JPWO2020059484A1 - Compositions, membranes, optical filters, solid-state image sensors, infrared sensors, methods for manufacturing optical filters, camera modules, compounds, and dispersion compositions. - Google Patents

Abstract

Provision of a composition having excellent light resistance, a film using the above composition, an optical filter, a solid-state image sensor, an infrared sensor, a method for manufacturing an optical filter, a camera module, a novel compound, and a dispersion composition having excellent light resistance. Provide things. The composition contains a compound having a structure represented by the formula (1) and at least one compound selected from the group consisting of a binder and a curable compound. In formula (1), X independently represents a single bond or a linking group, and Z ¹ and Z ² independently represent a group forming an aliphatic ring or an aromatic ring, respectively, from R ⁹ and R ¹⁰ . ^{R 9} or R ¹⁰ in which a group having a dye structure is bonded or coordinated in at least one selected from the group and the group having the dye structure is not bonded or coordinated represents a substituent. R ⁹ and R ¹⁰ may be bonded to each other to form a ring with a boron atom.

Description

The present disclosure relates to compositions, films, optical filters, solid-state image sensors, infrared sensors, methods for manufacturing optical filters, camera modules, compounds, and dispersion compositions.

CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors), which are solid-state image sensors for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. These solid-state image sensors use silicon photodiodes that are sensitive to infrared rays in their light-receiving parts. For this reason, an infrared cut filter may be used to correct the luminosity factor.

Further, as a conventional boron compound, those described in Patent Documents 1 to 3 are known.

Patent Document 1 describes a salt of an anion represented by the formula (1) and an onium cation derived from a dye capable of forming a salt with the anion.

（式（１）中、Ｚ^１及びＺ^２は、それぞれ独立に、１価のプロトン供与性置換基からプロトンを放出してなる置換基を２個有する基を表す。）

(In formula (1), Z ¹ and Z ² each independently represent a group having two substituents formed by releasing a proton from a monovalent proton-donating substituent.)

Further, Patent Document 2 describes a toner composition containing a 5,5'-spirobi (5H-dibenzoborol) salt having a specific structure.

Further, Patent Document 3 describes a boron compound having a specific structure exhibiting aggregation-induced luminescence (AIE).

Japanese Unexamined Patent Publication No. 2014-37530 U.S. Pat. No. 4898802 International Publication No. 2017/080357

Conventionally, an infrared cut filter has been used as a flat film. In recent years, it has been studied to form a pattern of an infrared cut filter. For example, it has been studied to form and use each pixel of a color filter (for example, a red pixel, a blue pixel, a green pixel, etc.) on an infrared cut filter.

However, the present inventors have found through studies that the infrared-absorbing dye used in an infrared cut filter or the like does not have sufficient durability, particularly light resistance.

An object to be solved by one embodiment of the present invention is to provide a composition having excellent light resistance.

Further, a problem to be solved by another embodiment of the present invention is to provide a film, an optical filter, a solid-state image sensor, an infrared sensor, a method for manufacturing an optical filter, and a camera module using the above composition. be.

Furthermore, a problem to be solved by other embodiments of the present invention is to provide a novel compound.

Furthermore, a problem to be solved by another embodiment of the present invention is to provide a dispersion composition having excellent light resistance.

Means for solving the above problems include the following aspects.

<1> A composition containing a compound having a structure represented by the following formula (1) and at least one compound selected from the group consisting of a binder and a curable compound.

In formula (1), X independently represents a single bond or a linking group, and Z ¹ and Z ² independently represent a group forming an aliphatic ring or an aromatic ring, respectively, from R ⁹ and R ¹⁰ . ^{R 9} or R ¹⁰ in which a group having a dye structure is bonded or coordinated in at least one selected from the group and the group having the dye structure is not bonded or coordinated represents a substituent. R ⁹ and R ¹⁰ may be bonded to each other to form a ring with a boron atom.

<2> X is independently in the formula (1) a single _{bond, -O -, - S -,} - CH 2 -, - N =, - CH = CH-, or, ^{-NR 11} - and is, R ¹¹ is the composition according to <1>, which represents a hydrogen atom, an alkyl group or an aryl group.

<3> The composition according to <1> or <2>, wherein the compound having the structure represented by the above formula (1) is a compound represented by the following formula (2).

In formula (2), X represents a single bond or a linking group, R ^{1 to} R ⁸ independently represent a hydrogen atom or a substituent, and in at least one selected from the group consisting of ^{R 9 and R 10. R 9} or R ^{10 in} which a group having a dye structure is bonded or coordinated and the group having the dye structure is not bonded or coordinated represents a substituent, and R ⁹ and R ¹⁰ are bonded to each other. The ring may be formed together with the boron atom.

<4> X in the above formula (2) is a single _{bond, -O -, - S -,} - CH 2 -, - CH = CH-, or, ^{-NR 11} - and ^{is, R 11} is a hydrogen atom, The composition according to <3>, which represents an alkyl group or an aryl group.

<5> The composition according to any one of <1> to <4>, wherein the maximum absorption wavelength of the compound having the structure represented by the above formula (1) is 650 nm to 1,500 nm.

<6> The pigment structure in the group having the pigment structure is a pyrolopyrrole pigment structure, a pyromethene pigment structure, a squarylium pigment structure, a croconium pigment structure, an indigo pigment structure, an anthraquinone pigment structure, a diimmonium pigment structure, a phthalocyanine pigment structure, and a naphthalocyanine pigment. One of <1> to <5>, which is at least one pigment structure selected from the group consisting of a structure, a polymethine pigment structure, a xanthene pigment structure, a quinacridone pigment structure, an azo pigment structure, and a quinoline pigment structure. The composition described.

<7> The composition according to any one of <1> to <6>, which contains the above-mentioned curable compound and further contains a photopolymerization initiator.

<8> The composition according to any one of <1> to <7>, wherein the binder contains a binder polymer.

<9> A film containing the composition according to any one of <1> to <8> or obtained by curing the composition.

<10> An optical filter having the film according to <9>.

<11> The optical filter according to <10>, which is an infrared cut filter or an infrared transmission filter.

<12> A solid-state image sensor having the film according to <9>.

<13> An infrared sensor having the film according to <9>.

<14> A step of applying the composition according to any one of <1> to <8> on a support to form a composition layer, and a step of exposing the composition layer in a pattern. A method for manufacturing an optical filter, which comprises a step of developing and removing an unexposed portion after the step of exposing to form a pattern.

<15> A step of applying the composition according to any one of <1> to <8> on a support to form a composition layer, and a step of curing the composition layer to form a cured layer. A step of forming a photoresist layer on the cured layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and drying the cured layer using the resist pattern as an etching mask. A step of etching and a method of manufacturing an optical filter including.

<16> A camera module having a solid-state image sensor and the optical filter according to <10> or <11>.

<17> A compound represented by the following formula (P1).

Wherein ^(P1), the X P1 ^{to X P6} are each independently a single _{bond, -O -, - S -,} - CH 2 -, - N =, - CH = CH- ^{or, -NR P11} - represents, R ^P1 and ^{R P2} are each independently an alkyl group, an aryl group, a group represented by a heteroaryl group or the following formula ^{(P2), R} P3 ~R ^P6 are each independently a cyano group, an acyl group, an alkoxy represents a carbonyl group, an alkyl group, an arylsulfinyl group or a heteroaryl ^group, R ^{P7 to R P10} each independently represent a hydrogen atom or a ^{substituent, R P11} represents a hydrogen atom, an alkyl group or an aryl group, p1 ~ P4 independently represent an integer from 0 to 4.

In the formula (P2), ^XP11 represents a divalent fused polycyclic aromatic ring group or a divalent heteroaromatic ring group in which two or more aromatic rings are condensed, and L ^{P11 represents an m-phenylene group, a p-phenylene group, or a divalent heteroaromatic ring group.} It represents a single bond or a divalent linking group, Y ^P11 represents a substituent, and * represents a linking site to the pyrolopyrrole ring in the formula (P1).

<18> A dispersion composition containing a compound having a structure represented by the following formula (1) and at least one compound selected from the group consisting of a solvent, a binder and a curable compound.

In formula (1), X independently represents a single bond or a linking group, and Z ¹ and Z ² independently represent a group forming an aliphatic ring or an aromatic ring, respectively, from R ⁹ and R ¹⁰ . ^{R 9} or R ¹⁰ in which a group having a dye structure is bonded or coordinated in at least one selected from the group and the group having the dye structure is not bonded or coordinated represents a substituent. R ⁹ and R ¹⁰ may be bonded to each other to form a ring with a boron atom.

According to one embodiment of the present invention, it is possible to provide a composition having excellent light resistance.

Further, according to another embodiment of the present invention, it is possible to provide a film, an optical filter, a solid-state image sensor, an infrared sensor, a method for manufacturing an optical filter, and a camera module using the above composition.

Furthermore, according to other embodiments of the present invention, novel compounds can be provided.

Furthermore, according to another embodiment of the present invention, it is possible to provide a dispersion composition having excellent light resistance.

It is the schematic which shows one Embodiment of the infrared sensor which concerns on this disclosure.

The contents of the present disclosure will be described in detail below.

As used herein, the term "total solid content" refers to the total mass of the components excluding the solvent from the total composition of the composition. Further, the "solid content" is a component excluding the solvent as described above, and may be, for example, a solid or a liquid at 25 ° C.

In the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam. Further, as the light used for exposure, generally, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation can be mentioned.

In the present specification, "~" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.

In the present specification, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacryl, or either, and "(meth) acrylate". ) Acryloyl ”represents both acryloyl and / or methacryloyl.

In the present specification, Me in the chemical formula is a methyl group, Et is an ethyl group, Pr is a propyl group, Bu is a butyl group, Ac is an acetyl group, Bn is a benzyl group, and Ph is a phenyl group. show.

In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..

Further, in the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.

Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

Further, the transmittance in the present disclosure is the transmittance at 25 ° C. unless otherwise specified.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-equivalent values measured by gel permeation chromatography (GPC).

<Composition>

The composition according to the present disclosure includes a compound having a structure represented by the following formula (1) and at least one compound selected from the group consisting of a binder and a curable compound.

In formula (1), X independently represents a single bond or a linking group, and Z ¹ and Z ² independently represent a group forming an aliphatic ring or an aromatic ring, respectively, from R ⁹ and R ¹⁰ . ^{R 9} or R ¹⁰ in which a group having a dye structure is bonded or coordinated in at least one selected from the group and the group having the dye structure is not bonded or coordinated represents a substituent. Further, R ⁹ and R ¹⁰ may be bonded to each other to form a ring together with a boron atom.

The composition according to this embodiment can be suitably used as a pattern-forming composition.

The pattern-forming composition may be a negative-type pattern-forming composition or a positive-type pattern-forming composition, but from the viewpoint of resolution, a negative-type pattern-forming composition may be used. It is preferably a thing.

In addition, the composition according to this embodiment can be suitably used as an infrared absorbing composition.

As described above, the infrared absorbing dye used for the infrared cut filter or the like has insufficient light resistance and is decomposed by light to reduce the infrared absorbing ability, and can be obtained from a composition containing an infrared absorbing dye. Many of the cured films did not have sufficient durability, especially light resistance.

As a result of diligent studies by the present inventors, it has been found that a composition having excellent light resistance can be provided by adopting the above structure.

The mechanism of action of this excellent effect is not clear, but it is presumed as follows.

The compound having a structure represented by the above formula (1) contains a boron complex having a dye structure, and the compound has a ring structure having a boron atom as a ring member, so that the dye structures are associated, particularly J-association. It is presumed that it will be easier to use and the light resistance will be improved.

Hereinafter, each component of the composition according to the present disclosure will be described.

(Compound having a structure represented by the formula (1))

The composition according to the present disclosure contains a compound having a structure represented by the above formula (1).

The compound having the structure represented by the above formula (1) may have only one structure represented by the above formula (1) or may have two or more structures, but has light resistance and light resistance. From the viewpoint of heat resistance, it is preferable to have one to four structures represented by the above formula (1), and it is more preferable to have one to three structures, one or two. It is particularly preferable to have.

When having two or more structures represented by the above formula (1), at least one selected from the group consisting ^{of R 9} and R ^{10 in the two structures represented by the above formula (1) is bound or bonded.} The dye structure in the group having a coordinated dye structure may be the same dye structure or a different dye structure, but from the viewpoint of light resistance and heat resistance, the dye structure may be the same. preferable.

The molecular weight of the compound having the structure represented by the above formula (1) is preferably 2,500 or less, more preferably 300 or more and 2,500 or less, and preferably 400 or more and 2,000 or less. It is more preferably 500 or more and 2,000 or less.

The compound having the structure represented by the above formula (1) is preferably an infrared absorbing dye. The infrared absorbing dye means a material having at least absorption in the infrared region.

The compound having the structure represented by the above formula (1) preferably has a wavelength in the range of 650 nm to 1,500 nm, more preferably has a wavelength in the range of 680 nm to 1,300 nm, and has a wavelength of 700 nm to 1,100 nm. It is more preferable to have a maximum absorption wavelength in the range of.

The compound having the structure represented by the above formula (1) may be a pigment or a dye, but is preferably a pigment from the viewpoint of light resistance and heat resistance, and absorbs infrared rays. It is more preferably a pigment.

The dye structure in the group having a dye structure bonded or coordinated in at least one selected from the group consisting ^{of R 9} and R ¹⁰ in the compound having the structure represented by the above formula (1) has light resistance and light resistance. , Pyrrolopyrrole pigment structure, pyromethene pigment structure, squarylium pigment structure, croconium pigment structure, indigo pigment structure, anthraquinone pigment structure, diimmonium pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, polymethine pigment structure, xanthene It is preferably at least one pigment structure selected from the group consisting of a pigment structure, a quinacridone pigment structure, an azo pigment structure, and a quinoline pigment structure, and is preferably a pyrrolopyrrole pigment structure, a pyromethene pigment structure, a squarylium pigment structure, and an indigo pigment structure. , And at least one pigment structure selected from the group consisting of anthraquinone pigment structure, and at least one selected from the group consisting of pyrrolopyrrole pigment structure, pyromethene pigment structure, squalylium pigment structure, and indigo pigment structure. It is more preferably one kind of pigment structure, and particularly preferably a pyrolopyrrole pigment structure.

Further, the portion of the group having the dye structure other than the dye structure is not particularly limited and may be any structure, but the structure as in the specific example described later is preferably mentioned.

^{The substituent in R 9} or R ¹⁰ to which the group having the dye structure is not bonded or coordinated is preferably an alkyl group or an aryl group, and more preferably an aryl group.

Further, when R ⁹ or R ¹⁰ is a substituent and the boron atom in the structure represented by the above formula (1) becomes a boron anion, it may have a counter cation. The counter cation is not particularly limited and may be a known cation.

The boron atom in the compound having the structure represented by the above formula (1) preferably has at least a coordination bond from the viewpoint of light resistance and heat resistance, and has three covalent bonds and one coordination bond. It is more preferable to have.

^{Further, from the viewpoint of light resistance and heat resistance, one of R 9} and R ¹⁰ in the compound having the structure represented by the above formula (1) is covalently bonded to the dye structure, and the other is arranged. It is preferably a coordinate bond, one is covalently bonded to the dye structure, the other is more preferably a coordinate bond with a hetero atom, and one is covalently bonded to the dye structure. The other is particularly preferably a covalent bond with a nitrogen atom.

Further, the coordination bond does not have to be coordinated all the time, and the coordination bond may be temporarily lost due to the rotational or vibrational motion of the molecule due to heat.

The linking group in X of the formula (1) is preferably an oxygen atom (O), a sulfur atom (S), an alkylene group, a nitrogen atom (N or NR ¹¹ ), an alkenylene group and the like. In addition, R ¹¹ represents a hydrogen atom, an alkyl group or an aryl group.

The number of carbon atoms (number of carbon atoms) of the linking group in X in the formula (1) is not particularly limited, but is preferably 0 to 8 carbon atoms, more preferably 0 to 2 carbon atoms, and more preferably 0 to 2 carbon atoms. It is more preferably 0.

X in the formula (1) is independently, from the viewpoint of light resistance and heat resistance, single bond, -O-, -S-, -CH _2- , -N =, -CH = CH-, or. is preferably a single ^{bond, -O - - -NR 11, -} S -, - CH = CH-, or, ^{-NR 11} - is more preferable.

Further, in the formula (1), the two Xs bonded to the boron atom are more preferably a single bond or −O− from the viewpoint of light resistance and heat resistance, and are a single bond. Is particularly preferred.

Further, in the formula (1), X not bonded to the boron atom is particularly preferably a single bond, −O− or −S− from the viewpoint of light resistance and heat resistance.

Further, the boron atom in the formula (1) is preferably a ring member of a 5-membered ring or a 6-membered ring from the viewpoint of light resistance and heat resistance.

^{Z 1} and Z ² in the formula (1) are preferably groups that independently form an aromatic ring, and more preferably groups that form a benzene ring (= CH-CH = CH-CH =). preferable.

Further, Z ¹ and Z ² may have a substituent on the formed aliphatic ring or aromatic ring, but preferably do not have a substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, a halogen atom and the like.

Further, Z ¹ and Z ² are preferably the same group from the viewpoint of light resistance and heat resistance.

Further, the compound having the structure represented by the above formula (1) is preferably a compound having the structure represented by the following formula (2) from the viewpoint of light resistance and heat resistance.

In formula (2), X represents a single bond or a linking group, R ^{1 to} R ⁸ independently represent a hydrogen atom or a substituent, and in at least one selected from the group consisting of ^{R 9 and R 10. R 9} or R ^{10 in} which a group having a dye structure is bonded or coordinated and the group having the dye structure is not bonded or coordinated represents a substituent, and R ⁹ and R ¹⁰ represent each other. They may be bonded to form a ring with a boron atom.

