KR102627682B1 - Compositions, membranes, optical filters and methods for producing the same, solid-state imaging devices, infrared sensors, camera modules, and compounds - Google Patents

Abstract

A composition comprising a pigment having a structure represented by formula (1), a binder, and at least one compound selected from the group consisting of curable compounds, a pigment having a structure represented by formula (1-1), and the composition. Provides a membrane using a membrane, an optical filter and its manufacturing method, a solid-state imaging device, an infrared sensor, and a camera module. A represents a group represented by formula (1S) or formula _{( 1C} ), and at least two of R ₁ to R ₆ are bonded to each other to form a ring.

Description

Compositions, membranes, optical filters and methods for producing the same, solid-state imaging devices, infrared sensors, camera modules, and compounds

The present disclosure relates to compositions, membranes, optical filters and methods for manufacturing the same, solid-state imaging devices, infrared sensors, camera modules, and compounds.

Members such as color filters are formed by adding a polyfunctional monomer, a photopolymerization initiator, an alkali-soluble resin, and other components to a pigment dispersion composition such as a curable composition in which an organic pigment or an inorganic pigment is dispersed to form a colored photosensitive composition. It is manufactured by photolithography methods, etc.

As the pigment, it is known to use a squarylium compound having a dihydroperimidine skeleton.

Examples of conventional squarylium compounds include those described in Patent Document 1 and Patent Document 2 below.

Patent Document 1 discloses a near-infrared absorbing composition containing a near-infrared absorbing dye [A], a basic resin-type dispersant [B], and an organic solvent [C] represented by the following general formula (1), wherein the basic resin-type dispersant [B] is , a basic resin-type dispersant [B1], which is a block copolymer consisting of an A block having a tertiary amino group and a quaternary ammonium base in the side chain, and a B block having no tertiary amino group and a quaternary ammonium base, and the basic resin-type dispersant [ The amine value in the solid content of [B1] is 10 to 200 mgKOH/g, the quaternary ammonium salt value is 10 to 90 mgKOH/g, the boiling point of the organic solvent [C] is 120 to 210°C at 760 mmHg, and the solubility parameter is 120 to 210°C at 760 mmHg. A near-infrared absorbing composition is described, characterized in that it contains an organic solvent [C1] of 9.0 to 13.0.

General formula (1)

[Formula 1]

[In General Formula (1 ₎ , X ₁ to Aralkyl group, alkoxy group which may have a substituent, aryloxy group which may have a substituent, amino group, substituted amino group, sulfo group, -SO ₂ NR ₁ R ₂ , -COOR ₁ , -CONR ₁ R ₂ , nitro group, Represents a cyano group or halogen atom. R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group which may have a substituent. For X ₁ to X ₁₀ , the substituents may combine with each other to form a ring.]

Patent Document 2 describes a squarylium compound characterized by being represented by the following formula (1).

[Formula 2]

[In formula (1), R ¹ and R ⁶ each independently represent a branched alkyl group with 3 or more carbon atoms which may have a substituent, and R ² and R ⁷ each independently represent a branched alkyl group with 5 or more carbon atoms which may have a substituent. Represents a chain alkyl group, R ³ , R ⁴ , R ⁸ and R ⁹ each independently represent a hydrogen atom, an organic group or a polar functional group, and ring A and ring B each independently represent a nitrogen-containing heterocycle of 5 or more members. and the nitrogen-containing heterocycle may have a substituent other than R ¹ and R ⁶ .]

Patent Document 1: Japanese Patent Publication No. 2018-87939 Patent Document 2: Japanese Patent Publication No. 2019-31637

The problem that one embodiment of the present disclosure seeks to solve is to provide a composition excellent in heat resistance and light resistance of the obtained film.

Additionally, the problem that another embodiment of the present disclosure seeks to solve is to provide a film using the composition, an optical filter and a method for manufacturing the same, a solid-state imaging device, an infrared sensor, and a camera module.

The problem that another embodiment of the present disclosure seeks to solve is to provide a new compound.

Means for solving the above problems include the following aspects.

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

[Formula 3]

In formula ₍ 1), A represents a group represented by the following formula (1S) or formula ( _1C ), represents a hydrogen atom or a substituent, and two or more of R ₁ to R ₆ may be bonded to each other to form a ring, provided that at least two of R ₁ to R ₆ are bonded to each other to form a ring, and the broken line The (波line) part indicates the bonding position with another structure.

[Formula 4]

In formula (1S) and formula (1C), * represents the bonding position with X in formula (1) or the bonding position with another structure.

<2> The composition according to <1>, where X is a group represented by any of the following formulas (Ar-1) to (Ar-6).

[Formula 5]

In formulas (Ar _- 1) to (Ar-6 ₎ , _{Xa 1 to 20} each independently represents a hydrogen atom or a substituent, R ₁₁ and R ₁₂ may be combined with each other to form a ring, and * represents the bonding position with another structure.

<3> The composition according to <1> or <2>, where X is a group represented by any of the following formulas (Ar-7) to (Ar-13).

[Formula 6]

In formulas (Ar-7) to (Ar-13), R ₂₁ represents an alkyl group, an aryl group, -X ₂₁ -R _21a , or -X ₂₁ -L ₂₁ -Z _{21 -R 21a} , and represents -CO-, -CS-, -SO ₂ -, -CONH-, -CSNH- or -COO-, L ₂₁ represents an alkylene group or arylene group, Z ₂₁ represents -CONR _Z21a -, -CSNR _Z21a -, -OCONR _Z21a -, -NR _Z21a CONR _Z21b -, -NR _Z21a CSNR _Z21b -, -OCOO- or -NR _Z21a SO ₂ -, R _Z21a and R _Z21b are each independently a hydrogen atom, represents an alkyl group or an aryl group, R _21a represents an alkyl group or an aryl group, R ₂₂ to R ₃₃ each independently represent a hydrogen atom or a substituent, R ₂₂ and R ₂₃ , R ₂₄ and R ₂₅ , R ₂₆ and R ₂₇ , R ₂₈ and R ₂₉ may be combined with each other to form a ring, and * indicates the bonding position with another structure.

<4> The composition according to any one of <1> to <3>, wherein the pigment having a structure represented by the above formula (1) is a pigment represented by any of the following formulas (2) to (6).

[Formula 7]

In formulas (2) to (6), A represents a group represented by the following formula (1S ₎ or formula (1C), R ₁₄₇ each independently represents a hydrogen atom or a substituent, R ₇₂ and R ₇₃ , R ₈₂ and R ₈₃ , R ₈₄ and R ₈₅ , R ₉₄ and R ₉₅ , R ₉₆ and R ₉₇ , R ₁₀₈ and R ₁₀₉ , R ₁₁₀ and R ₁₁₁ , R ₁₂₂ and R ₁₂₃ , R ₁₂₄ and R ₁₂₅ , R ₁₃₄ and R ₁₃₅ , R ₁₃₆ and R ₁₃₇ , and R ₁₄₆ and R ₁₄₇ may be combined with each other to form a ring.

[Formula 8]

In formulas (1S) and (1C), * represents the bonding position with X in formulas (2) to (6).

<5> The composition according to any one of <1> to <4>, which contains the curable compound and further contains a photopolymerization initiator.

<6> The composition according to any one of <1> to <5>, comprising a binder polymer as the binder.

<7> A film made of the curable composition according to any one of <1> to <6> or by curing the curable composition.

<8> An optical filter having the film according to <7>.

<9> The optical filter according to <8>, which is an infrared cut-off filter or an infrared-transmitting filter.

<10> A solid-state imaging device having the film according to <7>.

<11> An infrared sensor having the film according to <7>.

<12> A step of applying the curable composition according to any one of <1> to <6> on a support to form a composition layer, a step of exposing the composition layer in a pattern, and developing and removing the unexposed portion to form a pattern. A method of manufacturing an optical filter comprising a forming process.

<13> A step of applying the curable composition according to any one of <1> to <6> on a support to form a composition layer and curing to form a layer, a step of forming a photoresist layer on the layer, exposure and a step of patterning the photoresist layer by developing to obtain a resist pattern, and a step of dry etching the layer using the resist pattern as an etching mask.

<14> A camera module having a solid-state imaging device and the optical filter according to <9>.

<15> A compound having a structure represented by the following formula (1-2).

[Formula 9]

In formula (1-2), A represents a group represented by the following formula (1S) or formula (1C), and X _A and X and X _B are each independently an arylene group, a heteroarylene group, or a combination of two or more thereof represents one group, and R _1A to R _6A and R _1B to R _6B each independently represent a hydrogen atom or a substituent, and two or more of R _1A to R _6A and R _1B to R _6B may be bonded to each other to form a ring. However, at least two of R _1A to R _6A are bonded to each other to form a ring, and at least two of R _1B to R _6B are bonded to each other to form a ring.

[Formula 10]

In formula (1S) and formula (1C), * represents the bonding position with X _A or X _B in formula (1-2).

<16> The compound according to <15>, wherein X _{A and}

[Formula 11]

In formulas (Ar _- 1) to (Ar-6 ₎ , _{Xa 1 to 20} each independently represents a hydrogen atom or a substituent, R ₁₁ and R ₁₂ may be combined with each other to form a ring, and * represents the bonding position with another structure.

<17> The compound according to <15> or <16>, wherein X _A and X _B are each independently a group represented by any of the following formulas (Ar-7) to (Ar-13).

[Formula 12]

In formulas (Ar-7) to (Ar-13), R ₂₁ represents an alkyl group, an aryl group, -X ₂₁ -R _21a , or -X ₂₁ -L ₂₁ -Z _{21 -R 21a} , and represents -CO-, -CS-, -SO ₂ -, -CONH-, -CSNH- or -COO-, L ₂₁ represents an alkylene group or arylene group, Z ₂₁ represents -CONR _Z21a -, -CSNR _Z21a -, -OCONR _Z21a -, -NR _Z21a CONR _Z21b -, -NR _Z21a CSNR _Z21b -, -OCOO- or -NR _Z21a SO ₂ -, R _Z21a and R _Z21b are each independently a hydrogen atom, represents an alkyl group or an aryl group, R _21a represents an alkyl group or an aryl group, R ₂₂ to R ₃₃ each independently represent a hydrogen atom or a substituent, R ₂₂ and R ₂₃ , R ₂₄ and R ₂₅ , R ₂₆ and R ₂₇ , R ₂₈ and R ₂₉ may be combined with each other to form a ring, and * indicates the bonding position with another structure.

<18> The compound according to any one of <15> to <17>, wherein the pigment having a structure represented by the above formula (1-2) is a pigment represented by any of the following formulas (2) to (6).

[Formula 13]

In formulas (2) to (6), A represents a group represented by the following formula (1S ₎ or formula (1C), R ₁₄₇ each independently represents a hydrogen atom or a substituent, R ₇₂ and R ₇₃ , R ₈₂ and R ₈₃ , R ₈₄ and R ₈₅ , R ₉₄ and R ₉₅ , R ₉₆ and R ₉₇ , R ₁₀₈ and R ₁₀₉ , R ₁₁₀ and R ₁₁₁ , R ₁₂₂ and R ₁₂₃ , R ₁₂₄ and R ₁₂₅ , R ₁₃₄ and R ₁₃₅ , R ₁₃₆ and R ₁₃₇ , and R ₁₄₆ and R ₁₄₇ may be combined with each other to form a ring.

[Formula 14]

In formulas (1S) and (1C), * represents the bonding position with X in formulas (2) to (6).

<19> The compound according to any one of <15> to <18>, which is an infrared absorbing dye.

According to one embodiment of the present disclosure, a composition with excellent heat resistance and light resistance of the obtained film is provided.

In addition, according to another embodiment of the present disclosure, a film using the composition, an optical filter and a method for manufacturing the same, a solid-state imaging device, an infrared sensor, and a camera module are provided.

According to another embodiment of the present disclosure, a new compound is provided.

1 is a schematic diagram showing one embodiment of an infrared sensor according to the present disclosure.

Below, the content of the present disclosure will be described in detail.

In this specification, “total solid content” refers to the total mass of components excluding the solvent from the total composition of the composition. In addition, "solid content" refers to components excluding solvents, as described above, and may be solid or liquid at 25°C, for example.

In the notation of groups (atomic groups) in this specification, notations that do not describe substitution or unsubstitution include those that do not have a substituent as well as those that have a substituent. For example, an “alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group with a substituent (substituted alkyl group).

In this specification, unless otherwise specified, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. In addition, light used for exposure generally includes actinic rays or radiation such as the bright line spectrum of a mercury lamp, deep ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.

In this specification, "(meth)acrylate" represents both acrylate and methacrylate, or either one, and "(meth)acrylic" represents either acrylic and methacrylate. “(meth)acryloyl” represents both acryloyl and methacryloyl, or either one.

In this specification, in the formula, Me represents a methyl group, Et represents an ethyl group, PR represents a propyl group, Bu represents a butyl group, Ac represents an acetyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

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

In addition, in the present disclosure, “mass%” and “weight%” have the same meaning, and “mass parts” and “weight parts” have the same meaning.

In addition, in the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.

In addition, the transmittance in this disclosure is the transmittance at 25°C, unless otherwise specified.

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

(composition)

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

[Formula 15]

In formula ₍ 1), A represents a group represented by the following formula (1S) or formula ( _1C ), represents a hydrogen atom or a substituent, and two or more of R ₁ to R ₆ may be bonded to each other to form a ring, provided that at least two of R ₁ to R ₆ are bonded to each other to form a ring, and the broken line The part indicates the binding position with another structure.

[Formula 16]

In formula (1S) and formula (1C), * represents the bonding position with X in formula (1) or the bonding position with another structure.

By using the composition according to the present disclosure, a film excellent in heat resistance and light resistance is obtained.

Conventional squarylium compounds or croconium compounds, for example, the squarylium compounds described in Patent Document 1 or Patent Document 2, sometimes have insufficient heat resistance and light resistance in films containing the compounds.

As a result of intensive study by the present inventors, it has been found that excellent heat resistance and light resistance can be obtained by using a composition containing at least one compound selected from the group consisting of a pigment having a structure represented by the above formula (1), a binder, and a curing compound. It was found that a membrane was obtained.

The reason why the above effect is obtained is unclear, but by including a pigment having a structure represented by the above formula (1), the aryl directly bonds to the squarylium structure or croconium structure compared to the conventional squarylium compound or croconium compound. A ring structure or an aromatic ring having a rene group or a heteroarylene group and an aromatic ring bonded to an arylene group or heteroarylene group, a nitrogen atom is bonded to the aromatic ring, and the aromatic ring contains the nitrogen atom as a reduction. By having at least one of the ring structures condensed to, the rigidity of the molecule is improved, and also, a structure of a specific conjugated chain, and a ring structure containing the nitrogen atom as a reduction or a ring structure condensed to the aromatic ring. It is assumed that by having , the stability of the molecule itself against light and heat is improved, and a film with excellent heat resistance and light resistance is obtained.

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

<Pigment having a structure represented by formula (1)>

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

A dye having a structure represented by the above formula (1) can be suitably used as an infrared absorbing dye.

In addition, the pigment having the structure represented by the above formula (1) is a pigment (also referred to as a “colorant”), and is preferably a pigment or dye, and more preferably a dye. In addition, in this disclosure, pigment means a pigment insoluble in a solvent. Additionally, dye means a pigment that dissolves in a solvent.

In addition, the dye having the structure represented by the above formula (1) is exemplified in the case of a compound having a squarylium structure or a croconium structure shown below, but may be expressed by any resonance structure notation shown below. . The compounds having a squarylium structure or a croconium structure shown below represent compounds having the same squarylium structure or a croconium structure, except that the notation positions of the resonance structures of the cation and anion are different.

[Formula 17]

A in the formula (1) is preferably a group represented by the formula (1S) from the viewpoint of heat resistance, and is preferably a group represented by the formula (1C) from the viewpoint of light resistance.

It is preferable that X in formula (1) is an arylene group or a heteroarylene group.

As the arylene group, from the viewpoint of heat resistance and light resistance, a phenylene group which may have a substituent, or an arylene group in which two or three benzene rings which may have a substituent are fused is preferable, and a phenylene group which may have a substituent is preferable. Preferred, and particularly preferred is a phenylene group substituted with one or two hydroxy or amide groups.

The heteroarylene group may be a monocyclic heteroarylene group or a heteroarylene group in which at least one heteroaromatic ring is fused.

The heteroarylene group in which at least one heteroaromatic ring is fused may be a group in which only two or more heteroaromatic rings are fused, or a group in which one or more heteroaromatic rings and one or more aromatic rings are fused, but one heteroaromatic ring and one aromatic ring are fused. It is desirable that it be a ready-made machine.

From the viewpoint of heat resistance and light resistance, the heteroarylene group is preferably a heteroarylene group having a nitrogen atom or a sulfur atom as a reduction, more preferably a heteroarylene group having a nitrogen atom as a reduction, and may have a substituent. It is more preferable that it is a pyrrole diyl group or an indole diyl group which may have a substituent, and it is especially preferable that it is a pyrrole diyl group or an indole diyl group.

In An alkylamino group, an acyl group, an acyloxy group, an alkyloxycarbonyl group, a cyano group, etc. are mentioned.

Among them, from the viewpoint of heat resistance and light resistance, a hydroxy group or an amide group is preferable, and a hydroxy group or an alkylamide group is more preferable.

Moreover, when

Moreover, from the viewpoint of heat resistance and light resistance, It is more preferable that it is a group represented by any of the formulas (Ar-13), and it is especially preferable that it is a group represented by any of the following formulas (Ar-7) to (Ar-10).

[Formula 18]

In formulas (Ar _- 1) to (Ar-6 ₎ , _{Xa 1 to 20} each independently represents a hydrogen atom or a substituent, R ₁₁ and R ₁₂ may be combined with each other to form a ring, and * represents the bonding position with another structure.

