooling to room temperature.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by weight. Thus, a basic resin-type dispersant solution 2 having a poly(meth)acrylate skeleton and a quaternary ammonium base, having an amine value per non-volatile content of 29.4 mgKOH/g and a weight average molecular weight of 9800 (Mw) was obtained. rice field.

(Adjustment of basic resin type dispersant solution 3)
A reaction vessel equipped with a stirrer and a thermometer was charged with 55 parts of 4-dimethylamino-1,2-epoxybutane and 120 parts of tetrahydrofuran (THF), heated and stirred at 70° C., and 35 parts of methacrylic acid was added over 60 minutes. Dripped. After completion of the dropwise addition, the mixture was heated and stirred at 70° C. for another 2 hours, and after confirming completion of the reaction by ¹ H-NMR, 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 brine, 20 g of magnesium sulfate was added to the organic layer, and the mixture was stirred and filtered. The solvent of the resulting solution was distilled off using a rotary evaporator to obtain 31 parts of the following monomer (b-3) as a pale yellow transparent liquid (yield 42%). Identification of the obtained compound was carried out by ¹ H-NMR.

Monomer (b-3)

17.6 parts of methyl methacrylate, 52.8 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer, and the mixture was stirred for 50 minutes while flowing nitrogen. The mixture was stirred at ℃ for 1 hour, 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 added, 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 non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 25 parts of PGMAc and 25.1 parts of an ethylenically unsaturated monomer (b-3) as a second block monomer are added to the reactor, and stirred while maintaining the temperature at 110°C under a nitrogen atmosphere, Continue the reaction. Two hours after the addition of the ethylenically unsaturated monomer (b-3), the polymerization solution was sampled and the nonvolatile content was measured. confirmed.
Further, 4.5 parts of benzyl chloride was added to the reactor, stirred for 3 hours while maintaining the temperature at 110° C. under a nitrogen atmosphere, and then cooled.
PGMAc was added to the previously synthesized block copolymer solution so that the non-volatile content was 40% by weight. Thus, a basic resin-type dispersant solution having an amine value per non-volatile content of 50 mg KOH / g, a quaternary ammonium salt value of 20 mg KOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by weight got 3.

(Adjustment of acidic resin-type dispersant solution 1)
45 parts of methyl methacrylate, 5 parts of methacrylic acid, 50 parts of n-butyl methacrylate and 45.4 parts of PGMAc were introduced into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and the contents were purged with nitrogen gas. The inside of the reaction vessel was heated to 70° C., 6 parts of 3-mercapto-1,2-propanediol was added, and 0.12 part of AIBN (azobisisobutyronitrile) was further added and reacted for 12 hours. It was confirmed by measuring the non-volatile content that 95% had reacted. Next, add 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, and heat at 120°C. was reacted for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%. Thus, an acidic resin type dispersant solution 1 having an acid value of 75, a weight average molecular weight of 9000, a poly(meth)acrylate skeleton and an aromatic carboxyl group was obtained.

(Adjustment of acidic resin-type dispersant solution 2)
50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate and 45.4 parts of PGMAc were introduced into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and the contents were purged with nitrogen gas. The inside of the reaction vessel was heated to 70° C., 6 parts of 3-mercapto-1,2-propanediol was added, and 0.12 part of AIBN (azobisisobutyronitrile) was further added and reacted for 12 hours. It was confirmed by measuring the non-volatile content that 95% reacted. Next, add 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, and heat at 120°C. was reacted for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%. Thus, an acidic resin-type dispersant solution 2 having an acid value of 43, a weight average molecular weight of 9000, a poly(meth)acrylate skeleton and an aromatic carboxyl group was obtained.

(Adjustment of acidic resin-type dispersant solution 3)
50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate and 45.4 parts of PGMAc were introduced into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and the contents were purged with nitrogen gas. The inside of the reaction vessel was heated to 70° C., 6 parts of 3-mercapto-1,2-propanediol was added, and 0.12 part of AIBN (azobisisobutyronitrile) was further added and reacted for 12 hours. It was confirmed by measuring the non-volatile content that 95% had reacted. 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 heated to 120°C. was reacted for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%. Thus, an acidic resin-type dispersant solution 3 having an acid value of 90, a weight average molecular weight of 9000, a poly(meth)acrylate skeleton and an aromatic carboxyl group was obtained.

