WO2024024508A1

WO2024024508A1 - Composition, film, optical filter, solid state imaging device, image display device, infrared radiation sensor, and method for producing camera module

Info

Publication number: WO2024024508A1
Application number: PCT/JP2023/025709
Authority: WO
Inventors: 賢鮫島
Original assignee: 富士フイルム株式会社
Priority date: 2022-07-25
Filing date: 2023-07-12
Publication date: 2024-02-01
Also published as: TW202411358A

Abstract

This composition contains a colorant, a curable compound and a solvent. The solvent contains an aromatic compound having 8 or more carbon atoms and having a molecular weight of 500 or less. The content of the aromatic compound in the composition is 1-50,000 ppm by mass. Also provided are a film, an optical filter, a solid-state imaging device, an image display device, an infrared radiation sensor and a method for producing a camera module in which the composition is used.

Description

Compositions, and methods for producing films, optical filters, solid-state imaging devices, image display devices, infrared sensors, and camera modules

The present invention relates to a composition containing a pigment. The present invention also relates to methods of manufacturing films, optical filters, solid-state imaging devices, image display devices, infrared sensors, and camera modules using the compositions.

In recent years, with the spread of digital cameras, camera-equipped mobile phones, etc., demand for solid-state image sensors such as charge-coupled device (CCD) image sensors has increased significantly. Optical filters such as infrared cut filters and color filters are used in solid-state image sensors.

Optical filters such as infrared cut filters and color filters are formed using a composition containing a dye, a curable compound, and a solvent (see Patent Documents 1 and 2).

Japanese Patent Application Publication No. 2016-017152 JP2022-021823A

In recent years, there has been a strong demand for smaller size and thinner solid-state image sensors. For this reason, in recent years, it has been desired that dye-containing films such as infrared cut filters and color filters used in solid-state imaging devices be made thinner. In order to achieve thinning of the film while maintaining the desired spectral performance, it is necessary to increase the dye concentration in the composition used for film formation.

However, as the dye concentration in the total solid content of the composition increases, the proportion of components other than the dye becomes relatively small, so the dye tends to aggregate during film formation or storage of the composition, resulting in a film It was found that defects tend to occur easily.

Therefore, an object of the present invention is to provide a composition that can form a film that has excellent storage stability and suppresses the occurrence of defects. Another object of the present invention is to provide a method for manufacturing a film, an optical filter, a solid-state image sensor, an image display device, an infrared sensor, and a camera module using the composition.

The present invention provides the following.
<1> A composition containing a dye, a curable compound, and a solvent,
The solvent contains an aromatic compound having 8 or more carbon atoms and a molecular weight of 500 or less,
A composition in which the content of the aromatic compound in the composition is 1 to 50,000 ppm by mass.
<2> The above-mentioned dyes include a pyrrolopyrrole boron complex, a phthalocyanine compound, a naphthalocyanine compound, a subphthalocyanine compound, a porphyrin compound, a squarylium compound, a croconium compound, an iminium compound, an oxonol compound, a cyanine compound, a merocyanine compound, an aminium compound, an anthraquinone compound, selected from the group consisting of azo compounds, azomethine compounds, quinophthalone compounds, diketopyrrolopyrrole compounds, isoindoline compounds, triarylmethane compounds, xanthene compounds, pyrromethene compounds, indigo compounds, rylene compounds, perylene compounds, quaterrylene compounds, and quinacridone compounds The composition according to <1>, which is at least one type.
<3> The composition according to <1> or <2>, wherein the aromatic compound has a boiling point of 100 to 350°C.
<4> The composition according to any one of <1> to <3>, wherein the aromatic compound has a ClogP value of -1.00 to 10.00.
<5> The aromatic compound described in any one of <1> to <4> has a maximum molar extinction coefficient of 10 L·mol ⁻¹ ·cm ⁻¹ or less in the wavelength range of 400 to 700 nm. Composition of.
<6> The above aromatic compounds include m-xylene, o-xylene, p-xylene, tetralin, diphenyl ether, mesitylene, isobutylbenzene, tert-butylbenzene, sec-butylbenzene, n-butylbenzene, propylbenzene, cumene, p-cymene, o-cymene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene, 1,3-diethylbenzene, 2-propyl The composition according to <1> or <2>, which is at least one member selected from the group consisting of toluene, 2-tert-butyltoluene, and 2,3,5-trimethylanisole.
<7> The above solvent further includes propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, ethyl lactate, butyl acetate, cyclohexanone, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, and propylene glycol dimethyl ether acetate. The composition according to any one of <1> to <6>, which contains at least one member selected from the group consisting of acetate and anisole.
<8> A method for producing a membrane, including the step of applying the composition according to any one of <1> to <7> to a support.
<9> A method for manufacturing an optical filter, including the method for manufacturing the film according to <8>.
<10> A method for manufacturing a solid-state imaging device, including the method for manufacturing the film according to <8>.
<11> A method for manufacturing an image display device, including the method for manufacturing the film according to <8>.
<12> A method for manufacturing an infrared sensor, including the method for manufacturing the film according to <8>.
<13> A method for manufacturing a camera module, including the method for manufacturing the film according to <8>.

According to the present invention, it is possible to provide a composition that can form a film that has excellent storage stability and suppresses the occurrence of defects. Furthermore, the present invention can provide methods for manufacturing films, optical filters, solid-state imaging devices, image display devices, infrared sensors, and camera modules using the compositions.

FIG. 1 is a schematic diagram showing one embodiment of an infrared sensor.

The content of the present invention will be explained in detail below.
In this specification, "~" is used to include the numerical values described before and after it as a lower limit and an upper limit.
In the description of a group (atomic group) in this specification, the description that does not indicate substituted or unsubstituted includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the term "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth)acrylate" represents acrylate and/or methacrylate, "(meth)acrylic" represents both acrylic and/or methacrylic, and "(meth)acrylate" represents acrylic and/or methacrylate. ) "Acryloyl" refers to either or both of acryloyl and methacryloyl.
In this specification, the weight average molecular weight and number average molecular weight are defined as polystyrene equivalent values measured by gel permeation chromatography (GPC).
In this specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, infrared rays refer to light (electromagnetic waves) with a wavelength of 700 to 2,500 nm.
In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent.
In this specification, the term "process" is used not only to refer to an independent process, but also to include a process in which the intended effect of the process is achieved even if the process cannot be clearly distinguished from other processes. .

<Composition>
The composition of the present invention is a composition containing a dye, a curable compound, and a solvent,
The solvent contains an aromatic compound having 8 or more carbon atoms and a molecular weight of 500 or less,
It is characterized in that the content of the aromatic compound in the composition is 1 to 50,000 ppm by mass.

The composition of the present invention has excellent storage stability and can form a film in which the occurrence of defects is suppressed. The detailed reason why such an effect is obtained is unknown, but by containing a predetermined amount of an aromatic compound (hereinafter also referred to as a specific solvent) with a molecular weight of 500 or less, the specific solvent can prevent excessive interaction between dyes. It is presumed that this is because it was possible to suppress the aggregation of the dye by softening the stress, and as a result, it was possible to form a film that had excellent storage stability and suppressed the occurrence of defects.

Furthermore, the film obtained using the composition of the present invention also has excellent light resistance and moisture resistance.

The composition of the present invention can be used as a composition for optical filters. Types of optical filters include color filters, infrared cut filters, and infrared transmission filters, and infrared cut filters are preferred.

Each component used in the composition of the present invention will be explained below.

<<Pigment>>
The composition of the invention contains a pigment. Examples of the dye include infrared absorbing dyes and chromatic dyes. The dye used in the composition of the present invention preferably contains an infrared absorbing dye. Generally, infrared absorbing dyes have long conjugated systems in order to have absorption on the longer wavelength side. Therefore, infrared absorbing dyes tend to aggregate in the composition. However, by containing a predetermined amount of the above-mentioned specific solvent, the composition of the present invention can more effectively prevent the aggregation of infrared absorbing dyes in the composition without impairing the aggregation formation of infrared absorbing dyes during film formation. Can be suppressed. Therefore, when a dye containing an infrared absorbing dye is used, the effects of the present invention are more pronounced.

Dyes include pyrrolopyrrole boron complexes, phthalocyanine compounds, naphthalocyanine compounds, subphthalocyanine compounds, porphyrin compounds, squarylium compounds, croconium compounds, iminium compounds, oxonol compounds, cyanine compounds, merocyanine compounds, aminium compounds, anthraquinone compounds, azo compounds, and azomethine. At least one compound selected from the group consisting of a quinophthalone compound, a diketopyrrolopyrrole compound, an isoindoline compound, a triarylmethane compound, a xanthene compound, a pyrromethene compound, an indigo compound, a rylene compound, a perylene compound, a quaterrylene compound, and a quinacridone compound. It is preferably at least one selected from the group consisting of pyrrolopyrrole boron complexes, phthalocyanine compounds, squarylium compounds and cyanine compounds, and at least one selected from the group consisting of pyrrolopyrrole boron complexes and squarylium compounds. It is more preferable that

The pigment may be either a pigment or a dye, but it is preferable that it contains a pigment because the effects of the present invention are more pronounced. The pigment may be either an inorganic pigment or an organic pigment, but organic pigments are preferred because the effects of the present invention are more pronounced.

The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. When the average primary particle diameter of the pigment is within the above range, the dispersion stability of the pigment in the composition is good. In the present invention, the primary particle diameter of the pigment can be determined from a photograph obtained by observing the primary particles of the pigment using a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circular equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle diameter in the present invention is the arithmetic mean value of the primary particle diameters of 400 pigment primary particles. Moreover, the primary particles of pigment refer to independent particles without agglomeration.

The crystallite size determined from the half-value width of the peak derived from any crystal plane in the X-ray diffraction spectrum when the CuKα ray of the pigment is used as the X-ray source is preferably 0.1 to 100 nm, and preferably 0.1 to 100 nm. It is more preferably from 5 to 50 nm, even more preferably from 1 to 30 nm, and particularly preferably from 5 to 25 nm.

The specific surface area of the pigment is preferably 1 to 300 m ² /g. The lower limit is preferably 10 m ² /g or more, more preferably 30 m ² /g or more. The upper limit is preferably 250 m ² /g or less, more preferably 200 m ² /g or less. The value of the specific surface area is determined according to DIN 66131: determination of the specific surface area of solids by gas adsorption according to the BET (Brunauer, Emmett and Teller) method. (Measurement of specific surface area of solids).

(Infrared absorbing dye)
The infrared absorbing dye is preferably a compound that has a maximum absorption wavelength in a wavelength range of 690 to 2000 nm, more preferably a compound that has a maximum absorption wavelength in a wavelength range of 690 to 1500 nm, and has a maximum absorption wavelength in a wavelength range of 690 to 1200 nm. It is more preferable that the compound has a maximum absorption wavelength in the wavelength range of 690 to 900 nm, and it is particularly preferable that the compound has a maximum absorption wavelength in the wavelength range of 690 to 900 nm.
Further, the infrared absorbing dye is preferably a compound having a maximum absorption wavelength in a wavelength range of 690 to 2000 nm, more preferably a compound having a maximum absorption wavelength in a wavelength range of 690 to 1500 nm, and It is more preferable that the compound has a maximum absorption wavelength in the range of 1,200 nm to 1200 nm, and particularly preferably the compound that has a maximum absorption wavelength in the range of 690 to 900 nm.

Infrared absorbing dyes include pyrrolopyrrole boron complexes, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, Examples include azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, boradiazine compounds, etc., and it is preferably at least one selected from the group consisting of pyrrolopyrrole boron complexes, phthalocyanine compounds, squarylium compounds, and cyanine compounds, and pyrrolopyrrole boron complexes and More preferably, it is at least one selected from the group consisting of squarylium compounds.

The pyrrolopyrrole boron complex is preferably a compound represented by formula (PP-1).

In the formula, Rp ¹ and Rp ² each independently represent an alkyl group, an aryl group or a heteroaryl group,
Rp ³ to Rp ⁶ each independently represent a hydrogen atom or a substituent,
Rp ⁷ and Rp ⁸ each independently represent -BRp ¹¹ Rp ¹² ;
Rp ¹¹ and Rp ¹² each independently represent a substituent,
Rp ¹¹ and Rp ¹² may be bonded to each other to form a ring.

For details of formula (PP-1), see paragraph numbers 0017 to 0047 of JP 2009-263614, paragraph 0011 to 0036 of JP 2011-068731, and paragraph 0010 of WO 2015/166873. -0024, the contents of which are incorporated herein.

The number of carbon atoms in the alkyl group represented by Rp ¹ and Rp ² is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched.
The number of carbon atoms in the aryl group represented by Rp ¹ and Rp ² is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
The number of carbon atoms constituting the ring of the heteroaryl group represented by Rp ¹ and Rp ² is preferably 1 to 30, more preferably 1 to 12. Examples of the heteroatoms constituting the heteroaryl group include nitrogen atoms, oxygen atoms, and sulfur atoms. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring having 2 to 8 condensed rings, and even more preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings.