[Formula 19]

In formulas (Ar-7) to (Ar-13), R ₂₁ represents an alkyl group, an aryl group, -X ₂₁ -R _21a , or -X ₂₁ -L ₂₁ -Z _{21 -R 21a} , and represents -CO-, -CS-, -SO ₂ -, -CONH-, -CSNH- or -COO-, L ₂₁ represents an alkylene group or arylene group, Z ₂₁ represents -CONR _Z21a -, -CSNR _Z21a -, -OCONR _Z21a -, -NR _Z21a CONR _Z21b -, -NR _Z21a CSNR _Z21b -, -OCOO- or -NR _Z21a SO ₂ -, R _Z21a and R _Z21b are each independently a hydrogen atom, represents an alkyl group or an aryl group, R _21a represents an alkyl group or an aryl group, R ₂₂ to R ₃₃ each independently represent a hydrogen atom or a substituent, R ₂₂ and R ₂₃ , R ₂₄ and R ₂₅ , R ₂₆ and R ₂₇ , R ₂₈ and R ₂₉ may be combined with each other to form a ring, and * indicates the bonding position with another structure.

In formulas (Ar- ₂ ) to (Ar- ₆ ), Xa _{1 to} , NH is particularly preferred.

Substituents for R _xa in formulas (Ar-2) to (Ar-6) include alkyl groups, aryl groups, acyl groups, alkyl sulfonyl groups, and aryl sulfonyl groups. Among them, an alkyl group is preferable.

R _xa in formulas (Ar-1) to (Ar-6) is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom, from the viewpoint of heat resistance and light resistance.

Suitable substituents for R ₇ to R ₂₀ in formulas (Ar-1) to (Ar-6) include the substituents for X described above.

In formulas (Ar-1) to (Ar-6), R ₇ , R ₉ and R ₁₁ to R ₂₀ are each independently preferably a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and are preferably a hydrogen atom or An alkyl group is more preferable, and a hydrogen atom is particularly preferable.

R ₈ in the formula (Ar-1) is preferably a hydrogen atom, a hydroxy group, or an amide group, and more preferably a hydroxy group or an amide group, from the viewpoint of heat resistance and light resistance.

R ₁₀ in the formula (Ar-1) is preferably a hydrogen atom, a hydroxy group, or an amide group, and more preferably a hydrogen atom or a hydroxy group from the viewpoint of heat resistance and light resistance.

The ring that may be formed by combining R ₁₁ and R ₁₂ in the formula (Ar-2) may be an aliphatic ring or an aromatic ring, but is preferably a 5-membered ring or a 6-membered ring.

R ₂₁ in the formula (Ar-9) is preferably -X ₂₁ -R _21a or -X ₂₁ -L ₂₁ -Z ₂₁ -R _21a from the viewpoint of heat resistance and light resistance, and -X ₂₁ - It is more preferable that it is R _21a , and it is especially preferable that it is -CO-R _21a .

The L ₂₁ is preferably an alkylene group or phenylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms.

The Z ₂₁ is preferably -CONR _Z21a -, -OCONR _Z21a -, -NR _Z21a CONR _Z21b -, -OCOO- or -NR _Z21a SO ₂ -, and more preferably -CONR _Z21a - or -OCONR _Z21a - do.

The above R _Z21a and R _Z21b are each independently preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group with 1 to 8 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group with 1 to 4 carbon atoms.

The R _21a is preferably an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably a methyl group.

Suitable substituents for R ₂₂ to R ₃₃ in formulas (Ar-7) and (Ar-9) to (Ar-13) include the substituents for X described above.

R ₂₂ to R ₃₃ in formulas (Ar-7) and formulas (Ar-9) to (Ar-13) are preferably each independently a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and a hydrogen atom Alternatively, an alkyl group is more preferable, and a hydrogen atom is particularly preferable.

R ₂₂ and R ₂₃ , R ₂₄ and R ₂₅ , R ₂₆ and R ₂₇ , and R ₂₈ and R ₂₉ in formulas (Ar-7) and (Ar-9) to (Ar-11) are combined with each other The ring that may be formed may be an aliphatic ring or an aromatic ring, but is preferably a 5-membered ring or a 6-membered ring.

Substituents for R ₁ and R ₂ in formula (1) include an alkyl group, an aryl group, an acyl group, an alkyl sulfonyl group, and an aryl sulfonyl group. Among them, an alkyl group is preferable.

R ₁ and R ₂ in the formula (1) are each independently preferably a hydrogen atom, an alkyl group, or an alkoxy alkyl group, more preferably a hydrogen atom or an alkyl group, and still more an alkyl group, from the viewpoint of heat resistance and light resistance. It is preferable, and an alkyl group having 1 to 8 carbon atoms is particularly preferable.

Suitable examples of the substituent for R ₃ to R ₆ in Formula (1) include the substituent for X described above.

R ₃ in formula (1) is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 8 carbon atoms from the viewpoint of heat resistance and light resistance. Particularly desirable.

R ₅ in formula (1) is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms from the viewpoint of heat resistance and light resistance.

R ₄ and R ₆ in the formula (1) are each independently preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, from the viewpoint of heat resistance and light resistance, and a hydrogen atom It is particularly preferable that

In formula (1), two or more of R ₁ to R ₆ may be bonded to each other to form a ring, provided that at least two of R ₁ to R ₆ are bonded to each other to form a ring.

The ring that may be formed by combining two or more of R ₁ to R ₆ in formula (1) may be an aliphatic ring or an aromatic ring, and may contain a hetero atom other than the nitrogen atom in formula (1). It may be an aliphatic ring as a ring, but from the viewpoint of heat resistance and light resistance, it is preferable that it is a 5-membered ring or a 6-membered ring, and from the viewpoint of heat resistance and light resistance, it is preferable that it is an aliphatic ring.

Among them, from the viewpoint of heat resistance and light resistance, it is preferable that at least one set of R ₁ and R ₂ , R ₁ and R ₅ , or R ₂ and R ₃ forms a ring, and at least R ₂ and R ₃ form a ring. It is more preferable to form a .

In addition, the structure represented by the above formula (1) is preferably a structure represented by the following formula (1-1) from the viewpoint of heat resistance and light resistance.

[Formula 20]

In formula (1-1), A represents a group represented by the following formula ₍ 1S) or formula (1C), R ₆ each independently represents a hydrogen atom or a substituent, and two or more of R ₁ to R ₆ may be combined with each other to form a ring, provided that at least two of R ₁ to R ₆ are combined with each other to form a ring. It is formed, and the dashed line indicates the bonding position with other structures.

[Formula 21]

In _formulas (Ar _- 1) to (Ar-6 ₎ , _{Xa 1} to ₂₀ each independently represents a hydrogen atom or a substituent, R ₁₁ and R ₁₂ may be combined with each other to form a ring, and * represents the bonding position with another structure.

[Formula 22]

In formula (1S) and formula (1C), * represents the bonding position with X in formula (1-1) or the bonding position with another structure.

A and R 1 to R ₆ in the formula (1-1) are the same as A and R ₁ to R ₆ in the formula (1), respectively, and _the preferred embodiments are the same.

The group represented by any of the formulas (Ar-1) to (Ar-6) in The meaning is the same, and the preferred aspects are also the same.

The pigment having the structure represented by the formula (1) above is preferably a pigment represented by the following formula (1-2) from the viewpoint of heat resistance and light resistance.

[Formula 23]

In formula (1-2), A represents a group represented by the following formula (1S) or formula (1C), and X _A and X and X _B are each independently an arylene group, a heteroarylene group, or a combination of two or more thereof represents one group, and R _1A to R _6A and R _1B to R _6B each independently represent a hydrogen atom or a substituent, and two or more of R _1A to R _6A and R _1B to R _6B may be bonded to each other to form a ring. However, at least two of R _1A to R _6A are bonded to each other to form a ring, and at least two of R _1B to R _6B are bonded to each other to form a ring.

[Formula 24]

In formula (1S) and formula (1C), * represents the bonding position with X _A or X _B in formula (1-2).

A in formula (1-2) is the same as A in formula (1), and the preferred embodiment is also the same.

X _A and X _B in the formula (1-2) are each the same as

In addition, X _A and X _B in the formula (1-2) may be the same or different, but are preferably the same from the viewpoint of heat resistance and light resistance.

R _1A to R _6A and R _1B to R _6B in formula (1-2) are each the same as R ₁ to R ₆ in formula (1), and their preferred embodiments are also the same.

In addition, R _1A and R _1B in the formula (1-2) may be the same or different, but are preferably the same from the viewpoint of heat resistance and light resistance. Additionally, R _2A to R _6A and R _2B to R _6B in formula (1-2) are the same as R _1A and R _1B , respectively.

Moreover, from the viewpoint of heat resistance and light resistance, the pigment having the structure represented by the above formula (1) is more preferably a pigment represented by any of the following formulas (2) to (6), and is represented by the following formula (2) or the formula The pigment represented by (3) is particularly preferable.

[Formula 25]

In formulas (2) to (6), A represents a group represented by the following formula (1S ₎ or formula (1C), R ₁₄₇ each independently represents a hydrogen atom or a substituent, R ₇₂ and R ₇₃ , R ₈₂ and R ₈₃ , R ₈₄ and R ₈₅ , R ₉₄ and R ₉₅ , R ₉₆ and R ₉₇ , R ₁₀₈ and R ₁₀₉ , R ₁₁₀ and R ₁₁₁ , R ₁₂₂ and R ₁₂₃ , R ₁₂₄ and R ₁₂₅ , R ₁₃₄ and R ₁₃₅ , R ₁₃₆ and R ₁₃₇ , and R ₁₄₆ and R ₁₄₇ may be combined with each other to form a ring.

[Formula 26]

In formulas (1S) and (1C), * represents the bonding position with X in formulas (2) to (6).

A and X in formulas (2) to (6) are the same as A and In addition, the two

Substituents for R ₃₄ and R ₃₉ in formulas (2) to (6) include an alkyl group, an aryl group, an acyl group, an alkyl sulfonyl group, and an aryl sulfonyl group. Among them, an alkyl group is preferable.

In formulas (2) to (6), R ₃₄ and R ₃₉ each independently are preferably an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, from the viewpoint of heat resistance and light resistance, and more preferably 1 to 8 carbon atoms. It is more preferable that it is an alkyl group of 4, and an ethyl group is especially preferable.

Suitable substituents for R ₃₅ to R ₃₈ and R ₄₀ to R ₁₄₇ in formulas (2) to (6) include the substituents for X described above.

In formulas (2) to (6), R ₃₅ to R ₃₈ and R ₄₀ to R ₁₄₇ are each independently preferably a hydrogen atom or an alkyl group from the viewpoint of heat resistance and light resistance, and each represents a hydrogen atom or a carbon number of 1 to 1. An alkyl group of 8 is more preferable, a hydrogen atom or an alkyl group of 1 to 4 carbon atoms is more preferable, and a hydrogen atom or a methyl group is particularly preferable.

In equations (2) to (6), R ₇₂ and R ₇₃ , R ₈₂ and R ₈₃ , R ₈₄ and R ₈₅ , R ₉₄ and R ₉₅ , R ₉₆ and R ₉₇ , R ₁₀₈ and R ₁₀₉ , and R ₁₁₀ The ring that may be formed by combining R ₁₁₁ , R ₁₂₂ and R ₁₂₃ , R ₁₂₄ and R ₁₂₅ , R ₁₃₄ and R ₁₃₅ , R ₁₃₆ and R ₁₃₇ , or R ₁₄₆ and R ₁₄₇ may be an aliphatic ring or an aromatic ring. Although it may be a ring, it is preferable that it is a 5-membered ring or a 6-membered ring, and it is also preferable that it is an aliphatic ring.

Among them, R ₇₂ and R ₇₃ , R ₈₂ and R ₈₃ , R ₈₄ and R ₈₅ , R ₉₄ and R ₉₅ , R ₉₆ and R ₉₇ , R ₁₀₈ and R ₁₀₉ in formulas (2) to (6), R ₁₁₀ and R ₁₁₁ , R ₁₂₂ and R ₁₂₃ , R ₁₂₄ and R ₁₂₅ , R ₁₃₄ and R ₁₃₅ , R ₁₃₆ and R ₁₃₇ , or R ₁₄₆ and R ₁₄₇ are each independently, and from the viewpoint of heat resistance and light resistance, each other It is preferable not to combine to form a ring.

[Maximum absorption wavelength]

The maximum absorption wavelength of the pigment having the structure shown in formula (1) is preferably in the wavelength range of 650 nm or more, more preferably in the wavelength range of 700 nm to 1,100 nm, and more preferably in the wavelength range of 760 nm to 1,000 nm. It is more desirable.

The maximum absorption wavelength is measured using a Cary5000 UV-Vis-NIR spectrophotometer (manufactured by Agilent Technology Co., Ltd.).

[Half price width]

In the wavelength-absorbance curve obtained in the measurement of the maximum absorption wavelength, the half width of the wavelength peak at the maximum absorption wavelength is preferably 2,500 cm ^-1 or less, more preferably 2,000 cm ^-1 or less, and 1,800 cm. ^-1 or less is more preferable.

The lower limit of the half width is not particularly limited, but is preferably 500 cm ^-1 or more.

The half width is measured using a Cary5000 UV-Vis-NIR spectrophotometer (manufactured by Agilent Technology Co., Ltd.), and the half width is calculated by converting the wavelength to a wave number.

[Molar extinction coefficient]

The molar extinction coefficient at the maximum absorption wavelength of the dye having the structure shown in formula (1) is preferably 1.0Х10 ⁵ L/(mol·cm) or more, and more preferably 1.5Х10 ⁵ L/(mol·cm) or more. desirable.

The molar extinction coefficient is measured using a Cary5000 UV-Vis-NIR spectrophotometer (manufactured by Agilent Technology Co., Ltd.).

〔content〕

In the composition according to the present disclosure, the content of the pigment having the structure represented by formula (1) is preferably 5% by mass to 70% by mass, and is more preferably 10% by mass to 60% by mass, based on the total solid content of the composition. It is preferable, and 15% by mass to 50% by mass is more preferable. In the composition according to the present disclosure, the pigment having a structure represented by formula (1) may be used in combination of two or more types. When two or more types of pigments having a structure represented by formula (1) are included, it is preferable that the total amount is within the above range.

Hereinafter, SQ-1 to SQ-13 (squarylium compounds) and CR-1 to CR-10 (croconium compounds), which are specific examples of pigments having a structure represented by formula (1), are shown, but are limited thereto. That is not the case.

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

There is no particular limitation on the method for producing the pigment having the structure represented by Formula (1), and it can be appropriately produced by referring to known production methods.

For example, a suitable method is to perform dehydration condensation with two corresponding aromatic compounds using tetragonal acid (squaric acid) or croconic acid. Additionally, the aromatic compound may be synthesized by a known method.

Additionally, a method for adjusting the crystal form of the pigment having the structure represented by formula (1) will be explained. As a method for adjusting the crystal form, use formula (1) in an organic solvent such as N,N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, and 1,4-dioxane. ) can include a method of contacting a pigment with a structure represented by ). At that time, heating or cooling may be performed to adjust the particle size of the pigment having the structure represented by formula (1), and a separate solvent may be added before filtration.

<Other ingredients>

The composition according to the present disclosure is preferably a compound from which a film is obtained, and is preferably a curable composition from which a cured film is obtained by finally curing.

Moreover, it is preferable that the composition according to the present disclosure is a composition that can form a pattern of a cured film by, for example, pattern exposure. That is, it is preferable that the composition according to the present disclosure is a negative type composition.

When the composition according to the present disclosure is a negative composition, for example, an embodiment containing a polymerization initiator, a polymerizable compound, and an alkali-soluble resin is preferable.

In addition, when the composition according to the present disclosure is a positive type composition, for example, a photo acid generator, a polymer having a structural unit having a group whose acid group is protected by an acid-decomposable group, and a polymer having a structural unit having a crosslinkable group Aspects containing .

Hereinafter, each component contained in the composition according to the present disclosure is described as a negative composition.

In the aspect where the composition according to the present disclosure is a positive type composition, the components included include those described in International Publication No. 2014/003111, and the preferred embodiments are the same.

<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 formation.

Additionally, the binder is preferably a binder polymer from the viewpoint of film formation and dispersibility.

Additionally, as the binder polymer, a dispersant may be included.

Specific examples of the binder polymer include acrylic resin, enethiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene ether phosphine. Oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, siloxane resin, urethane resin, etc. are mentioned. Among them, those containing acrylic resin are preferable.

One type of these resins may be used individually, or two or more types may be mixed and used.

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

Examples of commercially available norbornene resins include the ARTON series (eg, ARTON F4520) manufactured by JSR Corporation. Commercially available products of polyimide resin include the Neoprem (registered trademark) series (for example, C3450) manufactured by Mitsubishi Gas Chemical Co., Ltd.

In addition, as the binder polymer, the resin described in the examples of International Publication No. 2016/088645, the resin described in Japanese Patent Application Publication No. 2017-57265, the resin described in Japanese Patent Application Publication No. 2017-32685, and the Japanese Patent Application Publication No. 2017- The resin described in No. 075248 and the resin described in Japanese Patent Application Laid-Open No. 2017-66240 can also be used, the contents of which are incorporated herein by reference.

Moreover, as a binder polymer, a resin having a fluorene skeleton can also be preferably used. Regarding the resin having a fluorene skeleton, the description of US Patent Application Publication No. 2017/0102610 can be referred to, and this content 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, and more preferably 500,000 or less. The lower limit is more preferably 3,000 or more, and more preferably 5,000 or more.

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

-Dispersant-

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

As a dispersant, a polymer dispersant [for example, resin having an amine group (polyamidoamine and its salt, etc.), oligoimine resin, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester. , modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formalin condensate], etc.