^{R 9} and ^{R 10} in Formula (2) has the same meaning as ^{R 9} and ^{R 10} in the formula (1), a preferable embodiment thereof is also the same.

X in the formula (2) is, light resistance, and, in view of heat resistance, a single _{bond, -O -, - S -,} - CH 2 -, - CH = CH-, or, ^{-NR 11} - it is Is preferable, and it is more preferably single bond, -O-, or -S-, and particularly preferably single bond. In addition, R ¹¹ represents a hydrogen atom, an alkyl group or an aryl group.

^{Each of R 1 to} R ⁸ in the formula (2) is preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group, more preferably a hydrogen atom or an alkyl group, and is a hydrogen atom. It is particularly preferable to have.

Further, the compound having the structure represented by the above formula (1) is particularly preferably a compound represented by the following formula (P1) from the viewpoint of light resistance and heat resistance.

Wherein ^(P1), the X P1 ^{to X P6} are each independently a single _{bond, -O -, - S -,} - CH 2 -, - N =, - CH = CH- ^{or, -NR P11} - represents, R ^P1 and ^{R P2} are each independently an alkyl group, an aryl group, a group represented by a heteroaryl group or the following formula ^{(P2), R} P3 ~R ^P6 are each independently a cyano group, an acyl group, an alkoxy represents a carbonyl group, an alkyl group, an arylsulfinyl group or a heteroaryl ^group, R ^{P7 to R P10} each independently represent a hydrogen atom or a ^{substituent, R P11} represents a hydrogen atom, an alkyl group or an aryl group, p1 ~ P4 independently represent an integer from 0 to 4.

In the formula (P2), ^XP11 represents a divalent fused polycyclic aromatic ring group or a divalent heteroaromatic ring group in which two or more aromatic rings are condensed, and L ^{P11 represents an m-phenylene group, a p-phenylene group, or a divalent heteroaromatic ring group.} It represents a single bond or a divalent linking group, Y ^P11 represents a substituent, and * represents a linking site to the pyrolopyrrole ring in the formula (P1).

Are each ^{X P1, X P2, X P4} and ^{X P5} in formula (P1) independently lightfastness, and, in view of heat resistance, a single bond, or is preferably -O-, and a single bond Is particularly preferred.

^{Further, X P1, X P2, X} P4 and ^{X P5} in formula (P1) is preferably the same group.

^{From the viewpoint of light resistance and heat resistance, XP 3} and ^{XP 6} in the formula (P1) are preferably single bonds, −O−, or −S−, respectively, from the viewpoint of light resistance and heat resistance.

^{Further, it is preferable that XP3} and ^XP6 in the formula (P1) have the same group.

^{R P1} and R ^P2 in the formula (P1) are each independently preferably an aryl group, a heteroaryl group or a group represented by the above formula (P2), and an aryl group or a group represented by the above formula (P2) is particularly preferable. preferable.

Further, the alkyl group, aryl group and heteroaryl group represented by ^RP1 and ^{RP2 may have a substituent or may be unsubstituted.} Examples of the substituent include an alkoxy group, a hydroxy group, a halogen atom, a cyano group, a nitro group, -OCOR ^11p , -SOR ^12p , and -SO ₂ R ^13p . R ^{11p to} R ^13p each independently represent a hydrocarbon group or a heteroaryl group. Examples of the substituent include the substituents described in paragraphs 0020 to 0022 of JP-A-2009-263614. Of these, as the substituent, an alkoxy group, a hydroxy group, a cyano group, a nitro group, -OCOR ^11p , -SOR ^12p , and -SO ₂ R ^13p are preferable.

Further, the aryl group in R ^P1 and R ^P2 represents an aryl group having an alkoxy group having a branched alkyl group as a substituent, an aryl group having a hydroxy group as a substituent, or a substituent group represented by -OCOR ^11p It is preferably an aryl group having as. The number of carbon atoms of the branched alkyl group is preferably 3 to 30, and more preferably 3 to 20.

^{From the viewpoint of dispersibility, XP11} in the formula (P2) is preferably an m-phenylene group, a p-phenylene group, a naphthylene group, a frangyl group, or a thiophendiyl group, preferably an m-phenylene group or a p-. It is more preferably a phenylene group or a naphthylene group, further preferably an m-phenylene group or a p-phenylene group, and particularly preferably a p-phenylene group.

^{From the viewpoint of dispersibility, LP11} in the formula (P2) is preferably a divalent linking group.

^{From the viewpoint of dispersibility, the number of carbon atoms of the divalent linking group in LP11} is preferably 1 or more and 30 or less, more preferably 1 or more and 20 or less, and further preferably 1 or more and 10 or less. ..

The ^{divalent linking group in LP11} is preferably an alkylene group, an ester bond, an ether bond, or an arylene group from the viewpoint of dispersibility.

Further, the ^{divalent linking group in LP11} is preferably a group having an oxygen atom from the viewpoint of dispersibility, and is a group having at least one structure selected from the group consisting of an ester bond and an ether bond. It is more preferable that the group has an ester bond.

^{From the viewpoint of dispersibility, Y P11} in the formula (P2) has an imide structure, an acid anhydride structure, a cyano group, an alkylsulfo group, an arylsulfone group, an alkylsulfoxide group, an arylsulfoxide group, a sulfonamide group, an amide group and a urethane. A group having at least one structure selected from the group consisting of a group, a urea group, and a hydroxy group is preferable, and the group has an imide structure, an acid anhydride structure, a cyano group, an alkylsulfone group, an arylsulfone group, and an alkylsulfoxide. More preferably, it is a group having at least one structure selected from the group consisting of a group, an arylsulfoxide group, a sulfonamide group, an amide group, a urethane group and a urea group, and an N-substituted imide structure and an acid anhydride. It has at least one structure selected from the group consisting of a structure, a cyano group, an alkylsulfone group, an arylsulfone group, an alkylsulfoxide group, an arylsulfoxide group, an N-disubstituted sulfonamide group, and an N-2-substituted amide group. It is more preferably a group, and particularly preferably a group having at least one structure selected from the group consisting of an N-substituted imide structure, an N-disubstituted sulfonamide group, and an N-disubstituted amide group. Most preferably, it is a group having an N-substituted imide structure.

Further, Y ^P11 is preferably a dye derivative that does not have an acidic group, a basic group, or a group having a salt structure, which will be described later.

Further, ^{from the viewpoint of dispersibility, Y P11} is preferably a group represented by any of the following formulas Y-1 to Y-14, and is preferably any of the following formulas Y-1 to Y-8. It is more preferably a group represented by the following formula Y-1 to a group represented by any of the following formulas Y-3, and further preferably a group represented by the following formula Y-1 or formula Y-2. It is particularly preferably a group, and most preferably a group represented by the following formula Y-1.

In the formula Y-. 1 to formula Y-14, ^{R Y} each independently represent a hydrogen atom, an alkyl group or an aryl group, if having an ^{R Y} 2 or more in one formula, two ^{R Y} is an alkylene group Alternatively, a ring may be formed by an alkylene group-O-alkylene group, and * represents a connection site with <sup>LP11 in the formula (P2).

From the viewpoint of dispersibility, RY</sup> is preferably an alkyl group or an aryl group, more preferably an alkyl group, further preferably an alkyl group having 1 to 8 carbon atoms, and a methyl group. Is particularly preferable.

^R P3 ^{to R P6} is independently in Formula (P1), from the viewpoint of the infrared absorbing, is preferably a cyano group or a heteroaryl group.

From the viewpoint of the infrared ^absorbing, two of R P3 ^{to R P6} is preferably a cyano ^group, more preferably ^{R P5} and ^{R P6} is a cyano group.

From the viewpoint of the infrared ^absorbing, two of R P3 ^{to R P6} is preferably a heteroaryl ^group, more preferably ^{R P3} and ^{R P4} is a heteroaryl group.

The heteroaryl group in R ^P3 to R ^P6, from the viewpoint of the infrared absorbing property, it is preferable that at least a nitrogen atom.

As the heteroaryl groups in R ^P3 to R ^P6, from the viewpoint of the infrared absorbing, preferably a benzene ring or a naphthalene ring heteroaryl ring is a heteroaryl group fused benzene ring heteroaryl ring is fused A heteroaryl group having a benzoxazole ring structure, a benzothiazole ring structure, or a quinoxalin ring structure is more preferable, and a 2-quinoxalyl group or 6,7-dichloro is more preferable. It is particularly preferably a -2-quinoxalyl group.

Furthermore, the heteroaryl ring in the heteroaryl group in R ^P3 to R ^P6 is preferably a 5- or 6-membered ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring, or, to be pyrazine ring More preferably, it is an oxazole ring, a thiazole ring, or a pyrazine ring.

The heteroaryl group in R ^P3 to R ^P6, the groups shown below are preferred. Note that * represents the binding site with the carbon-carbon double bond in the formula (1).

R ^P7 to R ^P10 each independently in Formula (P1), a hydrogen atom, a halogen atom, an alkyl group, preferably an aryl group or an alkoxy group, more preferably a hydrogen atom or an alkyl group, a hydrogen atom It is particularly preferable to have.

Independently, p1 to p4 in the formula (P1) are preferably integers of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

As a specific example of the compound having the structure represented by the above formula (1), the compound used in the examples described later is preferably mentioned.

When the compound having the structure represented by the above formula (1) is a pigment, preferably an infrared absorbing pigment, the compound having the structure represented by the above formula (1) is in the form of particles from the viewpoint of dispersibility. Is preferable.

When the compound having the structure represented by the above formula (1) is a pigment, preferably an infrared absorbing pigment, the volume average particle size of the compound having the structure represented by the above formula (1) is dispersibility. From the viewpoint, it is preferably 1 nm or more and 500 nm or less, more preferably 1 nm or more and 100 nm or less, and further preferably 1 nm or more and 50 nm or less.

The volume average particle size of the compound having the structure represented by the above formula (1) shall be measured using MICROTRAC UPA 150 manufactured by Nikkiso Co., Ltd.

Further, the composition according to the present disclosure may contain one kind of compound having a structure represented by the above formula (1) alone or two or more kinds.

The content of the compound having the structure represented by the above formula (1) is preferably 1% by mass to 90% by mass with respect to the total solid content of the composition from the viewpoint of infrared absorption and dispersibility. .. The lower limit is more preferably 5% by mass or more, further preferably 10% by mass or more. The upper limit is more preferably 80% by mass or less, further preferably 70% by mass or less.

(binder)

The composition according to the present disclosure contains at least one compound selected from the group consisting of a binder and a curable compound, and preferably contains a binder from the viewpoint of film forming property.

Further, the binder is preferably a binder polymer from the viewpoint of film forming property and dispersibility.

Further, the binder polymer may contain a dispersant.

Specific examples of the binder polymer include (meth) acrylic resin, epoxy resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene ether phosphine oxide resin. , Polygonide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, siloxane resin, urethane resin and the like.

One of these resins may be used alone, or two or more of these resins may be mixed and used.

As the cyclic olefin resin, a norbornene resin can be preferably used from the viewpoint of improving heat resistance.

Examples of commercially available norbornene resins include the ARTON series manufactured by JSR Corporation (for example, ARTON F4520). Examples of commercially available polyimide resins include Neoprim (registered trademark) series (for example, C3450) manufactured by Mitsubishi Gas Chemical Company, Inc.

Examples of the epoxy resin include an epoxy resin which is a glycidyl etherified product of a phenol compound, an epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester type. Epoxy resin, glycidylamine-based epoxy resin, epoxy resin obtained by glycidylizing halogenated phenols, condensate of silicon compound having an epoxy group and other silicon compounds, polymerizable unsaturated compound having an epoxy group and other Examples thereof include a copolymer with another polymerizable unsaturated compound.

As the epoxy resin, Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (NOF). An epoxy group-containing polymer manufactured by NOF CORPORATION) can also be used. As the urethane resin, 8UH-1006 and 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.) can also be used.

Examples of the binder polymer include the resin described in Examples of International Publication No. 2016/08864, the resin described in JP-A-2017-57265, and the resin described in JP-A-2017-32685. The resin described in Japanese Patent Application Laid-Open No. 2017-075248 and the resin described in JP-A-2017-66240 can also be used, and these contents are incorporated in the present specification.

Further, as the binder polymer, a resin having a fluorene skeleton can also be preferably used. For resins having a fluorene skeleton, the description of US Patent Application Publication No. 2017/0102610 can be taken into consideration, which is incorporated herein by reference.

The weight average molecular weight (Mw) of the binder polymer is preferably 2,000 to 2,000,000. The upper limit is more preferably 1,000,000 or less, still more preferably 500,000 or less. The lower limit is more preferably 3,000 or more, and even more preferably 5,000 or more.

The content of the binder polymer is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 60% by mass, based on the total solid content of the composition. The above composition may contain only one type of resin, or may contain two or more types of resin. When two or more types are included, the total amount is preferably in the above range.

-Dispersant-

The composition according to the present disclosure may contain a dispersant.

Examples of the dispersant include polymer dispersants [for example, resins having an amine group (polyamide amines and salts thereof), oligoimine resins, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, etc. Modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonate formalin condensate] and the like.

Polymer dispersants can be further classified into linear polymers, end-modified polymers, graft-type polymers, and block-type polymers based on their structures.

Further, as the polymer dispersant, a resin having an acid value of 60 mgKOH / g or more (more preferably, an acid value of 60 mgKOH / g or more and 300 mgKOH / g or less) can be preferably mentioned.

Examples of the terminal-modified polymer include the polymers having a phosphate group at the end described in JP-A-3-112992, JP-A-2003-533455, etc., and those described in JP-A-2002-273191. Examples thereof include polymers having a sulfonic acid group at the terminal, and polymers having a partial skeleton of an organic dye or a heterocycle described in JP-A-9-77994. Further, a polymer in which two or more anchor sites (acid groups, basic groups, partial skeletons of organic dyes, heterocycles, etc.) on the pigment surface are introduced into the polymer terminals described in JP-A-2007-277514 is also available. It has excellent dispersion stability and is preferable.

Examples of the graft type polymer include reaction products of poly (lower alkyleneimine) and polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668 and the like. , A reaction product of a polyallylamine and a polyester described in JP-A-9-169821, etc., a macromolecule described in JP-A-10-339949, JP-A-2004-37986, etc., and a copolymer of a nitrogen atom monomer. Coupling, graft-type polymer having a partial skeleton or heterocycle of an organic dye described in JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, etc., JP-A-2010-106268 Examples thereof include copolymers of macromolecules and acid group-containing monomers described in Japanese publications.

As a macromonomer used when producing a graft-type polymer by radical polymerization, a known macromonomer can be used, and a macromonomer AA-6 (polymethacrylic having a methacrylyl group as a terminal group) manufactured by Toa Synthetic Co., Ltd. can be used. Methyl acid acid), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (polymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (poly whose terminal group is a methacryloyl group). Butyl acrylate), PLAXEL FM5 (additional product of ε-caprolactone of 2-hydroxyethyl methacrylate with 5 molar equivalent), FA10L (addition of ε-caprolactone of 2-hydroxyethyl acrylate with 10 molar equivalent) manufactured by Daicel Chemical Industry Co., Ltd. ), And the polystyrene-based macromonomer described in Japanese Patent Application Laid-Open No. 2-272009. Among these, polyester-based macromonomers having excellent flexibility and solvent resistance are particularly preferable from the viewpoints of dispersibility and dispersion stability of the pigment dispersion and the developability exhibited by the composition using the pigment dispersion. The polyester-based macromonomer represented by the polyester-based macromonomer described in Japanese Patent Publication No. 2-272009 is most preferable.

As the block type polymer, the block type polymer described in JP-A-2003-49110, JP-A-2009-52010 and the like is preferable.

The resin (dispersant) is also available as a commercially available product, and specific examples thereof include "Disperbyk-101 (polypolymeramine phosphate), 107 (carboxylic acid ester), 110, 111 (acid) manufactured by BYK Chemie. Group-containing copolymer), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) EFKA 4047, 4050-4165 (polyurethane type), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate) , 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "," Azisper PB821, PB822, PB880, PB881 "manufactured by Ajinomoto Fine Techno Co., Ltd.," Floren TG-710 "manufactured by Kyoeisha Chemical Co., Ltd. (Urethane oligomer) ”,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid) manufactured by Kusumoto Kasei Co., Ltd.) , # 7004 (polyether ester), DA-703-50, DA-705, DA-725 ", Kao Co., Ltd." Demor RN, N (naphthalene sulfonate formalin polycondensate), MS, C, SN- B (Aromatic formalin sulfonate polycondensate) ”,“ Homogenol L-18 (polymer polycarboxylic acid) ”,“ Emargen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ Acetamine 86 (acetamine 86) Stearylamine acetate) ”,“ Solsparse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end) manufactured by Nippon Lubrizol Co., Ltd. , 24000, 28000, 32000, 38500 (graft type polymer) ", Nikko Chemicals Co., Ltd." Nikkor T106 (polyoxyethylene sorbitan monooleart), MYS-IEX (polyoxyethylene monoesterate) ", Kawaken "Hinoact T-8000E" manufactured by Fine Chemical Co., Ltd., "Organosiloxane Polymer KP341" manufactured by Shinetsu Chemical Industry Co., Ltd., "Organosiloxane Polymer KP341" manufactured by Morishita Sangyo Co., Ltd. EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 ", San Nopco Ltd." Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 ", ADEKA CORPORATION" Adeka Prulonic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P- 123 ”,“ Ionet S-20 ”manufactured by Sanyo Chemical Industries, Ltd., and the like.