(Adjustment of acidic resin-type dispersant solution 4)
45 parts of methyl methacrylate, 5 parts of methacrylic acid, 50 parts of n-butyl methacrylate and 45.4 parts of PGMAc were introduced into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and the contents were purged with nitrogen gas. The inside of the reaction vessel was heated to 70° C., 2 parts of 3-mercapto-1,2-propanediol was added, and 0.12 part of AIBN (azobisisobutyronitrile) was further added and reacted for 12 hours. It was confirmed by measuring the non-volatile content that 95% had reacted. 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 heated to 120°C. was reacted for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%. Thus, an acidic resin-type dispersant solution 4 having an acid value of 47, a weight average molecular weight of 18000, a poly(meth)acrylate skeleton and an aromatic carboxyl group was obtained.

(Adjustment of acidic resin-type dispersant solution 5)
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 in a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer. was introduced, and after purging with nitrogen gas, reaction was carried out at 120° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of solid content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate Parts, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, the inside of the reaction vessel was heated to 80° C., 1.2 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours. (Second step). Solid content measurement confirmed that 95% had reacted. 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 part of hydroquinone were charged. The reaction was continued until disappearance of the -1 peak was confirmed (third step). After confirming disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with PGMAc to obtain an acidic resin-type dispersant solution 5 having a non-volatile content of 40%. The resulting dispersant had an acid value of 68, an unsaturated double bond equivalent of 1,593, and a weight average molecular weight of 13,000.

(Adjustment of acidic resin-type dispersant solution 6)
50.0 parts of tert-butyl acrylate, 50.0 parts of methyl methacrylate, and 25.0 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and the mixture was purged with nitrogen gas. . The inside of 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 part of 2,2′-azobisisobutyronitrile dissolved in 45.7 parts of propylene glycol monomethyl ether acetate was added and reacted for 10 hours. It was confirmed by measuring the non-volatile content that 95% had reacted.
Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 38.0 parts of PGMAc, 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst was added and reacted at 120° C. for 5 hours. After that, 12.1 g of 3-methoxybutanol was added and reacted at 120° C. for 3 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. After completion of the reaction, propylene glycol monomethyl ether acetate was added so that the non-volatile content was 40% by mass, and an acidic resin-type dispersant solution 6 having an acid value of 95 mgKOH/g and a weight average molecular weight of 9,500 was obtained.

(Adjustment of acidic resin-type dispersant solution 7)
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 into a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, and nitrogen gas was added. replaced. The inside of the reaction vessel was heated to 100° C. and reacted for 5 hours. After that, 12.1 g of 3-methoxybutanol was added and reacted at 120° C. for 3 hours. After confirming that 98% or more of the acid anhydride is half-esterified by measuring the acid value, the temperature in the system is cooled to 70 ° C., 50.0 parts of t-butyl acrylate, 50.0 parts of methyl methacrylate. was charged, 38.0 parts of propylene glycol monomethyl ether acetate in which 0.1 part of 2,2'-azobisisobutyronitrile was dissolved was added, and the mixture was reacted for 10 hours. After confirming that the polymerization had progressed by 95% by measuring the non-volatile content, the reaction was terminated. After completion of the reaction, propylene glycol monomethyl ether acetate was added so that the non-volatile content was 40% by mass, and an acidic resin-type dispersant solution 7 having an acid value of 93 mgKOH/g and a weight average molecular weight of 10,800 was obtained.

(Adjustment of acidic resin-type dispersant solution 8)
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, t- 60 parts of butyl methacrylate and 45.4 parts of PGMAc were charged, and the mixture was purged with nitrogen gas. The inside of the reaction vessel was heated to 70° C., 6 parts of 3-mercapto-1,2-propanediol was added, and 0.12 part of AIBN (azobisisobutyronitrile) was further added and reacted for 12 hours. It was confirmed by measuring the non-volatile content that 95% reacted. Next, add 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, and heat at 120°C. was reacted for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%. Thus, an acidic 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 carboxyl group was obtained.

(Adjustment of acidic resin-type dispersant solution 9)
12 parts of 3-mercapto-1,2-propanediol, 12 parts of PMA, 11 parts of trimellitic anhydride, and 35 parts of PGMAc are charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, and replaced with nitrogen gas. bottom. The inside of the reaction vessel was heated to 100° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride is half-esterified by measuring the acid value, the temperature in the system is cooled to 70 ° C., 80 parts of methyl methacrylate, 80 parts of butyl acrylate, and 20 parts of hydroxyethyl methacrylate. , and 20 parts of 2-hydroxypropyl methacrylate were charged, and 200 parts of a PGMAc solution in which 0.5 part of 2,2'-azobisisobutyronitrile was dissolved was added and reacted for 10 hours. After confirming that the polymerization had progressed by 95% by measuring the solid content, the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%, and an acidic resin-type dispersant solution 9 having an acid value of 53 and a weight average molecular weight of 10,000 was obtained.