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

Additionally, suitable polymer dispersants include resins with an acid value of 60 mgKOH/g or more (more preferably, acid values of 60 mgKOH/g or more and 300 mgKOH/g or less).

Examples of end-modified polymers include polymers having a phosphate group at the terminal described in Japanese Patent Application Laid-Open No. 3-112992, Japanese Patent Application Publication No. 2003-533455, etc., and polymers having a sulfone group at the terminal described in Japanese Patent Application Laid-Open No. 2002-273191, etc. Examples include polymers having an acid group and polymers having a partial skeleton or heterocycle of an organic pigment described in Japanese Patent Application Laid-Open No. 9-77994, etc. In addition, the polymer described in Japanese Patent Application Laid-Open No. 2007-277514, in which two or more anchor sites (acidic groups, basic groups, partial skeletons of organic pigments, heterocycles, etc.) are introduced to the polymer terminals to the pigment surface, has excellent dispersion stability. desirable.

As graft-type polymers, for example, poly(lower alkyleneimine) and polyester described in Japanese Patent Application Laid-Open No. 54-37082, Japanese Patent Application Publication No. 8-507960, and Japanese Patent Application Publication No. 2009-258668. Reaction products, reaction products of polyallylamine and polyester described in Japanese Patent Application Laid-Open No. 9-169821, etc., macromonomers described in Japanese Patent Application Laid-Open No. 10-339949, Japanese Patent Application Laid-Open No. 2004-37986, etc., and nitrogen atoms Copolymers of monomers, graft-type polymers having partial skeletons or heterocycles of organic pigments described in Japanese Patent Application Laid-Open No. 2003-238837, Japanese Patent Application Publication No. 2008-9426, Japanese Patent Application Publication No. 2008-81732, etc., Japanese Patent Application Laid-Open Nos. Examples include copolymers of macromonomers and acid group-containing monomers described in Publication No. 2010-106268 and the like.

As the macromonomer used when producing a graft-type polymer by radical polymerization, known macromonomers can be used, such as macromonomer AA-6 (polymethyl methacrylate whose terminal group is a methacryloyl group) manufactured by Toagosei Co., Ltd. , AS-6 (polystyrene with a methacryloyl terminal group), AN-6S (copolymer of styrene with a methacryloyl terminal group and acrylonitrile), AB-6 (polymer with a methacryloyl terminal group) butyl acrylate), Flaxel FM5 (5 molar equivalent of ε-caprolactone of 2-hydroxyethyl methacrylate) manufactured by Daicel Chemical Industry Co., Ltd., FA10L (ε-capro of 2-hydroxyethyl acrylate) lactone 10 mole equivalent addition product), and the polyester-based macromonomer described in Japanese Patent Application Publication No. Hei 2-272009. Among these, a polyester-based macromonomer with excellent flexibility and solvent resistance is particularly preferable from the viewpoint of the dispersibility of the pigment dispersion, the dispersion stability, and the developability shown by the composition using the pigment dispersion. Japanese Patent Application Laid-Open No. 2-272009 Most preferred are the polyester-based macromonomers represented by the polyester-based macromonomers described in No.

As block-type polymers, block-type polymers described in Japanese Patent Application Laid-Open No. 2003-49110, Japanese Patent Application Laid-Open No. 2009-52010, etc. are preferable.

Resins (dispersants) are also available as commercial products, and specific examples thereof include "Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130" manufactured by BYK Chemie. (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", "EFKA4047, 4050~4165 (polymer) manufactured by EFKA. Urethane series), EFKA4330~4340 (block copolymer), 4400~4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (polyester) Talocyanine derivative), 6750 (azo pigment derivative)", "Azisper PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine Techno Co., Ltd., "Flolene TG-710" manufactured by Kyoeisha Chemical Co., Ltd. Lethene oligomer)", "Polyflo No. 50E, No. 300 (acrylic copolymer)", "Disparon KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid) manufactured by Kusumoto Kasei Co., Ltd. #7004 (polyetherester), DA-703-50, DA-705, DA-725", Gao Co., Ltd. "Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN- B (aromatic sulfonic acid formalin polycondensate)", "Homogenol L-18 (polymeric polycarboxylic acid)", "Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "acetamine 86 (stearylamine acetate)", manufactured by Nippon Lubrizol Co., Ltd. "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (at the end) Polymer with functional moiety), 24000, 28000, 32000, 38500 (graft-type polymer)", Nikko Chemicals Co., Ltd. "Niccol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostea) Rate)", "Hinoact T-8000E" manufactured by Kawaken Fine Chemical Co., Ltd., "Organosiloxane Polymer KP341" manufactured by Shin-Etsu Chemical Co., Ltd., "EFKA-46, EFKA" manufactured by Morishita Sangyo Co., Ltd. -47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450", Sannopco Co., Ltd. "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100", manufactured by ADEKA Co., Ltd. "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P- 123", and "Ionet S-20" manufactured by Sanyo Kasei Kogyo Co., Ltd., etc.

These resins may be used individually, or may be used in combination of two or more types. Additionally, an alkali-soluble resin described later can also be used as a dispersant. Examples of alkali-soluble resins include (meth)acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, etc., acidic cellulose derivatives having a carboxylic acid group in the side chain, and polymers having a hydroxyl group. Resins obtained by modifying acid anhydride include, but (meth)acrylic acid copolymers are particularly preferred. In addition, the N-position substituted maleimide monomer copolymer described in Japanese Patent Application Laid-Open No. 10-300922, the ether dimer copolymer described in Japanese Patent Application Laid-Open No. 2004-300204, and the polymerizable group described in Japanese Patent Application Laid-Open No. 7-319161. Alkali-soluble resins containing are also preferred.

Among these, from the viewpoint of dispersibility, the resin preferably contains a resin having a polyester chain, and more preferably contains a resin having a polycaprolactone chain. In addition, the resin (preferably an acrylic resin) preferably has a structural unit having an ethylenically unsaturated group from the viewpoints 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.

In addition, when the resin has an ethylenically unsaturated group in the side chain, especially a (meth)acryloyl group, the resin preferably has a divalent linking group having an alicyclic structure between the main chain and the ethylenically unsaturated group. .

When the content of the dispersant contains a compound having a partial structure represented by Formula (1) and a pigment, dye, or pigment derivative other than a compound having a partial structure represented by Formula (1), the partial structure represented by Formula (1) It is preferably 1 part by mass to 100 parts by mass, based on a total content of 100 parts by mass including pigments, dyes, and pigment derivatives other than the compound having the partial structure represented by formula (1), and 5 parts by mass. -90 parts by mass is more preferable, and 10 parts by mass -80 parts by mass are more preferable.

-Alkali soluble resin-

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

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

Groups that promote alkali solubility (hereinafter also referred to as acid groups) include, for example, carboxy groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups, but those that are soluble in organic solvents and can be developed in a weakly alkaline aqueous solution are preferred. And (meth)acrylic acid is mentioned as a particularly preferable one. The number of these acid groups may be one, or two or more types may be used. As an alkali-soluble resin, reference may be made to the description in paragraphs 0558 to 0571 of Japanese Patent Application Publication No. 2012-208494 (paragraphs 0685 to 0700 of corresponding U.S. Patent Application Publication No. 2012/0235099), the contents of which are incorporated herein by reference. do.

The alkali-soluble resin is also preferably a resin having a structural unit represented by the following formula (ED).

[Formula 33]

In formula (ED), R ^E1 and R ^E2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, and z represents 0 or 1.

There is no particular limitation on the hydrocarbon group having 1 to 25 carbon atoms represented by R ^E1 and R ^E2 , but examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t- Linear or branched alkyl groups such as butyl group, t-amyl group, stearyl group, lauryl group, and 2-ethylhexyl group; Aryl groups such as phenyl groups; Alicyclic groups such as cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, and 2-methyl-2-adamantyl group; Alkyl groups substituted with alkoxy groups such as 1-methoxyethyl group and 1-ethoxyethyl group; Alkyl groups substituted with aryl groups such as benzyl groups; etc. can be mentioned. Among these, primary or secondary hydrocarbon groups that are difficult to be separated by acid or heat, such as methyl group, ethyl group, cyclohexyl group, benzyl group, etc., are preferable in terms of heat resistance.

In addition, R ^E1 and R ^E2 may be the same substituent or different substituents.

Examples of compounds forming structural units represented by formula (ED) include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 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 structural units other than those represented by formula (ED).

Examples of monomers forming the structural unit include aryl (meth)acrylate, alkyl (meth)acrylate, polyethyleneoxy ( It is also preferable to include meth)acrylate as a copolymerization component, and aryl (meth)acrylate or alkyl (meth)acrylate is more preferable.

Moreover, from the viewpoint of alkaline developability, monomers having a carboxyl group such as (meth)acrylic acid or itaconic acid containing an acidic group, monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride, itaconic anhydride, etc. It is preferable to include a monomer having a carboxylic acid anhydride group as a copolymerization component, and (meth)acrylic acid is more preferable.

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

Regarding the resin having the structural unit represented by the formula (ED), the description in paragraphs 0079 to 0099 of Japanese Patent Application Publication No. 2012-198408 can be referred to, and this content is hereby incorporated in the 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 more preferably 7,000 or more. The upper limit is more preferably 45,000 or less, and more preferably 43,000 or less.

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

In addition, the acid value in this disclosure shall be measured by the following method.

The acid value represents the mass of potassium hydroxide required to neutralize the acidic component per 1g of solid content. The measurement sample was dissolved in a mixed solvent of tetrahydrofuran/water = 9/1 (mass ratio), and using a potentiometric titration device (product name: AT-510, manufactured by Kyoto Denshi Kogyo Co., Ltd.), at 25°C. Neutralization was titrated with 0.1 mol/L aqueous sodium hydroxide solution. Using the inflection point of the titration pH curve as the titration end point, the acid value was calculated using the following equation.

A=56.11ХVsХ0.1Хf/w

A: Acid value (mgKOH/g)

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

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

w: Measured sample mass (g) (converted to solid content)

<Hardability Compound>

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 the curable compound from the viewpoint of heat resistance and light resistance.

The curable compound that can be used in the present disclosure is preferably a polymerizable compound, more preferably an ethylenically unsaturated compound, and particularly preferably a compound having a terminal ethylenically unsaturated group.

As such a group of compounds, known ones can be used without particular limitation.

They have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides, preferably For example, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds are used. In addition, addition reactants of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, or mercapto groups and monofunctional or polyfunctional isocyanates or epoxies, and monofunctional or , dehydration condensation reaction products of polyfunctional carboxylic acids, etc. are also suitably used. In addition, addition reactants of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and mono- or polyfunctional alcohols, amines, thiols, halogen groups, tosyloxy groups, etc. Substitution reactants of unsaturated carboxylic acid esters or amides with a dissociable substituent and monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. Also, as another example, instead of the above unsaturated carboxylic acid, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether, etc.

Specific examples of monomers of aliphatic polyhydric alcohol compounds and esters of unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene. Glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloyloxypropyl)ether, trimethyl Olethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri(acrylic These include (royloxyethyl) isocyanurate, polyester acrylate oligomer, and isocyanuric acid EO-modified triacrylate.

As methacrylic acid ester, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, and trimethylolethane. Trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanedioldimethacrylate, hexanedioldimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate Rate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis[p-(3-methacrylate) These include kryloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(methacryloxyethoxy)phenyl]dimethylmethane, etc.

In addition, urethane-based addition polymerizable compounds produced using the addition reaction of an isocyanate group and a hydroxy group are also suitable, and specific examples thereof are described, for example, in Japanese Patent Publication No. 48-41708. A vinyl monomer containing a hydroxy group represented by the following general formula (I) is added to a polyisocyanate compound having two or more isocyanate groups in one molecule to form two or more polymerizable vinyl groups in one molecule. Containing vinyl urethane compounds, etc. can be mentioned.

CH ₂ =C(R)COOCH ₂ CH(R')OH (I)

(However, R and R' represent H or CH _3. )

In addition, urethane acrylates as described in Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765, and Japanese Patent Publication No. 58 Urethane compounds having an ethylene oxide-based skeleton described in -49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. In addition, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule are described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Publication No. 63-260909, and Japanese Patent Application Publication No. 1-105238. By using it, a composition with extremely excellent photosensitive speed can be obtained.

In addition, examples of the curable compound include compounds described in paragraphs 0178 to 0190 of Japanese Patent Application Laid-Open No. 2007-277514.

Moreover, as a curable compound, you may use the epoxy compound described in Unexamined-Japanese-Patent No. 2015-187211.

Additionally, the curable compound may contain a compound having a cyclic ether group. Examples of the cyclic ether group include epoxy group and oxetane group. The compound having a cyclic ether group is preferably a compound having an epoxy group.

Examples of the compound having an epoxy group include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. It is preferable to have 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups may be, for example, 10 or less, or 5 or less. The lower limit of the epoxy group is preferably two or more.

The compound having an epoxy group may be a low molecular compound (e.g., preferably less than 2,000 molecular weight, more preferably less than 1,000 molecular weight) or a macromolecule (e.g., molecular weight more than 1,000, in the case of a polymer, The weight average molecular weight may be 1,000 or more. The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, and more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

As a compound having an epoxy group, an epoxy resin can be preferably used. Examples of epoxy resins include epoxy resins that are glycidyl ethers of phenolic compounds, epoxy resins that are glycidyl ethers of various novolac resins, alicyclic epoxy resins, aliphatic epoxy resins, and heterocyclic epoxy resins. Glycidyl ester-based epoxy resins, glycidylamine-based epoxy resins, epoxy resins obtained by glycidylating halogenated phenols, condensates of silicon compounds having an epoxy group and other silicon compounds, polymerizable unsaturated compounds having an epoxy group. and copolymers of other polymerizable unsaturated compounds.

As an epoxy resin which is a glycidyl etherified product of a phenol compound, for example, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2) ,3-hydroxy)phenyl]ethyl]phenyl]propane, bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenol, 1-(4-hydroxyphenyl)-2-[4-( 1,1-bis(4-hydroxyphenyl)ethyl)phenyl]propane, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3 -methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, fluoroglucinol, phenols having a diisopropylidene skeleton; Phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; and epoxy resins that are glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene.

Epoxy resins that are glycidyl ethers of novolak resins include, for example, phenols, cresols, ethyl phenols, butyl phenols, octyl phenols, bisphenols such as bisphenol A, bisphenol F, and bisphenol S, and naphthols. Various types of novolak resins made from phenol, phenol novolak resins containing xylylene skeleton, phenol novolak resins containing dicyclopentadiene skeletons, phenol novolak resins containing biphenyl skeletons, phenol novolak resins containing fluorene skeletons, etc. Glycidyl ether products of novolak resins, etc. can be mentioned.

Examples of the alicyclic epoxy resin include those having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexylcarboxylate and bis(3,4-epoxycyclohexylmethyl)adipate. An alicyclic epoxy resin can be mentioned.

Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and pentaerythritol.

Examples of heterocyclic epoxy resins include heterocyclic epoxy resins having heterocyclic rings such as isocyanuric rings and hydantoin rings.

Examples of the glycidyl ester-based epoxy resin include epoxy resins made of carboxylic acid esters such as hexahydrophthalic acid diglycidyl ester.

Examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylating amines such as aniline and toluidine.

Examples of epoxy resins obtained by glycidylating halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolak, chlorinated bisphenol S, and chlorinated phenol. Examples include epoxy resins obtained by glycidylating halogenated phenols such as bisphenol A.

As a copolymer of an ethylenically unsaturated compound having an epoxy group and other ethylenically unsaturated compounds, products available on the market include Maproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (above, Nichiyu Co., Ltd. product, epoxy group-containing polymer), etc. Examples of ethylenically unsaturated compounds having an epoxy group include glycidyl acrylate, glycidyl methacrylate, and 4-vinyl-1-cyclohexene-1,2-epoxide. Additionally, copolymers of other ethylenically unsaturated compounds include, for example, methyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, styrene, vinylcyclohexane, etc. , especially methyl (meth)acrylate, benzyl (meth)acrylate, and styrene are preferred.

The epoxy equivalent of the epoxy resin is preferably 100 g/eq to 3,300 g/eq, more preferably 120 g/eq to 1,700 g/eq, and even more preferably 150 g/eq to 1,000 g/eq.

The epoxy resin can also be a commercially available product. For example, EPICLON HP-4700 (made by DIC Corporation), JER1031S (made by Mitsubishi Chemical Corporation), EHPE3150 (made by Daicel Corporation), EOCN-1020 (made by Nippon Kayaku Corporation), etc. I can hear it.

In the present disclosure, compounds having a cyclic ether group include paragraphs 0034 to 0036 of JP2013-011869, paragraphs 0147 to 0156 of JP2014-043556, and paragraphs 0085 to 0085 of JP2014-089408. The compounds described in 0092 can also be used. These contents are incorporated herein by reference.

When the composition according to the present disclosure contains a compound having a cyclic ether group, the content of the compound having a cyclic ether group is preferably 0.1% by mass to 90% by mass based on the total solid content of the composition. The lower limit is, for example, more preferably 0.5% by mass or more, and more preferably 1% by mass or more. As for the upper limit, for example, 85 mass% or less is more preferable, and 80 mass% or less is more preferable. The compound having a cyclic ether group may be used alone or in combination of two or more types. When two or more types of compounds having a cyclic ether group are used together, it is preferable that the total amount falls within the above range.

The content of the curable compound in the composition is preferably 1% by mass to 90% by mass, more preferably 5% by mass to 85% by mass, and 8% by mass to 80% by mass, based on the total solid content of the composition. It is more desirable. If the content of the curable compound is within the above range, the curability of the composition is excellent.

In particular, when the composition according to the present disclosure is used to form a colored pattern of a color filter, the above content range is preferably 5% by mass to 85% by mass, and more preferably 7% by mass to 80% by mass. , it is more preferable that it is 8 mass% to 75 mass%.