The alkyl group, aryl group and heteroaryl group represented by Rp ¹ and Rp ² may have a substituent or may be unsubstituted. Examples of the substituent include the substituent T shown below. Furthermore, when the alkyl group, aryl group, and heteroaryl group represented by Rp ¹ and Rp ² have two or more substituents, the substituents may bond to each other to form a ring.

In formula (PP-1), Rp ¹ and Rp ² are preferably each independently an alkyl group or an aryl group. A preferred embodiment of Rp ¹ and Rp ² is an embodiment in which Rp ¹ and Rp ² are each independently an alkyl group. Another preferred embodiment of Rp ¹ and Rp ² is an embodiment in which Rp ¹ and Rp ² are each independently an aryl group. Another preferred embodiment of Rp ¹ and Rp ² is an embodiment in which one of Rp ¹ and Rp ² is an alkyl group and the other is an aryl group.

(Substituent T)
Examples of the substituent T include the following groups. Halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an aryl group having 6 to 30 carbon atoms), a heteroaryl group (preferably a heteroaryl group having 1 to 30 carbon atoms), an amino group (preferably a heteroaryl group having 1 to 30 carbon atoms), an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), a heteroaryloxy group (preferably a carbon Heteroaryloxy group having 1 to 30 carbon atoms), acyl group (preferably an acyl group having 2 to 30 carbon atoms), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably aryloxycarbonyl group having 7 to 30 carbon atoms), heteroaryloxycarbonyl group (preferably heteroaryloxycarbonyl group having 2 to 30 carbon atoms), acyloxy group (preferably acyloxy group having 2 to 30 carbon atoms), acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an aminocarbonylamino group (preferably an aminocarbonylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms) , an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), a sulfamoylamino group (preferably a sulfamoyl group having 0 to 30 carbon atoms) sulfamoylamino group), carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms) ), a heteroarylthio group (preferably a heteroarylthio group having 1 to 30 carbon atoms), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms), an alkylsulfonylamino group (preferably a carbon number 1 to 30), 30 alkylsulfonylamino groups), arylsulfonyl groups (preferably arylsulfonylamino groups having 6 to 30 carbon atoms), arylsulfonylamino groups (preferably arylsulfonylamino groups having 6 to 30 carbon atoms), heteroarylsulfonyl groups (preferably is a heteroarylsulfonyl group having 1 to 30 carbon atoms), a heteroarylsulfonylamino group (preferably a heteroarylsulfonylamino group having 1 to 30 carbon atoms), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 30 carbon atoms) , an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 30 carbon atoms), a heteroarylsulfinyl group (preferably a heteroarylsulfinyl group having 1 to 30 carbon atoms), a ureido group (preferably a ureido group having 1 to 30 carbon atoms) ), hydroxy group, nitro group, carboxy group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonamide group, phosphino group, mercapto group, cyano group, alkylsulfino group, arylsulfino group, arylazo group, hetero Aryl azo group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, hydrazino group, imino group. These groups may further have a substituent when the group is a substitutable group. Examples of the substituent include the groups described above for the substituent T.

In formula (PP-1), Rp ³ to Rp ⁶ each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent T.

It is preferable that one of R ³ and R ⁴ is a heteroaryl group and the other is an electron-withdrawing group. Moreover, it is preferable that one of R ⁵ and R ⁶ is a heteroaryl group and the other is an electron-withdrawing group.

Here, a substituent having a positive Hammett's σp value (sigma para value) acts as an electron-withdrawing group. In this specification, a substituent having a Hammett's σp value of 0.2 or more can be exemplified as an electron-withdrawing group. The σp value is preferably 0.25 or more, more preferably 0.3 or more, particularly preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80 or less. Specific examples of electron-withdrawing groups include cyano group (0.66), carboxy group (-COOH: 0.45), alkoxycarbonyl group (for example, -COOCH ₃ : 0.45), aryloxycarbonyl group ( For example, -COOCH ₃ : 0.44), carbamoyl group (e.g. -CONH ₂ : 0.36), alkylcarbonyl group (e.g. -COCH ₃ : 0.50), arylcarbonyl group (e.g. -COPh: 0 .43), an alkylsulfonyl group (for example, -SO ₂ CH ₃ : 0.72), an arylsulfonyl group (for example, -SO ₂ Ph: 0.68), and the like. The electron-withdrawing group is preferably a cyano group, an alkylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group, and more preferably a cyano group. That is, it is preferable that one of R ¹ and R ² and one of R ³ and R ⁴ in formula (1) are each a cyano group. Here, Ph represents a phenyl group. Regarding Hammett's σp value, paragraphs 0024 to 0025 of JP-A No. 2009-263614 can be referred to, the contents of which are incorporated herein.

Constitutes a ring of a heteroaryl group represented by either R ³ or R ⁴ of formula (PP-1) and a heteroaryl group represented by either R ⁵ or R ⁶ of formula (PP-1) The number of carbon atoms is preferably 1 to 30, more preferably 1 to 12. Examples of the heteroatoms constituting the heteroaryl group include nitrogen atoms, oxygen atoms, and sulfur atoms. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring having 2 to 8 condensed rings, and even more preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings. The above heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the groups described above for the substituent T.

Rp ⁷ and Rp ⁸ in formula (PP-1) each independently represent -BRp ¹¹ Rp ¹² .
Substituents represented by Rp ¹¹ and Rp ¹² in the group represented by -BRp ¹¹ Rp ¹² include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, and a heteroaryloxy group. It is preferably a halogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a halogen atom, an alkyl group or an aryl group, and even more preferably an aryl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.
The number of carbon atoms in the alkyl group and the alkoxy group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group and alkoxy group may be linear, branched, or cyclic, but are preferably linear or branched. The alkyl group and alkoxy group may have a substituent or may be unsubstituted. Examples of the substituent include an aryl group, a heteroaryl group, and a halogen atom.
The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 2 to 8 carbon atoms. The alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkoxy group, an aryl group, a heteroaryl group, and a halogen atom.
The number of carbon atoms in the aryl group and the aryloxy group is preferably 6 to 20, more preferably 6 to 12. The aryl group and the aryloxy group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom.
The heteroaryl group and heteroaryloxy group may be a single ring or a fused ring. The number of heteroatoms constituting the heteroaryl ring of the heteroaryl group and the heteroaryloxy group is preferably 1 to 3. The heteroatom constituting the heteroaryl ring is preferably a nitrogen atom, oxygen atom or sulfur atom. The number of carbon atoms constituting the heteroaryl ring is preferably 1 to 30, more preferably 1 to 18, even more preferably 1 to 12. The heteroaryl ring is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group and heteroaryloxy group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom.

Rp ¹¹ and Rp ¹² in the group represented by -BRp ¹¹ Rp ¹² may be bonded to each other to form a ring. Examples of the ring formed include structures shown in formulas (B-1) to (B-5). In the following, Rb represents a substituent, Rb ¹ to Rb ⁴ each independently represent a hydrogen atom or a substituent, b1 to b3 each independently represent an integer of 0 to 4, and b4 represents 0 to 4. It represents an integer of 6, and * represents a connecting hand. Examples of the substituents represented by Rb and Rb ¹ to Rb ⁴ include the groups listed above for the substituent T, with halogen atoms, alkyl groups, and alkoxy groups being preferred.

It is also preferable that the pyrrolopyrrole boron complex is a compound represented by formula (PP-2).

In the formula, Lp ²¹ represents an n-valent linking group,
Rp ²¹ represents an alkyl group, an aryl group or a heteroaryl group,
Rp ²² to Rp ²⁵ each independently represent a hydrogen atom or a substituent,
Rp ²⁶ and Rp ²⁷ each independently represent -BRp ³¹ Rp ³² ;
Rp ³¹ and Rp ³² each independently represent a substituent,
Rp ³¹ and Rp ³² may be bonded to each other to form a ring,
n represents an integer of 2 or more.

In formula (PP-2), n represents an integer of 2 or more, preferably an integer of 2 to 4, and more preferably 2.

The n-valent linking group represented by Lp ²¹ in formula (PP-2) includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, -O-, -S-, -CO-, -COO- , -OCO-, -SO ₂ -, -NR ^L -, -NR ^L CO-, -CONR ^L -, -NR ^L SO ₂ -, -SO ₂ NR ^L -, and combinations thereof. R ^L represents a hydrogen atom, an alkyl group or an aryl group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 2 to 20, even more preferably 2 to 10, particularly preferably 2 to 5. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Furthermore, the cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic. The aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group is preferably a monocyclic or fused ring aromatic hydrocarbon group having 2 to 4 condensed rings. The aromatic hydrocarbon group is preferably a benzene ring group. The heterocyclic group is preferably a single ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The heteroatom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 1 to 30, more preferably 1 to 18, and even more preferably 1 to 12. The aliphatic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group may have a substituent. Examples of the substituent include the groups listed above for the substituent T. Further, the number of carbon atoms in the alkyl group represented by R ^L is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, preferably linear or branched, and more preferably linear. The alkyl group represented by R ^L may further have a substituent. Examples of the substituent include the substituent T described above. The number of carbon atoms in the aryl group represented by R ^L is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group represented by R ^L may further have a substituent. Examples of the substituent include the substituent T described above.

The number of carbon atoms in the alkyl group represented by Rp ²¹ in formula (PP-2) is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched.
The number of carbon atoms in the aryl group represented by Rp ²¹ in formula (PP-2) is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
The number of carbon atoms constituting the ring of the heteroaryl group represented by Rp ²¹ in formula (PP-2) is preferably 1 to 30, more preferably 1 to 12. Examples of the heteroatoms constituting the heteroaryl group include nitrogen atoms, oxygen atoms, and sulfur atoms. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring having 2 to 8 condensed rings, and even more preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings.
The alkyl group, aryl group and heteroaryl group represented by Rp ²¹ in formula (PP-2) may have a substituent or may be unsubstituted. Examples of the substituent include the substituent T described above. Furthermore, when the alkyl group, aryl group, and heteroaryl group represented by Rp ²¹ has two or more substituents, the substituents may bond to each other to form a ring.

Rp ²¹ in formula (PP-2) is preferably an alkyl group or an aryl group.

Rp ²² to Rp ²⁵ in formula (PP-2) each independently represent a hydrogen atom or a substituent. Examples of the substituent include the substituent T described above.

It is preferable that one of R ²² and R ²³ is a heteroaryl group and the other is an electron-withdrawing group. Moreover, it is preferable that one of R ²⁴ and R ²⁵ is a heteroaryl group and the other is an electron-withdrawing group. Examples of the electron-withdrawing group include the groups mentioned above, and a cyano group is preferred. A heteroaryl group is a heteroaryl group represented by either one of R ³ and R ⁴ in formula (PP-1), and a heteroaryl group represented by either one of R ⁵ and R ⁶ in formula (PP-1). Examples include the groups explained as follows, and the preferred ranges are also the same.

Rp ²⁶ and Rp ²⁷ in formula (PP-2) each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BRp ³¹ Rp ³² or a metal atom, and -BRp ³¹ Rp ³² is preferred.
The substituents represented by Rp ³¹ and Rp ³² in the group represented by -BRp ³¹ Rp ³² in formula (PP-2) include Rp ¹¹ in the group represented by -BRp ¹¹ Rp ¹² in formula (PP-1) The substituents represented by Rp ¹² include the groups described above, and the preferred ranges are also the same. Furthermore, Rp ³¹ and Rp ³² in the group represented by -BRp ³¹ Rp ³² may be bonded to each other to form a ring. Examples of the ring formed include the structures shown in the above-mentioned formulas (B-1) to (B-5).

Specific examples of the pyrrolopyrrole boron complex include compounds having the structures described in the examples below. In addition, examples of the pyrrolopyrrole boron complex include compounds described in paragraph numbers 0016 to 0058 of JP-A No. 2009-263614, compounds described in paragraph numbers 0037 to 0052 of JP-A-2011-068731, and WO 2015/ Examples include compounds described in paragraph numbers 0010 to 0033 of No. 166873.

The squarylium compound is preferably a compound represented by formula (SQ1).
In the formula, As ¹ and As ² each independently represent an aryl group, a heterocyclic group, or a group represented by formula (As-1);
In the formula, * represents a bond,
Rs ¹ to Rs ³ each independently represent a hydrogen atom or an alkyl group,
As ³ represents a heterocyclic group,
n _s1 represents an integer greater than or equal to 0,
Rs ¹ and Rs ² may be combined with each other to form a ring,
Rs ¹ and As ³ may be combined with each other to form a ring,
Rs ² and Rs ³ may be combined with each other to form a ring,
When n _s1 is 2 or more, the plurality of Rs ² and Rs ³ may be the same or different.

The number of carbon atoms in the aryl group represented by As ¹ and As ² is preferably 6 to 48, more preferably 6 to 22, and particularly preferably 6 to 12.