(Adjustment of acidic resin-type dispersant solution 10)
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 are placed in a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer. It was charged and purged with nitrogen gas. The inside of the reaction vessel was heated to 100° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride is half-esterified by acid value measurement, the temperature in the system is cooled to 70 ° C., 80 parts of methyl methacrylate, 100 parts of butyl acrylate, and 2-hydroxypropyl methacrylate. 20 parts of the reaction mixture was charged, 200 parts of a PGMAc solution containing 0.5 parts of 2,2'-azobisisobutyronitrile dissolved therein was added, and the mixture was reacted for 10 hours. After confirming that the polymerization had progressed by 95% by measuring the solid content, the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%, and an acidic resin-type dispersant solution 10 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 1)
As a high refractive index resin, a comparative high refractive index resin 1, which is a fluorene-based polyester, was synthesized.
A 1 L separable flask was charged with 45 g (0.25 mol, manufactured by Osaka Gas Chemicals Co., Ltd.) of 9-fluorenone, 188 g (1 mol) of ethylene glycol mono(2-naphthyl) ether, and 1 g of 3-mercaptopropionic acid. Afterwards, it was heated to 60° C. for complete dissolution. After that, 54 g of sulfuric acid was gradually added, and the mixture was stirred for 5 hours while maintaining the temperature at 60°C. A 48% by mass sodium hydroxide aqueous solution was added to the resulting reaction solution for neutralization, and then 400 g of xylene was added, washed several times with distilled water, and cooled to precipitate crystals. Further, after filtration and drying, 87 g (yield 67%) of crystals of 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF) were obtained. When the HPLC purity of the obtained crystals was measured, it was 98.3%. The obtained sample was confirmed to be 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF) by 1H-NMR and mass spectrum.

In a reactor, 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 (dimethyl ester of 9,9-di(carboxyethyl)fluorene or fluorene-9,9-dipropionic acid, hereinafter referred to as FDPM) 0.70 mol, transesterification As a catalyst, 2×10 ⁻⁴ mol of manganese acetate tetrahydrate and 8×10 ⁻⁴ mol of calcium acetate monohydrate were added and gradually heated and melted with stirring. The pressure was gradually reduced to Ethylene glycol was removed while gradually increasing the temperature and reducing the pressure until the temperature reached 270° C. and 0.13 kPa or less. After reaching a predetermined stirring torque, the contents were taken out from the reactor to obtain polyester resin pellets.

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

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

The weight average molecular weight Mw of the obtained polyester resin was 31300, and the refractive index at 589 nm was 1.66.

The obtained polyester resin was dissolved in cyclohexanone so that the non-volatile content was 20%, and a comparative high refractive index resin 1 was obtained.

<Production of pigment composition>
[Example 1]
(Production of pigment composition (D-1))
After uniformly stirring and mixing a mixture having the following composition, zirconia beads having a diameter of 0.5 mm were used to disperse the mixture with an Eiger mill for 3 hours, followed by filtration through a 0.5 μm filter to give a pigment composition (D-1). made.
Isoindoline-based finely divided pigment (a-1K): 8.0 parts Basic resin type dispersant 1 solution: 8.0 parts Binder resin solution 1: 44.0 parts PGMAc (methoxypropyl acetate): 40.0 parts

[Examples 2 to 34, 37 to 49, Comparative Examples 1 to 10, Production Examples 1 and 2]
(Pigment Compositions (D-2) to (D-56))
Pigment compositions (D-2) to (D-56) were prepared in the same manner as the pigment composition (D-1) except that the composition was changed as shown in Table 3.
The structure of dye derivative 1 is shown below.
(Dye derivative 1)

[Comparative Example 8]
(Production of dye composition (DD-1))
After uniformly stirring and mixing a mixture having the following composition, zirconia beads with a diameter of 0.5 mm were used to disperse with an Eiger mill for 3 hours, and then filtered through a 0.5 μm filter to obtain a dye composition (DD-1). made.
Red dye (DR-1): 10.0 parts Resin type dispersant 1 solution: 10.0 parts Binder resin solution 1: 30.0 parts PGMAc (methoxypropyl acetate): 50.0 parts

[Comparative Examples 9 and 10]
(Dye compositions (DD-2) to (DD-3))
Dye compositions (DD-2) to (DD-3) were prepared in the same manner as the dye composition (DD-1) except that the composition was changed as shown in Table 3.