<Polymerization initiator>

The composition according to the present disclosure preferably further contains a polymerization initiator, and more preferably contains a photopolymerization initiator.

Moreover, it is particularly preferable that the composition according to the present disclosure contains the above-described curable compound and further contains a photopolymerization initiator.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light from the ultraviolet region to the visible region are preferred. Additionally, it may be a compound that generates active radicals by producing some kind of effect with the photoexcited sensitizer. The photopolymerization initiator is preferably a radical photopolymerization initiator.

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, Organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. can be mentioned. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, and a metallocene. compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarins. Compounds selected from the group consisting of compounds are preferred, and compounds selected from the group consisting of oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds are more preferred, and oxime compounds are more preferred. desirable. Regarding the photopolymerization initiator, the descriptions in paragraphs 0065 to 0111 of Japanese Patent Application Laid-Open No. 2014-130173 and paragraphs 0274 to 0306 of Japanese Patent Application Publication No. 2013-29760 can be referred to, and these contents are incorporated in this disclosure.

Commercially available α-hydroxyketone compounds include OMNIRAD 184 (formerly IRGACURE 184), OMNIRAD 1173 (formerly IRGACURE 1173, formerly DAROCUR 1173), OMNIRAD 500 (formerly IRGACURE 500), OMNIRAD 2959 (formerly IRGACURE 2959), and OMNIRAD 127 (formerly IRGACURE 127). IRGACURE 127) (above, manufactured by IGM Resins (formerly manufactured by BASF)), etc. Commercially available α-aminoketone compounds include OMNIRAD 907 (formerly IRGACURE 907), OMNIRAD 369 (formerly IRGACURE 369), OMNIRAD 379 (formerly IRGACURE 379), and OMNIRAD 379EG (formerly IRGACURE 379EG) (above, manufactured by IGM Resins) (manufactured by BASF)), etc. may be mentioned. Commercially available acylphosphine compounds include OMNIRAD 819 (formerly IRGACURE 819), OMNIRAD TPO (formerly IRGACURE TPO, formerly DAROCUR TPO) (above, manufactured by IGM Resins (formerly BASF), etc.

Oxime compounds include, for example, compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-80068, compounds described in Japanese Patent Application Laid-Open No. 2006-342166, and J. C. S. Perkin II (1979). , pp. 1653-1660), a compound described in J. C. S. Perkin II (1979, pp. 156-162), a compound described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), published in Japan Compounds described in Japanese Patent Application Publication No. 2000-66385, compounds described in Japanese Patent Application Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2006-342166, compounds described in Japanese Patent Application Publication No. 2017-19766, Japanese Patent Application Publication No. Examples include compounds described in No. 6065596, compounds described in International Publication No. 2015/152153, and compounds described in International Publication No. 2017/051680. Specific examples of oxime compounds include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane. -3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2 -one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. As commercially available oxime compounds, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (manufactured by BASF) are also suitably used. In addition, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Ackles NCI- 930, Adeka Optomer N-1919 (photopolymerization initiator 2 of Japanese Patent Application Laid-Open No. 2012-14052) (manufactured by ADEKA Co., Ltd.).

Also, as oxime compounds other than the above, the compounds described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N position of a carbazole ring, the compounds described in U.S. Patent Publication No. 7626957 in which a heterosubstituent is introduced into the benzophenone moiety, and the compounds described in U.S. Patent No. 7626957 in which the oxime is linked to the N position of the carbazole ring, and the compounds described in U.S. Patent No. 7626957 in which a heterosubstituent is introduced into the benzophenone moiety Compounds described in Japanese Patent Application Publication No. 2010-15025 and U.S. Patent Application Publication No. 2009-292039 in which a nitro group is introduced, ketoxime compounds described in International Publication No. 2009/131189, and molecules having the same triazine skeleton and oxime skeleton Compounds described in U.S. Patent Publication No. 7556910, which contain an absorption maximum at 405 nm, and compounds described in Japanese Patent Application Laid-Open No. 2009-221114, which have good sensitivity to g-ray light sources, may be used.

This disclosure can also use an oxime compound having a fluorene ring as a photopolymerization initiator. Specific examples of oxime compounds having a fluorene ring include compounds described in Japanese Patent Application Publication No. 2014-137466. This content is incorporated into this disclosure.

The present disclosure can also use an oxime compound having a benzofuran skeleton as a photopolymerization initiator. Specific examples include compounds OE-01 to OE-75 described in International Publication No. 2015/036910.

The present disclosure may use, as a photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring becomes a naphthalene ring. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

This disclosure can also use an oxime compound having a fluorine atom as a photopolymerization initiator. Specific examples of oxime compounds having a fluorine atom include compounds described in JP2010-262028, compounds 24, 36 to 40 described in JP2014-500852, and compounds described in JP2013-164471. (C-3), etc. may be mentioned. This content is incorporated into this disclosure.

The present disclosure can use an oxime compound having a nitro group as a photopolymerization initiator. The oxime compound having a nitro group is also preferably used as a dimer. Specific examples of oxime compounds having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466, and compounds described in JP4223071. Examples include the compounds described in paragraph numbers 0007 to 0025 and Adeka Ackles NCI-831 (manufactured by ADEKA Co., Ltd.).

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

[Formula 34]

[Formula 35]

The oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500 nm, and a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm is more preferable. Additionally, the oxime compound is preferably a compound with high absorbance at a wavelength of 365 nm and 405 nm.

From the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 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 ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent.

In this disclosure, as a photopolymerization initiator, a difunctional or trifunctional or higher-functional photopolymerization initiator may be used. Specific examples of such photopolymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, paragraphs 0417 to 0412 of Japanese Patent Publication No. 2016-532675, International Publication No. Dimers of oxime compounds described in paragraphs 0039 to 0055 of Publication No. 2017/033680, compound (E) and compound (G) described in Japanese Patent Publication No. 2013-522445, International Publication No. 2016/ Cmpd1 to Cmpd7 described in No. 034963, etc. can be mentioned.

A polymerization initiator may be used individually by 1 type, or may be used in combination of 2 or more types.

The content of the polymerization initiator in the composition is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, particularly preferably 1% by mass, based on the total solid content of the composition. It is 20% by mass. In this range, good sensitivity and pattern formation are obtained.

<Epoxy hardener>

When the composition according to the present disclosure includes a compound having an epoxy group, it is preferable to further include an epoxy curing agent.

Examples of epoxy curing agents include amine-based compounds, acid anhydride-based compounds, amide-based compounds, phenol-based compounds, polyhydric carboxylic acids, and thiol compounds.

As an epoxy curing agent, polyhydric carboxylic acids are preferable from the viewpoint of heat resistance and transparency of the cured product, and compounds having two or more carboxylic acid anhydride groups in the molecule are more preferable.

Specific examples of epoxy curing agents include succinic acid, trimellitic acid, pyromellitic acid, N,N-dimethyl-4-aminopyridine, and pentaerythritol tetrakis(3-mercaptopropionate). The epoxy curing agent may be a compound described in paragraphs 0072 to 0078 of Japanese Patent Application Laid-Open No. 2016-075720, or a compound described in Japanese Patent Application Laid-Open No. 2017-036379, the contents of which are incorporated herein by reference.

The content of the epoxy curing agent is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.01 parts by mass to 10 parts by mass, and more preferably 0.1 parts by mass to 6.0 parts by mass, per 100 parts by mass of the compound having an epoxy group.

<Colorant>

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

Colorants include white pigments, black pigments, chromatic pigments, and near-infrared absorbing pigments. In addition, in the present disclosure, white pigments include not only pure white, but also pigments of light gray close to white (for example, grayish white, light gray, etc.). In addition, in this disclosure, a chromatic colorant means a colorant other than a white colorant and a black colorant. The chromatic colorant is preferably a colorant that has absorption in a wavelength range of 400 nm or more and less than 650 nm.

Examples of chromatic colorants include red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants. The chromatic colorant may be a pigment or a dye. Pigment and dye may be used together. Additionally, the pigment may be either an inorganic pigment or an organic pigment. Additionally, as the pigment, a material in which part of an inorganic pigment or an organic-inorganic pigment is replaced with an organic chromophore can also be used. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, color design can be made easier.

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

It is preferable that the chromatic colorant contains a pigment. The pigment content in the chromatic colorant is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and especially preferably 90% by mass or more. Pigments include those shown below.

Color Index (C.I.) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35 :1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94 , 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137 , 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 1 76 , 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228 (directly linked quinophthalone dimer described in International Publication No. 2013/098836), 231, 232 (metaine type), 233 (quinoline type), 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. (above, 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 (cups) Ten-based, Organo Ultramarine, Bluish Red), 295 (monoazo-based), 296 (diazo-based), etc. (red pigments),

C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, etc. (above, green pigment),

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane type), 61 (xanthene type), 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 (monoazoline) ), 88 (metaphosphorus series), etc. (above, blue pigment).

Additionally, as a green pigment, a halogenated zinc phthalocyanine pigment can be used, with an average number of halogen atoms per molecule of 10 to 14, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms. there is. Specific examples include compounds described in International Publication No. 2015/118720. Moreover, as a green pigment, a compound described in Chinese Patent Application No. 106909027, a phthalocyanine compound having a phosphoric acid ester described in International Publication No. 2012/102395 as a ligand, etc. can also be used.

Moreover, as a green colorant, you may use the green coloring agent described in Unexamined-Japanese-Patent No. 2019-8014 or Unexamined-Japanese-Patent No. 2018-180023.

Moreover, as a blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include compounds described in paragraphs 0022 to 0030 of Japanese Patent Application Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Application Publication No. 2011-157478.

Additionally, as a yellow pigment, Japanese Patent Application Laid-Open No. 2018-203798, Japanese Patent Application Publication No. 2018-62578, Japanese Patent Application Publication No. 6432077, Patent Publication No. 6432076, Japanese Patent Application Publication No. 2018-155881, Japanese Patent Application Publication No. 2018 -111757, Japanese Patent Publication No. 2018-40835, Japanese Patent Publication No. 2017-197640, Japanese Patent Publication No. 2016-145282, Japanese Patent Publication No. 2014-85565, Japanese Patent Publication No. 2014-21139, Japan Japanese Patent Publication No. 2013-209614, Japanese Patent Publication No. 2013-209435, Japanese Patent Publication No. 2013-181015, Japanese Patent Publication No. 2013-61622, Japanese Patent Publication No. 2013-54339, Japanese Patent Publication 2013- No. 32486, Japanese Patent Publication No. 2012-226110, Japanese Patent Publication No. 2008-74987, Japanese Patent Publication No. 2008-81565, Japanese Patent Publication No. 2008-74986, Japanese Patent Publication No. 2008-74985, Japanese Patent Publication No. Quinophthalone pigments described in Patent Publication No. 2008-50420, Japanese Patent Application Laid-Open No. 2008-31281, or Japanese Patent Publication No. 48-32765 can also be suitably used. Additionally, the pigment described in Japanese Patent Publication No. 6443711 can also be used.

In addition, as a yellow pigment, the quinophthalone compound described in paragraphs 0011 to 0034 of JP2013-54339, the quinophthalone compound described in paragraphs 0013 to 0058 of JP2014-26228, and the quinophthalone compound described in paragraphs 0013 to 0058 of JP2014-26228A. The yellow pigment described in No. 8014, etc. can also be used.

Moreover, as a yellow pigment, the compound described in Japanese Patent Application Publication No. 2018-062644 can also be used. This compound can also be used as a pigment derivative.

Additionally, as described in Japanese Patent Laid-Open No. 2018-155881, C.I. Pigment Yellow 129 may be added for the purpose of improving weather resistance.

As a red pigment, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in Japanese Patent Application Laid-Open No. 2017-201384, and a diketopyrrolopyrrole compound described in paragraph numbers 0016 to 0022 of Japanese Patent Application Publication No. 6248838. , diketopyrrolopyrrole compounds described in International Publication No. 2012/102399, diketopyrrolopyrrole compounds described in International Publication No. 2012/117965, naphtholazo compounds described in Japanese Patent Application Publication No. 2012-229344, etc. You can also use it. Additionally, as a red pigment, a compound having a structure in which a group in which an oxygen atom, a sulfur atom, or a nitrogen atom is bonded to the aromatic ring is introduced, and an aromatic ring group is bonded to a diketopyrrolopyrrole skeleton can also be used.

White pigments include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, and hollow resin. Particles, zinc sulfide, etc. can be mentioned. The white pigment is preferably particles having titanium atoms, and titanium oxide is more preferable. Additionally, the white pigment is preferably particles having a refractive index of 2.10 or more for light with a wavelength of 589 nm. The above-mentioned refractive index is preferably 2.10 to 3.00, and more preferably 2.50 to 2.75.

In addition, the white pigment can be made of titanium oxide as described in "Titanium Oxide Properties and Application Technology by Manabu Kiyono, pages 13 to 45, published on June 25, 1991 by Kiyodo Shuppan."

The white pigment may not only be made of a single inorganic material, but may also use particles composited with other materials. For example, particles with pores or other materials inside, particles with a large number of inorganic particles attached to the core particle, and core and shell composite particles consisting of a core particle made of polymer particles and a shell layer made of inorganic nanofine particles. It is desirable to use As a core and shell composite particle consisting of a core particle made of the polymer particle and a shell layer made of inorganic nanofine particles, for example, the description in paragraphs 0012 to 0042 of Japanese Patent Application Laid-Open No. 2015-047520 can be referred to, the contents of which are It is used herein.

The white pigment can also use hollow inorganic particles. Hollow inorganic particles are inorganic particles with a structure that has cavities inside, and refer to inorganic particles that have cavities surrounded by an outer shell. Examples of hollow inorganic particles include hollow inorganic particles described in Japanese Patent Application Laid-Open No. 2011-075786, International Publication No. 2013/061621, and Japanese Patent Application Publication No. 2015-164881, the contents of which are incorporated herein by reference.

The black pigment is not particularly limited, and known pigments can be used. Examples include carbon black, titanium black, graphite, etc., with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black is black particles containing titanium atoms, and low-order titanium oxide or titanium oxynitride is preferable. The surface of titanium black can be modified as needed for purposes such as improving dispersibility and suppressing cohesion. For example, it is possible to coat the surface of titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Additionally, treatment using a water-repellent material as shown in Japanese Patent Application Publication No. 2007-302836 is also possible. As a black pigment, color index (C.I.) Pigment Black 1, 7, etc. can be mentioned. For titanium black, both the primary particle diameter and the average primary particle diameter of individual particles are preferably small. Specifically, it is preferable that the average primary particle diameter is 10 to 45 nm. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles and the content ratio of Si atoms and Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50. Regarding the above-mentioned dispersion, reference can be made to the description in paragraphs 0020 to 0105 of Japanese Patent Application Laid-Open No. 2012-169556, the contents of which are incorporated herein by reference. Examples of commercially available products of titanium black include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (product name: Mitsubishi Materials Co., Ltd.), Tilack D (product name: Ako Kasei ( Co., Ltd.), etc. may be mentioned.

In the present disclosure, dye may be used as the colorant. There are no particular restrictions on the dye, and known dyes can be used. For example, pyrazoleazo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazoleazo, pyridonazo, cyanine, and phenothiazine. dyes such as dyes based on pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyromethene. Additionally, the thiazole compounds described in Japanese Patent Application Laid-Open No. 2012-158649, the azo compounds described in Japanese Patent Application Laid-Open No. 2011-184493, and the azo compounds described in Japanese Patent Application Laid-Open No. 2011-145540 can also be preferably used. Moreover, as a yellow dye, the quinophthalone compound described in Paragraphs 0011-0034 of Unexamined-Japanese-Patent No. 2013-054339, the quinophthalone compound described in Paragraphs 0013-0058 of Unexamined-Japanese-Patent No. 2014-026228, etc. can also be used.

When the composition according to the present disclosure contains a colorant, the content of the colorant is preferably 1% by mass to 50% by mass based on the total solid content of the composition. When the composition according to the present disclosure contains two or more colorants, it is preferable that their total amount is within the above range.

<Coloring agent that transmits near-infrared rays and blocks visible light>

The composition according to the present disclosure may contain a colorant that transmits near-infrared rays (light with a wavelength in the near-infrared region) and blocks visible light (light with a wavelength in the visible region) (hereinafter also referred to as a colorant that blocks visible light). A composition containing a colorant that blocks visible light is preferably used as a composition for forming a near-infrared transmission filter.

In the present disclosure, the colorant that blocks visible light is preferably a colorant that absorbs light in the violet to red wavelength range. In addition, in the present disclosure, the colorant that blocks visible light is preferably a colorant that blocks light in the wavelength range of 450 nm to 650 nm. Additionally, the colorant that blocks visible light is preferably a colorant that transmits light with a wavelength of 900 nm to 1,300 nm. In the present disclosure, the colorant that blocks visible light preferably satisfies at least one of the following requirements (A) and (B).

(A): Contains two or more types of chromatic colorants, and black is formed by a combination of two or more types of chromatic colorants.

(B): Contains an organic black colorant.

As a chromatic colorant, those mentioned above can be mentioned. Examples of the organic black colorant include bisbenzofuranone compounds, azomethane compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. Bisbenzofuranone compounds include compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, and Japanese Patent Publication No. 2012-515234, etc., for example, "Irgaphor" manufactured by BASF. It is available as “Black”. Examples of the perylene compound include compounds described in paragraphs 0016 to 0020 of Japanese Patent Application Laid-Open No. 2017-226821, C.I. Pigment Black 31, 32, and the like. Azometaine compounds include compounds described in Japanese Patent Application Laid-Open No. 01-170601, Japanese Patent Application Publication No. 02-034664, etc., for example, "Chromopine" manufactured by Dainichi Seika Kogyo Co., Ltd. It is available as “Black A1103”.