The heterocyclic group represented by As ¹ , As ² and As ³ is preferably a 5-membered or 6-membered heterocyclic group. Further, the heterocyclic group is preferably a monocyclic heterocyclic group or a fused ring heterocyclic group having 2 to 8 condensed rings; is more preferable, a monocyclic heterocyclic group or a fused ring heterocyclic group having 2 or 3 fused rings is more preferable, and a monocyclic heterocyclic group or a fused ring heterocyclic group having 2 fused rings is particularly preferable. Examples of the heteroatom constituting the ring of the heterocyclic group include nitrogen atom, oxygen atom, and sulfur atom, with nitrogen atom and sulfur atom being preferred. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3, more preferably 1 to 2.

Rs ¹ to Rs ³ in formula (As-1) each independently represent a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group represented by Rs ¹ to Rs ³ is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, and preferably linear or branched. It is preferable that Rs ¹ to Rs ³ are hydrogen atoms.

n _s1 in formula (As-1) represents an integer of 0 or more. n _s1 is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

In formula (As-1), Rs ¹ and Rs ² may be bonded to each other to form a ring, Rs ¹ and As ³ may be bonded to each other to form a ring, and Rs ² and Rs ³ may be combined with each other to form a ring. The linking group for forming the above ring is preferably a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, an alkylene group having 1 to 10 carbon atoms, and combinations thereof. . The alkylene group as a linking group may be unsubstituted or may have a substituent. Examples of the substituent include the substituent T described above.

In formula (SQ1), the groups represented by As ¹ and As ² preferably have a substituent. Examples of the substituent include the substituent T described above.

In formula (SQ1), As ¹ and As ² are each independently an aryl group or a heterocyclic group, or As ¹ and As ² are each independently a group represented by formula (As-1). It is preferable that there be.

Specific examples of squarylium compounds include compounds with structures described in the Examples below. In addition, as squarylium compounds, compounds described in paragraph numbers 0044 to 0049 of Japanese Patent Application Publication No. 2011-208101, compounds described in paragraph numbers 0060 to 0061 of Japanese Patent No. 6065169, and paragraphs of International Publication No. 2016/181987. Compound described in No. 0040, compound described in JP 2015-176046, compound described in paragraph number 0072 of WO 2016/190162, paragraph number 0196 to 0228 of JP 2016-074649 The compound described in paragraph number 0124 of JP 2017-067963, the compound described in WO 2017/135359, the compound described in JP 2017-114956, the compound described in JP 6197940, Examples include compounds described in International Publication No. 2016/120166.

In addition, as squarylium compounds and croconium compounds, squarylium compounds described in JP2017-197437A, squarylium compounds described in JP2017-025311A, squarylium compounds described in International Publication No. 2016/154782, patents Squarylium compounds described in Patent No. 5884953, squarylium compounds described in Patent No. 6036689, squarylium compounds described in Patent No. 5810604, squarylium compounds described in paragraphs 0090 to 0107 of International Publication No. 2017/213047 , compounds described in paragraph numbers 0019 to 0075 of JP 2018-054760, compounds described in paragraph numbers 0078 to 0082 of JP 2018-040955, and paragraph numbers 0043 to 0069 of JP 2018-002773. Compounds described in JP 2018-041047, paragraph numbers 0024 to 0086, squarylium compounds having an aromatic ring at the amide α-position, amide-linked squarylium compounds described in JP 2017-179131, JP Compounds having a pyrrole bis-type squarylium skeleton or croconium skeleton described in JP 2017-141215, dihydrocarbazole bis-type squarylium compounds described in JP 2017-082029, paragraph numbers 0027 to JP 2017-068120. Examples include the compound described in No. 0114, the compound described in JP-A No. 2017-067963, and the like.

Examples of the boradiazine compound include compounds described in paragraph numbers 0103 to 0117 of JP-A No. 2015-040231.

Examples of cyanine compounds include compounds described in paragraph numbers 0044 to 0045 of JP 2009-108267, compounds described in paragraph 0026 to 0030 of JP 2002-194040, and compounds described in JP 2015-172004. Compounds described in JP 2015-172102, compounds described in JP 2008-088426, compounds described in paragraph number 0090 of WO 2016/190162, JP 2017-031394 Examples include the compounds described in .

Examples of phthalocyanine compounds include compounds described in paragraph number 0093 of JP-A No. 2012-077153, oxytitanium phthalocyanine described in JP-A 2006-343631, and paragraphs 0013 to 0029 of JP-A 2013-195480. The vanadium phthalocyanine compound described in Patent No. 6081771, the vanadium phthalocyanine compound described in International Publication No. 2020/071486, and the phthalocyanine compound described in International Publication No. 2020/071470.

Examples of naphthalocyanine compounds include compounds described in paragraph number 0093 of JP-A No. 2012-077153.

(chromatic pigment)
Examples of chromatic pigments include yellow pigments, orange pigments, red pigments, green pigments, purple pigments, and blue pigments.

Examples of red pigments include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, thioindigo compounds, and diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds. is preferable, and a diketopyrrolopyrrole compound is more preferable. Moreover, it is preferable that the red dye is a pigment.

Specific examples of red pigments include C. I. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, Examples include red pigments such as 279, 291, 294, 295, 296, 297, and the like. Further, as the red dye, a compound described in paragraph number 0034 of International Publication No. 2022/085485 and a brominated diketopyrrolopyrrole compound described in JP-A-2020-085947 can also be used.

As the red pigment, C. I. Pigment Red 122, 177, 254, 255, 264, 269, 272 are preferred, and C.I. I. Pigment Red 254, 264, and 272 are more preferred, and C.I. I. Pigment Red 254 and 272 are more preferred, and C.I. I. Pigment Red 272 is particularly preferred.

Examples of the green pigment include phthalocyanine compounds and squarylium compounds, preferably phthalocyanine compounds, and more preferably phthalocyanine pigments. Moreover, it is preferable that the green dye is a pigment.

Specific examples of green pigments include C. I. Examples include green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. In addition, as a green pigment, halogenated zinc phthalocyanine pigments have an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12, and an average of 2 to 5 chlorine atoms. You can also use Specific examples include compounds described in International Publication No. 2015/118720. Further, as the green pigment, a compound described in paragraph number 0029 of International Publication No. 2022/085485, an aluminum phthalocyanine compound described in JP-A-2020-070426, etc. can also be used.

As a green pigment, C. I. Pigment Green 7, 36, 58, 62, 63 are preferred; I. Pigment Green 36 and 58 are more preferred.
used.

Specific examples of orange dyes include C.I. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. orange pigments.

Examples of yellow pigments include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. Specific examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, Examples include yellow pigments such as 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236.

As the yellow dye, an azobarbituric acid nickel complex having the following structure can also be used.

As a yellow pigment, compounds described in paragraph numbers 0031 to 0033 of International Publication No. 2022/085485, methine dyes described in JP 2019-073695, methine dyes described in JP 2019-073696, JP The methine dye described in JP2019-073697, the methine dye described in JP2019-073698, and the azo compound described in JP2020-093994 can be used.

Specific examples of purple pigments include C.I. I. Examples include purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

Specific examples of blue dyes include C.I. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc. Examples include pigments. Moreover, an aluminum phthalocyanine compound having a phosphorus atom can also be used as the blue dye. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A No. 2012-247591 and paragraph number 0047 of JP-A No. 2011-157478.

Diarylmethane compounds described in Japanese Patent Publication No. 2020-504758 can also be used as the green dye or blue dye.

Regarding the diffraction angles that various pigments preferably have, see the descriptions in Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, Japanese Patent Application Publication No. 2020-026503, and Japanese Patent Application Publication No. 2020-033526. , the contents of which are incorporated herein. Pyrrolopyrrole pigments include those whose crystallite size in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight (±1±1±1) crystal lattice planes is 140 Å or less. It is also preferable to use Further, the physical properties of the pyrrolopyrrole pigment are also preferably set as described in paragraph numbers 0028 to 0073 of JP-A-2020-097744.

As the pigment, it is also preferable to use a halogenated zinc phthalocyanine pigment having a Raman spectrum described in Japanese Patent No. 6744002 from the viewpoint of improving spectral characteristics. Further, as the pigment, it is also preferable to use a dioxazine pigment with a controlled contact angle described in International Publication No. 2019/107166 from the viewpoint of viscosity adjustment.

Dyes can also be used as chromatic pigments. There are no particular restrictions on the dye, and known dyes can be used. For example, pyrazole azo series, anilinoazo series, triarylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, xanthene series, Examples include phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes.

Pigment multimers can also be used as chromatic pigments. The dye multimer is preferably a dye that is dissolved in a solvent. Further, the dye multimer may form particles. When the dye multimer is in the form of particles, it is usually used in a state of being dispersed in a solvent. The dye multimer in a particle state can be obtained, for example, by emulsion polymerization, and specific examples include the compound and manufacturing method described in JP-A No. 2015-214682. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures contained in one molecule may be the same dye structure or may be different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. The lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. Dye multimers are described in JP 2011-213925, JP 2013-041097, JP 2015-028144, JP 2015-030742, WO 2016/031442, etc. Compounds can also be used.

As chromatic pigments, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in JP 2020-117638, and phthalocyanines described in International Publication No. 2020/174991 are used. Compound, isoindoline compound or salt thereof described in JP-A No. 2020-160279, compound represented by formula 1 described in Korean Unexamined Patent Publication No. 10-2020-0069442, Korean Unexamined Patent No. 10-2020- Compounds represented by formula 1 described in Korean Publication No. 0069730, compounds represented by formula 1 described in Korean Publication Patent No. 10-2020-0069070, compounds represented by formula 1 described in Korean Publication Patent No. 10-2020-0069067, Compound represented by formula 1, compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069062, halogenated zinc phthalocyanine pigment described in Patent No. 6809649, JP 2020-180176 Publication The isoindoline compound described in JP 2021-187913, the phenothiazine compound described in JP 2021-187913, the halogenated zinc phthalocyanine described in WO 2022/004261, the halogenated zinc phthalocyanine described in WO 2021/250883 can be used. The chromatic dye may be a rotaxane, and the dye skeleton may be used in a cyclic structure of the rotaxane, a rod-like structure, or both structures. As a chromatic coloring agent, a quinophthalone compound represented by formula 1 of Korean Patent Publication No. 10-2020-0030759, a polymer dye described in Korean Publication Patent No. 10-2020-0061793, and Japanese Patent Application Publication No. 2022-029701. You may use the coloring agent described in WO 2022/014635, the isoindoline compound described in WO 2022/024926, and the aluminum phthalocyanine compound described in WO 2022/024926.

Two or more chromatic dyes may be used in combination. Furthermore, when two or more chromatic pigments are used in combination, black may be formed by a combination of two or more chromatic pigments. Examples of such combinations include the following embodiments (1) to (7). In cases where the composition contains two or more types of chromatic dyes and exhibits black color by a combination of two or more types of chromatic dyes, the composition of the present invention can be used as a composition for forming an infrared transmission filter. It can be preferably used.
(1) Embodiment containing a red pigment and a blue pigment.
(2) An embodiment containing a red pigment, a blue pigment, and a yellow pigment.
(3) An embodiment containing a red pigment, a blue pigment, a yellow pigment, and a violet pigment.
(4) An embodiment containing a red pigment, a blue pigment, a yellow pigment, a purple pigment, and a green pigment.
(5) Embodiment containing a red pigment, a blue pigment, a yellow pigment, and a green pigment.
(6) An embodiment containing a red pigment, a blue pigment, and a green pigment.
(7) Embodiment containing a yellow pigment and a purple pigment.

The content of the pigment in the total solid content of the composition is preferably 0.5 to 80% by mass. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 50% by mass or less.

The content of pigment in the total solid content of the composition is preferably 0.5 to 80% by mass. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 50% by mass or less.

The content of pigment in the dye is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass.

The content of the infrared absorbing dye in the dye is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 70 to 100% by mass, and substantially absorbs infrared rays. Particularly preferred is only an absorbing dye. In this specification, the case where the dye is substantially only an infrared absorbing dye means that the content of the infrared absorbing dye in the dye is 99% by mass or more, and 99.9% by mass or more Preferably, there is one, and more preferably only an infrared absorbing dye.

<<Curable compound>>
The composition of the invention contains a curable compound. Examples of the curable compound include polymerizable compounds, resins, and the like. The resin may be a non-polymerizable resin (resin that does not have a polymerizable group) or a polymerizable resin (resin that has a polymerizable group). Examples of the polymerizable group include an ethylenically unsaturated bond-containing group, a cyclic ether group, a methylol group, and an alkoxymethyl group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, vinylphenyl group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamide group, etc. Allyl group, (meth)acryloyl group and (meth)acryloyloxy group are preferred, and (meth)acryloyloxy group is more preferred. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, with an epoxy group being preferred.

As the curable compound, it is preferable to use one containing at least a resin. Furthermore, when the composition of the present invention is used as a composition for photolithography, a resin and a polymerizable compound (preferably a polymerizable monomer that is a monomer-type polymerizable compound) may be used as the curable compound. is preferable, and it is more preferable to use a resin and a polymerizable monomer (monomer type polymerizable compound) having an ethylenically unsaturated bond-containing group.