These resins may be used alone or in combination of two or more. Further, the alkali-soluble resin described later can also be used as a dispersant. Examples of the alkali-soluble resin include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer and the like, and carboxylic acid in the side chain. Examples thereof include an acidic cellulose derivative having an acid cellulose and a resin obtained by modifying an acid anhydride with a polymer having a hydroxyl group, and a (meth) acrylic acid copolymer is particularly preferable. Further, the N-substituted maleimide monomer copolymer described in JP-A-10-300922, the ether dimer copolymer described in JP-A-2004-300204, and the polymerizable group described in JP-A-7-319161. An alkali-soluble resin containing the above is also preferable.

Among these, the resin preferably contains a resin having a polyester chain, and more preferably contains a resin having a polycaprolactone chain, from the viewpoint of dispersibility. ^{By interacting with R 1} and R ^{2 of the} compound represented by the formula (1), the polyester chain is more excellent in dispersibility.

Further, the resin (preferably an acrylic resin) preferably has a structural unit having an ethylenically unsaturated group from the viewpoint of dispersibility, transparency and suppression of film defects due to foreign substances.

The ethylenically unsaturated group is not particularly limited, but is preferably a (meth) acryloyl group.

When the resin has an ethylenically unsaturated group in the side chain, particularly a (meth) acryloyl group, the resin has a divalent chain having an alicyclic structure between the main chain and the ethylenically unsaturated group. It preferably has a group.

The content of the dispersant is a compound represented by the formula (1) when the compound represented by the formula (1) and a pigment, a dye or a pigment derivative other than the compound represented by the formula (1) are contained. , And the total content of pigments, dyes and pigment derivatives other than the compound represented by the formula (1) is preferably 1 part by mass to 100 parts by mass, and 5 parts by mass to 90 parts by mass. Parts are more preferable, and 10 parts by mass to 80 parts by mass are further preferable.

-Alkali-soluble resin-

From the viewpoint of developability, the composition according to the present disclosure preferably contains an alkali-soluble resin as the binder polymer.

The alkali-soluble resin is a linear organic polymer polymer that promotes at least one alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from the alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resin, polysiloxane resin, acrylic resin, acrylamide resin, and acrylic / acrylamide copolymer resin are preferable, and from the viewpoint of developability control, acrylic resin and acrylamide resin. , Acrylic / acrylamide copolymer resin is preferable.

Examples of the group that promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxy group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, which are soluble in an organic solvent and developed with a weak alkaline aqueous solution. Possible ones are preferred, and (meth) acrylic acids are particularly preferred. These acid groups may be only one kind or two or more kinds. As the alkali-soluble resin, the description in paragraphs 0558 to 0571 of JP2012-208494A (paragraphs 0685 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and these contents are described in the present specification. Incorporated into the book.

As the alkali-soluble resin, a resin having a structural unit represented by the following formula (ED) is also preferable.

In formula (ED), ^RE1 and ^RE2 each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent, and z represents 0 or 1.

Examples of the hydrocarbon group having 1 to 25 carbon atoms represented by R ^E1 and ^{R E2,} is not particularly limited, for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group , T-butyl group, t-amyl group, stearyl group, lauryl group, 2-ethylhexyl raw or other linear or branched alkyl group; aryl group such as phenyl group; cyclohexyl group, t-butylcyclohexyl group, di Alicyclic groups such as cyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group; substituted with alkoxy group such as 1-methoxyethyl group and 1-ethoxyethyl group Alkyl groups that have been added; alkyl groups substituted with aryl groups such as benzyl groups; and the like. Among these, a primary or secondary hydrocarbon group such as a methyl group, an ethyl group, a cyclohexyl group, a benzyl group or the like, which is difficult to be desorbed by acid or heat, is particularly preferable in terms of heat resistance.

In addition, ^RE1 and ^RE2 may be the same type of substituents or different substituents.

Examples of compounds forming the structural unit represented by the formula (ED) are dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate and diethyl-2,2'-[oxybis (methylene)). ] Bis-2-propenoate, di (n-propyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2,2'-[oxybis (methylene)] bis -2-propenoate, di (t-butyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate , Etc. can be mentioned. Among these, dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate is particularly preferable.

The alkali-soluble resin may have a structural unit other than the structural unit represented by the formula (ED).

Examples of the monomer forming the above-mentioned structural unit include aryl (meth) acrylate, alkyl (meth) acrylate, and polyethyleneoxy (meth) acrylate that impart oil solubility from the viewpoint of ease of handling such as solubility in a solvent. It is also preferable to include it as a copolymerization component, and aryl (meth) acrylate or alkyl (meth) acrylate is more preferable.

From the viewpoint of alkali developability, a monomer having a carboxy group such as (meth) acrylic acid or itaconic acid containing an acidic group, a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride or itacon anhydride A monomer having a carboxylic acid anhydride group such as an acid is preferably contained as a copolymerization component, and (meth) acrylic acid is more preferable.

The alkali-soluble resin is formed from, for example, a structural unit represented by the formula (ED), a structural unit formed from benzyl methacrylate, and at least one monomer selected from the group consisting of methyl methacrylate and methacrylic acid. A resin having a constituent unit to be formed is preferably mentioned.

For the resin having the structural unit represented by the formula (ED), the description in paragraphs 0079 to 00099 of JP2012-198408A can be referred to, and this content is incorporated in the present specification.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000. The lower limit is more preferably 5,000 or more, and even more preferably 7,000 or more. The upper limit is more preferably 45,000 or less, and even more preferably 43,000 or less.

The acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, and even more preferably 70 mgKOH / g or more. The upper limit is more preferably 150 mgKOH / g or less, and even more preferably 120 mgKOH / g or less.

The acid value in the present disclosure shall be measured by the following method.

The acid value represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g of solid content. The measurement sample was dissolved in a mixed solvent of tetrahydrofuran / water = 9/1 (mass ratio), and the obtained solution was prepared using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Denshi Kogyo Co., Ltd.). Titrate with 0.1 mol / L aqueous sodium hydroxide solution at ° C. The acid value is calculated by the following formula with the inflection point of the titration pH curve as the titration end point.

A = 56.11 × Vs × 0.1 × f / w

A: Acid value (mgKOH / g)

Vs: Amount of 0.1 mol / L sodium hydroxide aqueous solution required for titration (mL)

f: Titer of 0.1 mol / L sodium hydroxide aqueous solution

w: Measurement sample mass (g) (solid content conversion)

(Curable compound)

From the viewpoint of pattern forming property, the composition according to the present disclosure preferably contains a curable compound, and more preferably contains a curable compound and further contains a photopolymerization initiator described later.

As the curable compound, a compound having a polymerizable group (hereinafter, also referred to as “polymerizable compound”) is preferable.

The curable compound may be in any chemical form such as a monomer, an oligomer, a prepolymer, or a polymer. Examples of the curable compound include paragraphs 0070 to 0191 of Japanese Patent Application Laid-Open No. 2014-41318 (paragraphs 0071-0192 of the corresponding International Publication No. 2014/017669), paragraphs 0045 to 0216 of Japanese Patent Application Laid-Open No. 2014-32380, and the like. The description of the above can be taken into consideration, and this content is incorporated in the specification of the present application.

Examples of commercially available urethane resins having a methacryloyl group include 8UH-1006 and 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.).

The curable compound is preferably a polymerizable compound. The polymerizable compound may be a radically polymerizable compound or a cationically polymerizable compound, and for example, a compound containing a polymerizable group such as an ethylenically unsaturated group and a cyclic ether group (epoxy, oxetane) may be used. Can be mentioned. Of these, ethylenically unsaturated compounds are preferable.

As the ethylenically unsaturated group, a vinyl group, a styryl group, a (meth) acryloyl group, and a (meth) allyl group are preferable. The polymerizable compound may be a monofunctional compound having one polymerizable group or a polyfunctional polymerizable compound having two or more polymerizable groups, but it must be a polyfunctional polymerizable compound. Is preferable, and a polyfunctional (meth) acrylate compound is more preferable. When the composition contains a polyfunctional polymerizable compound, the film strength can be improved.

Examples of the curable compound include a monofunctional (meth) acrylate compound, a polyfunctional (meth) acrylate compound (preferably a 3 to 6-functional (meth) acrylate compound), a polybasic acid-modified acrylic oligomer, an epoxy resin, and a polyfunctional epoxy. Examples include resin.

As the curable compound, an ethylenically unsaturated compound can be preferably used. As an example of the ethylenically unsaturated compound, the description in paragraphs 0033 to 0034 of JP2013-253224A can be referred to, and the content thereof is incorporated in the present specification.

Examples of the ethylenically unsaturated compound include ethyleneoxy-modified pentaerythritol tetraacrylate (commercially available NK ester ATM-35E, manufactured by Shin-Nakamura Chemical Co., Ltd.) and dipentaerythritol triacrylate (commercially available KAYARAD D). -330, manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol tetraacrylate (commercially available, KAYARAD D-320, manufactured by Nihon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available, KAYARAD) D-310, manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexa (meth) acrylate (commercially available products include KAYARAD DPHA, manufactured by Nihon Kayaku Co., Ltd., A-DPH-12E, Shin-Nakamura Chemical Industry Co., Ltd. ) And these (meth) acryloyl groups are preferably structured through ethylene glycol and propylene glycol residues. Also, these oligomer types can be used.

Further, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available, M-460, manufactured by Toagosei Co., Ltd.) is preferable. Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-TMMT) and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) are also preferable. These oligomer types can also be used. For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned.

The ethylenically unsaturated compound may have an acid group such as a carboxy group, a sulfonic acid group, and a phosphoric acid group.

Examples of the ethylenically unsaturated compound having an acid group include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. A compound obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to have an acid group is preferable, and particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol. Or it is dipentaerythritol. Examples of commercially available products include M-510 and M-520 of the Aronix series as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The acid value of the ethylenically unsaturated compound having an acid group is preferably 0.1 mgKOH / g to 40 mgKOH / g. The lower limit is more preferably 5 mgKOH / g or more. The upper limit is more preferably 30 mgKOH / g or less.

In the present disclosure, a compound having an epoxy group or an oxetanyl group can be used as the curable compound. Examples of the compound having an epoxy group or an oxetanyl group include a polymer having an epoxy group in the side chain, a monomer or an oligomer having two or more epoxy groups in the molecule, and the like. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like can be mentioned. Further, a monofunctional or polyfunctional glycidyl ether compound is also mentioned, and a polyfunctional aliphatic glycidyl ether compound is preferable.

The weight average molecular weight is preferably 500 to 5,000,000, more preferably 1,000 to 500,000.

As these compounds, commercially available products may be used, or those obtained by introducing an epoxy group into the side chain of the polymer may be used. For example, the cyclomer P ACA 200M, the ACA 230AA, the ACA Z250, the ACA Z251, the ACA Z300, and the ACA Z320 (all manufactured by Daicel Chemical Industries, Ltd.) can be mentioned.

The curable compound may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably in the above range.

The content of the curable compound is preferably 1% by mass to 90% by mass with respect to the total solid content of the composition. The lower limit is more preferably 5% by mass or more, further preferably 10% by mass or more, and further preferably 20% by mass or more. The upper limit is more preferably 80% by mass or less, further preferably 75% by mass or less.

(Polymerization initiator)

The composition according to the present disclosure preferably contains a polymerization initiator together with a curable compound.

The polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator, but a photopolymerization initiator is preferable.

Further, the polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

Examples of the photoradical polymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxaziazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenone and the like can be mentioned. Examples of the halogenated hydrocarbon compound having a triazine skeleton include Wakabayashi et al., Bull. Chem. Soc. Japanese Patent No. 42, 2924 (1969), Compound described in British Patent No. 1388492, Compound described in JP-A-53-133428, Compound described in German Patent No. 3337024, F.I. C. J. by Schaefer et al. Org. Chem. 29, 1527 (1964), compound described in JP-A-62-58241, compound described in JP-A-5-281728, compound described in JP-A-5-341920, US Pat. Examples include the compounds described in No. 4212976.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator includes an oxime compound, a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, and an oxime. A compound selected from the group consisting of a compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxaziazole compound and a 3-aryl substituted coumarin compound is selected. Preferably, the oxime compound is more preferred.

Specific examples of the oxime compound include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, the compound described in JP-A-2006-342166, and JP-A-2016-21012. Examples thereof include the compounds described in the publication. In addition, J. C. S. Perkin II (1979, pp. 1653-1660), J. Mol. C. S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000-66385, JP-A-2000-80068, JP-A-2004. Examples thereof include compounds described in Japanese Patent Application Laid-Open No. 534977 and Japanese Patent Application Laid-Open No. 2006-342166.

As commercially available products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (all manufactured by BASF) are also preferably used. In addition, TR-PBG-304 (manufactured by Joshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831 (manufactured by ADEKA Corporation), ADEKA ARCULDS NCI-930 (manufactured by ADEKA Corporation), ADEKA PUTMER N -1919 (manufactured by ADEKA Corporation) can also be used.

Further, as an oxime compound other than the above, the compound described in JP-A-2009-5199004, in which an oxime is linked to the N-position of the carbazole ring, and a US Pat. No. 6,626,957 in which a heterosubstituted group is introduced at the benzophenone moiety are described. The compound described in JP-A-2010-15025 and US Patent Publication No. 2009-292039, the keto-oxime compound described in International Publication No. 2009/131189, and the triazine skeleton, in which a nitro group was introduced into the dye moiety. The compound described in US Pat. No. 7,556,910, which contains an oxime skeleton in the same molecule, and JP-A-2009-221114, which has an absorption maximum at 405 nm and has good sensitivity to a g-ray light source. Compounds and the like may be used.

Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, the contents of which are incorporated herein by reference.

Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. The oxime compound may be an oxime compound having an (E) -form NO bond, or an (Z) -form oxime compound having an (Z) -form NO bond. And (Z) form may be a mixture.

Wherein ^{(OX-1), R O1} and ^{R O2} independently denote a monovalent ^{substituent, R O3} is a divalent organic group, ^{Ar O1} represents an aryl group.

Wherein (OX-1), the monovalent substituent represented by R ^O1, is preferably a monovalent non-metallic atomic group.

Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, an arylthiocarbonyl group and the like. Further, these groups may have one or more substituents. Moreover, the above-mentioned substituent may be further substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, an aryl group and the like.

Wherein (OX-1), the monovalent substituent represented by R ^O2, an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group are preferred. These groups may have one or more substituents. Examples of the substituent include the above-mentioned substituents.

Wherein ^(OX-1), the divalent organic group represented by ^{R O3,} alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-mentioned substituents.

As the photopolymerization initiator, a compound represented by the following formula (X-1) or formula (X-2) can also be used.

In the formula (X-1), ^RX1 and ^RX2 independently have an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. represents an arylalkyl group having 7 to 30 carbon ^atoms, in the case of ^{R X1} and ^{R X2} are phenyl group may form a fluorene group and each other phenyl group is ^{bonded, R X3} and ^{R X4} are each independently, represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group or a heterocyclic group having 4 to 20 carbon atoms having 7 to 30 carbon atoms, ^{X a} represents a single bond or Indicates a carbonyl group.

In formula ^{(X2), R X1, R} X2, R X3 and ^{R X4} has the same meaning as ^{R X1, R X2, R X3} and ^{R X4} in Formula ^{(X1), R X5} is, -R ^{X6, -OR X6, -SR X6,} -COR X6, -CONR X6 R X6, -NR X6 COR X6, -OCOR X6, -COOR X6, -SCOR X6, -OCSR X6, -COSR X6, -CSOR X6, Representing −CN, halogen atom or hydroxyl group, ^RX6 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocycle having 4 to 20 carbon atoms. The group represents a group, X ^A represents a single bond or a carbonyl group, and xa represents an integer from 0 to 4.

In the above formulas (X-1) and (X-2), R ¹ and R ² are preferably methyl groups, ethyl groups, n-propyl groups, i-propyl, cyclohexyl groups or phenyl groups, respectively. R ^X3 is a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. ^RX4 is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. ^RX5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X ^A is preferably a single bond.

Specific examples of the compounds represented by the formulas (X-1) and (X-2) include the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein by reference.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466, and Japanese Patent Application Laid-Open No. 4223071. Examples thereof include the compounds described in paragraphs 0007 to 0025, and ADEKA ARCLUS NCI-831 (manufactured by ADEKA Corporation).

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm.

As the oxime compound, the molar extinction coefficient at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000 from the viewpoint of sensitivity, and is 5,000 to 300,000. It is more preferably 200,000.

The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

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

_{Examples of -OC 9} F ₁₇ in (C-12) above include the following groups.

As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include the compounds described in JP-A-2010-262028, the compounds 24, 36-40 described in JP-A-2014-500852, and the compounds described in JP-A-2013-164471. C-3) and the like can be mentioned. This content is incorporated herein by reference.

Examples of the photocationic polymerization initiator include a photoacid generator. Examples of the photoacid generator include onium salt compounds such as diazonium salt, phosphonium salt, sulfonium salt, and iodonium salt, which are decomposed by light irradiation to generate acid, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl. Examples thereof include sulfonate compounds such as sulfonate. For details of the photocationic polymerization initiator, the description in paragraphs 0139 to 0214 of JP2009-258603A can be referred to, and the content thereof is incorporated in the present specification.

Commercially available products can also be used as the photocationic polymerization initiator. Examples of commercially available photocationic polymerization initiators include ADEKA Corporation's ADEKA Arkuru's SP series (for example, ADEKA Arkuru's SP-606), BASF's IRGACURE250, IRGACURE270, and IRGACURE290.

The polymerization initiator may be of only one type or of two or more types, and in the case of two or more types, the total amount is preferably in the above range.

The content of the polymerization initiator is preferably 0.01% by mass to 30% by mass with respect to the total solid content of the composition. The lower limit is more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more. The upper limit is more preferably 20% by mass or less, further preferably 15% by mass or less.

(solvent)

The composition according to the present disclosure may contain a solvent.

The solvent is not particularly limited, and can be appropriately selected depending on the intended purpose as long as it can uniformly dissolve or disperse each component of the composition. For example, water and an organic solvent can be used, and an organic solvent is preferable.