When forming black by a combination of two or more types of chromatic colorants, examples of combinations of chromatic colorants include the following.

(1) A mode containing a yellow colorant, a blue colorant, a purple colorant, and a red colorant.

(2) A mode containing a yellow colorant, a blue colorant, and a red colorant.

(3) A mode containing a yellow colorant, a purple colorant, and a red colorant.

(4) A mode containing a yellow colorant and a purple colorant.

(5) A mode containing a green colorant, a blue colorant, a purple colorant, and a red colorant.

(6) A mode containing a purple colorant and an orange colorant.

(7) A mode containing a green colorant, a purple colorant, and a red colorant.

(8) A mode containing a green colorant and a red colorant.

The ratio (mass ratio) of each colorant is preferably as follows, for example.

[Formula 36]

Above no. In 1, the yellow colorant is more preferably 0.1 to 0.3, the blue colorant is more preferably 0.1 to 0.5, the purple colorant is more preferably 0.01 to 0.2, and the red colorant is more preferably 0.1 to 0.5. Above no. In 2, the yellow colorant is more preferably 0.1 to 0.3, the blue colorant is more preferably 0.1 to 0.5, and the red colorant is more preferably 0.1 to 0.5.

The composition may contain only one type of visible colorant or may contain two or more types.

The content of the visible colorant is preferably 0.1% by mass to 70% by mass, more preferably 0.5% by mass to 60% by mass, and still more preferably 1% by mass to 50% by mass, based on the total mass of the composition. .

<Pigment derivative>

The composition may contain a pigment derivative. Examples of the pigment derivative include compounds in which at least one group selected from the group consisting of an acid group, a basic group, and a hydrogen bonding group is bonded to the pigment skeleton. Examples of the acid group include sulfo group, carboxy group, phosphoric acid group, boronic acid group, sulfonimide group, sulfonamide group and salts thereof, and desalting structures of these salts. The atoms or atomic groups constituting the salt include alkali metal ions (Li ⁺ , Na ⁺ , K ^{+ ,} etc.), alkaline earth metal ions (Ca ²⁺ , Mg ^{2+ ,} etc.), ammonium ions, imidazolium ions, and pyridinium ions. , phosphonium ion, etc. In addition, examples of the desalting structure of the salt include groups in which salt-forming atoms or atomic groups are separated from the salt. For example, the desalting structure of a salt of a carboxylate group is a carboxylate group (-COO ^- ). Examples of basic groups include amino groups, pyridinyl groups, salts thereof, and desalted structures of these salts. Examples of the atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylic acid ions, sulfonic acid ions, and phenoxide ions. In addition, examples of the desalting structure of the salt include groups in which salt-forming atoms or atomic groups are separated from the salt. A hydrogen bonding group is a group that interacts through hydrogen atoms. Specific examples of hydrogen bonding groups include amide groups, hydroxy groups, -NHCONHR, -NHCOOR, and -OCONHR. R is preferably an alkyl group or an aryl group.

Examples of pigment derivatives include compounds represented by formula (B1).

[Formula 37]

In formula (B1), P represents a pigment skeleton, L represents a single bond or linking group, , when m is 2 or more, a plurality of L and X may be different from each other, and when n is 2 or more, a plurality of X may be different from each other.

As the pigment skeleton represented by P, squarylium pigment skeleton, croconium pigment skeleton, pyrrolopyrrole pigment skeleton, diketopyrrolopyrrole pigment skeleton, quinacridone pigment skeleton, anthraquinone pigment skeleton, dianthraquinone pigment skeleton, Benzoisoindole pigment skeleton, thiazine indigo pigment skeleton, azo pigment skeleton, quinophthalone pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, dioxazine pigment skeleton, perylene pigment skeleton, perrinone pigment skeleton. , at least one selected from the group consisting of a benzimidazolone dye skeleton, a benzothiazole pigment skeleton, a benzimidazole pigment skeleton, and a benzoxazole pigment skeleton is preferred, and squarylium pigment skeleton, croconium pigment skeleton, and pyrrolo pigment skeleton. At least one selected from the group consisting of pyrrole pigment skeleton, diketopyrrolopyrrole pigment skeleton, quinacridone pigment skeleton, and benzimidazolone pigment skeleton is more preferable, and squarylium pigment skeleton or croconium pigment skeleton is more preferred. Particularly desirable.

As the linking group represented by L, a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms is preferable. , may be unsubstituted, or may have additional substituents. Examples of the substituent include substituent T, which will be described later.

-substituent T-

As the substituent T, halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, -ORt ¹ , -CORt ¹ , -COORt ¹ , -OCORt ¹ , -NRt ¹ Rt ² , -NHCORt ¹ , -CONRt ¹ Rt ² , -NHCONRt ¹ Rt ² , -NHCOORt ¹ , -SRt ¹ , -SO ₂ Rt ¹ , -SO ₂ ORt ¹ , -NHSO ₂ Rt ¹ or -SO ₂ NRt ¹ Rt ² can be mentioned. Rt ¹ and Rt ² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. Rt ¹ and Rt ² may combine to form a ring.

Examples of the acid group, basic group, and hydrogen bonding group represented by X include the groups described above.

When using a pigment-type compound as a near-infrared absorbing dye, the pigment derivative is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 nm to 1,200 nm, and a compound having a maximum absorption wavelength in the wavelength range of 700 nm to 1,100 nm. It is also preferable that it is a compound having a maximum absorption wavelength in the wavelength range of 700 nm to 1,000 nm. A pigment derivative having a maximum absorption wavelength in the above wavelength range can easily allow the expansion of the ð plane to approach the near-infrared absorbing dye, improve the adsorption of the near-infrared absorbing dye, and facilitate better dispersion stability. Moreover, the pigment derivative is preferably a compound containing an aromatic ring, and is more preferably a compound containing a structure in which two or more aromatic rings are condensed. Additionally, the pigment derivative is preferably a compound having a conjugate plane, and more preferably a compound having a conjugate plane with the same structure as the conjugate plane contained in the near-infrared absorbing dye. In addition, it is preferable that the number of electrons included in the conjugate plane of the pigment derivative is 8 to 100. The upper limit is preferably 90 or less, and more preferably 80 or less. The lower limit is preferably 10 or more, and more preferably 12 or more. Moreover, the pigment derivative is also preferably a compound having a ð conjugate plane containing a partial structure represented by the following formula (SQ-a).

[Formula 38]

In the formula (SQ-a), the dashed line indicates the bonding position with another structure.

The pigment derivative is also preferably a compound represented by the following formula (Syn1).

[Formula 39]

In formula (Syn1), Rsy ¹ and Rsy ² each independently represent an organic group, L ¹ represents a single bond or a (p1+1) valent group, and A ¹ represents a sulfo group, a carboxy group, a phosphate group, a boronic acid group, or a sulfone group. It represents a group selected from the group consisting of a mid group, a sulfonamide group, an amino group, a pyridinyl group, a salt thereof, or a desalted structure thereof, and p1 and q1 each independently represent an integer of 1 or more. When p1 is 2 or more, a plurality of A ¹ may be the same or different. When q1 is 2 or more, a plurality of L ¹ and A ¹ may be the same or different.

Examples of the organic groups represented by Rsy ¹ and Rsy ² in the formula (Syn1) include an aryl group and a heteroaryl group. Additionally, suitable examples of the organic group include parts other than A in formula (1).

Examples of the (p1+1) valent group represented by L ¹ in the formula (Syn1) include hydrocarbon group, heterocyclic group, -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NR ^L -, -NR ^L CO-, -CONR ^L -, -NR ^L SO ₂ -, -SO ₂ NR ^L -, and groups consisting of combinations thereof can be mentioned. R ^L represents a hydrogen atom, an alkyl group, or an aryl group. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Examples of the hydrocarbon group include alkylene groups, arylene groups, and groups obtained by removing one or more hydrogen atoms from these groups. The number of carbon atoms of the alkylene group is preferably 1 to 30, more preferably 1 to 15, and still more preferably 1 to 10. The alkylene group may be linear, branched, or cyclic. Additionally, the cyclic alkylene group may be either monocyclic or polycyclic. The number of carbon atoms of the arylene group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. The heterocyclic group is preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 4. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The heteroatom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and more preferably 3 to 12. Hydrocarbon groups and heterocyclic groups may have substituents. Examples of the substituent include groups represented by the substituent T described later. Moreover, the number of carbon atoms of the alkyl group represented by R ^L is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 8. The alkyl group may be straight-chain, branched, or cyclic, and is preferably straight-chain or branched, and more preferably straight-chain. The alkyl group represented by R ^L may further have a substituent. Examples of the substituent include the substituent T described above. The number of carbon atoms of the aryl group represented by R ^L is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. The aryl group represented by R ^L may further have a substituent. Examples of the substituent include substituent T, which will be described later.

-substituent T-

As the substituent T, halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, -ORt ¹ , -CORt ¹ , -COORt ¹ , -OCORt ¹ , -NRt ¹ Rt ² , -NHCORt ¹ , -CONRt ¹ Rt ² , -NHCONRt ¹ Rt ² , -NHCOORt ¹ , -SRt ¹ , -SO ₂ Rt ¹ , -SO ₂ ORt ¹ , -NHSO ₂ Rt ¹ or -SO ₂ NRt ¹ Rt ² can be mentioned. Rt ¹ and Rt ² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. Rt ¹ and Rt ² may combine to form a ring.

Specific examples of pigment derivatives include compounds having the following structures. Additionally, Japanese Patent Application Laid-Open No. 56-118462, Japanese Patent Application Publication No. 63-264674, Japanese Patent Application Publication No. 1-217077, Japanese Patent Application Publication No. 3-9961, and Japanese Patent Application Publication No. 3-26767. , Japanese Patent Application Laid-Open No. 3-153780, Japanese Patent Application Publication No. 3-45662, Japanese Patent Application Publication No. 4-285669, Japanese Patent Application Publication No. 6-145546, Japanese Patent Application Publication No. 6-212088 , Japanese Patent Publication No. 6-240158, Japanese Patent Publication No. 10-30063, Japanese Patent Publication No. 10-195326, paragraphs 0086 to 0098 of International Publication No. 2011/024896, International Publication No. 2012. / The compounds described in paragraphs 0063 to 0094 of No. 102399, etc. can be mentioned.

In addition, as pigment derivatives, Japanese Patent Laid-Open No. 2015-172732 (metal salt of quinophthalone compound having a sulfo group), Japanese Patent Laid-Open No. 2014-199308, Japanese Patent Laid-Open No. 2014-85562, and Japanese Patent Laid-open No. 2014. Compounds described in -35351 or Japanese Patent Application Laid-Open No. 2008-81565 can also be used, the contents of which are incorporated herein by reference.

[Formula 40]

When the composition contains a pigment derivative, the content of the pigment derivative is preferably 1 part by mass to 30 parts by mass, with respect to 100 parts by mass of the pigment in the compound having the structure represented by formula (1) and the colorant. 20 parts by mass is more preferable. As for the pigment derivative, only one type may be used, or two or more types may be used together.

<Polymerization inhibitor>

The composition according to the present disclosure preferably contains a polymerization inhibitor from the viewpoint of storage stability.

The polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used.

As polymerization inhibitors, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, 2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2, 6,6-Tetramethyl-4-hydroxypiperidine-1-oxyl, t-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2, 2'-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, cerium salt, etc.), 2,2,6,6-tetramethylpipery Dean-1-oxyl, etc. can be mentioned. Additionally, the polymerization inhibitor may function as an antioxidant in some cases.

Polymerization inhibitors may be used individually by one type, or may be used in combination of two or more types.

From the viewpoint of storage stability, the content of the polymerization inhibitor is preferably 0.1 ppm to 1,000 ppm, more preferably 1 ppm to 500 ppm, and particularly preferably 1 ppm to 100 ppm, based on the total solid content of the composition.

<Solvent>

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

As solvents, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl Esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3- 3-oxypropionate alkyl esters such as methyl oxypropionate and ethyl 3-oxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate) ), and 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2-methylpropionate methyl, 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.;

Ethers, such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol Lycol propyl etheracetate, etc.; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; Aromatic hydrocarbons, such as toluene and xylene, can be mentioned. However, in some cases, it is better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents for reasons such as environmental reasons (for example, relative to the total mass of organic solvents, It may be set to 50 mass ppm (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less).

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, and 2-heptanone. , cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, etc. are suitable.

The solvent may be used alone or in combination of two or more types.

In the present disclosure, it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably 10 mass ppb (parts per billion) or less, for example. If necessary, an organic solvent of mass ppt (parts per trillion) level may be used. Such an organic solvent is provided by, for example, Toyo Kosei Kogyo Co., Ltd. (Kagaku Kogyo Nippo, November 2015) 13th).

Methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.

The organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one type of isomer may be contained, or multiple types may be contained.

It is preferable that the content of peroxide in the organic solvent is 0.8 mmol/L or less, and it is more preferable that it contains substantially no peroxide.

The total solid content of the composition according to the present disclosure changes depending on the application method and the presence or absence of a solvent, but is preferably, for example, 1% by mass to 100% by mass. The lower limit is more preferably 10% by mass or more.

<Sensitizer>

The composition according to the present disclosure may contain a sensitizer for the purpose of improving the generation efficiency of polymerization initiating species such as radicals and cations of the polymerization initiator and increasing the photosensitive wavelength. As a sensitizer that can be used in the present disclosure, it is preferable to sensitize the photopolymerization initiator described above using an electron transfer mechanism or an energy transfer mechanism.

Sensitizers that can be used in the present disclosure include those that belong to the compounds listed below and have an absorption wavelength in the wavelength range of 300 nm to 450 nm.

Examples of preferable sensitizers include those that belong to the following compounds and have an absorption wavelength in the range of 330 nm to 450 nm.

For example, polynuclear aromatics (e.g., phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (e.g., fluorescein, eosine, erythrosine) , rhodamine B, rose bengal), thioxanthone (isopropyl thioxanthone, diethyl thioxanthone, chlorothioxanthone), cyanines (e.g. thiacarbocyanine, oxacarbocyanin), Merocyanines (e.g., merocyanine, carbomerocyanine), phthalocyanines, thiazines (e.g., thionine, methylene blue, toluidine blue), acridines (e.g. , acridine orange, chloroflavin, acriflavin), anthraquinones (e.g. anthraquinone), squarylliums (e.g. squaryllium), acridine orange, coumarins (e.g. For example, 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, Carbazole, porphyrin, spiro compound, quinacridone, indigo, styryl, pyrylium compound, pyromethene compound, pyrazolotriazole compound, benzothiazole compound, barbituric acid derivative, thiobarbituric acid derivative, aceto Aromatic ketone compounds such as phenone, benzophenone, and Michler's ketone; heterocyclic compounds such as N-aryloxazolidinone; and the like. In addition, compounds described in European Patent Publication No. 568,993, US Patent Publication Nos. 4,508,811, 5,227,227, Japanese Patent Application Laid-Open No. 2001-125255, and Japanese Patent Application Publication No. Hei 11-271969, etc. can be mentioned.

Sensitizers may be used individually, or two or more types may be used in combination.

The content of the sensitizer in the composition according to the present disclosure is preferably 0.1% by mass to 20% by mass, based on the total solid content of the composition, from the viewpoint of light absorption efficiency into the deep portion and initiation decomposition efficiency, and is preferably 0.5% by mass. Mass% to 15 mass% is more preferable.

<Notarization system>

The composition according to the present disclosure may contain a sensitizing agent. The co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye or initiator to actinic radiation, or suppressing inhibition of polymerization of the polymerizable compound by oxygen.

In addition, examples of the notary sensitizer include the compounds described in paragraphs 0233 to 0241 of Japanese Patent Application Laid-Open No. 2007-277514.

The content of these co-sensitizers is preferably in the range of 0.1% by mass to 30% by mass, based on the mass of the total solid content of the composition, from the viewpoint of improving the curing speed by balancing the polymerization growth rate and chain transfer, and is 0.5% by mass. A range of ~25 mass% is more preferable, and a range of 1 mass%~20 mass% is more preferable.

<Other ingredients>

The composition according to the present disclosure includes, if necessary, a fluorine-based organic compound, a thermal polymerization inhibitor, a photopolymerization initiator, other fillers, a polymer compound other than an alkali-soluble resin and a dispersant, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-agglomeration agent. It may contain various additives such as:

Other components include, for example, compounds described in paragraphs 0238 to 0249 of Japanese Patent Application Laid-Open No. 2007-277514.

<Preparation of composition>

The composition according to the present disclosure can be prepared by mixing the components described above. Additionally, for purposes such as removal of foreign substances or reduction of defects, it is preferable to filter using a filter. As a filter, there is no particular limitation and can be used as long as it has been conventionally used for filtration purposes. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (e.g. nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP). Filters using (including high density and ultra-high molecular weight) and the like can be mentioned. Among these materials, polypropylene (including high-density polypropylene) or nylon is preferable.

The hole diameter of the filter is preferably 0.01 μm to 7.0 μm, more preferably 0.01 μm to 3.0 μm, and more preferably 0.05 μm to 0.5 μm. By setting this range, it becomes possible to reliably remove fine foreign substances that impede the preparation of a uniform and smooth composition in subsequent processes. In addition, it is also preferable to use a fibrous filter medium. Examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber, etc., specifically SBP type series (SBP008, etc.) and TPR type series (SBP008, etc.) manufactured by Loki Techno. Filter cartridges of the SHPX type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) can be used.

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

Additionally, first filters with different pore diameters within the above-mentioned range may be combined. The hole diameter here can refer to the filter manufacturer's nominal value. As commercially available filters, one can select from, for example, various filters provided by Japan Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd., or Kits Micro Filter Co., Ltd.