(Polymerizable compound)
Examples of the polymerizable compound include a compound having an ethylenically unsaturated bond-containing group, a compound having a cyclic ether group, a compound having a methylol group, a compound having an alkoxymethyl group, and the like. A compound having an ethylenically unsaturated bond-containing group can be preferably used as a radically polymerizable compound. Moreover, a compound having a cyclic ether group can be preferably used as a cationically polymerizable compound.

Examples of resin-type polymerizable compounds include resins containing repeating units having polymerizable groups.

The molecular weight of the monomer-type polymerizable compound (polymerizable monomer) is preferably less than 2,000, more preferably 1,500 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 200 or more. The weight average molecular weight (Mw) of the resin type polymerizable compound is preferably 2,000 to 2,000,000. The upper limit of the weight average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit of the weight average molecular weight is preferably 3,000 or more, more preferably 5,000 or more.

The compound having an ethylenically unsaturated bond-containing group as a polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples include paragraph numbers 0095 to 0108 of JP 2009-288705, paragraph 0227 of JP 2013-029760, paragraph 0254 to 0257 of JP 2008-292970, and JP 2013-253224. Described in paragraph numbers 0034 to 0038 of the publication, paragraph number 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, JP 6031807, JP 2017-194662. , the contents of which are incorporated herein.

Examples of compounds having an ethylenically unsaturated bond-containing group include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available) Examples of commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available products are KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol hexa (meth) ) acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.; NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and the (meth)acryloyl group of these compounds is ethylene glycol and and/or compounds having a structure in which they are bonded via a propylene glycol residue (eg, SR454, SR499, commercially available from Sartomer). Further, as compounds having an ethylenically unsaturated bond-containing group, diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available product is M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (Shin Nakamura Chemical Co., Ltd.) (manufactured by Nippon Kayaku Co., Ltd., NK ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Nippon Kayaku Co., Ltd.) Toagosei Co., Ltd.), NK Oligo UA-7200 (Shin Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (Kyoeisha Chemical Co., Ltd.) ) etc. can also be used.

In addition, examples of compounds having an ethylenically unsaturated bond-containing group include trimethylolpropane tri(meth)acrylate, trimethylolpropanepropylene oxide-modified tri(meth)acrylate, trimethylolpropaneethylene oxide-modified tri(meth)acrylate, and isocyanuric acid ethylene oxide. It is also preferable to use trifunctional (meth)acrylate compounds such as modified tri(meth)acrylate and pentaerythritol tri(meth)acrylate. Commercially available trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Examples include.

The compound having an ethylenically unsaturated bond-containing group may further have an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group. Commercially available products of such compounds include Aronix M-305, M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), and the like.

As the compound having an ethylenically unsaturated bond-containing group, a compound having a caprolactone structure can also be used. Regarding the compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP-A No. 2013-253224 can be referred to, the contents of which are incorporated herein. Examples of compounds having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, and DPCA-120, which are commercially available as a series from Nippon Kayaku Co., Ltd.

As the compound having an ethylenically unsaturated bond-containing group, a compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used. Such a compound is preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group and/or a propyleneoxy group, and preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group. More preferably, it is a 3- to 6-functional (meth)acrylate compound having 4 to 20 ethyleneoxy groups. Commercially available products include, for example, SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer, and trifunctional (meth)acrylate having three isobutyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. Examples include KAYARAD TPA-330.

As the compound having an ethylenically unsaturated bond-containing group, a polymerizable compound having a fluorene skeleton can also be used. Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).

As the compound having an ethylenically unsaturated bond-containing group, it is also preferable to use a compound substantially free of environmentally regulated substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT, KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.), and the like.

Examples of the compound having a cyclic ether group include a compound having an epoxy group, a compound having an oxetanyl group, etc., and a compound having an epoxy group is preferable. Examples of compounds having epoxy groups include compounds having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably 2 or more.

The compound having a cyclic ether group may be a low molecular compound (for example, molecular weight less than 1000) or a macromolecule (for example, molecular weight 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more). The weight average molecular weight of the cyclic ether group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

Examples of compounds having a cyclic ether group include compounds described in paragraph numbers 0034 to 0036 of JP-A No. 2013-011869, compounds described in paragraph numbers 0147 to 0156 of JP-A-2014-043556, and JP-A No. 2014. Compounds described in paragraph numbers 0085 to 0092 of JP-A-089408 and compounds described in JP-A-2017-179172 can also be used.

Commercially available compounds having a cyclic ether group include Denacol EX-212L, EX-212, EX-214L, EX-214, EX-216L, EX-216, EX-321L, EX-321, EX-850L, EX -850 (manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC -7300, XD-1000, EPPN-501, EPPN-502 (all manufactured by ADEKA Co., Ltd.), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (all manufactured by ADEKA Co., Ltd.) Daicel), Cyclomer P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, ACA Z320 (manufactured by Daicel Corporation), jER1031S, jER157S65, j ER152, jER154, jER157S70 (all manufactured by Mitsubishi Chemical Corporation) ), Aronoxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.), ADEKA Glycilol ED-505 (manufactured by ADEKA Co., Ltd., epoxy group-containing monomer), Proof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation, epoxy group) containing polymer), OXT-101, OXT-121, OXT-212, OXT-221 (all manufactured by Toagosei Co., Ltd., oxetanyl group-containing monomer), OXE-10, OXE-30 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) Co., Ltd., oxetanyl group-containing monomer).

Examples of compounds having a methylol group (hereinafter also referred to as methylol compounds) include compounds in which a methylol group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Examples of compounds having an alkoxymethyl group (hereinafter also referred to as alkoxymethyl compounds) include compounds in which an alkoxymethyl group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Compounds in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxymethylated Preferred are urea and methylolated urea. Further, compounds described in paragraphs 0134 to 0147 of JP-A No. 2004-295116 and paragraphs 0095 to 0126 of JP-A No. 2014-089408 can also be used.

(resin)
The composition of the present invention can use a resin as a curable compound. It is preferable to use a curable compound containing at least a resin. The resin is blended, for example, for dispersing pigments and the like in the composition or for use as a binder. Note that a resin used mainly for dispersing pigments and the like in a composition is also referred to as a dispersant. However, this use of the resin is just one example, and the resin can also be used for purposes other than this use. Note that the resin having a polymerizable group also corresponds to a polymerizable compound.

The weight average molecular weight of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.

Examples of resins include (meth)acrylic resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, Examples include polyamide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, vinyl acetate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyurethane resin, and polyurea resin. One type of these resins may be used alone, or two or more types may be used in combination. As the cyclic olefin resin, norbornene resin is preferable from the viewpoint of improving heat resistance. Commercially available norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (eg, ARTON F4520). In addition, the resins include the resin described in the examples of International Publication No. 2016/088645, the resin described in JP 2017-057265, the resin described in JP 2017-032685, and the resin described in JP 2017-032685. The resin described in JP 2017-075248, the resin described in JP 2017-066240, the resin described in JP 2017-167513, the resin described in JP 2017-173787, Resins described in paragraph numbers 0041 to 0060 of JP 2017-206689, resins described in paragraph numbers 0022 to 0071 of JP 2018-010856, and blocks described in JP 2016-222891. Polyisocyanate resin, resin described in JP 2020-122052, resin described in JP 2020-111656, resin described in JP 2020-139021, JP 2017-138503 It is also possible to use a resin containing a constitutional unit having a ring structure in the main chain and a constitutional unit having a biphenyl group in the side chain as described in . Further, as the resin, a resin having a fluorene skeleton can also be preferably used. Regarding the resin having a fluorene skeleton, the description in US Patent Application Publication No. 2017/0102610 can be referred to, the contents of which are incorporated herein. In addition, examples of the resin include resins described in paragraphs 0199 to 0233 of JP2020-186373A, alkali-soluble resins described in JP2020-186325A, and Korean Patent Publication No. 10-2020-0078339. A copolymer containing an epoxy group and an acid group described in International Publication No. 2022/030445 can also be used.

It is preferable to use a resin having acid groups as the resin. Examples of the acid group include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group. The number of these acid groups may be one, or two or more. A resin having an acid group can also be used as a dispersant. The acid value of the resin having acid groups is preferably 30 to 500 mgKOH/g. The lower limit is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more. The upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, even more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.

As the resin, a resin containing a repeating unit derived from a compound represented by formula (ED1) and/or a compound represented by formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer") is used. It is also preferable to include.

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of formula (ED2), the description in JP-A No. 2010-168539 can be referred to.

For specific examples of ether dimers, paragraph number 0317 of JP-A-2013-029760 can be referred to, the contents of which are incorporated herein.

As the resin, it is also preferable to use a resin having a polymerizable group. The polymerizable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, and more preferably an ethylenically unsaturated bond-containing group.

As the resin, it is also preferable to use a resin containing a repeating unit derived from a compound represented by formula (X).
In the formula, R ¹ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represent an alkylene group, and n represents an integer of 0 to 15. The alkylene group represented by R ²¹ and R ²² preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly 2 or 3 carbon atoms. preferable. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 3.

Examples of the compound represented by formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylate of paracumylphenol. Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).

It is preferable that the resin contains a resin as a dispersant. Examples of the dispersant include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %. The acid group that the acidic dispersant (acidic resin) has is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. Moreover, the basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%. The basic group that the basic dispersant has is preferably an amino group.

It is also preferable that the resin used as a dispersant is a graft resin. For details of the graft resin, the descriptions in paragraphs 0025 to 0094 of JP-A No. 2012-255128 can be referred to, the contents of which are incorporated herein.

It is also preferable that the resin used as a dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain. Preferably, the resin has The basic nitrogen atom is not particularly limited as long as it exhibits basicity. Regarding the polyimine dispersant, the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.

It is also preferable that the resin used as the dispersant has a structure in which a plurality of polymer chains are bonded to the core portion. Examples of such resins include dendrimers (including star-shaped polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A No. 2013-043962.

The resin used as a dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in its side chain. The content of the repeating unit having an ethylenically unsaturated bond-containing group in its side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and more preferably 20 to 70 mol% of the total repeating units of the resin. More preferably, it is mol%.

In addition, as a dispersant, resins described in JP 2018-087939, block copolymers (EB-1) to (EB-9) described in paragraph numbers 0219 to 0221 of Patent No. 6432077, Polyethyleneimine having a polyester side chain as described in International Publication No. 2016/104803, block copolymer as described in International Publication No. 2019/125940, block polymer having an acrylamide structural unit as described in JP-A No. 2020-066687 , a block polymer having an acrylamide structural unit described in JP-A No. 2020-066688, etc. can also be used.

Dispersants are also available as commercial products, and specific examples include the DISPERBYK series manufactured by BYK Chemie, the SOLSPERSE series manufactured by Japan Lubrizol, the Efka series manufactured by BASF, and Ajinomoto Fine Techno Co., Ltd. Examples include the Ajisper series manufactured by Manufacturer. Further, the product described in paragraph number 0129 of JP 2012-137564A and the product described in paragraph number 0235 of JP 2017-194662A can also be used as a dispersant.

The content of the curable compound is preferably 1 to 95% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 94% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, and particularly preferably 80% by mass or less.

When the composition of the present invention contains a polymerizable compound as a curable compound, the content of the polymerizable compound is preferably 1 to 85% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.

When the composition of the present invention contains a polymerizable monomer as a curable compound, the content of the polymerizable monomer is preferably 1 to 50% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less.

When the composition of the present invention contains a compound having an ethylenically unsaturated bond-containing group as a curable compound, the content of the compound having an ethylenically unsaturated bond-containing group is 1 to 70% by mass in the total solid content of the composition. % is preferred. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.

When the composition of the present invention contains a compound having a cyclic ether group as a curable compound, the content of the compound having a cyclic ether group is preferably 1 to 70% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.

When the composition of the present invention contains a resin as a curable compound, the content of the resin is preferably 1 to 85% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 40% by mass or less.

When the composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant is preferably 0.1 to 40% by mass based on the total solid content of the composition. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. Further, the content of the resin as a dispersant is preferably 1 to 100 parts by weight per 100 parts by weight of the pigment. The upper limit is preferably 80 parts by mass or less, more preferably 75 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, more preferably 5 parts by mass or more.

The composition of the present invention may contain only one type of curable compound, or may contain two or more types. When two or more types of curable compounds are included, the total amount thereof is preferably within the above range.

<<Solvent>>
The composition of the present invention contains a solvent. The solvent contained in the composition of the present invention contains an aromatic compound (specific solvent) having 8 or more carbon atoms and a molecular weight of 500 or less.

(Specific solvent)
The melting point of the specific solvent is preferably 30°C or lower, more preferably 20°C or lower, and even more preferably 0°C or lower.

The molecular weight of the specific solvent is 500 or less, preferably 300 or less, and more preferably 200 or less. The lower limit is preferably 104 or more.

The specific solvent preferably has a boiling point of 100 to 350°C. The upper limit is preferably 260°C or lower, more preferably 220°C or lower. The lower limit is preferably 110°C or higher, more preferably 120°C or higher.