Preferable examples of the organic solvent include alcohols (for example, methanol), ketones, esters, aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane and the like. .. These may be used alone or in combination of two or more.

Among them, at least one organic solvent selected from the group consisting of esters having a cyclic alkyl group and ketones is preferably mentioned.

Specific examples of alcohols, aromatic hydrocarbons, and halogenated hydrocarbons include those described in paragraph 0136 of JP2012-194534A, and the contents thereof are incorporated in the present specification.

Specific examples of esters, ketones, and ethers include those described in Japanese Patent Application Laid-Open No. 2012-208494, paragraph 0497 (corresponding US Patent Application Publication No. 2012/0235099, paragraph 0609), and further. , Acetic acid-n-amyl, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, ethylene glycol monobutyl ether acetate and the like.

Solvents include ethanol, methanol, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, N-methyl-2-pyrrolidone, ethyl cellosolve acetate, ethyl lactate. , Butyl acetate, cyclohexyl acetate, diethylene glycol dimethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. One or more is preferable.

The solvent content is preferably such that the total solid content of the composition is 10% by mass to 90% by mass. The lower limit is more preferably 15% by mass or more, further preferably 20% by mass or more. The upper limit is more preferably 80% by mass or less, further preferably 70% by mass or less.

The solvent may be only one type or two or more types, and in the case of two or more types, the total amount is preferably in the above range.

(Dye derivative)

The composition according to the present disclosure preferably further contains a dye derivative (hereinafter, also simply referred to as "dye derivative") other than the compound having the structure represented by the formula (1). By including the dye derivative, particularly when the compound having the structure represented by the formula (1) is a pigment, the dispersibility of the compound having the structure represented by the formula (1) is enhanced, and the compound represented by the formula (1) is represented by the formula (1). Aggregation of compounds having the represented structure can be efficiently suppressed. The pigment derivative is preferably a pigment derivative.

The dye derivative preferably has a structure in which a part of the dye is replaced with a group having an acidic group, a basic group, or a salt structure, and a dye derivative represented by the following formula (3) is more preferable. The dye derivative represented by the following formula (3) is represented by the formula (1) in the composition because the dye structure P is easily adsorbed on the surface of the compound having the structure represented by the formula (1). The dispersibility of the compound having a structure can be improved. Further, when the composition contains a resin, the terminal portion X of the dye derivative is adsorbed on the resin by the interaction with the adsorption portion (polar group or the like) of the resin, so that the structure represented by the formula (1) can be obtained. The dispersibility of the compound can be further improved.

In formula (3), P ³ represents a dye structure, L ³ independently represents a single bond or a linking group, and X ³ independently represents a group having an acidic group, a basic group or a salt structure. , M represents an integer of 1 or more, and n represents an integer of 1 or more.

Dye structure in P ^3, pyrrolo pyrrole pigment structure, squarylium dye structure, croconium dye structure, diimmonium dye structure, oxonol dye structure, diketopyrrolopyrrole dye structures, quinacridone dye structures, anthraquinone dye structures, dianthraquinone dye structure, Benzoiso Consists of indol pigment structure, thiazine indigo pigment structure, azo pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, dioxazine pigment structure, pyromethene pigment structure, perylene pigment structure, perinone pigment structure and benzoimidazolinone pigment structure. At least one selected from the group is preferable, and at least one selected from the group consisting of a pyrolopyrrolop pigment structure, a diketopyrrolopyrrole pigment structure, a quinacridone pigment structure, a squarylium pigment structure, a croconium pigment structure and a benzoimidazolinone pigment structure is more preferable. Preferably, the pyrrolopyrrole dye structure is particularly preferred. When the dye derivative has these dye structures, the dispersibility of the compound represented by the formula (1) can be further improved.

The linking groups in L ³ are 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20. A group consisting of a single sulfur atom is preferable, and it may be unsubstituted or further having a substituent. As the substituent, an alkyl group, an aryl group, a hydroxy group or a halogen atom is preferable.

Linking group is an alkylene group, an arylene group, a nitrogen-containing heterocyclic _{group, -NR '-, - SO 2} -, - S -, - O -, - CO -, - COO -, - CONR'-, or they A group in which two or more of these are combined is preferable, and an alkylene group, an arylene group, -SO _2- , -COO-, or a group in which two or more of these are combined is more preferable. R'represents a hydrogen atom, an alkyl group (preferably 1 to 30 carbon atoms) or an aryl group (preferably 6 to 30 carbon atoms).

The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms. The alkylene group may have a substituent. The alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be either monocyclic or polycyclic.

The arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, further preferably 6 to 10 carbon atoms, and particularly preferably a phenylene group.

The nitrogen-containing heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The nitrogen-containing heterocyclic group is preferably a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 8, and more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4. The number of nitrogen atoms contained in the nitrogen-containing heterocyclic group is preferably 1 to 3, more preferably 1 or 2. The nitrogen-containing heterocyclic group may contain a hetero atom other than the nitrogen atom. Examples of heteroatoms other than nitrogen atoms include oxygen atoms and sulfur atoms. The number of heteroatoms other than nitrogen atoms is preferably 0 to 3, more preferably 0 or 1.

Examples of the nitrogen-containing heterocyclic group include a piperazine ring group, a pyrrolidine ring group, a pyrrol ring group, a piperazine ring group, a pyridine ring group, an imidazole ring group, a pyrazole ring group, an oxazole ring group, a thiazole ring group, a pyrazine ring group, and a morpholine ring. Group, thiazine ring group, indole ring group, isoindole ring group, benzimidazole ring group, purine ring group, quinoline ring group, isoquinoline ring group, quinoxaline ring group, cinnoline ring group, carbazole ring group and the following formula (L-1). ) ~ A group represented by any of the formulas (L-7) can be mentioned.

* In the formula ^{represents a binding site with P 3} , L ³ or X ^3, and R represents a hydrogen atom or a substituent. Examples of the substituent include a substituent T. Examples of the substituent T include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a thioalkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a carboxy group, an acetyl group, a cyano group, and a halogen. Examples include atoms (fluorine atom, chlorine atom, bromine atom, iodine atom). These substituents may further have a substituent.

Specific examples of the linking group include an alkylene group, an arylene group, -SO _2- , a group represented by the above formula (L-1), a group represented by the above formula (L-5), -O- and an alkylene group. A group consisting of a combination of groups, a group consisting of a combination of -NR'-and an alkylene group, a group consisting of a combination of -NR'-, -CO- and an alkylene group, a group consisting of -NR'-, -CO- and an alkylene group. A group consisting of a combination of a group and an arylene group, a group consisting of a combination of -NR'-, -CO- and an arylene group, a group consisting of a combination of -NR'-, -SO _2- and an alkylene group, -NR' - and -SO 2 _- and an alkylene group and a combination consisting of groups of the arylene group, a group formed of a combination of a group and the alkylene group represented by the formula (L-1), is represented by the (L-1) that group combination consists group and an arylene group, group and -SO 2 represented by the above formula (L-1) _- a combination of a an alkylene group group, represented by formula (L-1) A group consisting of a combination of a group, -S- and an alkylene group, a group consisting of a combination of a group represented by the above formula (L-1), an -O- and an arylene group, and a group consisting of a combination of an arylene group, represented by the above formula (L-1). A group consisting of a combination of a group to be formed, -NR'-, -CO-, and an arylene group, a group consisting of a combination of a group represented by the above formula (L-3) and an arylene group, an arylene group and -COO- Examples thereof include a group consisting of a combination of and an arylene group, a group consisting of a combination of -COO- and an alkylene group, and the like.

Wherein (3), X ³ represents a group having an acidic group, basic group, or salt structure.

Examples of the acidic group include a carboxy group, a sulfo group, a phospho group, a sulfonimide group and the like.

Examples of the basic group include groups represented by the formulas (X-3) to (X-8) described later.

Examples of the group having a salt structure include the above-mentioned salts of acidic groups and salts of basic groups. Examples of the atom or atomic group constituting the salt include a metal atom and tetrabutylammonium. As the metal atom, an alkali metal atom or an alkaline earth metal atom is more preferable. Examples of the alkali metal atom include lithium, sodium and potassium. Examples of the alkaline earth metal atom include calcium and magnesium.

X ³ is preferably at least one group selected from the group consisting of a carboxy group, a sulfo group, a sulfonimide group, and a group represented by any of the following formulas (X-1) to (X-11). ..

In formulas (X-1) to (X-11), * represents a bond site with ^{L 3 in formula (3), and R 100 to} R ¹⁰⁶ are independent hydrogen atoms, alkyl groups, and alkenyl groups, respectively. Alternatively, it represents an aryl group, and R ¹⁰⁰ and R ¹⁰¹ may be linked to each other to form a ring, and M represents an atom or atomic group constituting an anion and a salt.

The alkyl group may be linear, branched or cyclic. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 8 carbon atoms. The number of carbon atoms of the branched alkyl group is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 8. The cyclic alkyl group may be monocyclic or polycyclic. The cyclic alkyl group preferably has 3 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 6 to 10 carbon atoms.

The alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 4 carbon atoms.

The aryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms.

R ¹⁰⁰ and R ¹⁰¹ may be connected to each other to form a ring. The ring may be an alicyclic ring or an aromatic ring. The ring may be a single ring or a double ring. When R ¹⁰⁰ and R ¹⁰¹ are bonded to form a ring, the linking group includes -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a combination thereof. Can be linked with a divalent linking group selected from the group. Specific examples include, for example, a piperazine ring, a pyrrolidine ring, a pyrrole ring, a piperazine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, a thiazine ring, an indole ring, and an isoindole ring. Examples thereof include a benzimidazole ring, a purine ring, a quinoline ring, an isoquinoline ring, a quinoxalin ring, a cinnoline ring, and a carbazole ring.

R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ each independently represent a hydrocarbon group having 1 or more carbon atoms which may contain a halogen atom, a hydroxy group or a substituent. The ^{hydrocarbon group represented by R 107} , R ¹⁰⁸ , and R ¹⁰⁹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be linear, branched or cyclic. The aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms. The upper limit is preferably 20 or less, more preferably 10 or less, and even more preferably 5 or less. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20. The upper limit is preferably 18 or less, more preferably 15 or less, and even more preferably 12 or less. Examples of the substituent that the hydrocarbon group represented by R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ may contain include a halogen atom, a hydroxyl group, a carboxyl group, an alkoxy group, a phenoxy group, an acyl group and a sulfo group. The alkoxy group may have at least a part of hydrogen atoms substituted with halogen atoms. The above-mentioned substituent is preferably an alkoxy group in which at least a part of a halogen atom or a hydrogen atom may be substituted with a halogen atom, and more preferably a halogen atom. Further, as the halogen atom, a chlorine atom, a fluorine atom, or a bromine atom is preferable, and a fluorine atom is more preferable.

M represents an atom or a group of atoms constituting an anion and a salt. These include those described above, and the preferred range is also the same.

The upper limit of m represents the number of substituents that the dye structure P can take, for example, preferably 10 or less, and more preferably 5 or less. When m is 2 or more, a plurality of L and X may be different from each other.

n is preferably an integer of 1 to 3, more preferably 1 or 2. When n is 2 or more, a plurality of Xs may be different from each other.

Specific examples include the following groups.

The dye derivative is preferably a dye derivative represented by the following formula (4). The dye derivative represented by the following formula (4) is a compound in which P in the formula (3) has a pyrolopyrrole dye structure.

In formula (4), R ^{43 to} R ⁴⁶ independently represent a cyano group, an acyl group, an alkoxycarbonyl group, an alkylsulfinyl group, an arylsulfinyl group or a heteroaryl group, and R ⁴⁷ and R ⁴⁸ independently represent each. Represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ⁴⁹ R ⁵⁰ or a metal atom, where R ⁴⁷ may be covalently or coordinated with ^{R 43} or R ^{45 , where R 48} is. , R ⁴⁴ or R ⁴⁶ may be covalently bonded or coordinated, and R ⁴⁹ and R ⁵⁰ are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, heteroaryl group, alkoxy. A group, an aryloxy group, or a heteroaryloxy group may be represented, and R ⁴⁹ and R ⁵⁰ may be bonded to each other to form a ring, and L ⁴¹ and L ⁴² are independently single-bonded or L 42, respectively. Represents an alkylene group, an arylene group, a nitrogen-containing heterocyclic group, -O-, -S-, -NR'-, -CO-, -SO _2- or a linking group in which two or more of these are combined, and R'is hydrogen. Represents an atom, an alkyl group or an aryl group, X ⁴¹ and X ⁴² independently represent a group having an acidic group, a basic group or a salt structure, and n 41 and n 42 independently represent an integer of 0 to 4, respectively. , N41 and n42 are at least one.

^{R 43 to} R ⁴⁸ in the formula (4) are ^{synonymous with R 3 to} R ⁸ in the formula (1), and the preferred embodiments are also the same.

X ⁴¹ and X ⁴² of the formula (4) are ^{synonymous with X 3} of the formula (3), and the preferred embodiments are also the same.

In the formula (4), L ⁴¹ and L ^{42 are synonymous with L 3 in the} formula (3), and the preferred embodiment is also the same. Further, the following linking groups are particularly preferable from the viewpoint of synthetic suitability and visible transparency.

Further, ^{it is preferable that L 41} has 1 to 20 atoms constituting a chain connecting ^{X 41} and a benzene ring directly connected to a pyrrolopyrrole structure which is a mother nucleus structure of a pigment derivative. The lower limit is more preferably 2 or more, and further preferably 3 or more. The upper limit is more preferably 15 or less, and even more preferably 10 or less. It ^{is preferable that L 42} has 1 to 20 atoms constituting a chain connecting the benzene ring directly connected to the pyrrolopyrrole structure, which is the mother nucleus structure of the pigment derivative, and X ^42. The lower limit is more preferably 2 or more, and further preferably 3 or more. The upper limit is more preferably 15 or less, and even more preferably 10 or less. According to this aspect, the dispersibility of the pigment can be further improved. Although the detailed reason is unknown, by increasing the distance between the pyrrolopyrrole structure, which is the mother nucleus structure of the pigment derivative, and X ⁴¹ and X ^{42 , X 41} and X ⁴² are less susceptible to steric hindrance, and the resin and the like are used. It is presumed that the interaction between the two became easier to work, and as a result, the dispersibility of the pigment could be improved.

The compound represented by the formula (4) preferably has a solubility in a solvent (25 ° C.) contained in the composition of 0 g / L to 0.1 g / L, preferably 0 g / L to 0.01 g / L. Is more preferable. According to this aspect, the dispersibility of the pigment can be further improved.

The compound represented by the formula (1) is preferably a compound having a maximum absorption wavelength in the range of 700 nm to 1200 nm. Further, the ratio A1 / A2 of the absorbance A1 at the wavelength of 500 nm and the absorbance A2 at the maximum absorption wavelength is preferably 0.1 or less, and more preferably 0.05 or less.

The absorbance of the compound in the present disclosure is a value obtained from the absorption spectrum of the compound in a solution. Examples of the measuring solvent used for measuring the absorption spectrum of the compound represented by the formula (4) in a solution include chloroform, dimethyl sulfoxide, tetrahydrofuran and the like. When the compound represented by the formula (4) is dissolved in chloroform, chloroform is used as a measurement solvent. Further, when it is not soluble in chloroform but is soluble in dimethyl sulfoxide or tetrahydrofuran, dimethyl sulfoxide or tetrahydrofuran is used as the measurement solvent.

Specific examples of the dye derivative represented by the formula (3) include the following (3-1) to (3-25). In the following equation, m, m1, m2, and m3 independently represent an integer of 1 or more.

Specific examples of the compound represented by the formula (4) include the following compounds. In the following structural formula, Me represents a methyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In the table below, Ar-1 to Ar-31 and R-1 to R-7 are as follows. The "*" in the structure shown below is a connecting hand.

Further, the composition according to the present disclosure may contain the above-mentioned dye derivative alone or in combination of two or more.

The content of the dye derivative is preferably 0.1% by mass to 30% by mass, and 0.5% by mass to 25% by mass, based on the total solid content of the composition, from the viewpoint of infrared absorption and dispersibility. It is more preferably 1% by mass to 20% by mass.

The content of the dye derivative is preferably 1% by mass to 80% by mass with respect to the total mass of the compound represented by the formula (1) from the viewpoint of infrared absorption and dispersibility. It is more preferably from mass% to 50% by mass, and even more preferably from 5% by mass to 40% by mass.

(Coloring agent for chromatic color, black colorant, colorant for blocking visible light)

The composition according to the present disclosure can contain at least one selected from the group consisting of a chromatic colorant and a black colorant (hereinafter, a visible colorant is combined with the chromatic colorant and the black colorant). Also called). In the present disclosure, the chromatic colorant means a colorant other than the white colorant and the black colorant. The chromatic colorant is preferably a colorant having absorption in a wavelength range of 400 nm or more and less than 650 nm.

-Coloring agent-

In the present disclosure, the chromatic colorant may be a pigment or a dye.

The average particle size (r) of the pigment preferably satisfies 20 nm ≦ r ≦ 300 nm, more preferably 25 nm ≦ r ≦ 250 nm, and even more preferably 30 nm ≦ r ≦ 200 nm. The "average particle size" here means the average particle size of the secondary particles in which the primary particles of the pigment are aggregated.

Further, the particle size distribution of the secondary particles of the pigment that can be used (hereinafter, also simply referred to as “particle size distribution”) is such that the secondary particles within (average particle size ± 100) nm are 70% by mass or more of the whole. It is preferably 80% by mass or more. The particle size distribution of the secondary particles can be measured using the scattering intensity distribution.

The average particle size of the primary particles is observed with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and 100 particle sizes are measured at the portion where the particles are not aggregated, and the average value is calculated. It can be obtained by.