<Use of the composition>

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

When forming a film by application, the viscosity of the composition according to the present disclosure at 25°C is preferably 1 mPa·s to 100 mPa·s from the viewpoint of applicability. The lower limit is more preferably 2 mPa·s or more, and more preferably 3 mPa·s or more. The upper limit is more preferably 50 mPa·s or less, more preferably 30 mPa·s or less, and particularly preferably 15 mPa·s or less.

The viscosity in this disclosure is measured at 25°C using a viscometer (brand name: VISCOMETER TV-22) manufactured by Toki Sangyo Co., Ltd.

The use of the composition according to the present disclosure is not particularly limited. For example, it can be suitably used to form an infrared cut-off filter, etc. For example, an infrared cut filter on the light-receiving side of a solid-state image sensor (for example, for an infrared cut-off filter for a wafer level lens, etc.), and an infrared cut filter on the back side of the solid-state image sensor (the side opposite to the light-receiving side). It can be preferably used as an infrared cut-off filter, etc. In particular, it can be suitably used as an infrared cut-off filter on the light-receiving side of a solid-state imaging device. In addition, by further containing a colorant that blocks visible light in the composition according to the present disclosure, an infrared transmission filter capable of transmitting infrared rays of a specific wavelength or more can be formed. For example, it is possible to form an infrared transmission filter capable of transmitting infrared rays with a wavelength of 850 nm or more by blocking light from a wavelength of 400 nm to 850 nm.

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

As a storage container, for the purpose of preventing impurities from mixing into the raw materials or composition, it is also preferable to use a multi-layer bottle whose inner wall is made of 6 types of 6-layer resin or a bottle whose inner wall is made of 6 types of resin in a 7-layer structure. Examples of these containers include those described in Japanese Patent Application Publication No. 2015-123351.

<Act>

The film according to the present disclosure is a film made of the composition according to the present disclosure or by curing the composition. Additionally, when the composition contains a solvent, drying may be performed. The film according to the present disclosure can be suitably used as an infrared cut filter. Additionally, it can also be used as a heat ray shielding filter or an infrared transmission filter. The membrane according to the present disclosure may be used by being laminated on a support, or may be used by peeling from the support. The film according to the present disclosure may have a pattern or may be a film without a pattern (flat film).

“Drying” in the present disclosure just needs to remove at least part of the solvent, and there is no need to completely remove the solvent, and the amount of solvent removed can be set depending on the purpose.

In addition, the above-mentioned curing may be performed so 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 adjusted appropriately depending on the 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 thickness of the film is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still 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 or more, more preferably has a maximum absorption wavelength in the wavelength range of 650 nm to 1,500 nm, and has a maximum absorption wavelength in the wavelength range of 700 nm to 1,100 nm. It is more preferable to have it, and it is especially preferable to have a maximum absorption wavelength in the wavelength range of 760 nm to 1,000 nm.

When using the film according to the present disclosure as an infrared cut-off filter, it is preferable that the film according to the present disclosure satisfies at least one of the following conditions (1) to (4), and all conditions (1) to (4) are satisfied. It is more desirable to meet

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

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

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

(4) The transmittance at a wavelength of 650 nm is preferably 70% or more, more preferably 80% or more, more preferably 90% or more, and especially 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. A color filter can be manufactured using a coloring composition containing a chromatic colorant. Examples of the chromatic colorant include the chromatic colorant described in the section on the composition of the present disclosure. The coloring composition may further contain a resin, a polymerizable compound, a polymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber, etc. For details about these, the above-mentioned materials can be mentioned, and these can be used.

When using the film according to the present disclosure in combination with a color filter, it is preferable that the color filter is disposed on the optical path of the film according to the present disclosure. For example, the film according to the present disclosure and the color filter can be stacked and used as a laminate. In the laminate, the film and the color filter according to the present disclosure may be adjacent to each other in the thickness direction, or may not be adjacent to each other. 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 separate from the support on which the color filter is formed, and the film according to the present disclosure and the color filter may be formed on a support body separate from the support on which the color filter is formed. In between, other members constituting the solid-state imaging device (for example, microlens, planarization layer, etc.) may be interposed.

In addition, in the present disclosure, an infrared cut filter refers to a filter that transmits light (visible light) with a wavelength in the visible region and blocks at least a portion of light (infrared rays) with a wavelength in the near-infrared region. The infrared cut filter may transmit all light in the visible range, or may allow light in a specific wavelength range to pass among the visible range light and block light in the specific wavelength range. In addition, in the present disclosure, a color filter refers to a filter that passes light in a specific wavelength range among light in the visible range and blocks light in the specific wavelength range. In addition, in the present disclosure, an infrared transmission filter refers to a filter that blocks visible light and transmits at least a portion of infrared rays.

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

<Method for manufacturing membrane>

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

In the method for producing a membrane according to the present disclosure, the composition is preferably applied on a support. Examples of the support include substrates made of materials such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, and quartz glass. An organic film, an inorganic film, etc. may be formed on these substrates. Examples of materials for the organic film include the resins described above. Additionally, as a support, a substrate made of the above-mentioned resin can also be used. Additionally, a charge coupled device (CCD), complementary metal oxide semiconductor (CMOS), transparent conductive film, etc. may be formed on the support. Additionally, in some cases, a black matrix is formed on the support to isolate each pixel. Additionally, if necessary, an undercoating layer may be provided on the support to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface of the support, such as a substrate. In addition, when using a glass substrate as a support, it is preferable to form an inorganic film on the glass substrate or to use the glass substrate after dealkalizing it. According to this aspect, it is easy to manufacture a film in which the generation of foreign substances is further suppressed.

As a method of applying the composition, a known method can be used. For example, drop casting; slit coat method; spray method; roll coat method; Rotational application (spin coating); Flexible application method; Slit and spin method; prewet method (for example, the method described in Japanese Patent Application Publication No. 2009-145395); Various printing methods such as inkjet (e.g., on-demand, piezo, thermal) and nozzle jet printing, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; Transfer method using a mold, etc.; Nanoimprint method, etc. can be mentioned. There is no particular limitation on the application method for inkjet, for example, the method shown in "Diffuse and Usable Inkjet - Infinite Possibilities Viewed as a Patent", published in February 2005, Sumibe Techno Research (in particular, page 115) ~133 pages) or, Japanese Patent Publication No. 2003-262716, Japanese Patent Publication No. 2003-185831, Japanese Patent Publication No. 2003-261827, Japanese Patent Publication No. 2012-126830, and Japanese Patent Publication No. 2006-169325. Methods described in the above may be mentioned.

The composition layer formed by applying the composition may be dried (prebaked). When forming a pattern by a low-temperature process, prebaking does not need to be performed. When performing prebaking, 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 setting the prebake temperature to 150°C or lower, for example, when the photoelectric conversion film of an image sensor is made of an organic material, these characteristics can be maintained more effectively.

The prebake time is preferably 10 seconds to 3,000 seconds, more preferably 40 seconds to 2,500 seconds, and more preferably 80 seconds to 220 seconds. Drying can be performed using a hot plate, oven, etc.

The film manufacturing method according to the present disclosure may further include a step of forming a pattern. Examples of the pattern formation method include a photolithography method and a dry etching method. Additionally, when using the film according to the present disclosure as a flattening film, there is no need to perform a pattern forming process. Hereinafter, the process of forming a pattern will be described in detail.

-When forming patterns using photolithography-

The pattern formation method in the photolithography method includes a process of exposing the composition layer formed by applying the composition according to the present disclosure in a pattern (exposure process), and a process of developing and removing the composition layer in the unexposed area to form a pattern. (Development process) is preferably included. If necessary, a process for baking the developed pattern (post-bake process) may be provided. Hereinafter, each process will be described.

<<Exposure process>>

In the exposure process, 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. Thereby, the exposed portion can be cured. As radiation (light) that can be used during exposure, ultraviolet rays such as g-rays and i-rays are preferable, and i-rays are more preferable. The irradiation amount (exposure amount) is preferably, for example, 0.03 J/cm ² to 2.5 J/cm ² , more preferably 0.05 J/cm ² to 1.0 J/cm ² , and 0.08 J/cm ² to 0.5 J/cm 2 cm ² is particularly preferred. The oxygen concentration at the time of exposure can be appropriately selected. In addition to performing under the atmosphere, for example, under a hypoxic atmosphere with an oxygen concentration of 19 vol% or less (e.g., 15 vol%, 5 vol%, substantially oxygen-free) may be exposed, or may be exposed under a high-oxygen atmosphere in which the oxygen concentration exceeds 21 vol% (for example, 22 vol%, 30 vol%, 50 vol%). Additionally, the exposure illuminance can be set appropriately, preferably between 1,000 W/m ² and 100,000 W/m ² (for example, 5,000 W/m ² , 15,000 W/m ² , 35,000 W/m ² ). You can select from a range. The oxygen concentration and exposure illuminance may be combined with appropriate conditions, for example, the oxygen concentration is 10 volume% and the illuminance is 10,000 W/m ² , the oxygen concentration is 35 volume% and the illuminance is 20,000 W/m ² , etc.

<<Development process>>

Next, the composition layer in the unexposed portion of the composition layer after exposure is developed and removed to form a pattern. Development and removal of the composition layer in the unexposed area can be performed using a developing solution. As a result, the composition layer of the unexposed portion in the exposure process is eluted into the developing solution, and only the photocured portion remains on the support. As a developing solution, an alkaline developing solution that does not cause damage to the underlying solid-state imaging device or circuit is preferable. The temperature of the developing solution is preferably 20 to 30°C, for example. The development time is preferably 20 seconds to 180 seconds. Additionally, in order to improve residue removal, the process of shaking off the developer every 60 seconds and supplying new developer may be repeated several more times.

Examples of alkaline agents used in developing solutions include ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, and tetramethylammonium hydroxide. Ethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine , organic alkaline compounds such as 1,8-diazabicyclo[5.4.0]-7-undecene, and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. I can hear it. As a 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, and more preferably 0.01% by mass to 1% by mass. Additionally, a surfactant may be used in the developer. Examples of the surfactant include the surfactants described in the composition described above, and nonionic surfactants are preferred. From the viewpoint of convenience of transportation and storage, etc., the developer may be prepared as a concentrated solution and then diluted to the concentration required for use. The dilution ratio is not particularly limited, but can be set in the range of 1.5 times to 100 times, for example. In addition, when using a developer consisting of such an alkaline aqueous solution, it is preferable to wash (rinse) with pure water after development.

After development and drying, heat treatment (post-baking) may be performed. Post-baking is a heat treatment after development to ensure complete curing of the film. When performing post-bake, the post-bake temperature is preferably 100°C to 240°C, for example. From the viewpoint of film hardening, 200°C to 230°C is more preferable. In addition, when an organic electroluminescence (organic EL) element is used as a light emitting light source or when the photoelectric conversion film of the image sensor is made of an organic material, the post-bake temperature is preferably 150°C or lower, and more preferably 120°C or lower. Preferred, 100°C or lower is more preferred, and 90°C or lower is particularly preferred. The lower limit can be, for example, 50°C or higher. Post-baking can be performed continuously or in a batch manner on the film after development using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater so that the above conditions are met. In addition, when forming a pattern by a low-temperature process, post-baking does not need to be performed, and a re-exposure process (post-exposure process) may be added.

-When forming a pattern using dry etching-

Pattern formation in the dry etching method involves applying a composition to a support, curing the formed composition layer to form a cured layer, then forming a patterned photoresist layer on this cured layer, and then patterning. This can be done by using the photoresist layer as a mask and dry etching the cured layer using an etching gas. In forming the photoresist layer, it is preferable to additionally perform a prebake process. In particular, the photoresist formation process is preferably one in which heat treatment after exposure and heat treatment after development (post-bake treatment) are performed. Regarding pattern formation in the dry etching method, reference can be made to the description in paragraph numbers 0010 to 0067 of Japanese Patent Application Laid-Open No. 2013-64993, the contents of which are incorporated herein by reference.

<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 suitably used as an infrared cut-off filter or an infrared-transmitting filter, and can be more suitably used as an infrared cut-off filter.

Additionally, 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 is also a preferred embodiment of the optical filter according to the present disclosure.

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

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

In addition, the infrared cutoff filter according to the present disclosure may be a filter that blocks only infrared waves of a part of the infrared region, or may be a filter that blocks the entire infrared region. Examples of filters that block only infrared rays of a part of the infrared region include near-infrared ray cutoff filters. In addition, near infrared rays include infrared rays with a wavelength of 750 nm to 2,500 nm.

In addition, the infrared cut-off filter according to the present disclosure is preferably a filter that blocks infrared rays in the wavelength range of 750 nm to 1,000 nm, and more preferably is a filter that blocks infrared rays in the wavelength range of 750 nm to 1,200 nm, and has a wavelength of 750 nm. It is more preferable to use a filter that blocks infrared rays of ~1,500 nm.

The infrared cut filter according to the present disclosure may further include a layer containing copper, a dielectric multilayer film, an ultraviolet absorbing layer, etc. in addition to the above film. When the infrared cutoff filter according to the present disclosure further has at least a layer containing copper or a dielectric multilayer film, an infrared cutoff filter having a wide viewing angle and excellent infrared shielding properties can easily be obtained. In addition, the infrared cut filter according to the present disclosure can be used as an infrared cut filter with excellent ultraviolet ray blocking properties by further including an ultraviolet absorbing layer. As the ultraviolet absorbing layer, for example, reference can be made to the absorbing layer described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/099060, the contents of which are incorporated herein by reference. As a dielectric multilayer film, the description of paragraphs 0255 to 0259 of Japanese Patent Application Laid-Open No. 2014-41318 can be referred to, and this content is incorporated herein by reference. As the layer containing copper, a glass substrate made of glass containing copper (copper-containing glass substrate) or a layer containing a copper complex (copper complex-containing layer) can also be used. Examples of copper-containing glass substrates include copper-containing phosphate glass and copper-containing fluorophosphate glass. Commercially available copper-containing glasses include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (above, manufactured by Schott Corporation), and CD5000 (manufactured by HOYA Co., Ltd.).

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

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

The manufacturing method of the optical filter according to the present disclosure is not particularly limited, but includes the steps of applying the composition according to the present disclosure on a support to form a composition layer, exposing the composition layer in a pattern, and unexposed portions. It is preferable that the method includes a process of removing development to form a pattern.

In addition, a method for manufacturing an optical filter according to the present disclosure includes a step of applying the composition according to the present disclosure on a support to form a composition layer and curing it to form a layer, a step of forming a photoresist layer on the layer, It is also preferable that the method includes a step of patterning the photoresist layer through exposure and development to obtain a resist pattern, and a step of dry etching the layer using the resist pattern as an etching mask.

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-state imaging device>

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

On the support, a plurality of photodiodes constituting the light receiving area of the solid-state imaging device and a transfer electrode made of polysilicon, etc. are provided, and on the photodiodes and the transfer electrode, only the light receiving part of the photodiode is opened, and a light shielding film made of tungsten or the like is provided, It has a device protective film made of silicon nitride or the like formed to cover the entire surface of the light shielding film and the photodiode light receiving portion on the light shielding film, and has a film according to the present disclosure on the device protective film. In addition, a configuration having a light condensing means (e.g., micro lens, etc., hereinafter the same) above the device protective film and below the film according to the present disclosure (closer to the support), or a configuration having a light condensing means above the film according to the present disclosure. etc. may also be used. Moreover, the color filter used in a solid-state imaging device may have a structure in which the film forming each pixel fills the space partitioned by partitions, for example, in a grid shape. In this case, the partition wall preferably has a lower refractive index than each pixel. Examples of imaging devices having such a structure include devices described in Japanese Patent Application Laid-Open No. 2012-227478 and Japanese Patent Application Publication No. 2014-179577.

<Image display device>

The image display device according to the present disclosure has a film according to the present disclosure. Examples of image display devices include liquid crystal display devices and organic electroluminescence (organic EL) display devices. For definitions and details of image display devices, see, for example, "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)" and "Display Device (Written by Ibuki Sumiaki, Sankyo Tosho Co., Ltd.) Hei. (published in the first year of Sei)", etc. Additionally, liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd., 1994)." There is no particular limitation on the liquid crystal display device to which the present disclosure can be applied, and for example, it can be applied to various types of liquid crystal display devices described in the "Next Generation Liquid Crystal Display Technology" above. The image display device may have a white organic EL element. As a white organic EL element, it is preferable to have a tandem structure. Regarding the tandem structure of organic EL elements, Japanese Patent Publication No. 2003-45676, supervised by Akiyoshi Mikami, "The forefront of organic EL technology development - high brightness, high precision, long life, know-how collection -", Kijutsu Joho Kyokai, 326 It is listed on page 328, 2008, etc. The spectrum of white light emitted by an organic EL device preferably has strong maximum emission peaks in the blue region (430 nm to 485 nm), green region (530 nm to 580 nm), and yellow region (580 nm to 620 nm). In addition to these emission peaks, it is more preferable to further have a maximum emission peak in the red region (650 nm to 700 nm).

<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 an infrared sensor according to the present disclosure will be described using the drawings.

In FIG. 1, symbol 110 denotes a solid-state imaging device. The imaging area provided on the solid-state imaging device 110 has an infrared ray cutoff filter 111 and an infrared ray transmission filter 114. Additionally, a color filter 112 is stacked on the infrared cut-off filter 111. A micro lens 115 is disposed on the incident light (h*?*) side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed to cover the micro lens 115.

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

The color filter 112 is a color filter formed with a pixel that transmits and absorbs light of a specific wavelength in the visible region. There is no particular limitation, and a conventionally known color filter for forming a pixel can be used. For example, a color filter with red (R), green (G), and blue (B) pixels is used. For example, reference may be made to the description in paragraphs 0214 to 0263 of Japanese Patent Application Laid-Open No. 2014-43556, the contents of which are incorporated herein by reference.