The ClogP value of the specific solvent is preferably -1.00 to 10.00. The upper limit is preferably 7.00 or less, more preferably 5.00 or less. The lower limit is preferably 0.50 or more, more preferably 1.00 or more. Note that the CLogP value is a calculated value of LogP, which is the common logarithm of the partition coefficient P of 1-octanol/water. In this specification, the CLogP value is determined by ChemDraw Professional ver. This is a value obtained by predictive calculation using 20.1.1.125 (manufactured by PerkinElmer).

The maximum value of the molar extinction coefficient of the specific solvent in the wavelength range of 400 to 700 nm is preferably 10 L·mol ⁻¹ ·cm ⁻¹ or less, more preferably 5 L·mol ⁻¹ ·cm ⁻¹ or less, More preferably, it is 1 L·mol ⁻¹ ·cm ⁻¹ or less.

The specific solvent is preferably a compound containing a carbon atom and a hydrogen atom, and optionally further containing an atom selected from an oxygen atom, a nitrogen atom, and a halogen atom; Furthermore, it is more preferable that the compound is a compound that may contain an oxygen atom, and even more preferable that it is a compound formed only of carbon atoms and hydrogen atoms.

Specific examples of specific solvents include m-xylene, o-xylene, p-xylene, tetralin, diphenyl ether, mesitylene, isobutylbenzene, tert-butylbenzene, sec-butylbenzene, n-butylbenzene, propylbenzene, cumene, and p-xylene. -cymene, o-cymene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene, 1,3-diethylbenzene, 2-propyltoluene , 2-tert-butyltoluene, 2,3,5-trimethylanisole, 2,4-dimethylacetophenone, 1,3-dihydro-1-methoxyisobenzofuran, methyl o-toluate, 2,3-dimethylnitrobenzene, 2 , 5-dimethylbenzyl chloride, 3,4-dimethylbenzyl chloride, 2,4-dimethylbenzyl chloride, 1,2-dimethylnaphthalene, 1,2,3,4-tetrahydronaphthalene-1-carbonitrile, 2a,3, 4,5-tetrahydroacenaphthene, 2-methylbenzotrifluoride, 5-acetylindane, 1,2,3,5-tetramethylbenzene, 4-ethyl-m-xylene, 2-ethyl-p-xylene, 3- Ethyl-o-xylene, 4-ethyl-o-xylene, 2-(o-tolyl)ethanol, 2-methylbenzyl chloride, 4-chloro-o-xylene, 3-chloro-o-xylene, α-tetralone, β -tetralone, isochroman, 1-isochromanone, 1,2,3,4,-tetrahydronaphthalen-2-ol, benzocyclobutene, indane, 4-fluoro-o-xylene, 3-fluoro-o-xylene, o-tolnitrile , m-tolnitrile, p-tolnitrile, 2,3-dimethylbenzonitrile, 3-cyanobenzyl alcohol, 2-ethoxybenzonitrile, 4-tertbutylbenzonitrile, 2-acetoxybenzonitrile, 3-(trifluoromethyl)benzo Nitrile, 2-(trifluoromethyl)benzonitrile, 3-(trifluoromethoxy)benzonitrile, 2-(trifluoromethoxy)benzonitrile, 4-(trifluoromethoxy)benzonitrile, 4-phenoxybenzonitrile, 4- Heptylbenzonitrile, 2-chloro-4-(trifluoromethyl)benzonitrile, 3-chloro-5-(trifluoromethyl)benzonitrile, 3-fluoro-5-(trifluoromethyl)benzonitrile, 4-cyano- 4'-pentylbiphenyl, 4-cyano-4'-hexylbiphenyl, o-xylylcyanide, o-xylylene oxide, ethylbenzene, ethyl 2,4,6-trimethylbenzoate, dimethyl phthalate, 2-methoxy-6-methyl Mention may be made of ethyl benzoate, 2-(trifluoromethyl)benzyl chloride, diethyl phthalate, dipropyl phthalate and diisobutyl phthalate.
Specific solvents include m-xylene, o-xylene, p-xylene, tetralin, diphenyl ether, mesitylene, isobutylbenzene, tert-butylbenzene, sec-butylbenzene, n-butylbenzene, propylbenzene, cumene, p-cymene, o -cymene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene, 1,3-diethylbenzene, 2-propyltoluene, 2-tert -Butyltoluene, 2,3,5-trimethylanisole, methyl o-toluate, 1,2-dimethylnaphthalene, 2-methylbenzotrifluoride, 1,2,3,5-tetramethylbenzene, 4-ethyl-m -xylene, 2-ethyl-p-xylene, 3-ethyl-o-xylene, 4-ethyl-o-xylene, 4-chloro-o-xylene, 3-chloro-o-xylene, α-tetralone, β-tetralone , 1,2,3,4,-tetrahydronaphthalen-2-ol, indane, o-tolnitrile, m-tolnitrile, p-tolnitrile, ethylbenzene, ethyl 2,4,6-trimethylbenzoate, dimethyl phthalate, 2- It is preferably at least one selected from the group consisting of ethyl methoxy-6-methylbenzoate, 2-(trifluoromethyl)benzyl chloride, diethyl phthalate, dipropyl phthalate, and diisobutyl phthalate, and is preferably at least one selected from the group consisting of tetralin, diphenyl ether, and mesitylene. , isobutylbenzene, tert-butylbenzene, sec-butylbenzene, n-butylbenzene, propylbenzene, cumene, p-cymene, o-cymene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene, 1,3-diethylbenzene, 2-propyltoluene, 2-tert-butyltoluene, 2,3,5-trimethylanisole, methyl o-toluate, 1, 2-dimethylnaphthalene, 2-methylbenzotrifluoride, 1,2,3,5-tetramethylbenzene, 4-ethyl-m-xylene, 2-ethyl-p-xylene, 3-ethyl-o-xylene, 4- Ethyl-o-xylene, 4-chloro-o-xylene, 3-chloro-o-xylene, α-tetralone, β-tetralone, 1,2,3,4,-tetrahydronaphthalen-2-ol, indan, o- At least one member selected from the group consisting of tolnitrile, m-tolnitrile, and p-tolnitrile is more preferable, and tetralin, mesitylene, isobutylbenzene, and tert-butylbenzene are preferred because the effects of the present invention are significantly exhibited. , n-butylbenzene, propylbenzene, cumene, p-cymene, o-cymene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyl It is more preferably at least one selected from the group consisting of toluene, 1,3-diethylbenzene, 2-propyltoluene, 2-tert-butyltoluene and 2,3,5-trimethylanisole, and in addition to the above effects, Further, it is preferable that at least one member selected from the group consisting of tetralin, mesitylene, propylbenzene, tert-butylbenzene, and 2,3,5-trimethylanisole is used because it can improve the moisture resistance of the obtained film. More preferably, it is at least one selected from the group consisting of tetralin and mesitylene.

(other solvents)
It is preferable that the solvent contained in the composition of the present invention further contains a solvent other than the above-mentioned specific solvent (hereinafter also referred to as other solvent).
Examples of other solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, and ether solvents. For these details, paragraph number 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein. Ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used.

Specific examples of other solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbide Tall acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3- Methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as Examples include diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.

Other solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, ethyl lactate, butyl acetate, cyclohexanone, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate and anisole. It is preferable that it contains at least one kind selected from the group consisting of:

The content of the other solvent in the solvent is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more.

The content of the above-mentioned specific solvent in the composition is 1 to 50,000 ppm by mass. The upper limit is preferably 30,000 mass ppm or less, more preferably 10,000 mass ppm or less, and even more preferably 5,000 mass ppm or less. The lower limit is preferably 3 mass ppm or more, more preferably 5 mass ppm or more, and even more preferably 10 mass ppm or more.
The content of the solvent in the composition is preferably 10 to 97% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and 70% by mass. It is particularly preferable that it is above. The upper limit is preferably 96% by mass or less, more preferably 95% by mass or less.
The content of the above-mentioned other solvents in the composition is preferably 10 to 97% by mass. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and 70% by mass. It is particularly preferable that it is above. The upper limit is preferably 96% by mass or less, more preferably 95% by mass or less.
The composition may contain only one kind of solvent, or may contain two or more kinds. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Pigment derivative>>
The composition of the invention may further contain a pigment derivative. When the dye used in the composition of the present invention contains a pigment, it is preferred that the composition of the present invention further contains a pigment derivative. Pigment derivatives are used, for example, as dispersion aids. Examples of the pigment derivative include compounds having at least one structure selected from the group consisting of a pigment structure and a triazine structure, and an acid group or a basic group.

The above pigment skeletons include squarylium pigment skeleton, pyrrolopyrrole pigment skeleton, diketopyrrolopyrrole pigment skeleton, quinacridone pigment skeleton, anthraquinone pigment skeleton, dianthraquinone pigment skeleton, benzisoindole pigment skeleton, thiazine indigo pigment skeleton, and azo pigment skeleton. , quinophthalone dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, dioxazine dye skeleton, perylene dye skeleton, perinone dye skeleton, benzimidazolone dye skeleton, benzothiazole dye skeleton, benzimidazole dye skeleton and benzoxazole dye skeleton, Squarylium dye skeleton, pyrrolopyrrole dye skeleton, diketopyrrolopyrrole dye skeleton, phthalocyanine dye skeleton, quinacridone dye skeleton and benzimidazolone dye skeleton are preferred, and squarylium dye skeleton and pyrrolopyrrole dye skeleton are more preferred.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imide acid group, and salts thereof. Atoms or atomic groups constituting the salt include alkali metal ions (Li ⁺ , Na ⁺ , K ^{+ ,} etc.), alkaline earth metal ions (Ca ²⁺ , Mg ^{2+ ,} etc.), ammonium ions, imidazolium ions, pyridinium ions, Examples include phosphonium ions. As the carboxylic acid amide group, a group represented by -NHCOR ^A1 is preferable. As the sulfonamide group, a group represented by -NHSO ₂ R ^A2 is preferable. The imide acid group is preferably a group represented by -SO ₂ NHSO ₂ R ^A3 , -CONHSO ₂ R ^A4 , -CONHCOR ^A5 or -SO ₂ NHCOR ^A6 , and -SO ₂ NHSO ₂ R ^A3 is more preferred. R ^A1 to R ^A6 each independently represent an alkyl group or an aryl group. The alkyl group and aryl group represented by R ^A1 to R ^A6 may have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom.

Examples of the basic group include an amino group, a pyridinyl group and its salts, an ammonium group salt, and a phthalimidomethyl group. Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

Specific examples of pigment derivatives include compounds described in Examples below. Pigment derivatives include compounds described in JP-A-56-118462, compounds described in JP-A-63-264674, compounds described in JP-A-01-217077, and JP-A-03-009961. Compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, compounds described in JP-A-03-045662, JP-A-04-285669 Compounds described in JP-A No. 06-145546, compounds described in JP-A No. 06-212088, compounds described in JP-A No. 06-240158, compounds described in JP-A No. 10-030063 Compounds described in JP-A-10-195326, compounds described in paragraph numbers 0086 to 0098 of International Publication No. 2011/024896, compounds described in paragraph numbers 0063 to 0094 of International Publication No. 2012/102399 , the compound described in paragraph number 0082 of International Publication No. 2017/038252, the compound described in paragraph number 0171 of JP 2015-151530, the compound described in paragraph number 0162 to 0183 of JP 2011-252065, , Compounds described in JP 2003-081972, Compounds described in JP 5299151, Compounds described in JP 2015-172732, Compounds described in JP 2014-199308, JP 2014 Compounds described in -085562, compounds described in JP 2014-035351, compounds described in JP 2008-081565, compounds described in JP 2019-109512, JP 2019-133154 Compounds described in Japanese Patent No. 2020/002106, diketopyrrolopyrrole compounds having a thiol linking group described in International Publication No. 2020/002106, benzimidazolone compounds or their salts described in JP 2018-168244, Patent No. 6996282 It is also possible to use a compound having an isoindoline skeleton described in the general formula (1) of No.

The content of the pigment derivative is preferably 1 to 50 parts by weight based on 100 parts by weight of the pigment. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. Only one type of pigment derivative may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.

<<Photopolymerization initiator>>
When the composition of the present invention contains a polymerizable compound, it is preferable that the composition of the present invention further contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet to visible range are preferred. The photopolymerization initiator is preferably a radical photopolymerization initiator.

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and the like. From the viewpoint of exposure sensitivity, photopolymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and hexaarylbylene compounds. Preferred are imidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds, oxime compounds, α-hydroxyketones The compound is more preferably a compound selected from a compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound. In addition, as photopolymerization initiators, compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3,2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 The photopolymerization initiator described in JP-A No. 2019-044030, the peroxide-based initiator described in JP-A No. 2019-167313, the photopolymerization initiator described in JP-A No. 2020-055992 The aminoacetophenone initiator having an oxazolidine group as described, the oxime photopolymerization initiator described in JP 2013-190459, the polymer described in JP 2020-172619, the WO 2020/152120 The compound represented by the formula 1 described in JP-A No. 2021-181406, the photopolymerization initiator described in JP-A No. 2022-013379, the formula (1) described in JP-A No. 2022-015747 ), a fluorine-containing fluorene oxime ester photoinitiator described in Japanese Patent Publication No. 2021-507058, and the like can also be used.

Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole, etc. can be mentioned.

Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, and Irgacure 117. 3, Irgacure 2959, Irgacure 127 (all BASF (manufactured by a company). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, and Irgacure 36. 9, Irgacure 369E, Irgacure 379EG (all manufactured by BASF) (manufactured by). Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (manufactured by BASF), and the like.

Examples of oxime compounds include the compounds described in JP-A No. 2001-233842, the compounds described in JP-A No. 2000-080068, the compounds described in JP-A No. 2006-342166, and the compounds described in JP-A No. 2006-342166. C. S. Perkin II (1979, pp. 1653-1660); C. S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000-0 Compounds described in Publication No. 66385, Compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2006-342166, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, International Publication No. 2015 /152153, the compound described in International Publication No. 2017/051680, the compound described in JP 2017-198865, the compound described in paragraph numbers 0025 to 0038 of International Publication No. 2017/164127, Examples include compounds described in International Publication No. 2013/167515. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (manufactured by BASF), TR-PBG-304, TR-PBG-327 (manufactured by TRONLY), and Adeka Optomer N-19. 19 (Co., Ltd. ) Photopolymerization initiator 2) manufactured by ADEKA and described in JP-A-2012-014052. Further, as the oxime compound, it is also preferable to use a compound without coloring property or a compound with high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Co., Ltd.).

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include compounds described in JP-A No. 2014-137466, compounds described in Japanese Patent No. 6636081, compounds described in Korean Patent Publication No. 10-2016-0109444, Examples include fluorenylaminoketone photoinitiators described in Japanese Patent Publication No. 2020-507664 and oxime ester compounds described in International Publication No. 2021/023144.

As the photopolymerization initiator, it is also possible to use an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

As a photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of oxime compounds having a fluorine atom include compounds described in JP-A No. 2010-262028, compounds 24, 36 to 40 described in Japanese Patent Application Publication No. 2014-500852, and compounds described in JP-A No. 2013-164471. Examples include compound (C-3).

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is in the form of a dimer. Specific examples of oxime compounds having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP 2013-114249, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466, Examples include compounds described in paragraph numbers 0007 to 0025 of Japanese Patent No. 4223071, and Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

As a photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

As a photopolymerization initiator, it is also possible to use an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019/088055.

Specific examples of oxime compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.

The oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm. In addition, from the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably from 1000 to 300,000, even more preferably from 2000 to 300,000, and even more preferably from 5000 to 200,000. It is particularly preferable that there be. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photopolymerization initiator, a difunctional, trifunctional or more functional photoradical polymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained. Furthermore, when a compound with an asymmetric structure is used, the crystallinity is reduced and the solubility in solvents is improved, making it difficult to precipitate over time, thereby improving the stability of the composition over time. Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include those listed in Japanese Translated Patent Publication No. 2010-527339, Japanese Translated Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Translated Patent Publication No. 2016-532675. Dimers of oxime compounds described in paragraph numbers 0407 to 0412, paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compound ( G), Cmpd 1 to 7 described in International Publication No. 2016/034963, oxime ester initiator described in paragraph number 0007 of Japanese Patent Application Publication No. 2017-523465, paragraph of Japanese Patent Application Publication No. 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP2017-151342A, oxime described in Japanese Patent No. 6469669 Examples include ester-based initiators.

The content of the photopolymerization initiator is preferably 0.1 to 40% by weight, more preferably 0.5 to 35% by weight, and even more preferably 1 to 30% by weight based on the total solid content of the composition. The composition may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Curing agent>>
When the composition of the present invention contains a compound having a cyclic ether group, it is preferable that the composition further contains a curing agent. Examples of the curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, polyhydric carboxylic acids, and thiol compounds. Specific examples of the curing agent include succinic acid, trimellitic acid, pyromellitic acid, N,N-dimethyl-4-aminopyridine, pentaerythritol tetrakis (3-mercaptopropionate), and the like. As the curing agent, compounds described in paragraph numbers 0072 to 0078 of JP-A No. 2016-075720 and compounds described in JP-A No. 2017-036379 can also be used. The content of the curing agent is preferably 0.01 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and 0.1 to 6.0 parts by weight per 100 parts by weight of the compound having a cyclic ether group. is even more preferable.

<<Surfactant>>
Preferably, the composition of the invention contains a surfactant. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. The surfactant is preferably a silicone surfactant or a fluorine surfactant. Examples of the surfactant include the surfactants described in paragraph numbers 0238 to 0245 of International Publication No. 2015/166779, the contents of which are incorporated herein.

As the fluorine-based surfactant, compounds described in paragraph numbers 0167 to 0169 of International Publication No. 2022/085485 can be used.

A block polymer can also be used as the fluorosurfactant. As a fluorine-based surfactant, a (meth) having a repeating unit derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. Further, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A No. 2010-032698 and the following compounds are also exemplified as the fluorine-containing surfactant used in the present invention.
The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example 14,000. In the above compounds, % indicating the proportion of repeating units is mol%.

As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in its side chain can also be used. Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A No. 2010-164965, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation, Examples include RS-72-K. Further, as the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 can also be used.

It is also preferable from the viewpoint of environmental regulations to use the surfactant described in International Publication No. 2020/084854 as a substitute for a surfactant having a perfluoroalkyl group having 6 or more carbon atoms.

It is also preferable to use a fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant.
In formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, a represents 1 or 2, and X ^a+ represents an a-valent metal ion, a primary ammonium ion, a Represents a secondary ammonium ion, a tertiary ammonium ion, a quaternary ammonium ion, or NH ₄ ⁺ .

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.) (manufactured by Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) Examples include.

Examples of the cationic surfactant include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridium salts, imidazolium salts, and the like. Specific examples include dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, stearamidemethylpyridium chloride, and the like.

Anionic surfactants include dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyl ether disulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl Sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate, t-octylphenoxyethoxypolyethoxyethyl Examples include sodium sulfate salt.

Examples of silicone surfactants include SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), TSF-4440, TS F-4300 , TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (manufactured by BYK Chemie Co., Ltd.), and the like.

Moreover, a compound having the following structure can also be used as the silicone surfactant.

The content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and even more preferably 0.001 to 0.2% by mass based on the total solid content of the composition. . The composition may contain only one kind of surfactant, or may contain two or more kinds of surfactants. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Polymerization inhibitor>>
The composition of the present invention may contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), Examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.), with p-methoxyphenol being preferred. The content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the composition. The composition may contain only one kind of polymerization inhibitor, or may contain two or more kinds of polymerization inhibitors. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Silane coupling agent>>
The composition of the present invention may contain a silane coupling agent. In this specification, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Furthermore, the term "hydrolyzable group" refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkoxy group is preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups. (meth)acryloyl group and epoxy group are preferred. Examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A No. 2009-288703 and compounds described in paragraph numbers 0056 to 0066 of JP-A No. 2009-242604, the contents of which are incorporated herein by reference. Incorporated into the specification. The content of the silane coupling agent is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass based on the total solid content of the composition. The composition may contain only one type of silane coupling agent, or may contain two or more types. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Ultraviolet absorber>>
The composition of the present invention can contain a UV absorber. Examples of the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, dibenzoyl compounds, and the like. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraphs 0052 to 0072 of JP2012-208374A, and paragraphs 0317 to 0317 of JP2013-068814A. 0334, the compounds described in paragraph numbers 0061 to 0080 of JP 2016-162946, and paragraph numbers 0022 to 0024 of International Publication No. 2021/132247, the contents of which are incorporated herein. Commercially available UV absorbers include the Tinuvin series and Uvinul series manufactured by BASF. Furthermore, examples of the benzotriazole compound include the MYUA series manufactured by Miyoshi Yushi (Kagaku Kogyo Nippo, February 1, 2016). Further, as the ultraviolet absorber, compounds described in paragraph numbers 0049 to 0059 of Patent No. 6268967 and paragraph numbers 0059 to 0076 of International Publication No. 2016/181987 can also be used. The content of the ultraviolet absorber is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass based on the total solid content of the composition. The composition may contain only one type of ultraviolet absorber, or may contain two or more types of ultraviolet absorbers. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Antioxidant>>
Compositions of the invention may contain antioxidants. Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. Examples of phenolic antioxidants include hindered phenol compounds. The phenolic antioxidant is preferably a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position). The above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms. Preferably, the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine- 6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepine-2- yl)oxy]ethyl]amine, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and the like. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Co., Ltd.), and JP-650 (manufactured by Johoku Kagaku Kogyo Co., Ltd.). The antioxidants include compounds described in paragraph numbers 0023 to 0048 of Patent No. 6268967, compounds described in International Publication No. 2017/006600, compounds described in International Publication No. 2017/164024, and Korean Publication No. Compounds described in Patent No. 10-2019-0059371 can also be used. The content of the antioxidant is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass based on the total solid content of the composition. The composition may contain only one kind of antioxidant, or may contain two or more kinds. When two or more types are included, it is preferable that their total amount falls within the above range.

＜＜Other ingredients＞＞
The composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers, and other auxiliary agents (e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, etc.). agent, peeling accelerator, fragrance, surface tension regulator, chain transfer agent, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. These components are described, for example, in paragraphs 0183 and after of JP-A-2012-003225 (corresponding paragraph 0237 of U.S. Patent Application Publication No. 2013/0034812), and in paragraphs of JP-A-2008-250074. The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated into the present specification. The composition of the present invention may also contain a latent antioxidant, if necessary. A latent antioxidant is a compound whose moiety that functions as an antioxidant is protected with a protecting group, and is heated at 100 to 250°C or heated at 80 to 200°C in the presence of an acid/base catalyst. Examples include compounds that function as antioxidants by removing protective groups. Examples of the latent antioxidant include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219. Commercially available latent antioxidants include Adeka Arcles GPA-5001 (manufactured by ADEKA Co., Ltd.).

It is also preferred that the compositions of the invention are substantially free of terephthalic acid esters. Here, "substantially not containing" means that the content of terephthalic acid ester is 1000 mass ppb or less in the total amount of the resin composition, more preferably 100 mass ppb or less, Particularly preferred is zero.
The composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less. Further, the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Examples of methods for reducing free metals and halogens in the composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification using ion-exchange resins.

<Storage container>
The container for storing the composition of the present invention is not particularly limited, and any known container can be used. In addition, in order to prevent impurities from entering raw materials and compositions, we use multi-layer bottles whose inner walls are made of 6 types of 6 layers of resin, and bottles with 7 layers of 6 types of resin as storage containers. It is also preferable to use Examples of such a container include the container described in JP-A No. 2015-123351. Further, the inner wall of the container is preferably made of glass, stainless steel, or the like for the purpose of preventing metal elution from the inner wall of the container, increasing stability of the composition over time, and suppressing deterioration of components.

<Method for preparing composition>
The composition of the present invention can be prepared by mixing the components described above. When preparing a composition, the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time, or if necessary, two or more solutions or dispersions containing each component may be prepared in advance. The composition may be prepared by mixing these at the time of use (at the time of application).

The preparation of the composition may include a process of dispersing the pigment. In the process of dispersing pigments, mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like. In addition, when pulverizing pigments in a sand mill (bead mill), it is preferable to use small-diameter beads or increase the filling rate of the beads, thereby increasing the pulverizing efficiency. Further, it is preferable to remove coarse particles by filtration, centrifugation, etc. after the pulverization treatment. In addition, the process and dispersion machine for dispersing pigments are described in ``Complete Works of Dispersion Technology, Published by Information Technology Corporation, July 15, 2005'' and ``Dispersion technology centered on suspension (solid/liquid dispersion system) and industrial The process and dispersion machine described in Paragraph No. 0022 of JP 2015-157893 A, "Practical Application Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be suitably used. Further, in the process of dispersing the pigment, the pigment may be subjected to a finer treatment in a salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling process, the descriptions in JP-A No. 2015-194521 and JP-A No. 2012-046629 can be referred to, for example. Bead materials used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. Moreover, an inorganic compound having a Mohs hardness of 2 or more can also be used for the beads. The composition may contain 1 to 10,000 ppm of the beads.

When preparing the composition, it is preferable to filter the composition with a filter for the purpose of removing foreign substances and reducing defects. Examples of the type of filter and filtration method used for filtration include the filters and filtration methods described in paragraph numbers 0196 to 0199 of International Publication No. 2022/085485.

<Membrane manufacturing method>
The method for producing a membrane of the present invention includes the step of applying the composition of the present invention to a support.