The pigment is preferably an organic pigment. Moreover, the following can be mentioned as a pigment. However, the present disclosure is not limited to these.

Color Index (CI) 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, 129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 etc. (above, yellow pigment),

C. 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. (The above is orange pigment),

C. I. 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, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279,294 (xanthene system) , Organo Ultramarine, Bluish Red), etc. (above, red pigment),

C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigment),

C. I. Pigment Violet 1,19,23,27,32,37,42, etc. (above, purple pigment),

C. 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 (monoazo system), 88 (methine / polymethine type) and the like (above, blue pigment).

These pigments can be used alone or in various combinations.

The dye is not particularly limited, and known dyes can be used. The chemical structures include pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes such as xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes can be used. Moreover, you may use the multimer of these dyes. Further, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.

Further, as the dye, at least one of an acid dye and a derivative thereof may be preferably used. In addition, at least one of direct dyes, basic dyes, mordant dyes, acidic mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, derivatives thereof and the like can also be usefully used.

Specific examples of acid dyes are given below, but the present invention is not limited thereto. For example, the following dyes and derivatives of these dyes can be mentioned.

acid alizarin violet N,

acid blue 1,7,9,15,18,23,25,27,29,40-45,62,70,74,80,83,86,87,90,92,103,112,113,120, 129,138,147,158,171,182,192,243,324: 1,

acid chrome violet K,

acid Fuchsin; acid green 1,3,5,9,16,25,27,50,

acid orange 6,7,8,10,12,50,51,52,56,63,74,95,

acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274,

acid violet 6B, 7, 9, 17, 19,

acid yellow 1,3,7,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116,184 243,

Food Yellow 3

In addition to the above, azo-based, xanthene-based, and phthalocyanine-based acid dyes are also preferable. I. Solvent Blue 44, 38; C.I. I. Acid dyes such as Solvent orange 45; Rhodamine B and Rhodamine 110 and derivatives of these dyes are also preferably used.

Among them, the dyes include triarylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazoleazomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyrazoleazo. , Anilinoazo-based, pyrazorotriazole-azo-based, pyridone-azo-based, anthrapyridone-based, and pyrromethene-based coloring agents are preferable.

Further, a pigment and a dye may be used in combination.

-Black colorant-

As the black colorant, an organic black colorant is preferable. In the present disclosure, a black colorant as a colorant that blocks visible light means a material that absorbs visible light but transmits at least a part of infrared rays. Therefore, in the present disclosure, the black colorant as a colorant that blocks visible light does not include carbon black and titanium black. As the black colorant as a colorant that blocks visible light, a bisbenzofuranone compound, an azomethine compound, a perylene compound, an azo compound and the like can also be used.

Examples of the bisbenzofuranone compound include those described in JP-A-2010-534726, JP-A-2012-515233, and JP-A-2012-515234. For example, it is available as "Irgaphor Black" manufactured by BASF.

Examples of the perylene compound include C.I. I. Pigment Black 31, 32 and the like can be mentioned.

Examples of the azomethine compound include those described in JP-A-1-170601, JP-A-2-34664, etc., and can be obtained as, for example, "Chromofine Black A1103" manufactured by Dainichiseika Kogyo Co., Ltd. .. The azo compound is not particularly limited, but a compound represented by the following formula (A-1) and the like can be preferably mentioned.

-Coloring agent that blocks visible light-

When the composition according to the present disclosure is used to produce an infrared transmission filter that transmits infrared rays in a region that is not absorbed by the infrared absorbing dye contained therein, it is preferable to include a colorant that blocks visible light.

The colorant that blocks visible light preferably exhibits a color of black, gray, or a color close to them, depending on the combination of the plurality of colorants.

Further, the colorant that blocks visible light is preferably a material that absorbs light in the wavelength range of purple to red.

Further, the colorant that blocks visible light is preferably a colorant that blocks light in the wavelength range of 450 nm to 650 nm.

In the present disclosure, the colorant that blocks visible light preferably satisfies at least one of the following requirements (1) and (2), and more preferably satisfies the requirement (1).

(1): An embodiment containing two or more kinds of chromatic colorants.

(2): An embodiment containing a black colorant.

Further, in the present disclosure, a black colorant as a colorant that blocks visible light means a material that absorbs visible light but transmits at least a part of infrared rays. Therefore, in the present disclosure, the organic black colorant as a colorant that blocks visible light does not include a black colorant that absorbs both visible light and infrared rays, such as carbon black and titanium black.

The colorant that blocks visible light has, for example, an A / B of 4 which is a ratio of the minimum absorbance A in the wavelength range of 450 nm to 650 nm and the minimum absorbance B in the wavelength range of 900 nm to 1,300 nm. It is preferably 5.5 or more.

The above characteristics may be satisfied with one kind of material, or may be satisfied with a combination of a plurality of materials. For example, in the case of the above aspect (1), it is preferable to combine a plurality of chromatic colorants to satisfy the above spectral characteristics.

When two or more kinds of chromatic colorants are included as colorants that block visible light, the chromatic colorants are red colorant, green colorant, blue colorant, yellow colorant, purple colorant and orange colorant. It is preferable that the colorant is selected from.

Examples of the combination of chromatic colorants when the chromatic colorant is combined with two or more kinds of chromatic colorants to form a colorant that blocks visible light include the following.

(1) An embodiment containing a yellow colorant, a blue colorant, a purple colorant, and a red colorant.

(2) Aspect containing a yellow colorant, a blue colorant, and a red colorant

(3) Aspect containing a yellow colorant, a purple colorant and a red colorant

(4) Aspect containing a yellow colorant and a purple colorant

(5) An embodiment containing a green colorant, a blue colorant, a purple colorant, and a red colorant.

(6) Aspect containing a purple colorant and an orange colorant

(7) Aspect containing a green colorant, a purple colorant and a red colorant

(8) Aspect containing a green colorant and a red colorant

As a specific example of the aspect (1) above, C.I. I. Pigment Yellow 139 or 185 and C.I. as a blue pigment. I. Pigment Blue 15: 6 and C.I. as a purple pigment. I. Pigment Violet 23 and C.I. as a red pigment. I. Examples include an embodiment containing Pigment Red 254 or 224.

As a specific example of the aspect (2) above, C.I. I. Pigment Yellow 139 or 185 and C.I. as a blue pigment. I. Pigment Blue 15: 6 and C.I. as a red pigment. I. Examples include an embodiment containing Pigment Red 254 or 224.

As a specific example of the aspect (3) above, C.I. I. Pigment Yellow 139 or 185 and C.I. I. Pigment Violet 23 and C.I. as a red pigment. I. Examples include an embodiment containing Pigment Red 254 or 224.

As a specific example of the aspect (4) above, C.I. I. Pigment Yellow 139 or 185 and C.I. I. An embodiment containing Pigment Violet 23 can be mentioned.

As a specific example of the aspect (5) above, C.I. I. Pigment Green 7 or 36 and C.I. as a blue pigment. I. Pigment Blue 15: 6 and C.I. as a purple pigment. I. Pigment Violet 23 and C.I. as a red pigment. I. Examples include an embodiment containing Pigment Red 254 or 224.

As a specific example of the aspect (6) above, C.I. I. Pigment Violet 23 and C.I. as an orange pigment. I. An embodiment containing Pigment Orange 71 can be mentioned.

As a specific example of the above (7), C.I. I. Pigment Green 7 or 36 and C.I. as a purple pigment. I. Pigment Violet 23 and C.I. as a red pigment. I. Examples include an embodiment containing Pigment Red 254 or 224.

As a specific example of the above (8), C.I. I. Pigment Green 7 or 36 and C.I. as a red pigment. I. Examples include an embodiment containing Pigment Red 254 or 224.

Examples of the ratio (mass ratio) of each colorant include the following.

When the composition according to the present disclosure contains a visible colorant, the content of the visible colorant is preferably 0.01% by mass to 50% by mass with respect to the total solid content of the composition. The lower limit is more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 15% by mass or less.

The content of the visible colorant is preferably 10 parts by mass to 1,000 parts by mass, and more preferably 50 parts by mass to 800 parts by mass with respect to 100 parts by mass of the infrared absorbing dye.

(Silane coupling agent)

The composition according to the present disclosure may contain a silane coupling agent. In the present disclosure, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by 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 the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Further, the functional group other than the hydrolyzable group is preferably a group that exhibits an affinity by forming an interaction or bond with a resin or the like. For example, vinyl group, styryl group, (meth) acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group, isocyanate group and the like can be mentioned, and (meth) acryloyl group and epoxy group are preferable. As the silane coupling agent, the compounds described in paragraphs 0018 to 0036 of JP2009-288703, the compounds described in paragraphs 0056 to 0066 of JP2009-242604A, and paragraphs 0229 of International Publication No. 2015/166779. ~ 0236 are mentioned, the contents of which are incorporated herein.

The content of the silane coupling agent is preferably 0.01% by mass to 15.0% by mass, more preferably 0.05% by mass to 10.0% by mass, based on the total solid content of the composition. .. The silane coupling agent may be only one type or two or more types. When two or more types are used, the total amount is preferably in the above range.

(Surfactant)

The composition according to the present disclosure may contain a surfactant from the viewpoint of further improving the coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Surfactants can be referred to in paragraphs 0238-0245 of WO 2015/166779, the contents of which are incorporated herein by reference.

By containing a fluorine-based surfactant in the composition according to the present disclosure, the liquid characteristics (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved. be able to. Further, it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.

The fluorine atom content in the fluorine-based surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving property, and has good solubility in the composition.

Specific examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of JP-A-2014-41318 (paragraphs 0060-0064 of the corresponding International Publication No. 2014/17669) and the like, JP-A-2011. The surfactants described in paragraphs 0117 to 0132 of JP-A-132503 are mentioned and their contents are incorporated herein by reference. Commercially available products of fluorine-based surfactants include, for example, Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (or more, DIC). (Manufactured by Sumitomo 3M Ltd.), Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC- 381, SC-383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA) and the like.

Further, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied is also suitable. Can be used. Examples of such fluorine-based surfactants include Megafuck DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafuck DS. -21 can be mentioned.

A block polymer can also be used as the fluorine-based surfactant. For example, the compounds described in JP-A-2011-89090 can be mentioned. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.

The weight average molecular weight of the block polymer is preferably 3,000 to 50,000.

Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. As specific examples, the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP2010-164965, for example, Megafuck RS-101, RS-102, RS-718K, RS manufactured by DIC Corporation. -72-K and the like can be mentioned. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP2015-117327A can also be used.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc. 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), Solspers 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.) Industrial Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orphine E1010, Surfinol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) And so on.

The content of the surfactant is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005 to 3.0% by mass, based on the total solid content of the composition. The surfactant may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably in the above range.

(UV absorber)

The composition according to the present disclosure preferably contains an ultraviolet absorber. Examples of the ultraviolet absorber include a conjugated diene compound and a diketone compound, and a conjugated diene compound is preferable. The conjugated diene compound is more preferably a compound represented by the following formula (UV-1).

In the formula (UV-1), ^RU1 and ^RU2 independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and ^RU1 and ^RU2 are mutually exclusive. It may be the same or different, but it does not represent a hydrogen atom at the same time.

R ^U1 and ^{R U2,} together with the nitrogen atom ^{to which R U1} and ^{R U2} are attached, may form a cyclic amino group. Examples of the cyclic amino group include a piperidino group, a morpholino group, a pyrrolidino group, a hexahydroazepino group, a piperazino group and the like.

^RU1 and ^RU2 are each independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 5 carbon atoms.

^RU3 and ^RU4 represent electron-attracting groups. The ^RU3 and ^RU4 are preferably an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group or a sulfamoyl group, preferably an acyl group or a carbamoyl group. More preferred are groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, cyano groups, alkylsulfonyl groups, arylsulfonyl groups, sulfonyloxy groups or sulfamoyl groups. Further, ^RU3 and ^RU4 may be bonded to each other to form a cyclic electron-attracting group. ^{Examples of the cyclic electron-attracting group formed by bonding RU3} and ^RU4 with each other include a 6-membered ring containing two carbonyl groups.

At ^{least one of the above RU1} , ^RU2 , ^RU3 and ^RU4 may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with another monomer.

For the description of the substituent of the ultraviolet absorber represented by the formula (UV-1), the description in paragraphs 0320 to 0327 of JP2013-68814A can be referred to, and this content is incorporated in the present specification. Examples of commercially available products of the ultraviolet absorber represented by the formula (UV-1) include UV503 (manufactured by Daito Kagaku Co., Ltd.).

The diketone compound used as an ultraviolet absorber is preferably a compound represented by the following formula (UV-2).

In formula (UV-2), R ¹⁰¹ and R ¹⁰² each independently represent a substituent, and m1 and m2 each independently represent an integer of 0-4. Substituents include alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heteroaryloxycarbonyl groups, acyloxy groups, Amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heteroarylthio group, alkylsulfonyl group, aryl Sulfonyl group, heteroarylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, heteroarylsulfinyl group, ureido group, phosphate amide group, mercapto group, sulfo group, carboxy group, nitro group, hydroxamic acid group, sulfino group, hydrazino group , Imino group, silyl group, hydroxy group, halogen atom, cyano group and the like, and an alkyl group or an alkoxy group is preferable.

The alkyl group preferably has 1 to 20 carbon atoms. Examples of the alkyl group include linear, branched and cyclic, and linear or branched is preferable, and branching is more preferable.

The alkoxy group preferably has 1 to 20 carbon atoms. Examples of the alkoxy group include linear, branched and cyclic, and linear or branched is preferable, and branched is more preferable.

A combination in which one of R ¹⁰¹ and R ¹⁰² is an alkyl group and the other is an alkoxy group is preferable.

Independently, m1 and m2 are preferably integers of 0 to 2, more preferably 0 or 1, and particularly preferably 1.

Examples of the compound represented by the formula (UV-2) include the following compounds.

Ubinal A (manufactured by BASF) can also be used as the ultraviolet absorber. Further, as the ultraviolet absorber, an ultraviolet absorber such as an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound and a triazine compound can be used, and specific examples thereof are described in JP2013-68814. Examples include compounds. As the benzotriazole compound, the MYUA series (The Chemical Daily, February 1, 2016) manufactured by Miyoshi Oil & Fat Co., Ltd. may be used.

The content of the ultraviolet absorber is preferably 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass, based on the total solid content of the composition.

(Polymerization inhibitor)

The composition according to the present disclosure may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-tert-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, primary cerium salt, etc.). Of these, p-methoxyphenol is preferable. The polymerization inhibitor may also function as an antioxidant. The content of the polymerization inhibitor is preferably 0.01% by mass to 5% by mass with respect to the total solid content of the composition.

(Other ingredients)

The compositions according to the present disclosure are optionally sensitizers, crosslinkers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (eg, conductive particles, fillers, defoamers). It may contain a foaming agent, a flame retardant, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, a surface tension adjusting agent, a chain transfer agent, etc.). By appropriately containing these components, it is possible to adjust the properties such as the stability and physical characteristics of the optical filter such as the target infrared cut filter. These components are described in, for example, paragraphs 0183 and after of JP2012-3225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraphs 0101 to JP2008-250074. Descriptions such as 0104 and 0107 to 0109 can be taken into account, the contents of which are incorporated herein by reference.

As the antioxidant, for example, a phenol compound, a phosphorus-based compound (for example, the compound described in paragraph 0042 of JP-A-2011-90147), a thioether compound and the like can be used. Commercially available products include, for example, the ADEKA stub series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-" manufactured by ADEKA Corporation. 330, etc.). The content of the antioxidant is preferably 0.01% by mass to 20% by mass, more preferably 0.3% by mass to 15% by mass, based on the total solid content of the composition. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

(Preparation of composition)

The composition according to the present disclosure can be prepared by mixing each of the above-mentioned components. Further, it is preferable to filter with a filter for the purpose of removing foreign substances and reducing defects. The filter can be used without particular limitation as long as it has been conventionally used for filtration purposes and the like. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultrahigh molecular weight). ) Etc.) and the like. Among these materials, polypropylene (including high-density polypropylene) or nylon is preferable.

The pore size of the filter is preferably 0.01 μm to 7.0 μm, more preferably 0.01 μm to 3.0 μm, and even more preferably 0.05 μm to 0.5 μm. Within this range, it is possible to reliably remove fine foreign substances that hinder the preparation of uniform and smooth compositions in the subsequent step. Further, it is also preferable to use a fibrous filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Specifically, SBP type series (SBP008, etc.) and TPR type series (TPR002) manufactured by Roki Techno Co., Ltd. , TPR005, etc.), SHPX type series (SHPX003, etc.) filter cartridges can be used.

When using filters, different filters may be combined. At that time, the filtration with the first filter may be performed only once or twice or more.

Further, first filters having different pore diameters within the above-mentioned range may be combined. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Paul Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Entegris Japan Co., Ltd., KITZ Micro Filter Co., Ltd., and the like. ..

(Use of composition)

Since the composition according to the present disclosure can be liquid, for example, a film can be easily produced by applying the composition according to the present disclosure to a substrate or the like and drying it.

When a film is formed by coating, the viscosity of the composition according to the present disclosure is preferably 1 mPa · s to 100 mPa · s from the viewpoint of coatability. The lower limit is more preferably 2 mPa · s or more, and further preferably 3 mPa · s or more. The upper limit is more preferably 50 mPa · s or less, further preferably 30 mPa · s or less, and particularly preferably 15 mPa · s or less.

The total solid content of the composition according to the present disclosure varies depending on the coating method, but is preferably 1% by mass to 50% by mass, for example. The lower limit is more preferably 10% by mass or more. The upper limit is more preferably 30% by mass or less.