The characteristics of the infrared transmission filter 114 are selected depending on the emission wavelength of the infrared LED used. For example, when the emission wavelength of the infrared LED is 850 nm, the maximum value of the light transmittance of the infrared transmission filter 114 in the thickness direction of the film in the wavelength range of 400 nm to 650 nm is preferably 30% or less, It is more preferable that it is 20% or less, more preferably 10% or less, and especially preferably 0.1% or less. It is desirable that this transmittance satisfies the above conditions throughout the wavelength range of 400 nm to 650 nm.

The minimum value of the light transmittance in the thickness direction of the infrared transmission filter 114 in the wavelength range of 800 nm or more (preferably 800 nm to 1,300 nm) is preferably 70% or more, and more preferably 80% or more. And it is more preferable that it is 90% or more. It is preferable that the above-mentioned transmittance satisfies the above-mentioned conditions in a part of the wavelength range of 800 nm or more, and more preferably, it satisfies the above-mentioned conditions 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, more preferably 5 μm or less, and especially preferably 1 μm or less. The lower limit is preferably 0.1 μm. If the film thickness is within the above range, a film that satisfies the spectral characteristics described above can be obtained.

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

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

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

Also, for example, when the emission wavelength of the infrared LED is 940 nm, the maximum value of the light transmittance in the thickness direction of the film of the infrared LED is 20% or less in the wavelength range of 450 nm to 650 nm, It is preferable that the light transmittance with a wavelength of 835 nm in the film thickness direction is 20% or less, and the minimum value of the light transmittance in the film thickness direction in the wavelength range of 1,000 nm to 1,300 nm is 70% or more.

In the infrared sensor shown in FIG. 1, an infrared cutoff filter (another infrared cutoff filter) separate from the infrared cutoff filter 111 may be further disposed on the planarization layer 116. Other infrared cut filters include those having a layer containing copper or at least a dielectric multilayer film. Details of these can be mentioned above. Additionally, as another infrared cut-off filter, a dual band pass filter may be used.

In addition, the absorption wavelengths of the infrared transmission filter and the infrared cutoff filter used in the present disclosure are used in appropriate combination according to the light source used, etc.

(camera module)

The camera module according to the present disclosure has a solid-state imaging element and an infrared cut-off filter according to the present disclosure.

Additionally, the camera module according to the present disclosure preferably further includes a lens and a circuit that processes images obtained from the solid-state imaging device.

The solid-state imaging device used in the camera module according to the present disclosure may be the solid-state imaging device described above or a known solid-state imaging device.

In addition, as the lens used in the camera module according to the present disclosure and the circuit for processing the image captured from the solid-state imaging device, known ones can be used.

As an example of a camera module, reference may be made to the camera module described in Japanese Patent Application Publication No. 2016-6476 or Japanese Patent Application Publication No. 2014-197190, the contents of which are incorporated herein by reference.

The film according to the present disclosure can be used as a heat insulating material or a heat storage material. Additionally, the composition according to the present disclosure can be used for paints, inkjet inks, security inks, etc.

(compound)

The compound according to the present disclosure is a compound having a structure represented by the following formula (1-2).

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

[Formula 41]

In formula (1-2), A represents a group represented by the following formula (1S) or formula (1C), and X _A and X and X _B are each independently an arylene group, a heteroarylene group, or a combination of two or more thereof represents one group, and R _1A to R _6A and R _1B to R _6B each independently represent a hydrogen atom or a substituent, and two or more of R _1A to R _6A and R _1B to R _6B may be bonded to each other to form a ring. However, at least two of R _1A to R _6A are bonded to each other to form a ring, and at least two of R _1B to R _6B are bonded to each other to form a ring.

[Formula 42]

In formula (1S) and formula (1C), * represents the bonding position with X _A or X _B in formula (1-2).

The compound having a structure represented by formula (1-2) in the compound according to the present disclosure is the same as the pigment having the structure represented by formula (1-2) described above in the composition according to the present disclosure, and is also a preferred embodiment. It is the same as the pigment having the structure shown in formula (1-2).

Example

Hereinafter, the present disclosure will be described in detail through examples, but the present disclosure is not limited to these.

In this embodiment, “%” and “part” mean “% by mass” and “part by mass”, respectively, unless otherwise specified. In addition, in polymer compounds, unless otherwise specified, the molecular weight is the weight average molecular weight (Mw), and the ratio of structural units is the mole percentage.

The weight average molecular weight (Mw) is a value measured as a polystyrene conversion value by gel permeation chromatography (GPC) method.

In addition, SQ-1 to SQ-13 and CR-1 to CR-10 used in this example are the same compounds as SQ-1 to SQ-13 and CR-1 to CR-10 described above, respectively.

<Synthesis of SQ-1>

SQ-1 was synthesized by the method shown below.

[Formula 43]

-Synthesis of Compound A-

Under a nitrogen atmosphere, 100 parts by mass of 2,3,3-trimethylindolenine, 447 parts by mass of THF (tetrahydrofuran), and 195.9 parts by mass of ethyl iodide (EtI) were added to the flask, and the mixture was heated and stirred under reflux for 20 hours. This reaction liquid was cooled to room temperature, and the precipitated solid was filtered and washed with 447 parts by mass of THF. The obtained solid was blown and dried at 50°C to obtain 125.1 parts by mass of Compound A (yield 63%).

-Synthesis of Compound B-

Under a nitrogen atmosphere, 125 parts by mass of Compound A, 625 parts by mass of distilled water, and 634.5 parts by mass of a 10% aqueous sodium hydroxide solution were added to the flask, and stirred at room temperature for 15 minutes. 409 parts by mass of hexane was added to this reaction liquid, and the mixture was stirred at room temperature for 5 minutes. This reaction liquid was subjected to liquid separation treatment, the aqueous layer was discarded, and the obtained organic layer was concentrated under reduced pressure to obtain 74.3 parts by mass of Compound B.

-Synthesis of Compound C-

Under a nitrogen atmosphere, 74.3 parts by mass of Compound B and 588 parts by mass of methanol were added to the flask, and the flask was cooled to 5°C. To this reaction solution, 22.5 parts by mass of NaBH ₄ was slowly added so that the internal temperature did not exceed 30°C. After the addition was completed, the mixture was stirred at room temperature for 1 hour, cooled to 5°C, and 743 parts by mass of distilled water was slowly added dropwise so that the internal temperature did not exceed 30°C. 666 parts by mass of ethyl acetate was added to this reaction liquid, and the mixture was stirred at room temperature for 5 minutes. This reaction liquid was subjected to liquid separation treatment, the aqueous layer was discarded, and the obtained organic layer was concentrated under reduced pressure to obtain 60.3 parts by mass of Compound C (80% yield in 2 steps from Compound A).

-Synthesis of Compound D-

Under a nitrogen atmosphere, 60.3 parts by mass of Compound C and 1,138 parts by mass of dimethylformamide (DMF) were added to the flask, and the flask was cooled to 5°C. 62.4 parts by mass of N-bromosuccinimide (NBS) was slowly added to this reaction solution so that the internal temperature did not exceed 30°C. After the addition was completed and stirred at 0 to 5°C for 2 hours, 1,206 parts by mass of distilled water was slowly added dropwise so that the internal temperature did not exceed 30°C. 541 parts by mass of ethyl acetate and 395 parts by mass of hexane were added to this reaction liquid, and the mixture was stirred at room temperature for 5 minutes. This reaction liquid was subjected to liquid separation treatment, the aqueous layer was discarded, and the obtained organic layer was concentrated under reduced pressure to obtain 78.7 parts by mass (yield 92%) of Compound D.

-Synthesis of Compound E-

Under a nitrogen atmosphere, 10 parts by mass of Compound D, 7.5 parts by mass of 3,5-dimethoxyboronic acid, 94 parts by mass of dimethylacetamide (DMAc), and a 2 M (mol/L) potassium carbonate aqueous solution were added to the flask in a total amount of 94% of the DMAc. When the mass part was 100 parts by volume, 27 parts by volume, 2.15 parts by mass of tetrakistriphenylphosphine palladium (Pd(PPh ₃ ) ₄ ) was added, and the mixture was stirred at 100°C for 3 hours. After cooling this reaction liquid to room temperature, 100 parts by mass of distilled water and 89.7 parts by mass of ethyl acetate were added, and the mixture was stirred at room temperature for 5 minutes. This reaction liquid was subjected to liquid separation, the aqueous layer was discarded, and the obtained organic layer was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 6.07 parts by mass of compound E (yield 50%).

-Synthesis of Compound F-

Under a nitrogen atmosphere, 6 parts by mass of Compound E and 80 parts by mass of dichloromethane were added to the flask, and the flask was cooled to 5°C. To this reaction solution, 1 M (mol/L) boron tribromide dichloromethane solution was slowly added at 18.4 parts by volume when the total amount of dichloromethane was 80 parts by mass to 60 parts by volume so that the internal temperature did not exceed 30°C. After the addition was completed and stirred at room temperature for 20 hours, the reaction liquid was cooled to 5°C, and 60 parts by mass of distilled water was added dropwise. After stirring this reaction solution at room temperature for 5 minutes, liquid separation was performed, the aqueous layer was discarded, and the obtained organic layer was washed twice with 60 mL of saturated saline solution. The obtained organic layer was dried over sodium sulfate, concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 2.36 parts by mass of compound F (yield 43%).

-Synthesis of SQ-1-

Under a nitrogen atmosphere, 0.4 parts by mass of squaric acid, 2.29 parts by mass of Compound F, 26 parts by mass of toluene, and 8.1 parts by mass of 1-butanol were added to the flask, and the mixture was stirred for 19 hours under heating and reflux. This reaction liquid was concentrated under reduced pressure, and 33.3 parts by mass of a mixture of methanol:water = 4:1 was added to the obtained residue at room temperature and stirred for 30 minutes. This reaction liquid was filtered and washed with 33.3 parts by mass of a mixed solution of methanol:water = 4:1. The obtained filtrate was blown and dried at 50°C to obtain 0.99 parts by mass of SQ-1 (yield 42%).

SQ-1 MS: m/z 672.32

<Synthesis of CR-1>

It was synthesized by the method shown below.

[Formula 44]

In the synthesis of Compound E, 3-methoxyboronic acid was used instead of 3,5-dimethoxyboronic acid, and in the synthesis of SQ-1, crochonic acid was used in the same equivalent amount instead of squaric acid, using the same synthesis method. synthesized.

CR-1 MS: m/z 668.33[M+]

<Synthesis of SQ-2 to SQ-13 and CR-2 to CR-10>

Except for changing the reaction substrate, each was synthesized using the same method as the synthesis of SQ-1 or CR-1.

<Preparation of dye solution>

A dye solution was prepared by mixing the dyes and solvents shown in Table 1 or Table 2 below in the mass ratio shown in Table 1 or Table 2.

(Examples 1 to 37, and Comparative Examples 1 to 3)

Each curable composition was produced according to the method for preparing any of the following curable compositions shown in Table 1 or Table 2.

<Preparation A of curable composition>

The following components were mixed in the mass ratio shown in Table 1 or Table 2 to prepare a curable composition.

-Composition of curable composition-

· Pigment solution listed in Table 1 or Table 2

Resin shown in Table 1 or Table 2 (30% cyclopentanone solution)

· Polymerizable compounds listed in Table 1 or Table 2

· Photopolymerization initiator listed in Table 1 or Table 2

·Polymerization inhibitor (p-methoxyphenol) listed in Table 1 or Table 2

·Megapark RS-72-K

<Preparation B of curable composition>

The following components were mixed in the mass ratio shown in Table 1 or Table 2 to prepare a curable composition.

-Composition of curable composition-

· Dye solution listed in Table 1 or Table 2

·Epoxy resin (30% cyclopentanone solution) listed in Table 1 or Table 2

·Epoxy curing agent listed in Table 1 or Table 2

Cured films were each produced using one of the following methods for producing a cured film shown in Table 1 or Table 2.

<Production of cured film A>

The curable composition was applied on a glass substrate by spin coating, 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 dose of 500 mJ/cm ² using an i-line stepper. Next, a curing treatment was performed on the composition layer after exposure at 220°C for 5 minutes using a hot plate to obtain a cured film with a thickness of 0.7 μm.

<Production of cured film B>

Each of the curable compositions prepared above was applied on a glass substrate by spin coating, then heated (pre-baked) at 80°C for 10 minutes using a hot plate, and then heated at 150°C for 3 hours to form a layer with a thickness of 0.7 μm. obtained the curtain.

<Evaluation of heat resistance>

The obtained membrane was heated at 260°C for 300 seconds using a hot plate. The transmittance of the film before and after heating to light with a wavelength of 400 nm to 1,200 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High Technologies Co., Ltd.). In the range of wavelength 400 nm to 1,200 nm, the residual ratio was calculated from the formula below for the absorbance at the maximum absorption wavelength before and after heating, and the residual ratio was evaluated based on the following criteria.

Residual rate (%) = {(absorbance after heating) χ (absorbance before heating)}Х100

A: Residual rate is greater than 90% and less than 100%

B: Residual rate greater than 70% but less than 90%

C: Residual rate is 70% or less

<Evaluation of lightfastness>

The obtained film was set on a fading tester equipped with a super xenon lamp (100,000 lux), and irradiated with 100,000 lux light for 50 hours under the condition of not using an ultraviolet ray blocking filter. Next, the transmission spectrum of the film after light irradiation was measured using a spectrophotometer U-4100 (manufactured by Hitachi High Technologies Co., Ltd.). In the range of wavelength 400 nm to 1,200 nm, the residual ratio was calculated from the formula below for the absorbance at the maximum absorption wavelength before and after light irradiation, and evaluated based on the following criteria.

Residual rate (%) = {(absorbance after light irradiation) χ (absorbance before light irradiation)}Х100

A: Residual rate is greater than 90% and less than 100%

B: Residual rate greater than 70% but less than 90%

C: Residual rate is 70% or less

<Evaluation of spectral characteristics>

The transmittance of the obtained film to light with a wavelength of 400 nm to 1,200 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High Technologies Co., Ltd.). In the range of wavelength 400 nm to 1,200 nm, the wavelength at which the absorbance is 0.5 when the maximum absorbance is 1 was calculated from the formula below, and the spectral characteristics were evaluated based on the following standards. In addition, when there are two or more wavelengths with an absorbance of 0.5, the longest wavelength is evaluated.

Spectral characteristics (nm) = (wavelength at absorbance 0.5) - (wavelength at absorbance 1)

A: Spectral characteristics are 115nm or less.

B: Spectral characteristics are greater than 115nm

The evaluation results are summarized in Table 1 and Table 2. It is preferable that at least one of the heat resistance evaluation and the light fastness evaluation is A, and it is more preferable that both the heat resistance evaluation and the light fastness evaluation are A.

[Table 1]

[Table 2]

In Tables 1 and 2, “M-1/M-2=1/1” in the column for each component means that the composition ratio (mass ratio) of M-1 and M-2 is 1:1, and other identical The description also has the same meaning as above.

Below, details of the abbreviations listed in Table 1 other than those described above are shown.

Comparison-1 to Comparison-3 in Table 2 are the following compounds.

[Formula 45]

<Suzy>

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

E-2: ARTON F4520 (made by JSR Co., Ltd.)

E-3: Resin with the following structure (Mw = 40,000, acid value 100 mgKOH/g, the numbers added to the main chain indicate the mass ratio of each structural unit. Alkali-soluble resin.)

[Formula 46]

<Photopolymerization initiator>

C-1: The following compound (IRGACURE OXE-01, manufactured by BASF)

C-2: The following compound (IRGACURE OXE-02, manufactured by BASF)

[Formula 47]

<Polymerizable compound>

M-1: Aronics M-305 (manufactured by Toagosei Co., Ltd., mixture of the following compounds. Triacrylate content is 55% by mass to 63% by mass)

[Formula 48]

M-2: KAYARAD RP-1040 (ethylene oxide modified pentaerythritol tetraacrylate, manufactured by Nippon Kayaku Co., Ltd.)

M-3: Aronix M-510 (multifunctional acrylate compound having a carboxyl group, manufactured by Toagosei Co., Ltd.)

<Epoxy Resin>

F-1: Glycidyl methacrylate skeleton random polymer (Nichiyu Co., Ltd., Maproof G-0150M, weight average molecular weight 10,000)

F-2: EPICLON HP-4700 (manufactured by DIC Corporation)

F-3: JER1031S (manufactured by Mitsubishi Chemical Corporation)

F-4: EHPE3150 (made by Daicel Co., Ltd.)

<Epoxy hardener>

G-1: trimellitic acid

G-2: Pyromellitic anhydride

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

G-4: Pentaerythritol tetrakis (3-mercaptopropionate)

<Solvent>

PGMEA: propylene glycol monomethyl ether acetate

CYP: Cyclopentanone

CYH: cyclohexanone

From the results shown in Table 1, it can be seen that the curable compositions of Examples 1 to 23, which are compositions according to the present disclosure, are superior to the compositions of Comparative Examples 1 to 3 in the heat resistance and light resistance of the obtained film. The same effect can be obtained even if an asymmetric pigment is included.

(Example 101 to Example 137)

Using the compositions of Examples 1 to 37, rectangular patterns (infrared cutoff filters) with a side of 2 μm were formed using the following method.

Examples 1 to 4, Examples 6 to 9, Examples 11 to 14, Examples 16 to 21, Examples 23 to 27, Examples 29, 31, Examples The curable compositions of Examples 33, 35, and 37 were patterned using the following method.

The curable composition was applied by spin coating so that the film thickness after film formation was 1.0 μm. Next, using a hot plate, it was heated at 100°C for 2 minutes. Next, using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Co., Ltd.), exposure was performed at 1,000 mJ/cm ² through a mask of a square dot pattern with a side of 2 μm. Next, puddle development was performed at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). After that, it was rinsed with a spin shower and further washed with pure water. Next, a square pattern (infrared cut-off filter) with a side of 2 μm was formed by heating at 200°C for 5 minutes using a hot plate.