The support is not particularly limited and can be appropriately selected depending on the application. Examples include transparent base materials, silicon substrates, and the like.
A charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on the silicon substrate. Further, a black matrix that isolates each pixel may be formed on the silicon substrate. Further, the silicon substrate may be provided with a base layer for improving adhesion with the upper layer, preventing substance diffusion, or flattening the substrate surface. The surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferable that the angle is 30 to 80° when measured with water.
The transparent base material is not particularly limited as long as it is made of a material that can transmit at least visible light. Examples include base materials made of materials such as glass and resin. Examples of resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymers, acrylic resins such as norbornene resins, polyacrylates, and polymethyl methacrylates, urethane resins, and vinyl chloride resins. , fluororesin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin, and the like. Examples of the glass include soda lime glass, borosilicate glass, alkali-free glass, quartz glass, and glass containing copper. Examples of glass containing copper include phosphate glass containing copper, fluorophosphate glass containing copper, and the like. A commercially available glass containing copper can also be used. Examples of commercially available glass containing copper include NF-50 (manufactured by AGC Techno Glass Co., Ltd.).

A known method can be used to apply the composition. For example, drop casting method; slit coating method; spray method; roll coating method; spin coating method; casting coating method; slit and spin method; Various methods such as inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Examples include printing method; transfer method using a mold etc.; nanoimprint method. The application method for inkjet is not particularly limited, and for example, the method shown in "Expanding and Usable Inkjet - Infinite Possibilities Seen in Patents," Published February 2005, Sumibe Techno Research (especially from page 115). 133 pages), and methods described in JP-A No. 2003-262716, JP-A No. 2003-185831, JP-A No. 2003-261827, JP-A No. 2012-126830, JP-A No. 2006-169325, etc. Can be mentioned.

The composition layer formed by applying the composition may be dried (prebaked). When prebaking is performed, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, or 80°C or higher. The prebake time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 220 seconds. Drying can be performed using a hot plate, oven, or the like.

The film manufacturing method may further include a step of forming a pattern. Examples of the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method, and a pattern forming method using a photolithography method is preferable. Note that when the film of the present invention is used as a flat film, the step of forming a pattern may not be performed. Hereinafter, the process of forming a pattern will be described in detail.

(When forming a pattern using photolithography)
The pattern forming method using the photolithography method includes a step of exposing a composition layer formed by applying the composition of the present invention to light in a pattern (exposure step), and developing and removing the unexposed portions of the composition layer. It is preferable to include a step of forming a pattern (developing step). If necessary, a step of baking the developed pattern (post-bake step) may be provided. Each step will be explained below.

In the exposure step, the composition layer is exposed in a pattern. For example, the composition layer can be exposed in a pattern by exposing the composition layer to light through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. This allows the exposed portion to be cured.

Radiation (light) that can be used during exposure includes g-line, i-line, etc. Furthermore, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm). Furthermore, a long-wave light source of 300 nm or more can also be used.

Furthermore, during exposure, light may be exposed by continuous irradiation, or exposure may be performed by irradiation in pulses (pulse exposure). Note that pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and pauses in short cycles (for example, on the millisecond level or less).

The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J/cm ² , more preferably 0.05 to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being carried out in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially The exposure may be performed in an oxygen-free environment (in the absence of oxygen), or in a high oxygen atmosphere with an oxygen concentration of more than 21 volume % (for example, 22 volume %, 30 volume %, or 50 volume %). Further, the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000W/m ² to 100000W/m ² (for example, 5000W/m ² , 15000W/m ² , or 35000W/m ² ). Can be done. The oxygen concentration and the exposure illuminance may be appropriately combined. For example, the illumination intensity may be 10,000 W/m ² at an oxygen concentration of 10% by volume, or 20,000 W/m ² at an oxygen concentration of 35% by volume.

Next, the unexposed portions of the composition layer after exposure are removed by development to form a pattern. The composition layer in the unexposed area can be removed by development using a developer. As a result, the unexposed portions of the composition layer in the exposure step are eluted into the developer, and only the photocured portions remain on the support. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. Furthermore, in order to improve the ability to remove residues, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

Examples of the developer include organic solvents and alkaline developers, and alkaline developers are preferably used. Regarding the developer and the cleaning (rinsing) method after development, the developer and cleaning method described in paragraph number 0214 of International Publication No. 2022/085485 can be used.

After development, it is preferable to perform additional exposure treatment or heat treatment (post-bake) after drying. Additional exposure processing and post-bake are post-development curing processing to complete curing. The heating temperature in post-baking is, for example, preferably 100 to 240°C, more preferably 200 to 240°C. Post-baking can be carried out in a continuous or batch manner using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to maintain the developed film under the above conditions. . When performing additional exposure processing, the light used for exposure is preferably light with a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

(When forming a pattern using dry etching method)
Pattern formation by the dry etching method involves applying the above composition onto a support and curing the composition layer to form a cured product layer, and then forming a patterned photoresist layer on this cured product layer. This can be carried out by forming a patterned photoresist layer as a mask, and dry etching the cured material layer using an etching gas. In forming the photoresist layer, it is preferable to perform a prebaking process. Regarding pattern formation by the dry etching method, the descriptions in paragraphs 0010 to 0067 of JP-A No. 2013-064993 can be referred to, and the contents thereof are incorporated into the present specification.

The thickness of the film produced by the film production method of the present invention can be adjusted as appropriate depending on the purpose. For example, the film thickness can be 200 μm or less, 150 μm or less, 120 μm or less, 20 μm or less, 10 μm or less, and 5 μm or less. You can also do that. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more.

The film obtained by the film manufacturing method of the present invention can be preferably used as an optical filter. Applications of the optical filter are not particularly limited, but include infrared cut filters, infrared transmission filters, and the like. Examples of the infrared cut filter include an infrared cut filter on the light receiving side of the solid-state image sensor (for example, an infrared cut filter for a wafer level lens, etc.), and an infrared cut filter on the back side of the solid-state image sensor (opposite side to the light receiving side). , infrared cut filters for environmental light sensors (for example, illuminance sensors that detect the illuminance and color tone of the environment in which the information terminal device is placed and adjust the color tone of the display, and color correction sensors that adjust the color tone). It will be done. In particular, it can be preferably used as an infrared cut filter on the light receiving side of a solid-state image sensor. Examples of the infrared transmission filter include a filter that can block visible light and selectively transmit infrared rays having a specific wavelength or more.

The film obtained by the film manufacturing method of the present invention can be used in various devices such as solid-state imaging devices such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), infrared sensors, and image display devices. can.

<Manufacturing method of optical filter>
The method of manufacturing an optical filter of the present invention includes the method of manufacturing a film of the present invention described above. Types of optical filters include infrared cut filters and infrared transmission filters.

The optical filter may further include a layer containing copper, a dielectric multilayer film, an ultraviolet absorbing layer, etc. Examples of the ultraviolet absorbing layer include the absorbing layers described in paragraph numbers 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/099060. Examples of the dielectric multilayer film include the dielectric multilayer films described in paragraph numbers 0255 to 0259 of JP-A No. 2014-041318. As the layer containing copper, a glass substrate made of glass containing copper (copper-containing glass substrate) or a layer containing a copper complex (copper complex-containing layer) can also be used. Examples of the copper-containing glass substrate include phosphate glass containing copper, fluorophosphate glass containing copper, and the like. Commercially available copper-containing glasses include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (all manufactured by Schott Co., Ltd.), and CD5000 (manufactured by HOYA Co., Ltd.).

<Method for manufacturing solid-state image sensor>
The method of manufacturing a solid-state image sensor of the present invention includes the method of manufacturing a film of the present invention described above. The configuration of the solid-state image sensor is not particularly limited as long as it functions as a solid-state image sensor. For example, the following configurations may be mentioned.

On the support, there is a plurality of photodiodes that constitute the light-receiving area of the solid-state image sensor and a transfer electrode made of polysilicon, etc., and a light-shielding material made of tungsten or the like with only the light-receiving part of the photodiode opened above the photodiode and transfer electrode. A device protective film made of silicon nitride or the like is formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion, and a color filter is provided on the device protective film. Furthermore, a configuration in which a light condensing means (for example, a microlens, etc., the same applies hereinafter) is provided on the device protective film and below the color filter (on the side closer to the support), or a configuration in which the condensing means is provided on the color filter. etc. may be used. Further, the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned into, for example, a lattice shape by partition walls. In this case, the partition wall preferably has a lower refractive index than each pixel. Examples of an imaging device having such a structure include devices described in Japanese Patent Laid-Open Nos. 2012-227478 and 2014-179577.

<Method for manufacturing image display device>
The method of manufacturing an image display device of the present invention includes the method of manufacturing a film of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device. For definitions and details of image display devices, see, for example, "Electronic Display Devices (written by Akio Sasaki, published by Industrial Research Institute Co., Ltd., 1990)" and "Display Devices (written by Junaki Ibuki, published by Sangyo Tosho Co., Ltd., published in 1989). Publication)” etc. Further, liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994)". There is no particular restriction on the liquid crystal display device to which the present invention can be applied, and for example, the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology." The image display device may include a white organic EL element. The white organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, see Japanese Patent Application Laid-open No. 2003-045676, supervised by Akiyoshi Mikami, "The forefront of organic EL technology development - High brightness, high precision, long life, collection of know-how", Technical Information Association, It is described in pages 326-328, 2008, etc. The spectrum of white light emitted by the organic EL element preferably has strong maximum emission peaks in the blue region (430 to 485 nm), green region (530 to 580 nm), and yellow region (580 to 620 nm). In addition to these emission peaks, it is more preferable to have a maximum emission peak in the red region (650 to 700 nm).

<Method for manufacturing infrared sensor>
The infrared sensor of the present invention includes the method for manufacturing the film of the present invention described above. The configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. An embodiment of an infrared sensor will be described below with reference to the drawings.

In FIG. 1, reference numeral 110 indicates a solid-state image sensor. An infrared cut filter 111 and an infrared transmission filter 114 are arranged on the imaging area of the solid-state image sensor 110. Further, a color filter 112 is arranged on the infrared cut filter 111. A microlens 115 is arranged on the incident light hv side of the color filter 112 and the infrared transmission filter 114. A flattening layer 116 is formed to cover the microlens 115.

In the infrared sensor shown in FIG. 1, an infrared cut filter other than the infrared cut filter 111 (another infrared cut filter) may be further disposed on the flattening layer 116. Other infrared cut filters include those having a layer containing copper and/or a dielectric multilayer film. Details of these are mentioned above. Moreover, a dual band pass filter may be used as another infrared cut filter.

<Camera module manufacturing method>
The method of manufacturing a camera module of the present invention includes the method of manufacturing a film of the present invention described above. Preferably, the camera module further includes a lens and a circuit that processes images obtained from the solid-state image sensor. The solid-state image sensor used in the camera module may be the solid-state image sensor according to the present disclosure described above, or may be a known solid-state image sensor. Further, as the lens used in the camera module and the circuit that processes the image obtained from the solid-state image sensor, known ones can be used. As an example of the camera module, camera modules described in JP-A No. 2016-006476 and JP-A No. 2014-197190 can be referred to, and the contents thereof are incorporated into this specification.

The present invention will be described in more detail with reference to Examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Me in the structural formula shown below is a methyl group, and Ph is a phenyl group.

<Preparation of dispersion>
1.902 parts by mass of the dyes (pigments) listed in the table below, 0.36 parts by mass of the derivatives listed in the table below, 9 parts by mass of the dispersants listed in the table below, 18 parts by mass of the solvents listed in the table below. 74 parts by mass and 40 parts by mass of zirconia beads having a diameter of 0.3 mm were mixed, subjected to a dispersion treatment for 5 hours using a paint shaker, and the beads were separated by filtration to produce a dispersion liquid.

(dye)
PPB-A-1 to PPB-A-3: Compounds with the following structure (infrared absorbing pigments)
SQ-A-1, SQ-A-2: Compounds with the following structure (infrared absorbing pigments)
PR254: C. I. Pigment Red 254 (red pigment)
PB15:6: C. I. Pigment Blue 15:6 (blue pigment)
PV23: C. I. Pigment Violet 23 (purple pigment)
PG58: C. I. Pigment Green 58 (green pigment)
PY185: C. I. Pigment Yellow 185 (yellow pigment)

(derivative)
PPB-1 to PPB-3: Compounds with the following structure SQ-B-1, SQ-B-2: Compounds with the following structure B1: Compounds with the following structure

(dispersant)
D-1: A resin with the following structure (the number added to the main chain is the molar ratio, and the number added to the side chain represents the number of repeating units. Weight average molecular weight 38,900, acid value 99.1 mgKOH/g) was added to propylene. A solution in which the solid content concentration was adjusted to 20% by mass with a mixed solution of glycol monomethyl ether acetate: propylene glycol monomethyl ether = 9:1 (mass ratio) D-2: Resin with the following structure (the numbers appended to the main chain are molar ratios) The numbers attached to the side chains represent the number of repeating units.Weight average molecular weight 21000, acid value 36.0 mgKOH/g, amine value 47.0 mgKOH/g) as propylene glycol monomethyl ether acetate: propylene glycol monomethyl ether = A solution in which the solid content concentration was adjusted to 20% by mass with a mixed solution of 9:1 (mass ratio)

(solvent)
S-1: Propylene glycol monomethyl ether acetate S-2: Propylene glycol monomethyl ether S-5: Diethylene glycol monoethyl ether acetate S-6: Dipropylene glycol methyl ether acetate S-7: Propylene glycol diacetate S-8: Ethyl lactate S-9: Butyl acetate S-10: Anisole

<Preparation of dye solution>
A dye solution was prepared by mixing 8.02 parts by mass of the pigment (dye) listed in the table below and 91.98 parts by mass of the solvent listed in the table below.