The use of the composition according to the present disclosure is not particularly limited. For example, it can be preferably used for forming an infrared cut filter or the like. For example, it is preferably used as an infrared cut filter on the light receiving side of the solid-state image sensor (for example, for an infrared cut filter for a wafer level lens), an infrared cut filter on the back surface side (opposite to the light receiving side) of the solid-state image sensor, and the like. can. In particular, it can be preferably used as an infrared cut filter on the light receiving side of the solid-state image sensor. Further, by further adding a colorant that blocks visible light to the composition according to the present disclosure, an infrared transmission filter capable of transmitting infrared rays having a specific wavelength or higher can be formed. For example, it is also possible to form an infrared transmission filter capable of transmitting infrared rays having a wavelength of 900 nm or more by blocking light from a wavelength of 400 nm to 900 nm.

In addition, the composition according to the present disclosure is preferably stored in a storage container.

As a storage container, a multi-layer bottle in which the inner wall of the container is composed of 6 types and 6 layers of resin or a bottle in which 6 types of resin is composed of 7 layers may be used for the purpose of preventing impurities from being mixed into raw materials and compositions. preferable. Examples of these containers include the containers described in Japanese Patent Application Laid-Open No. 2015-123351.

<Membrane>

The film according to the present disclosure is a film made of the composition according to the present disclosure or obtained by curing the composition. If the composition contains a solvent, it may be dried. The film according to the present disclosure can be preferably used as an infrared cut filter. It can also be used as a heat ray shielding filter or an infrared ray transmitting filter. The film according to the present disclosure may be used by being laminated on a support, or may be peeled off from the support and used. The film according to the present disclosure may have a pattern or may be a film having no pattern (flat film).

In the "drying" in the present disclosure, it is sufficient to remove at least a part of the solvent, it is not necessary to completely remove the solvent, and the amount of the solvent removed can be set as desired.

Further, the above-mentioned curing may be performed as long as the hardness of the film is improved, but curing by polymerization is preferable.

The thickness of the film according to the present disclosure can be appropriately adjusted according to the intended purpose. The thickness of the film is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

The film according to the present disclosure preferably has a maximum absorption wavelength in the wavelength range of 650 nm to 1,500 nm, more preferably has a maximum absorption wavelength in the wavelength range of 680 nm to 1,300 nm, and has a wavelength of 700 nm to 1,100 nm. It is more preferable to have a maximum absorption wavelength in the range of.

When the film according to the present disclosure is used as an infrared cut filter, the film according to the present disclosure preferably satisfies at least one of the following (1) to (4), and the above (1) to (4). It is more preferable that all the conditions are satisfied.

(1) The transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 80% or more, further preferably 85% or more, and particularly preferably 90% or more.

(2) The transmittance at a wavelength of 500 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.

(3) The transmittance at a wavelength of 600 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.

(4) The transmittance at a wavelength of 650 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.

The film according to the present disclosure can also be used in combination with a color filter containing a chromatic colorant. The color filter can be produced by using a coloring composition containing a chromatic colorant. Examples of the chromatic colorant include the chromatic colorant described in the section of the composition according to the present disclosure. The coloring composition can further contain a resin, a polymerizable compound, a polymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber and the like. For these details, the above-mentioned materials can be mentioned, and these can be used.

When the film according to the present disclosure and the color filter are used in combination, it is preferable that the color filter is arranged on the optical path of the film according to the present disclosure. For example, the film and the color filter according to the present disclosure can be laminated and used as a laminated body. In the laminated body, the film and the color filter according to the present disclosure may or may not be adjacent to each other in the thickness direction. When the film according to the present disclosure and the color filter are not adjacent to each other in the thickness direction, the film according to the present disclosure may be formed on a support different from the support on which the color filter is formed. Other members (for example, a microlens, a flattening layer, etc.) constituting the solid-state image sensor may be interposed between the film and the color filter according to the disclosure.

In the present disclosure, the infrared cut filter means a filter that transmits light having a wavelength in the visible region (visible light) and blocks at least a part of light having a wavelength in the near infrared region (infrared light). The infrared cut filter may transmit all the light having a wavelength in the visible region, and among the light having a wavelength in the visible region, the light having a specific wavelength region is passed through and the light having a specific wavelength region is blocked. It may be a thing. Further, in the present disclosure, the color filter means a filter that passes light in a specific wavelength region and blocks light in a specific wavelength region among light having a wavelength in the visible region. Further, in the present disclosure, the infrared transmission filter means a filter that blocks visible light and transmits at least a part of infrared rays.

The film according to the present disclosure can be used for solid-state imaging devices such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor), and various devices such as infrared sensors and image display devices.

<Membrane manufacturing method>

Next, a method for producing a film according to the present disclosure will be described. The film according to the present disclosure can be produced through a step of applying the composition according to the present disclosure.

In the method for producing a film according to the present disclosure, it is preferable that the composition is applied on a support. Examples of the support include a substrate made of a material such as silicon, non-alkali glass, soda glass, Pyrex (registered trademark) glass, and quartz glass. An organic film, an inorganic film, or the like may be formed on these substrates. Examples of the material of the organic film include the above-mentioned resin. Further, as the support, a substrate made of the above-mentioned resin can also be used. Further, the support may be formed with a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like. Further, the support may be formed with a black matrix that isolates each pixel. Further, if necessary, the support may be provided with an undercoat layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the substrate. When a glass substrate is used as the support, it is preferable to form an inorganic film on the glass substrate or to dealkalinate the glass substrate before use. According to this aspect, it is easy to manufacture a film in which the generation of foreign substances is further suppressed.

As a method for applying the composition, a known method can be used. For example, a drop method (drop cast); a slit coating method; a spray method; a roll coating method; a rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395). Methods described in the publication); Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Various printing methods; transfer method using a mold or the like; nanoimprint method and the like can be mentioned. The method of application to inkjet is not particularly limited, and for example, the method shown in "Expandable / usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). (Page 133), and the methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned.

The composition layer formed by applying the composition may be dried (prebaked). Prebaking may not be required if the pattern is formed by a low temperature process. 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 is, for example, preferably 50 ° C. or higher, and more preferably 80 ° C. or higher. By performing the prebaking temperature at 150 ° C. or lower, for example, when the photoelectric conversion film of the image sensor is made of an organic material, these characteristics can be maintained more effectively.

The prebaking time is preferably 10 seconds to 3,000 seconds, more preferably 40 seconds to 2,500 seconds, and even more preferably 80 seconds to 220 seconds. Drying can be performed on a hot plate, an oven, or the like.

The film manufacturing method according to the present disclosure 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. When the film according to the present disclosure is used as a flat film, it is not necessary to perform the step of forming the pattern. Hereinafter, the process of forming the pattern will be described in detail.

-When forming a pattern by photolithography-

The pattern forming method in the photolithography method includes a step of exposing the composition layer formed by applying the composition according to the present disclosure in a pattern (exposure step) and developing and removing the composition layer of the unexposed portion. It is preferable to include a step of forming a pattern (development step). If necessary, a step of baking the developed pattern (post-baking step) may be provided. Hereinafter, each step will be described.

<< Exposure process >>

In the exposure step, the composition layer is exposed in a pattern. For example, the composition layer can be pattern-exposed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure device such as a stepper. As a result, the exposed portion can be cured. As the radiation (light) that can be used for exposure, ultraviolet rays such as g-ray and i-line are preferable, and i-ray is more preferable. Irradiation dose (exposure dose), for example, preferably ^{0.03J / cm 2 ~2.5J / cm 2} , more preferably ^{0.05J / cm 2 ~1.0J / cm 2} , 0.08J / cm 2 ~ 0.5 J / cm ² is particularly preferable. The oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially anoxic). ), Or in a high oxygen atmosphere where the oxygen concentration exceeds 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume). The exposure illuminance can be set as appropriate, preferably 1,000 W / m ^{2 to} 100,000 W / m ² (for example, 5,000 W / m ² , 15,000 W / m 2, 35,000 ^{W / m 2).} It can be selected from the range of m ^2). Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10,000 W / m ² at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20,000W / m ^2.

<< Development process >>

Next, the composition layer in the unexposed portion of the composition layer after exposure is developed and removed to form a pattern. The development and removal of the composition layer in the unexposed portion can be performed using a developing solution. As a result, the composition layer of the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion remains on the support. As the developing solution, an alkaline developing solution that does not damage the underlying solid-state image sensor or circuit is desirable. The temperature of the developing solution is preferably, for example, 20 ° C to 30 ° C. The development time is preferably 20 seconds to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.

Examples of the alkaline agent used in the developing solution include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. Organic alkalinity such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrol, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene. Examples thereof include compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. As the developing solution, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 1% by mass. Moreover, you may use a surfactant as a developer. Examples of the surfactant include the surfactant described in the above-mentioned composition, and a nonionic surfactant is preferable. The developer may be once produced as a concentrated solution and diluted to a concentration required for use from the viewpoint of convenience of transfer and storage. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 by 100 times. When a developer composed of such an alkaline aqueous solution is used, it is preferable to wash (rinse) it with pure water after development.

It is also possible to perform heat treatment (post-baking) after development and drying. Post-baking is a post-development heat treatment to complete the curing of the film. When post-baking is performed, the post-baking temperature is preferably, for example, 100 ° C. to 240 ° C. From the viewpoint of film curing, 200 ° C. to 230 ° C. is more preferable. Further, when an organic electroluminescence (organic EL) element is used as the light emitting light source, or when the photoelectric conversion film of the image sensor is made of an organic material, the postbake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower. Preferably, 100 ° C. or lower is more preferable, and 90 ° C. or lower is particularly preferable. The lower limit can be, for example, 50 ° C. or higher. Post-baking should be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the above conditions are met. Can be done. Further, when the pattern is formed by the low temperature process, post-baking may not be performed, and a step of re-exposure (post-exposure step) may be added.

-When forming a pattern by dry etching method-

In the pattern formation by the dry etching method, the composition layer formed by applying the composition on a support or the like is cured to form a cured product layer, and then a photoresist layer patterned on the cured product layer is formed. Then, using the patterned photoresist layer as a mask, the cured product layer can be dry-etched with an etching gas. In forming the photoresist layer, it is preferable to further perform a prebaking treatment. In particular, as the photoresist forming process, it is desirable to carry out a heat treatment after exposure and a heat treatment (post-baking treatment) after development. Regarding the pattern formation by the dry etching method, the description of paragraphs 0010 to 0067 of JP2013-64993A can be referred to, and this content is incorporated in the present specification.

<Optical filter and laminate>

The optical filter according to the present disclosure has a film according to the present disclosure.

The optical filter according to the present disclosure can be preferably used as at least one optical filter selected from the group consisting of an infrared cut filter and an infrared transmission filter, and can be more preferably used as an infrared cut filter.

A preferred embodiment of the optical filter according to the present disclosure is also an embodiment having a film according to the present disclosure and pixels selected from the group consisting of red, green, blue, magenta, yellow, cyan, black and colorless.

Further, the laminate according to the present disclosure is a laminate having a film according to the present disclosure and a color filter containing a chromatic colorant.

The infrared cut filter according to the present disclosure has a film according to the present disclosure.

The infrared cut filter according to the present disclosure may be a filter that cuts only infrared rays having a wavelength of a part of the infrared region, or a filter that cuts the entire infrared region. Examples of the filter that cuts only infrared rays having a wavelength of a part of the infrared region include a near-infrared ray cut filter. Examples of near-infrared rays include infrared rays having a wavelength of 750 nm to 2,500 nm.

Further, the infrared cut filter according to the present disclosure is preferably a filter that cuts infrared rays in the wavelength range of 750 nm to 1,000 nm, and more preferably a filter that cuts infrared rays in the wavelength range of 750 nm to 1,200 nm. It is preferable that the filter cuts infrared rays having a wavelength of 750 nm to 1,500 nm.

In addition to the above film, the infrared cut filter according to the present disclosure may further have a copper-containing layer, a dielectric multilayer film, an ultraviolet absorbing layer, and the like. Since the infrared cut filter according to the present disclosure further has at least a copper-containing layer or a dielectric multilayer film, it is easy to obtain an infrared cut filter having a wide viewing angle and excellent infrared shielding property. Further, the infrared cut filter according to the present disclosure can be made into an infrared cut filter having excellent ultraviolet shielding property by further having an ultraviolet absorbing layer. As the ultraviolet absorbing layer, for example, the absorbing layers described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/09960 can be referred to, and the contents thereof are incorporated in the present specification. As the dielectric multilayer film, the description in paragraphs 025 to 0259 of JP2014-413118A can be referred to, and the contents thereof are incorporated in the present specification. As the copper-containing layer, a glass base material made of copper-containing glass (copper-containing glass base material) or a layer containing a copper complex (copper complex-containing layer) can also be used. Examples of the copper-containing glass base material include copper-containing phosphate glass and copper-containing fluoride glass. Examples of commercially available copper-containing glass products include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (manufactured by Schott AG), CD5000 (manufactured by HOYA Corporation), and the like.

The infrared cut filter according to the present disclosure can be used for solid-state imaging devices such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor), and various devices such as infrared sensors and image display devices.

The infrared cut filter according to the present disclosure is selected from at least a group consisting of film pixels (patterns) obtained by using the composition according to the present disclosure, red, green, blue, magenta, yellow, cyan, black and colorless. A mode having one type of pixel (pattern) is also a preferred mode.

The method for producing the optical filter according to the present disclosure is not particularly limited, but a step of applying the composition according to the present disclosure on a support to form a composition layer and exposing the composition layer in a pattern. A method including a step of developing and removing an unexposed portion to form a pattern, or a method of applying the composition according to the present disclosure on a support to form a composition layer, and curing the layer. A step of forming a photoresist layer on the layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of drying the layer using the resist pattern as an etching mask. It is preferable that the method includes a step of etching.

As each step in the method for manufacturing an optical filter according to the present disclosure, each step in the method for manufacturing a film according to the present disclosure can be referred to.

<Solid image sensor>

The solid-state image sensor according to the present disclosure has a film according to the present disclosure. The configuration of the solid-state image sensor is not particularly limited as long as it has a film according to the present disclosure and functions as a solid-state image sensor. For example, the following configuration can be mentioned.

On the support, a transfer electrode made of a plurality of photodiodes and polysilicon or the like constituting the light receiving area of the solid-state image sensor is provided, and light shielding made of tungsten or the like in which only the light receiving portion of the photodiode is opened on the photodiode and the transfer electrode. A configuration having a film, a device protective film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and a photodiode light-receiving portion on the light-shielding film, and a film according to the present disclosure on the device protective film. Is. Further, on the device protective film, a structure having a light collecting means (for example, a microlens or the like; the same applies hereinafter) under the film according to the present disclosure (the side closer to the support), or on the film according to the present disclosure. It may be configured to have a light collecting means or the like. Further, the color filter used in the solid-state image sensor may have a structure in which a film forming each pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. The partition wall in this case preferably has a lower refractive index than each pixel. Examples of the image pickup apparatus having such a structure include the apparatus described in JP-A-2012-227478 and JP-A-2014-179757.

<Image display device>

The image display device according to the present disclosure has a film according to the present disclosure. Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device. For the definition and details of the image display device, see, for example, "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., 1990)", "Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd., 1989)" ) ”And so on. The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994)". The liquid crystal display device applicable to the present disclosure is not particularly limited, and for example, it 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 have a white organic EL element. The white organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, Japanese Patent Application Laid-Open No. 2003-45676, supervised by Akiyoshi Mikami, "Frontiers of Organic EL Technology Development-High Brightness, High Accuracy, Long Life, Know-how Collection-", Technical Information Association, It is described on pages 326-328, 2008 and the like. The spectrum of white light emitted by the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm-485 nm), the green region (530 nm-580 nm), and the yellow region (580 nm-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm-700 nm) are more preferable.

<Infrared sensor>

The infrared sensor according to the present disclosure has a film according to the present disclosure. The configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. Hereinafter, an embodiment of the infrared sensor according to the present disclosure will be described with reference to the drawings.

In FIG. 1, reference numeral 110 is a solid-state image sensor. The image pickup region provided on the solid-state image sensor 110 includes an infrared cut filter 111 and an infrared transmission filter 114. Further, a color filter 112 is laminated on the infrared cut filter 111. A microlens 115 is arranged on the incident light hν side of the color filter 112 and the infrared transmission filter 114. The flattening layer 116 is formed so as to cover the microlens 115.

The infrared cut filter 111 can be formed by using the composition according to the present disclosure. The spectral characteristics of the infrared cut filter 111 are selected according to the emission wavelength of the infrared light emitting diode (infrared LED) used.

The color filter 112 is a color filter on which pixels that transmit and absorb light of a specific wavelength in the visible region are formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used. For example, the description in paragraphs 0214 to 0263 of JP2014-43556A can be referred to, and this content is incorporated in the present specification.

The characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used. For example, when the emission wavelength of the infrared LED is 850 nm, the infrared transmittance filter 114 preferably has a maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 nm to 650 nm of 30% or less. % Or less, more preferably 10% or less, and particularly preferably 0.1% or less. It is preferable that the transmittance satisfies the above conditions in the entire wavelength range of 400 nm to 650 nm.

The infrared transmittance filter 114 preferably has a minimum value of the light transmittance in the film thickness direction in the wavelength range of 800 nm or more (preferably 800 nm to 1,300 nm) of 70% or more, and preferably 80% or more. More preferably, it is more preferably 90% or more. The above-mentioned transmittance preferably satisfies the above condition in a part of the wavelength range of 800 nm or more, and more preferably the above-mentioned condition at a wavelength corresponding to the emission wavelength of the infrared LED.

The film thickness of the infrared transmission filter 114 is preferably 100 μm or less, more preferably 15 μm or less, further preferably 5 μm or less, and particularly preferably 1 μm or less. The lower limit is preferably 0.1 μm. When the film thickness is in the above range, the film can be a film satisfying the above-mentioned spectral characteristics.

The method for measuring the spectral characteristics, film thickness, etc. of the infrared transmission filter 114 is shown below.