The curable compositions of Example 5, Example 10, Example 15, Example 22, Example 28, Example 30, Example 32, Example 34, and Example 36 were patterned by the following method.

The curable compositions of Example 5, Example 10, Example 15, Example 22, Example 28, Example 30, Example 32, Example 34, and Example 36 were coated with silicone so that the film thickness after forming the film was 1.0 μm. It was applied on the wafer by spin coating. After that, it was heated at 100°C for 2 minutes using a hot plate. Next, using a hot plate, it was heated at 200°C for 5 minutes. Next, a square pattern (infrared cut-off filter) with a side of 2 μm was formed by dry etching.

Next, the Red composition was applied onto the pattern of the infrared cut filter by spin coating so that the film thickness after film formation was 1.0 μm. Next, using a hot plate, it was heated at 100°C for 2 minutes. Next, using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Co., Ltd.), exposure was performed at 1,000 mJ/cm ² through a mask of a square dot pattern with a side of 2 μm. Next, puddle development was performed at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). After that, it was rinsed with a spin shower and further washed with pure water. Next, the Red composition was patterned on the pattern of the infrared cut filter by heating at 200°C for 5 minutes using a hot plate. In the same way, the green composition and the blue composition were sequentially patterned to form red, green, and blue colored patterns (Bayer patterns).

In addition, the Bayer pattern refers to a color filter element having one red element, two green elements, and one blue element, as disclosed in U.S. Patent Publication No. 3,971,065. Although it is a pattern that repeats the 2Х2 array, in this embodiment, the filter has one red element, one green element, one blue element, and one infrared transmission filter element. A Bayer pattern was formed by repeating the 2Х2 array of elements.

Next, a composition for forming an infrared transmission filter (composition 100 or composition 101 below) was applied onto the patterned film by spin coating so that the film thickness after film formation was 2.0 μm. Next, using a hot plate, it was heated at 100°C for 2 minutes. Next, using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Co., Ltd.), exposure was performed at 1,000 mJ/cm ² through a square Bayer pattern mask with a side of 2 μm. Next, puddle development was performed at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). After that, it was rinsed with a spin shower and further 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 where the colored pattern was not formed in the Bayer pattern of the infrared cut filter. This was introduced into a solid-state imaging device according to a known method.

The obtained solid-state imaging device was irradiated with infrared rays using an infrared light-emitting diode (infrared LED) in a low-illuminance environment (0.001 lux (Lux)), the image was read, and the image performance was evaluated. When any of the curable compositions obtained in Examples 1 to 37 were used, images 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 for the above patterning are as follows.

-Red Composition-

The following components were mixed, stirred, and then filtered through a nylon filter with a pore diameter of 0.45 μm (manufactured by Nippon Pol Co., Ltd.) 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 with a pore diameter of 0.45 μm (manufactured by Nippon Pol Co., Ltd.) 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 Chemical Co., Ltd.): 0.5 parts by mass

PGMEA: 19.5 parts by mass

-Blue composition-

The following components were mixed, stirred, and filtered through a nylon filter with a pore diameter of 0.45 μm (manufactured by Nippon Pol Co., Ltd.) 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 in the following composition were mixed, stirred, and then filtered through a nylon filter with a pore diameter of 0.45 μm (manufactured by Nippon Pol Co., Ltd.) 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 parts 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-octanedione-2-(O-benzoyloxime)): 10 parts by mass

PGMEA: 179 parts by mass

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

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

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

<Pigment dispersion 2-1>

60 parts by mass of C. I. Pigment Black 32, 20 parts by mass of C. I. Pigment Blue 15:6, 20 parts by mass of C. I. Pigment Yellow 139, and 80 parts by mass of Solsperse 76500 manufactured by Nippon Lubrizol Co., Ltd. (solid content) Concentration 50% by mass), 120 parts by mass of a solution containing alkali-soluble polymer F-1 (solid content concentration 35% by mass), and 700 parts by mass of propylene glycol monomethyl ether acetate were mixed, and then mixed with 8 parts by mass using a paint shaker. By time dispersion, colorant dispersion 2-1 was obtained.

The raw materials used for the red composition, green composition, blue composition, and composition for forming an infrared transmission filter are as follows.

·Red pigment dispersion

A mixed solution consisting of 9.6 parts by mass of CI Pigment Red 254, 4.3 parts by mass of CI 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 with a diameter of 0.3 mm). By mixing and dispersing for 3 hours, a pigment dispersion was prepared. After that, dispersion treatment was performed using a high-pressure disperser NANO-3000-10 (manufactured by Nippon Biei Co., Ltd.) equipped with a pressure reduction mechanism 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

A mixed solution consisting of 6.4 parts by mass of CI Pigment Green 36, 5.3 parts by mass of CI 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 was placed in a bead mill (zirconia beads 0.3 mm diameter). By mixing and dispersing for 3 hours, a pigment dispersion was prepared. After that, dispersion treatment was performed using a high-pressure disperser NANO-3000-10 (manufactured by Nippon Biei Co., Ltd.) equipped with a pressure reduction mechanism 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

A mixture consisting of 9.7 parts by mass of CI Pigment Blue 15:6, 2.4 parts by mass of CI Pigment Violet 23, 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts by mass of PGMEA was mixed with a bead mill (0.3 mm zirconia beads). By mixing and dispersing for 3 hours, a pigment dispersion was prepared. After that, dispersion treatment was performed using a high-pressure disperser NANO-3000-10 (manufactured by Nippon Biei Co., Ltd.) equipped with a pressure reduction mechanism 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.

·Pigment dispersion 1-1

The mixed solution of the following composition was mixed and dispersed for 3 hours using zirconia beads with a diameter of 0.3 mm using a bead mill (high-pressure disperser NANO-3000-10 equipped with a pressure reduction mechanism (manufactured by Nippon Biei Co., Ltd.)) to form a pigment. Dispersion 1-1 was prepared.

·Mixed pigment consisting of red pigment (C.I. Pigment Red 254) and yellow pigment (C.I. 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 1-2

The mixed solution of the following composition was mixed and dispersed for 3 hours using zirconia beads with a diameter of 0.3 mm using a bead mill (high-pressure disperser NANO-3000-10 equipped with a pressure reduction mechanism (manufactured by Nippon Biei Co., Ltd.)) to form a pigment. Dispersion 1-2 was prepared.

·Mixed pigment consisting of blue pigment (C.I. Pigment Blue 15:6) and purple pigment (C.I. 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

Details of the abbreviations for the components used above are shown below.

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

[Formula 49]

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

・Polymerizable compound 4: structure below

[Formula 50]

Polymerizable Compound 5: Structure below (mixture with a molar ratio of the left compound and the right compound of 7:3)

[Formula 51]

Resin 4: Structure below (acid value: 70mgKOH/g, Mw=11,000, ratio in each structural unit is molar ratio.)

[Formula 52]

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

· Photopolymerization initiator 2: structure below

[Formula 53]

· Surfactant 1: 1% by mass PGMEA solution of the following mixture (Mw = 14,000). In the formula below, % (62% and 38%) representing the ratio of structural units is a molar ratio.

[Formula 54]

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

[Formula 55]

In Composition 100, a composition for forming an infrared transmission filter was manufactured and evaluated using C. I. Pigment Red 177 instead of C. I. Pigment Red 254 as the red pigment, and the same results were obtained.

(Example 201)

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

Curable composition of Example 1: 22.67 parts by mass

Pigment dispersion 2-1: 51.23 parts by mass

As a result of evaluating light resistance and heat resistance in the same manner as Example 101 using the pattern forming composition of Example 201, the same effect as Example 101 was obtained. In addition, the cured film obtained using the pattern forming composition of Example 201 was able to block light with a wavelength in the visible region and transmit at least a part of light with a wavelength in the near-infrared region (near-infrared rays).

(Example 202)

The following composition was mixed, stirred, and then filtered through a nylon filter with a pore diameter of 0.45 μm (manufactured by Nippon Pol Co., Ltd.) to prepare a composition for forming a pattern of Example 202.

Curable composition 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

As a result of evaluating light resistance and heat resistance in the same manner as Example 101 using the pattern forming composition of Example 202, the same effect as Example 101 was obtained. In addition, the cured film obtained using the composition for forming a pattern in Example 202 was able to block light with a wavelength in the visible region and transmit at least a part of light with a wavelength in the near-infrared region (near-infrared rays).

(Example 301)

The same as Example 101 except that the curable compositions of Examples 1 to 37 were used respectively and changed to a different substrate (in the case of a glass substrate, it was changed to a silicon wafer, and in the case of a silicon wafer, it was changed to a glass substrate). Even when evaluated similarly, the same effects as Examples 101 to 137 are obtained.

(Example 302)

Example 101 and Example 202, except that the pattern forming composition obtained in Example 201 or Example 202 was used as a different substrate (in the case of a glass substrate, it was changed to a silicon wafer, and in the case of a silicon wafer, it was changed to a glass substrate). Even when evaluated in the same way, the same effect as Example 101 is obtained.

(Example 401)

Except that the curable composition of Example 1 used in Example 201 was replaced with the curable composition of Examples 2 to 37, a composition for forming a pattern was prepared in the same manner as in Example 201, and the light resistance and heat resistance were the same as in Example 201. As a result of the evaluation, the same effect as Example 201 was obtained. In addition, the cured film obtained using the pattern forming composition of Example 401 was able to block light with a wavelength in the visible region and transmit at least a part of light with a wavelength in the near-infrared region (near-infrared rays).

(Example 402)

Except that the curable composition of Example 1 used in Example 202 was replaced with the curable composition of Examples 2 to 37, a composition for forming a pattern was prepared in the same manner as in Example 202, and the light resistance and heat resistance were tested in the same manner as in Example 202. As a result of evaluation, the same effect as Example 202 was obtained. Additionally, the cured film obtained using the pattern forming composition of Example 402 was able to block light with a wavelength in the visible region and transmit at least a portion of light with a wavelength in the near-infrared region (near-infrared rays).

The disclosure of Japanese Patent Application No. 2019-148563 filed on August 13, 2019 is incorporated herein by reference in its entirety.

All documents, patent applications, and technical standards described in this specification are incorporated by reference in this specification to the same extent as if each individual document, patent application, or technical standard were specifically and individually recorded. It is invoked by .

110: solid-state imaging device
111: Infrared blocking filter
112: Color filter
114: Infrared transmission filter
115: micro lens
116: Flattening layer

Claims (19)

A pigment having a structure represented by the following formula (1),
A composition comprising a binder and at least one compound selected from the group consisting of curable compounds.
[Formula 1]

In formula ₍ 1), A represents a group represented by the following formula (1S) or formula ( _1C ), represents a hydrogen atom or a substituent, and two or more of R ₁ to R ₆ may be bonded to each other to form a ring, provided that at least two of R ₁ to R ₆ are bonded to each other to form a ring, and the broken line The part indicates the binding position with another structure.
[Formula 2]

In formula (1S) and formula (1C), * represents the bonding position with X in formula (1) or the bonding position with another structure. In claim 1,
A composition where X is a group represented by any of the following formulas (Ar-1) to (Ar-6).
[Formula 3]

In _formulas (Ar _- 1) to (Ar-6 ₎ , _{Xa 1} to ₂₀ each independently represents a hydrogen atom or a substituent, R ₁₁ and R ₁₂ may be combined with each other to form a ring, and * represents the bonding position with another structure. In claim 1 or claim 2,
A composition where X is a group represented by any of the following formulas (Ar-7) to (Ar-13).
[Formula 4]

In formulas (Ar-7) to (Ar-13), R ₂₁ represents an alkyl group, an aryl group, -X ₂₁ -R _21a , or -X ₂₁ -L ₂₁ -Z _{21 -R 21a} , and represents -CO-, -CS-, -SO ₂ -, -CONH-, -CSNH- or -COO-, L ₂₁ represents an alkylene group or arylene group, Z ₂₁ represents -CONR _Z21a -, -CSNR _Z21a -, -OCONR _Z21a -, -NR _Z21a CONR _Z21b -, -NR _Z21a CSNR _Z21b -, -OCOO- or -NR _Z21a SO ₂ -, R _Z21a and R _Z21b are each independently a hydrogen atom, represents an alkyl group or an aryl group, R _21a represents an alkyl group or an aryl group, R ₂₂ to R ₃₃ each independently represent a hydrogen atom or a substituent, R ₂₂ and R ₂₃ , R ₂₄ and R ₂₅ , R ₂₆ and R ₂₇ , R ₂₈ and R ₂₉ may be combined with each other to form a ring, and * indicates the bonding position with another structure. In claim 1 or claim 2,
A composition wherein the pigment having a structure represented by the above formula (1) is a pigment represented by any of the following formulas (2) to (6).
[Formula 5]

In formulas (2) to (6), A represents a group represented by the following formula (1S ₎ or formula (1C), R ₁₄₇ each independently represents a hydrogen atom or a substituent, R ₇₂ and R ₇₃ , R ₈₂ and R ₈₃ , R ₈₄ and R ₈₅ , R ₉₄ and R ₉₅ , R ₉₆ and R ₉₇ , R ₁₀₈ and R ₁₀₉ , R ₁₁₀ and R ₁₁₁ , R ₁₂₂ and R ₁₂₃ , R ₁₂₄ and R ₁₂₅ , R ₁₃₄ and R ₁₃₅ , R ₁₃₆ and R ₁₃₇ , and R ₁₄₆ and R ₁₄₇ may be combined with each other to form a ring.
[Formula 6]

In formulas (1S) and (1C), * represents the bonding position with X in formulas (2) to (6). In claim 1 or claim 2,
A composition comprising the curable compound and further comprising a photopolymerization initiator. In claim 1 or claim 2,
As the binder, a composition comprising a binder polymer. A film comprising the curable composition according to claim 1 or 2 or by curing the curable composition. An optical filter having the membrane according to claim 7. In claim 8,
Optical filters that are either infrared blocking filters or infrared transmitting filters. A solid-state imaging device having the film according to claim 7. An infrared sensor having the film according to claim 7. A process of forming a composition layer by applying the curable composition according to claim 1 or claim 2 on a support,
A process of exposing the composition layer in a pattern;
A method of manufacturing an optical filter including a process of developing and removing unexposed areas to form a pattern. A process of applying the curable composition according to claim 1 or 2 on a support to form a composition layer and curing to form a layer,
A process of forming a photoresist layer on the layer,
A process of patterning the photoresist layer by exposure and development to obtain a resist pattern, and
A method of manufacturing an optical filter including a step of dry etching the layer using the resist pattern as an etching mask. A camera module having a solid-state imaging device and the optical filter according to claim 9. A compound having a structure represented by the following formula (1-2).
[Formula 7]

In formula (1-2), A represents a group represented by the following formula (1S) or _formula (1C ₎ , and represents one group, and R _1A to R _6A and R _1B to R _6B each independently represent a hydrogen atom or a substituent, and two or more of R _1A to R _6A and R _1B to R _6B may be bonded to each other to form a ring. However, at least two of R _1A to R _6A are bonded to each other to form a ring, and at least two of R _1B to R _6B are bonded to each other to form a ring.
[Formula 8]

In formula (1S) and formula (1C), * represents the bonding position with X _A or X _B in formula (1-2). In claim 15,
A compound in which X _A and X _B are each independently represented by any one of the formulas (Ar-1) to (Ar-6).
[Formula 9]

In _formulas (Ar _- 1) to (Ar-6 ₎ , _{Xa 1} to ₂₀ each independently represents a hydrogen atom or a substituent, R ₁₁ and R ₁₂ may be combined with each other to form a ring, and * represents the bonding position with another structure. In claim 15 or claim 16,
A compound in which X _A and X _B are each independently represented by any of the following formulas (Ar-7) to (Ar-13).
[Formula 10]

In formulas (Ar-7) to (Ar-13), R ₂₁ represents an alkyl group, an aryl group, -X ₂₁ -R _21a , or -X ₂₁ -L ₂₁ -Z _{21 -R 21a} , and represents -CO-, -CS-, -SO ₂ -, -CONH-, -CSNH- or -COO-, L ₂₁ represents an alkylene group or arylene group, Z ₂₁ represents -CONR _Z21a -, -CSNR _Z21a -, -OCONR _Z21a -, -NR _Z21a CONR _Z21b -, -NR _Z21a CSNR _Z21b -, -OCOO- or -NR _Z21a SO ₂ -, R _Z21a and R _Z21b are each independently a hydrogen atom, represents an alkyl group or an aryl group, R _21a represents an alkyl group or an aryl group, R ₂₂ to R ₃₃ each independently represent a hydrogen atom or a substituent, R ₂₂ and R ₂₃ , R ₂₄ and R ₂₅ , R ₂₆ and R ₂₇ , R ₂₈ and R ₂₉ may be combined with each other to form a ring, and * indicates the bonding position with another structure. In claim 15 or claim 16,
A compound in which the pigment having a structure represented by the above formula (1-2) is a pigment represented by any of the following formulas (2) to (6).
[Formula 11]

In formulas (2) to (6), A represents a group represented by the following formula (1S ₎ or formula (1C), R ₁₄₇ each independently represents a hydrogen atom or a substituent, R ₇₂ and R ₇₃ , R ₈₂ and R ₈₃ , R ₈₄ and R ₈₅ , R ₉₄ and R ₉₅ , R ₉₆ and R ₉₇ , R ₁₀₈ and R ₁₀₉ , R ₁₁₀ and R ₁₁₁ , R ₁₂₂ and R ₁₂₃ , R ₁₂₄ and R ₁₂₅ , R ₁₃₄ and R ₁₃₅ , R ₁₃₆ and R ₁₃₇ , and R ₁₄₆ and R ₁₄₇ may be combined with each other to form a ring.
[Formula 12]

In formulas (1S) and (1C), * represents the bonding position with X in formulas (2) to (6). In claim 15 or claim 16,
A compound that is an infrared absorbing pigment.