(dye)
PPB-C-1 to PPB-C-4: Compounds with the following structure SQ-C-1 to SQ-C-5: Compounds with the following structure

(solvent)
S-3: Cyclopentanone S-4: Cyclohexanone

<Manufacture of composition>
After mixing each material in the proportions of formulations 1 to 4 shown below, adjust the content of the specific solvent so that the content of the specific solvent contained in the composition becomes the content listed in the table below, Next, each composition was manufactured by filtering through a nylon filter (manufactured by Nippon Pall Co., Ltd.) with a pore size of 0.45 μm.

<Prescription 1>
Dispersion liquid listed in the table below: 15.873 parts by mass Resin listed in the table below: 2.943 parts by mass Polymerizable compound listed in the table below: 0.45 parts by mass Photopolymerization initiator: 0.45 part by mass Polymerization inhibitor (p-methoxyphenol): 0.001 part by mass Surfactant described in the table below: 0.0075 part by mass As described in the table below: Solvent: 10.276 parts by mass

<Prescription 2>
Dispersion liquid listed in the table below: 15.873 parts by mass Resin listed in the table below: 2.943 parts by mass Epoxy compound listed in the table below: 0.9 parts by mass Polymerization inhibitor (p- methoxyphenol)...0.001 parts by mass Surfactants listed in the table below...0.0075 parts by mass Solvents listed in the table below...10.276 parts by mass

<Prescription 3>
Dye solution listed in the table below...14.921 parts by mass Resin listed in the table below...3.895 parts by mass Polymerizable compound listed in the table below...0.45 parts by mass... Photopolymerization initiator: 0.45 parts by mass Polymerization inhibitor (p-methoxyphenol): 0.001 part by mass Surfactant described in the table below: 0.00075 parts by mass As described in the table below: Solvent: 10.276 parts by mass

<Prescription 4>
Dye solution listed in the table below: 14.921 parts by mass Resin listed in the table below: 3.895 parts by mass Epoxy compound listed in the table below: 0.9 part by mass Polymerization inhibitor (p- methoxyphenol)...0.001 parts by mass Surfactants listed in the table below...0.0075 parts by mass Solvents listed in the table below...10.276 parts by mass

Among the materials listed in the table above, details of the materials other than the dispersion liquid, dye solution, and specific solvent are as follows.

(resin)
E-1: Copolymer resin of benzyl methacrylate, methacrylic acid, and 2-hydroxyethyl methacrylate (weight average molecular weight 14,000, acid value 77 mgKOH/g, alkali-soluble resin)
E-2: ARTON F4520 (manufactured by JSR Corporation, cyclic polyolefin resin)
E-3: Resin with the following structure (weight average molecular weight 40,000, acid value 100 mgKOH/g, the numerical value appended to the main chain represents the mass ratio of repeating units. Alkali-soluble resin)

(Polymerizable compound)
M-1: Aronix M-305 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate. The content of pentaerythritol triacrylate is 55% by mass to 63% by mass.)
M-2: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd., ethylene oxide modified pentaerythritol tetraacrylate)
M-3: Aronix M-510 (manufactured by Toagosei Co., Ltd., polybasic acid-modified acrylic oligomer)

(Photopolymerization initiator)
C-1: Irgacure OXE01 (manufactured by BASF, oxime ester initiator)
C-2: Irgacure OXE02 (manufactured by BASF, oxime ester initiator)
C-3: Omnirad 907 (manufactured by IGM Resins B.V., α-aminoalkylphenone initiator)

(epoxy compound)
F-1: Glycidyl methacrylate skeleton random polymer (manufactured by NOF Corporation, Marproof G-0150M, weight average molecular weight 10,000)
F-2: EPICLON N-695 (manufactured by DIC Corporation, novolac type epoxy resin)
F-3: JER1031S (manufactured by Mitsubishi Chemical Corporation, polyfunctional epoxy resin)
F-4: EHPE3150 (manufactured by Daicel Corporation, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol)

(surfactant)
H-1: Megafac RS-72-K (manufactured by DIC Corporation, fluorine-based surfactant)
H-2: Compound with the following structure (weight average molecular weight 14,000, the numerical value of % indicating the proportion of repeating units is mol%)
H-3: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane modified with carbinol at both ends, hydroxyl value 62 mgKOH/g)

(solvent)
S-1: Propylene glycol monomethyl ether acetate S-2: Propylene glycol monomethyl ether S-3: Cyclopentanone S-4: Cyclohexanone S-5: Diethylene glycol monoethyl ether acetate S-6: Dipropylene glycol methyl ether acetate S-7: Propylene glycol diacetate S-8: Ethyl lactate S-9: Butyl acetate S-10: Anisole

(Specific solvent)
Q-1: Mesitylene (boiling point 164.7°C, melting point -44.8°C, ClogP value 3.639, molecular weight 120)
Q-2: 2-propyltoluene (boiling point 177°C, melting point -68°C, ClogP value 4.148, molecular weight 134)
Q-3: Tetralin (boiling point 207°C, melting point -35.8°C, ClogP value 3.714, molecular weight 132)
Q-4: Propylbenzene (boiling point 159°C, melting point -99°C, ClogP value 3.699, molecular weight 120)
Q-5: tert-butylbenzene (boiling point 168°C, melting point -58°C, ClogP value 3.968, molecular weight 134)
Q-6: Diphenyl ether (boiling point 258°C, melting point 25°C, ClogP value 4.24, molecular weight 170)
Q-7: 2-tert-butyltoluene (boiling point 200°C, melting point 0°C or less, ClogP value 4.417, molecular weight 148)
Q-8: 2,3,5-trimethylanisole (boiling point 216°C, melting point 0°C or less, ClogP value 3.508, molecular weight 150)
Q-9: m-xylene (boiling point 139°C, melting point -48°C, ClogP value 3.14, molecular weight 106)
Q-10: Isobutylbenzene (boiling point 170°C, melting point -51°C, ClogP value 4.098, molecular weight 134)
Q-11: 1,3-diethylbenzene (boiling point 182°C, melting point -84°C, ClogP value 4.198, molecular weight 134)
q-1: Benzene q-2: Toluene

The maximum value of the molar extinction coefficient of the specific solvents Q-1 to Q-11, q-1, and q-2 in the wavelength range of 400 to 700 nm is all 10 L·mol ⁻¹ ·cm ⁻¹ or less.

<Membrane production>
(Production Example 1) Method for producing films using the compositions of Examples 1 to 59 and Comparative Examples 1 to 12 Each composition was applied onto a glass substrate by spin coating, and then heated at 100°C using a hot plate. A composition layer was obtained by heating for 2 minutes. The obtained composition layer was exposed to light using an i-line stepper at an exposure dose of 500 mJ/cm ² . Next, the exposed composition layer was cured by heating at 220° C. for 5 minutes using a hot plate to obtain a film with a thickness of 1.5 μm.

(Production Example 2) Method for producing films using the compositions of Examples 201 to 259 and Comparative Examples 101 to 112 Each of the compositions prepared above was applied onto a glass substrate by spin coating, and then a hot plate was applied. The film was heated at 100° C. for 10 minutes (prebaking), and then heated at 200° C. for 8 minutes to perform a curing treatment, thereby obtaining a film with a thickness of 1.5 μm.

<Defect evaluation>
The obtained film was observed using an optical microscope at 200 times bright field to see if there was any precipitation of foreign matter on the film, and defects were evaluated according to the following criteria.
A: No precipitation of foreign matter is observed B: Slight precipitation of foreign matter is observed, but there is no practical problem C: Precipitation of foreign matter is observed, posing a practical problem D: Foreign matter is violently precipitated

<Evaluation of composition stability over time>
For the film obtained from the composition immediately after production and the film obtained from the composition aged one month at room temperature after production, use an optical microscope to check whether there is any precipitation of foreign matter on the film under bright field magnification of 200 times. After observation, the increase in the number of foreign substances was calculated using the following formula, and storage stability was evaluated.
Increased number of foreign substances = Number of foreign substances present in a film obtained from a composition aged one month at room temperature after production - Number of foreign substances present in a film obtained from a composition immediately after production A: Foreign substances B: The increase in the number of foreign substances is 5 to 9. C: The increase in the number of foreign substances is 10 to 20. D: The increase in the number of foreign substances is 21 to 50. E: The increase in the number of foreign substances is 51. that's all

<Evaluation of light resistance>
The transmittance of the obtained membrane was measured. Next, this film was set in a fading tester equipped with a super xenon lamp (100,000 lux), and a light resistance test was performed by irradiating it with 100,000 lux light for 50 hours without using a UV cut filter. Ta. Next, the transmittance of the film after the light resistance test was measured. The amount of change in transmittance (ΔT) at each wavelength in the wavelength range of 400 to 1200 nm is determined for the film before and after the light resistance test, and the light resistance is determined based on the largest value of ΔT in the entire measurement wavelength range using the following criteria. was evaluated. The smaller the value of ΔT, the better the light resistance. The transmittance of the film was measured using a spectrophotometer (manufactured by Hitachi High-Tech Corporation, UH-4150).
Amount of change in transmittance (ΔT) = | (Transmittance of film after light resistance test - Transmittance of film before light resistance test) |
A: ΔT is less than 3% B: ΔT is 3% or more and less than 5% C: ΔT is 5% or more

<Evaluation of moisture resistance>
The transmittance of the obtained membrane was measured. Next, this film was stored in a constant temperature chamber at 85° C. and 95% humidity for 6 months, and a humidity test was conducted. After the moisture resistance test, the film was observed using an optical microscope at 200x bright field to see if there was any precipitation of foreign matter, and the moisture resistance was evaluated by the increase in the number of foreign matter before and after the humidity test.
A: Increased number of foreign objects is 0 to 10 B: Increased number of foreign objects is 11 to 20 C: Increased number of foreign objects is 21 to 50 D: Increased number of foreign objects is 51 or more

As shown in the table above, the examples have excellent storage stability and can form a film with suppressed defects.

110: solid-state image sensor, 111: infrared cut filter, 112: color filter, 114: infrared transmission filter, 115: microlens, 116: flattening layer

Claims

A composition comprising a dye, a curable compound, and a solvent,
The solvent contains an aromatic compound having 8 or more carbon atoms and a molecular weight of 500 or less,
A composition in which the content of the aromatic compound in the composition is 1 to 50,000 ppm by mass.
The dye includes a pyrrolopyrrole boron complex, a phthalocyanine compound, a naphthalocyanine compound, a subphthalocyanine compound, a porphyrin compound, a squarylium compound, a croconium compound, an iminium compound, an oxonol compound, a cyanine compound, a merocyanine compound, an aminium compound, an anthraquinone compound, an azo compound, At least one member selected from the group consisting of azomethine compounds, quinophthalone compounds, diketopyrrolopyrrole compounds, isoindoline compounds, triarylmethane compounds, xanthene compounds, pyrromethene compounds, indigo compounds, rylene compounds, perylene compounds, quaterylene compounds, and quinacridone compounds. The composition according to claim 1.
The composition according to claim 1 or 2, wherein the aromatic compound has a boiling point of 100 to 350°C.
The composition according to claim 1 or 2, wherein the aromatic compound has a ClogP value of -1.00 to 10.00.
The composition according to claim 1 or 2, wherein the aromatic compound has a maximum molar extinction coefficient of 10 L·mol −1 ·cm −1 or less in the wavelength range of 400 to 700 nm.
The aromatic compounds include m-xylene, o-xylene, p-xylene, tetralin, diphenyl ether, mesitylene, isobutylbenzene, tert-butylbenzene, sec-butylbenzene, n-butylbenzene, propylbenzene, cumene, p-cymene. , o-cymene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene, 1,3-diethylbenzene, 2-propyltoluene, 2 The composition according to claim 1 or 2, which is at least one selected from the group consisting of -tert-butyltoluene and 2,3,5-trimethylanisole.
The solvent further includes propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, ethyl lactate, butyl acetate, cyclohexanone, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate and anisole. The composition according to claim 1 or 2, comprising at least one selected from the group consisting of.
A method for producing a membrane, comprising the step of applying the composition according to claim 1 or 2 to a support.
A method for manufacturing an optical filter, comprising the method for manufacturing a film according to claim 8.
A method for manufacturing a solid-state imaging device, comprising the method for manufacturing a film according to claim 8.
A method for manufacturing an image display device, comprising the method for manufacturing a film according to claim 8.
A method for manufacturing an infrared sensor, comprising the method for manufacturing a film according to claim 8.
A method for manufacturing a camera module, comprising the method for manufacturing a film according to claim 8.