The film thickness is measured by using a stylus type surface shape measuring device (DEKTAK150 manufactured by ULVAC) on the dried substrate having the film.

The spectral characteristics of the film are values obtained by measuring the transmittance in the wavelength range of 300 nm to 1,300 nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

Further, for example, when the emission wavelength of the infrared LED is 940 nm, the infrared transmittance filter 114 has a maximum value of the light transmittance in the film thickness direction in the wavelength range of 450 nm to 650 nm of 20% or less, and the film. The transmittance of light having a wavelength of 835 nm in the thickness direction of the film is 20% or less, and the minimum value of the transmittance of light in the thickness direction of the film in the wavelength range of 1,000 nm to 1,300 nm is 70% or more. Is preferable.

In the infrared sensor shown in FIG. 1, an infrared cut filter (another infrared cut filter) different from the infrared cut filter 111 may be further arranged on the flattening layer 116. Examples of other infrared cut filters include those having a copper-containing layer or at least a dielectric multilayer film. These details include those mentioned above. Further, as another infrared cut filter, a dual bandpass filter may be used.

Further, the absorption wavelengths of the infrared transmission filter and the infrared cut filter used in the present disclosure are appropriately combined and used according to the light source used and the like.

(The camera module)

The camera module according to the present disclosure includes a solid-state image sensor and an infrared cut filter according to the present disclosure.

Further, it is preferable that the camera module according to the present disclosure further includes a lens and a circuit for processing an image pickup obtained from the solid-state image sensor.

The solid-state image sensor used in the camera module according to the present disclosure may be the solid-state image sensor according to the present disclosure or a known solid-state image sensor.

Further, as the lens used in the camera module according to the present disclosure and the circuit for processing the image pickup obtained from the solid-state image sensor, known ones can be used.

As an example of the camera module, the camera modules described in JP-A-2016-6476 or JP-A-2014-197190 can be referred to, and the contents thereof are incorporated in the present specification.

(Compound)

The compound according to the present disclosure is a compound having a structure represented by the above formula (1), and is preferably a compound represented by the following formula (P1) from the viewpoint of light resistance and heat resistance.

The compound according to the present disclosure can be suitably used as an infrared absorbing dye.

Wherein ^(P1), the X P1 ^{to X P6} are each independently a single _{bond, -O -, - S -,} - CH 2 -, - N =, - CH = CH- ^{or, -NR P11} - represents, R ^P1 and ^{R P2} are each independently an alkyl group, an aryl group, a group represented by a heteroaryl group or the following formula ^{(P2), R} P3 ~R ^P6 are each independently a cyano group, an acyl group, an alkoxy represents a carbonyl group, an alkyl group, an arylsulfinyl group or a heteroaryl ^group, R ^{P7 to R P10} each independently represent a hydrogen atom or a ^{substituent, R P11} represents a hydrogen atom, an alkyl group or an aryl group, p1 ~ P4 independently represent an integer from 0 to 4.

In the formula (P2), ^XP11 represents a divalent fused polycyclic aromatic ring group or a divalent heteroaromatic ring group in which two or more aromatic rings are condensed, and L ^{P11 represents an m-phenylene group, a p-phenylene group, or a divalent heteroaromatic ring group.} It represents a single bond or a divalent linking group, Y ^P11 represents a substituent, and * represents a linking site to the pyrolopyrrole ring in the formula (P1).

The compound having the structure represented by the formula (1) in the compound according to the present disclosure and the compound represented by the formula (P1) have the structure represented by the above-mentioned formula (1) in the composition according to the present disclosure. It has the same meaning as the compound having the above and the compound represented by the formula (P1), and the preferred embodiments are also the same.

The method for producing the compound according to the present disclosure is not particularly limited, and the compound can be appropriately produced with reference to a known production method.

For example, a method of producing by reacting a compound having a dye structure with a boron compound can be preferably mentioned.

(Dispersion composition)

The dispersion composition according to the present disclosure includes a compound having a structure represented by the following formula (1) and at least one compound selected from the group consisting of a solvent, a binder and a curable compound.

In formula (1), X independently represents a single bond or a linking group, and Z ¹ and Z ² independently represent a group forming an aliphatic ring or an aromatic ring, respectively, from R ⁹ and R ¹⁰ . ^{R 9} or R ¹⁰ in which a group having a dye structure is bonded or coordinated in at least one selected from the group and the group having the dye structure is not bonded or coordinated represents a substituent. Further, R ⁹ and R ¹⁰ may be bonded to each other to form a ring together with a boron atom.

The compound, solvent, binder and curable compound having the structure represented by the above formula (1) in the dispersion composition according to the present disclosure have the structure represented by the above formula (1) in the composition according to the present disclosure. It has the same meaning as the compound having the above, the solvent, the binder and the curable compound, and the preferred embodiments are also the same.

Further, as for the components other than those described above, the components described above can be preferably contained in the composition according to the present disclosure.

When the compound having the structure represented by the above formula (1) is a pigment, the dispersion composition according to the present disclosure preferably contains a dispersant from the viewpoint of dispersibility and dispersion stability.

When the compound having the structure represented by the above formula (1) is a pigment, the dispersion composition according to the present disclosure preferably contains a dye derivative from the viewpoint of dispersibility and dispersion stability. More preferably, it contains a pigment derivative.

The dispersant and dye derivative in the dispersion composition according to the present disclosure are synonymous with the above-mentioned dispersant and dye derivative in the composition according to the present disclosure, and the preferred embodiments are also the same.

The present disclosure will be described in more detail with reference to Examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present disclosure. Therefore, the scope of the present disclosure is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

(Synthesis Example 1)

PPB-A-2 was synthesized by the method shown in the scheme below. Details are shown below.

<Synthesis of Intermediate-2>

10.52 g of 5,5-dimethyl-5H-dibenzo [b, d] siror was added to the flask, and the inside of the flask was replaced with nitrogen. To this, 25 g of boron tribromide was added, and the mixture was stirred at 50 ° C. for 24 hours. The reaction mixture was returned to room temperature, cooled to −30 ° C., and then 100 mL of ice water and 150 mL of ethyl acetate (EtOAc) prepared separately were added dropwise while maintaining an internal temperature of −10 ° C. or lower. After stirring this solution for 20 minutes, a liquid separation operation was performed, and the obtained organic layer was washed with 100 mL of saline solution. The organic layer was dried over magnesium sulfate, filtered to remove salts, and 2.9 g of ethanolamine was added to the obtained filtrate for concentration. After adding 100 mL of hexane to the concentrated solution and stirring, hexane was removed by decanting, and then 100 mL of hexane was added again and stirred, and then hexane was removed by decanting. 30 mL of water / methanol (1: 1 solution) was added to the obtained residue, and the mixture was stirred for 30 minutes. By filtering this solution, 4.1 g of Intermediate-2 was obtained.

<Synthesis of Intermediate-3>

It was synthesized with reference to the description of WO2018 / 020861 and Japanese Patent No. 6329626.

<Synthesis of PPB-A-2>

1.04 g of Intermediate-2 and 8 mL of o-dichlorobenzene were added to the flask, and the inside of the flask was replaced with nitrogen. 1.48 g of titanium tetrachloride was added dropwise thereto, and the mixture was stirred at 40 ° C. for 30 minutes. 0.5 g of Intermediate-3 was added to this solution, and the solution was washed with 2 mL of o-dichlorobenzene. The reaction mixture was stirred at 40 ° C. for 20 minutes, then at 85 ° C. for 1 hour, and further at 125 ° C. for 2.5 hours. The reaction was cooled to room temperature, 20 mL of hexane was added, and the mixture was stirred for 30 minutes. This solution was filtered to obtain 1.0 g of PPB-A-2.

^{1 1} H-NMR (dTHF): δ = 6.03 (d, 4H), 6.13 (d, 4H), 7.00 to 7.60 (m, 16H), 8.13 (s, 2H), 8.24 (s, 2H), 8.63 (brs, 2H), 9.14 (s, 2H).

The λmax of PPB-A-2 was 898 nm in tetrahydrofuran (THF).

(Synthesis Example 2)

PPB-C-4 was synthesized by the method shown in the scheme below. Details are shown below.

<Synthesis of Intermediate-5>

Under a nitrogen atmosphere, 8.3 g of trimethoxyborane, 400 mL of acetonitrile and 14.9 g of 2,2'-dihydroxybiphenyl were added to the flask, and the mixture was stirred at 60 ° C. for 1 hour. 4.9 g of ethanolamine was added to this solution, and the mixture was stirred for 2 hours. The solution was cooled to room temperature, filtered and washed with 100 mL of acetonitrile. The obtained filter medium was dried to obtain 16 g of Intermediate-5.

<Synthesis of Intermediate-6>

It was synthesized with reference to the description of WO2018 / 020861 and Japanese Patent No. 6329626.

<Synthesis of PPB-C-4>

3.2 g of Intermediate-5 and 25 g of dehydrated toluene were added to the flask, and the inside of the flask was replaced with nitrogen. 3.58 g of titanium tetrachloride was added dropwise to this solution, and the mixture was stirred at 30 ° C. for 30 minutes. 2.5 g of Intermediate-6 was added to this reaction solution, and the mixture was stirred under heating under reflux for 2.5 hours. After cooling this reaction solution to room temperature, 100 mL of water and 100 mL of chloroform were added to carry out a liquid separation operation, and the obtained organic layer was washed with 100 mL of saturated layered water. The organic layer was dried over magnesium sulfate, filtered to remove salts, and the obtained filtrate was concentrated. The concentrate was purified by silica gel column chromatography (solvent: chloroform) to obtain 1.05 g of PPB-C-4.

^{1 1} H-NMR (deuterated chloroform): δ = 7.32 to 7.46 (m, 6H), 7.03 to 7.18 (m, 6H), 6.80 to 7.02 (m, 12H), 6.59 to 6.71 (m, 4H), 6.31 to 6.47 (m, 4H), 3.34 to 3.89 (m, 4H), 0.60 to 1.89 (m, 78H) ).

The λmax of PPB-C-4 was 696 nm in chloroform.

The compounds used in Examples and Comparative Examples other than those described above are shown below.

In addition, * in the following structure represents a joint portion with −O−.

<Dyes and dye derivatives>

SQ-D-1 is a compound described in JP-A-2017-165857.

<Dispersed resin>

D-1: Resin having the following structure (acid value = 100 mgKOH / g, weight average molecular weight = 37,600, the numerical value added to the main chain represents the molar ratio of the repeating unit, and the numerical value added to the side chain is the repeating unit. Represents a number.)

D-2: Resin having the following structure (acid value = 32.3 mgKOH / g, amine value = 45.0 mgKOH / g, weight average molecular weight = 22,900, the numerical values added to the main chain represent the molar ratio of the repeating unit. The numerical value added to the side chain represents the number of repeating units.)

<Resin>

E-1: Acrybase FF-426 (manufactured by Fujikura Kasei Co., Ltd., alkali-soluble resin)

E-2: ARTON F4520 (Cyclic polyolefin resin manufactured by JSR Corporation)

E-3: Resin having the following structure (Mw = 40,000, acid value 100 mgKOH / g, the numerical value added to the main chain represents the mass ratio of the repeating unit. Alkaline-soluble resin.)

<Photopolymerization initiator>

<Polymerizable compound>

M-1: Aronix M-305 (manufactured by Toagosei Co., Ltd., a mixture of the following two compounds. The content of 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)

<Solvent>

PGMEA: Propylene glycol monomethyl ether acetate

PGME: Propylene glycol monomethyl ether

CYP: Cyclopentanone

<Preparation of pigment dispersion liquid>

10 parts by mass of the pigment shown in Table 3 or 5, 3 parts by mass of the derivative shown in Table 3 or 5, 7.8 parts by mass of the dispersant shown in Table 3 or 5, propylene glycol methyl ether acetate ( PGMEA) 150 parts by mass and 230 parts by mass of zirconia beads having a diameter of 0.3 mm were mixed and dispersed for 5 hours using a paint shaker, and the beads were separated by filtration to produce a dispersion.

<Evaluation of dispersibility>

-Viscosity-

The viscosity of the dispersion at 25 ° C. was measured using an E-type viscometer under the condition of a rotation speed of 1,000 rpm, and evaluated according to the following criteria.

A: 1 mPa ・ s or more and 15 mPa ・ s or less

B: Over 15 mPa · s and below 30 mPa · s

C: Exceeds 30 mPa · s

-Particle size-

The average particle size of the pigment in the dispersion was measured on a volume basis using MICROTRACUPA 150 manufactured by Nikkiso Co., Ltd.

A: The average particle size of the pigment is 1 nm or more and 50 nm or less.

B: The average particle size of the pigment is more than 50 nm and less than 100 nm.

C: The average particle size of the pigment exceeds 100 nm

(Examples 1 to 39 and Comparative Examples 1 to 3)

<Evaluation method of pigment type examples and comparative examples>

<< Preparation of curable composition 1 >>

The following components were mixed to prepare a curable composition.

-Composition of curable composition-

-Dispersion obtained above: 55 parts by mass

-Resin: 7.0 parts by mass

-Polymerizable compound: 4.5 parts by mass

-Photopolymerization initiator: 0.8 parts by mass

-Polymerization inhibitor (p-methoxyphenol): 0.001 part by mass

-Surfactant (the following mixture (Mw = 14,000). In the following formula,% indicating the ratio of the repeating unit is mass%.): 0.03 parts by mass.

-Ultraviolet absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.): 1.3 parts by mass

-Solvent: 31 parts by mass

<< Preparation of cured film 1 >>

The curable composition was applied onto a glass substrate by a spin coating method, and then heated at 100 ° C. for 2 minutes using a hot plate to obtain a composition layer. The obtained composition layer was exposed to an exposure amount of ^{500 mJ / cm 2} using an i-line stepper. Next, the composition layer after exposure was cured at 220 ° C. for 5 minutes using a hot plate to obtain a cured film having a thickness of 0.7 μm.

<< Evaluation of heat resistance >>

The resulting membrane was heated at 260 ° C. for 300 seconds using a hot plate. The transmittance of the film before and after heating with respect to light having a wavelength of 400 nm to 1200 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). In the wavelength range of 400 nm to 1200 nm, the change in transmittance at the wavelength at which the change in transmittance before and after heating was the largest was calculated from the following formula, and the change in transmittance was evaluated according to the following criteria.

Change in transmittance = | (Transmittance after heating-Transmittance before heating) |

A: Transmittance change is less than 3%

B: Transmittance change is 3% or more and less than 5%

C: Transmittance change is 5% or more

Further, regarding the absorbance at the maximum absorption wavelength before and after heating, the residual rate was calculated from the following formula, and the residual rate was evaluated according to the following criteria.

Residual rate (%) = {(absorbance after heating) ÷ (absorbance before heating)} x 100

A: Survival rate exceeds 95% and 100% or less

B: Survival rate exceeds 80% and 95% or less

C: Residual rate is 80% or less

<< Evaluation of light resistance >>

The obtained film was set in a fading tester equipped with a super xenon lamp (100,000 lux) and irradiated with light of 100,000 lux for 50 hours under the condition that no ultraviolet cut filter was used. Next, the transmission spectrum of the film after light irradiation was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). In the wavelength range of 400 nm to 1200 nm, the change in transmittance at the wavelength where the change in transmittance before and after light irradiation was the largest was calculated from the following formula, and the heat resistance was evaluated according to the following criteria.

Change in transmittance = | (Transmittance after light irradiation-Transmittance before light irradiation) |

A: Transmittance change is less than 3%

B: Transmittance change is 3% or more and less than 5%

C: Transmittance change is 5% or more

In addition, the absorbance at the maximum absorption wavelength before and after light irradiation was calculated from the following formula and evaluated according to the following criteria.

Residual rate (%) = {(absorbance after light irradiation) ÷ (absorbance before light irradiation)} x 100

A: Survival rate exceeds 95% and 100% or less

B: Survival rate exceeds 80% and 95% or less

C: Residual rate is 80% or less

<Evaluation method of dye type examples and comparative examples>

<< Preparation of dye solution >>

A dye solution was produced by mixing 2.34 parts by mass of the dye and 72.2 parts by mass of the solvent shown in Table 3 or Table 5 below.

<< Preparation of curable composition 2 >>

The following components were mixed to prepare a curable composition.

-Composition of curable composition-

-Dye solution: 74.5 parts by mass

-Resin (30% cyclopentanone solution): 20.1 parts by mass

-Polymerizable compound: 1.3 parts by mass

-Photopolymerization initiator: 1.4 parts by mass

-Polymerization inhibitor (p-methoxyphenol): 0.001 part by mass

-Megafuck RS-72-K (fluorine-based surfactant, manufactured by DIC Corporation): 2.6 parts by mass

<< Preparation of curable composition 3 >>

The following components were mixed to prepare a curable composition.

-Composition of curable composition-

-Dye solution: 74.5 parts by mass

-Epoxy resin (30% cyclopentanone solution): 20.1 parts by mass

-Epoxy curing agent: 0.05 parts by mass

The details of the epoxy resin and the epoxy curing agent used in Examples and Comparative Examples are shown below.

-Epoxy resin-

F-1: Random polymer with glycidyl methacrylate skeleton (manufactured by NOF CORPORATION, Marproof G-0150M, weight average molecular weight 10,000)

F-2: EPICLON HP-4700 (manufactured by DIC Corporation, naphthalene 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-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol)

-Epoxy hardener-

G-1: Trimellitic acid

G-2: pyromellitic anhydride

G-3: N, N-dimethyl-4-aminopyridine

G-4: Pentaerythritol tetrakis (3-mercaptopropionate)

<< Preparation of cured film 2 >>

Each curable composition prepared above is applied onto a glass substrate by a spin coating method, then heated (prebaked) at 80 ° C. for 10 minutes using a hot plate, and then heated at 150 ° C. for 3 hours to thicken. A 0.7 μm film was obtained.