[Example 35]
(Pigment composition (E-1))
A mixture having the following composition was uniformly stirred and mixed to prepare a pigment composition (E-1).
Pigment composition (D-42): 20.0 parts Pigment composition (D-43): 20.0 parts Pigment composition (D-6): 60.0 parts It is a dispersion containing 70% of the isoindoline-based finely divided pigment (a-2K) as a pigment concentration in the solid content, and the solid content of the pigment composition (E-1) contains the isoindoline-based finely divided pigment (a −2K) is contained at 42%. This is shown in Table 4.

[Example 36]
(Pigment composition (E-2))
A mixture having the following composition was uniformly stirred and mixed to prepare a pigment composition (E-2).
Pigment composition (D-5): 100.0 parts Tinuvin326: 2.0 parts PGMAc: 18.0 parts Tinuvin326 is an ultraviolet absorber manufactured by BASF.
Incidentally, the pigment composition (D-5) is a dispersion containing the isoindoline-based finely divided pigment (a-2K) at a pigment concentration of 50% in the solid content, and the solid content of the pigment composition (E-2) Contains 45.5% isoindoline micronized pigment (a-2K). This is shown in Table 5.

<Preparation of film for evaluation>
The pigment composition (D-1) produced in Example 1 is applied to a glass substrate of 100 mm × 100 mm and 1.1 mm thickness by adjusting the number of rotations using a spin coater, and dried at 100 ° C. for 10 minutes. , a substrate on which a film having a thickness of 1.0 μm was formed was obtained.

For Examples 2 to 49 and Comparative Examples 1 to 10, the same operation as in Example 1 was performed to obtain substrates on which a film having a thickness of 1.0 μm was formed.

<Evaluation>
Using the film for evaluation described above, the following evaluations were carried out. Table 6 shows the results.
[transparency]
The haze of the substrate on which the film was formed was measured with a haze meter, and the transparency was determined 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

[Refractive index]
Spectroscopic ellipsometry measurement was performed on the substrate on which the film was formed, and the refractive indices at 850 nm, 940 nm and 1550 nm were obtained.

[Lightfastness]
The substrate on which the above film was formed was subjected to a light resistance test by exposing it for 20 hours at an illumination intensity of 60 W/m ² from 300 to 400 nm using a xenon weather meter.
Changes in absorbance at the maximum absorption wavelength between 400 and 700 nm were 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 and less than 30% ×: The rate of decrease in absorbance at the maximum absorption wavelength is 30% or more

[Heat-resistant]
A heat resistance test was performed by heating the substrate on which the film was formed at 250° C. for 1 hour.
Changes in absorbance at the maximum absorption wavelength between 400 and 700 nm were 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 and less than 30% ×: The rate of decrease in absorbance at the maximum absorption wavelength is 30% or more

<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, dried at 70° C. for 20 minutes, and then heat-treated at 230° C. for 30 minutes. .
In the above operation, the rotation speed of spin coating was adjusted to obtain a substrate on which a film having a thickness of 1.0 μm was formed, and spectroscopic ellipsometry measurement was performed to obtain the refractive index at 850 nm, 940 nm, and 1550 nm. The refractive index was 1.63, 1.62 at 940 nm, and 1.60 at 1550 nm.

<Production of curable composition>
[Example 50]
(Production of curable composition (DC-1))
A curable composition (XR-1) was prepared by stirring and mixing a mixture having the following composition so as to be uniform.
Pigment composition (D-3): 100 parts EHPE3150 (epoxy curing agent, manufactured by Daicel Chemical Industries, Ltd.): 3.3 parts PGMAc: 13.3 parts

[Example 51]
(Production of curable composition (DC-2))
A curable composition (DC-2) was prepared in the same manner as the curable composition (DC-1), except that the composition was changed as shown in Table 7.

<Production of photosensitive composition>
[Example 52]
(Production of photosensitive composition (DR-1))
A mixture having the following composition was uniformly stirred and mixed to prepare a photosensitive composition (XR-1).
Pigment composition (D-3): 100.0 parts photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "Aronix M-402"): 6.4 parts photopolymerization initiator (manufactured by BASF "Irgacure 907") : 1.6 parts PGMAc: 32.0 parts

[Examples 53-55]
(Production of photosensitive compositions (DR-2) to (DR-4))
Photosensitive compositions (DR-2) to (DR-4) were prepared in the same manner as the photosensitive composition (DR-1) except that the composition was changed as shown in Table 8.