<< Evaluation of heat resistance and light resistance >>

The heat resistance and light resistance were evaluated by the same method as described above.

The evaluation results are summarized in Tables 4 and 6.

From the results shown in Tables 4 and 6, it is clear that the compositions according to the present disclosure are superior in light resistance to the compositions of Comparative Examples. Further, it can be seen that the composition according to the present disclosure is also excellent in heat resistance.

Further, in Example 1, the same result as in Example 1 was obtained even when the polymerization inhibitor was not added.

In Example 1, the same results as in Example 1 were obtained even when no surfactant was added.

In Example 1, the same result as in Example 1 was obtained even when 1/2 the mass of the dispersion liquid 1 was replaced with the dispersion liquid 3.

(Examples 101-139)

Using the compositions obtained in Examples 1 to 39, a 2 μm square pattern (infrared cut filter) was formed by the following method.

<In the case of the above composition preparation method 1 or 2>

The compositions obtained in Examples 1 to 22 or 27 to 38 were applied by a spin coating method so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at 1,000 mJ / cm ² through a mask with a 2 μm square dot pattern. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. Next, a 2 μm square pattern (infrared cut filter) was formed by heating at 200 ° C. for 5 minutes using a hot plate.

<In the case of the above composition preparation method 3>

The compositions obtained in Examples 23 to 26 or 39 were applied onto a silicon wafer by a spin coating method so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Then, using a hot plate, it was heated at 200 ° C. for 5 minutes. Next, a 2 μm square pattern (infrared cut filter) was formed by a dry etching method.

Next, the Red composition was applied onto the pattern of the infrared cut filter by a spin coating method so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at 1,000 mJ / cm ² through a mask with a 2 μm square dot pattern. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. The Red composition was then patterned on the pattern of the infrared cut filter by heating at 200 ° C. for 5 minutes using a hot plate. Similarly, the Green composition and the Blue composition were sequentially patterned to form red, green and blue coloring patterns (Bayer patterns).

The Bayer pattern is a red element, two green elements, and one blue element, as disclosed in US Pat. No. 3,971,065. ) This is a pattern in which a 2 × 2 array of color filter elements having elements is repeated. In this embodiment, one red element, one green element, and one blue element are used. A Bayer pattern was formed by repeating a 2 × 2 array of an element and a filter element having one infrared transmission filter element.

Next, the composition for forming an infrared transmission filter (the following composition 100 or composition 101) was applied onto the patterned film by a spin coating method so that the film thickness after film formation was 2.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at 1,000 mJ / cm ² through a 2 μm square Bayer pattern mask. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. Next, by heating at 200 ° C. for 5 minutes using a hot plate, the infrared transmission filter was patterned in the missing portion of the Bayer pattern of the infrared cut filter in which the coloring pattern was not formed. This was incorporated into a solid-state image sensor according to a known method.

The obtained solid-state image sensor was irradiated with infrared rays by an infrared light emitting diode (infrared LED) in a low illuminance environment (0.001 lux), and an image was captured to evaluate the image performance. When any of the compositions obtained in Examples 1 to 32 was used, the image could be clearly recognized even in a low-light environment.

The Red composition, Green composition, Blue composition, and composition for forming an infrared transmission filter used in Examples 101 to 139 are as follows.

-Red composition-

The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a Red composition.

Red pigment dispersion: 51.7 parts by mass

Resin 4 (40% by mass PGMEA solution): 0.6 parts by mass

Polymerizable compound 4: 0.6 parts by mass

Photopolymerization Initiator 1: 0.3 parts by mass

Surfactant 1: 4.2 parts by mass

PGMEA: 42.6 parts by mass

-Green composition-

The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a Green composition.

Green pigment dispersion: 73.7 parts by mass

Resin 4 (40% by mass PGMEA solution): 0.3 parts by mass

Polymerizable compound 1: 1.2 parts by mass

Photopolymerization Initiator 1: 0.6 parts by mass

Surfactant 1: 4.2 parts by mass

Ultraviolet absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.): 0.5 parts by mass

PGMEA: 19.5 parts by mass

-Blue composition-

The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a Blue composition.

Blue pigment dispersion: 44.9 parts by mass

Resin 4 (40% by mass PGMEA solution): 2.1 parts by mass

Polymerizable compound 1: 1.5 parts by mass

Polymerizable compound 4: 0.7 parts by mass

Photopolymerization Initiator 1: 0.8 parts by mass

Surfactant 1: 4.2 parts by mass

PGMEA: 45.8 parts by mass

-Composition for forming an infrared transmission filter-

The components having the following composition were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a composition for forming an infrared transmission filter.

<Composition 100>

Pigment dispersion 1-1: 46.5 parts by mass

Pigment dispersion 1-2: 37.1 parts by mass

Polymerizable compound 5: 1.8 parts by mass

Resin 4: 1.1 parts by mass

Photopolymerization initiator 2: 0.9 parts by mass

Surfactant 1: 4.2 parts by mass

Polymerization inhibitor (p-methoxyphenol): 0.001 part by mass

Silane coupling agent: 0.6 parts by mass

PGMEA: 7.8 parts by mass

<Composition 101>

Pigment dispersion 2-1: 1,000 parts by mass

Polymerizable compound (dipentaerythritol hexaacrylate): 50 parts by mass

Resin: 17 parts by mass

Photopolymerization Initiator (1- [4- (Phenylthio)] -1,2-octandion-2- (O-benzoyloxime)): 10 parts by mass

PGMEA: 179 parts by mass

Alkali-soluble polymer F-1: 17 parts by mass (solid content concentration 35 parts by mass)

<Synthesis example of alkali-soluble polymer F-1>

In a reaction vessel, 14 parts of benzyl methacrylate, 12 parts of N-phenylmaleimide, 15 parts of 2-hydroxyethyl methacrylate, 10 parts of styrene and 20 parts of methacrylic acid are dissolved in 200 parts of propylene glycol monomethyl ether acetate, and further 2,2'-. 3 parts of azoisobutyronitrile and 5 parts of α-methylstyrene dimer were added. After purging the inside of the reaction vessel with nitrogen, the mixture was heated at 80 ° C. for 5 hours with stirring and nitrogen bubbling to obtain a solution containing the alkali-soluble polymer F-1 (solid content concentration: 35% by mass). This polymer had a polystyrene-equivalent weight average molecular weight of 9,700, a number average molecular weight of 5,700, and a Mw / Mn of 1.70.

<Pigment dispersion liquid 2-1>

C. I. 60 copies of Pigment Black 32, C.I. I. 20 copies of Pigment Blue 15: 6, C.I. I. 20 parts of Pigment Yellow 139, 80 parts of Solsparse 76500 manufactured by Nippon Lubrizol Co., Ltd. (solid content concentration 50% by mass), 120 parts of solution containing alkali-soluble polymer F-1 (solid content concentration 35% by mass) , 700 parts of propylene glycol monomethyl ether acetate was mixed and dispersed for 8 hours using a paint shaker to obtain a colorant dispersion liquid 2-1.

The raw materials used for the Red composition, the Green composition, the Blue composition, and the composition for forming an infrared transmission filter are as follows.

・ Red pigment dispersion

C. I. Pigment Red 254 at 9.6 parts by mass, C.I. I. A mixed solution consisting of 4.3 parts by mass of Pigment Yellow 139, 6.8 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0.3 mm diameter). ) Was mixed and dispersed for 3 hours to prepare a pigment dispersion. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform a dispersion treatment at a flow rate of 500 g / min under a pressure of ^{2,000 kg / cm 3.} This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion liquid.

・ Green pigment dispersion

C. I. Pigment Green 36 at 6.4 parts by mass, C.I. I. A mixed solution consisting of 5.3 parts by mass of Pigment Yellow 150, 5.2 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by mass of PGMEA is used in a bead mill (zirconia beads 0.3 mm diameter). To prepare a pigment dispersion liquid by mixing and dispersing for 3 hours. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform a dispersion treatment at a flow rate of 500 g / min under a pressure of ^{2,000 kg / cm 3.} This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion liquid.

・ Blue pigment dispersion

C. I. Pigment Blue 15: 6 at 9.7 parts by mass, C.I. I. A mixed solution consisting of 2.4 parts by mass of Pigment Violet 23, 5.5 parts of dispersant (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts of PGMEA was prepared by a bead mill (zirconia beads 0.3 mm diameter). A pigment dispersion was prepared by time mixing and dispersion. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform a dispersion treatment at a flow rate of 500 g / min under a pressure of ^{2,000 kg / cm 3.} This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion liquid.

-Pigment dispersion liquid 1-1

The mixed solution having the following composition is mixed and dispersed in a bead mill (high pressure disperser with decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.)) for 3 hours using zirconia beads having a diameter of 0.3 mm. To prepare a pigment dispersion liquid 1-1.

-Mixed pigment consisting of red pigment (CI Pigment Red 254) and yellow pigment (CI Pigment Yellow 139): 11.8 parts by mass.

-Resin (Disperbyk-111, manufactured by BYK Chemie): 9.1 parts by mass

-PGMEA: 79.1 parts by mass

-Pigment dispersion liquid 1-2

The mixed solution having the following composition is mixed and dispersed in a bead mill (high pressure disperser with decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.)) for 3 hours using zirconia beads having a diameter of 0.3 mm. The pigment dispersion liquid 1-2 was prepared.

-Mixed pigment consisting of blue pigment (CI Pigment Blue 15: 6) and purple pigment (CI Pigment Violet 23): 12.6 parts by mass.

-Resin (Disperbyk-111, manufactured by BYK Chemie): 2.0 parts by mass

-Resin A: 3.3 parts by mass

-Cyclohexanone: 31.2 parts by mass

・ PGMEA: 50.9 parts by mass

Resin A: The following structure (Mw = 14,000, the ratio in each structural unit is a molar ratio)

-Polymerizable compound 1: KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

-Polymerizable compound 4: The following structure

Polymerizable compound 5: The following structure (a mixture of the left compound and the right compound having a molar ratio of 7: 3)

-Resin 4: The following structure (acid value: 70 mgKOH / g, Mw = 11,000, the ratio in each structural unit is a molar ratio)

-Photopolymerization initiator 1: IRGACURE-OXE01 (1- [4- (phenylthio)] -1,2-octanedione-2- (O-benzoyloxime), manufactured by BASF)

-Photopolymerization initiator 2: The following structure

Surfactant 1: 1 mass% PGMEA solution of the following mixture (Mw = 14,000). In the following formula, the unit of% (62% and 38%) indicating the ratio of the constituent units is mass%.

-Silane coupling agent: A compound having the following structure. In the following structural formula, Et represents an ethyl group.

(Example 201)

The following composition was mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare the pattern-forming composition of Example 201.

Composition for pattern formation of Example 1: 22.67 parts by mass

Pigment dispersion 2-1: 51.23 parts by mass

When the heat resistance, the pattern shape, and the development residue were evaluated in the same manner as in Example 1 using the pattern-forming composition of Example 201, the same effects as in Example 1 were obtained. Further, the cured film obtained by using the pattern-forming composition of Example 201 blocks light having a wavelength in the visible region and transmits at least a part of light having a wavelength in the near infrared region (near infrared ray). I was able to.

(Example 202)

The following composition was mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare the pattern-forming composition of Example 202.

Composition for pattern formation of Example 1: 36.99 parts by mass

Pigment dispersion 1-1: 46.5 parts by mass

Pigment dispersion 1-2: 37.1 parts by mass

When the heat resistance, the pattern shape, and the development residue were evaluated in the same manner as in Example 1 using the pattern-forming composition of Example 202, the same effects as in Example 1 were obtained. Further, the cured film obtained by using the pattern-forming composition of Example 202 shields light having a wavelength in the visible region and transmits at least a part of light having a wavelength in the near infrared region (near infrared ray). I was able to.

(Example 301)

Infrared shielding, heat resistance, pattern shape, as in Example 1, except that the compositions obtained in Examples 1 to 39 were used, a glass substrate was used as a substrate, and the composition was applied onto the glass substrate. And, even if the development residue is evaluated, the same effect as in Examples 1 to 39 can be obtained.

(Example 302)

Similar to Example 201 or Example 202, the heat resistance and pattern are the same as those of Example 201 or 202, except that the compositions obtained in Examples 201 and 202 are used, a glass substrate is used as a substrate, and the composition is applied onto the glass substrate. Even if the shape and the development residue are evaluated, the same effects as those of Examples 201 and 202 can be obtained.

110: Solid-state image sensor, 111: Infrared cut filter, 112: Color filter, 114: Infrared transmission filter, 115: Microlens, 116: Flattening layer

Claims (18)

A compound having a structure represented by the following formula (1) and

A composition comprising at least one compound selected from the group consisting of a binder and a curable compound.

In formula (1), X independently represents a single bond or a linking group, and Z ¹ and Z ² independently represent a group forming an aliphatic ring or an aromatic ring, respectively, from R ⁹ and R ¹⁰ . ^{R 9} or R ¹⁰ in which a group having a dye structure is bonded or coordinated in at least one selected from the group and the group having a dye structure is not bonded or coordinated represents a substituent. R ⁹ and R ¹⁰ may be bonded to each other to form a ring with a boron atom.

Formula X are each independently of (1) a single _{bond, -O -, - S -,} - CH 2 -, - N =, - CH = CH-, or, ^{-NR 11} - and ^{is, R 11} is The composition according to claim 1, which represents a hydrogen atom, an alkyl group or an aryl group.

The composition according to claim 1 or 2, wherein the compound having a structure represented by the formula (1) is a compound having a structure represented by the following formula (2).

In formula (2), X represents a single bond or a linking group, R ^{1 to} R ⁸ independently represent a hydrogen atom or a substituent, and in at least one selected from the group consisting of ^{R 9 and R 10. R 9} or R ^{10 in} which a group having a dye structure is bonded or coordinated and the group having the dye structure is not bonded or coordinated represents a substituent, and R ⁹ and R ¹⁰ are bonded to each other. The ring may be formed together with the boron atom.

Formula X is at (2) a single _{bond, -O -, - S -,} - CH 2 -, - CH = CH-, or, ^{-NR 11} - and ^{is, R 11} is a hydrogen atom, an alkyl group or The composition according to claim 3, which represents an aryl group.

The composition according to any one of claims 1 to 4, wherein the maximum absorption wavelength of the compound having the structure represented by the formula (1) is 650 nm to 1,500 nm.

The pigment structures in the group having the pigment structure are pyrolopyrrole pigment structure, pyromethene pigment structure, squarylium pigment structure, croconium pigment structure, indigo pigment structure, anthraquinone pigment structure, diimmonium pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, and polymethine. The composition according to any one of claims 1 to 5, which is at least one pigment structure selected from the group consisting of a pigment structure, a xanthene pigment structure, a quinacridone pigment structure, an azo pigment structure, and a quinoline pigment structure. thing.

The composition according to any one of claims 1 to 6, further comprising a photopolymerization initiator, which comprises the curable compound.

The composition according to any one of claims 1 to 7, wherein the binder contains a binder polymer.

A film containing the composition according to any one of claims 1 to 8 or obtained by curing the composition.

The optical filter having the film according to claim 9.

The optical filter according to claim 10, which is an infrared cut filter or an infrared transmission filter.

The solid-state imaging device having the film according to claim 9.

An infrared sensor having the film according to claim 9.

A step of applying the composition according to any one of claims 1 to 8 onto a support to form a composition layer,

The step of exposing the composition layer in a pattern and

A method for manufacturing an optical filter, comprising a step of developing and removing an unexposed portion after the step of exposing to form a pattern.

A step of applying the composition according to any one of claims 1 to 8 onto a support to form a composition layer,

A step of curing the composition layer to form a cured layer, and

The step of forming a photoresist layer on the cured layer and

A step of patterning the photoresist layer by exposing and developing to obtain a resist pattern.

A method for manufacturing an optical filter, comprising a step of dry etching the cured layer using the resist pattern as an etching mask.

A camera module having a solid-state image sensor and the optical filter according to claim 10 or 11.

A compound represented by the following formula (P1).

Wherein ^(P1), the X P1 ^{to X P6} are each independently a single _{bond, -O -, - S -,} - CH 2 -, - N =, - CH = CH- ^{or, -NR P11} - represents, R ^P1 and ^{R P2} are each independently an alkyl group, an aryl group, a group represented by a heteroaryl group or the following formula ^{(P2), R} P3 ~R ^P6 are each independently a cyano group, an acyl group, an alkoxy represents a carbonyl group, an alkyl group, an arylsulfinyl group or a heteroaryl ^group, R ^{P7 to R P10} each independently represent a hydrogen atom or a ^{substituent, R P11} represents a hydrogen atom, an alkyl group or an aryl group, p1 ~ P4 independently represent an integer from 0 to 4.

In the formula (P2), ^XP11 represents a divalent fused polycyclic aromatic ring group or a divalent heteroaromatic ring group in which two or more aromatic rings are condensed, and L ^{P11 represents an m-phenylene group, a p-phenylene group, or a divalent heteroaromatic ring group.} It represents a single bond or a divalent linking group, Y ^P11 represents a substituent, and * represents a linking site to the pyrolopyrrole ring in the formula (P1).

A compound having a structure represented by the following formula (1) and

A dispersion composition containing at least one compound selected from the group consisting of a solvent, a binder and a curable compound.

In formula (1), X independently represents a single bond or a linking group, and Z ¹ and Z ² independently represent a group forming an aliphatic ring or an aromatic ring, respectively, from R ⁹ and R ¹⁰ . ^{R 9} or R ¹⁰ in which a group having a dye structure is bonded or coordinated in at least one selected from the group and the group having a dye structure is not bonded or coordinated represents a substituent. R ⁹ and R ¹⁰ may be bonded to each other to form a ring with a boron atom.

Images