<Preparation of film for evaluation of curable composition and photosensitive composition>
The curable compositions (DC-1) and (DC-2) are applied to a glass substrate of 100 mm × 100 mm and 1.1 mm thickness by adjusting the rotation speed using a spin coater, and dried at 100 ° C. for 10 minutes. After that, a substrate on which a film having a thickness of 1.0 μm was formed was obtained.

The photosensitive compositions (DR-1) to (DR-4) were 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. Then, after cooling this substrate to room temperature, it was exposed to ultraviolet rays using an extra-high pressure mercury lamp.
Thereafter, the substrate was developed by spraying with a 0.2% by mass sodium carbonate aqueous solution at 23° C. for 30 seconds, washed with deionized water, and dried. Furthermore, heat treatment was performed at 230° C. for 30 minutes in a clean oven.
A substrate having a film having a thickness of 1.0 μm formed thereon was obtained by adjusting the rotational speed of the spin coating in the above steps.

<Evaluation of curable composition and photosensitive composition>
Using the film for evaluation described above, the following evaluations were carried out. Table 9 shows the results.
[transparency]
For the substrates on which the films of the curable composition and the photosensitive composition were formed, the haze was measured with a haze meter, and the transparency was determined 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

[Refractive index]
Spectroscopic ellipsometry measurement was performed on the substrate on which the film was formed, and the refractive indices at 850 nm, 940 nm and 1550 nm were obtained.

[chemical resistance]
The substrate on which the film was formed was subjected to heat treatment at 200° C. for 5 minutes, then rubbed 50 times with a hammer wrapped with gauze swollen with methyl ethyl ketone, and the surface of the coating film was observed. As a chemical resistance test, determination was made according to the following criteria.
◯: The coating film was intact.
Δ: Part of the coating film is peeled off.
x: The coating film is completely dissolved.

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 be a film having excellent transparency, heat resistance, and light resistance. It is useful as a lens or as an optical waveguide for infrared sensors or infrared communication devices.

Claims (10)

An optical lens used in an infrared sensor or an infrared communication device, or a pigment composition used in an optical waveguide used in an infrared sensor or an infrared communication device,
containing an isoindoline pigment and a resin,
The content of the isoindoline pigment is 40% by mass or more based on the total mass of solids in the pigment composition,
A pigment composition having a refractive index of 1.65 or more at 23° C. and a wavelength of 850 nm when formed into a film having a thickness of 1.0 μm. 2. The pigment composition according to claim 1, wherein the isoindoline pigment has a structure represented by general formula (1).
General formula (1)

(X ₁ and X ₂ each independently represent the following general formula (2), (3) or (4); Y ₁ to Y ₄ each independently represent a hydrogen atom, a hydroxy group, a carboxy group , cyano group, nitro group, sulfo group, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, alkoxycarbonyl group having 2 to 4 carbon atoms, alkylcarboxy group having 2 to 4 carbon atoms, halogen atom , an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, —SO ₂ —OR ₁₁₁ , or —SO ₂ -NH-R ₁₁₂ , two of which may form a ring in the form of removing a hydrogen atom, respectively, and a divalent organic group may be inserted between them when forming the ring. ₁₁₁ and R ₁₁₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

general formula (2)

(Y ₅ and Y ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cyclo represents an alkyl group or an aryl group having 6 to 12 carbon atoms, and * represents a bond.)

General formula (3)

(Y ₇ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, Or represents an aryl group having 6 to 12 carbon atoms, * represents a bond.)

general formula (4)

3. The pigment composition according to claim 1, further comprising a curing agent and a solvent. 3. The pigment composition according to claim 1, which is used as a high refractive index material at 800 nm to 1600 nm. A film comprising the pigment composition of claim 1 . An optical material comprising the pigment composition according to claim 1 . An optical lens comprising the pigment composition of claim 1 . An optical waveguide comprising the pigment composition according to claim 1 . An infrared sensor comprising the film according to claim 5, the optical material according to claim 6, the optical lens according to claim 7, or the optical waveguide according to claim 8. An infrared communication device comprising the film according to claim 5, the optical material according to claim 6, the optical lens according to claim 7, or the optical waveguide according to claim 8.