TW202113023A - Near-infrared absorption composition, film, optical filter and manufacturing method thereof, solid-state imaging element, infrared sensor, camera module, and inkjet ink - Google Patents

Abstract

Provided are: a near-infrared absorption composition having excellent storage stability; a film using the near-infrared absorption composition; and an application thereof. The near-infrared absorption composition includes: a near-infrared absorption pigment; a basic group-containing resin; and a binder resin which has an SP value of 19.7 MPa1/2 to 21.2 MPa1/2 and an acid value of 70 mgKOH/g to 105 mgKOH/g, and which is a resin other than the basic group-containing resin.

Description

Near-infrared absorbing composition, film, filter and manufacturing method thereof, solid-state imaging element, infrared sensor, camera module, and inkjet ink

The present invention relates to a near-infrared absorbing composition, film, filter and manufacturing method thereof, solid-state imaging element, infrared sensor, camera module and inkjet ink.

As an example of the optical filter, an infrared cut filter, an infrared transmission filter, etc. containing near-infrared absorbing pigments are known. As a curable composition for obtaining the above-mentioned optical filter, for example, Patent Document 1 discloses the following: a curable composition containing a near-infrared absorbing pigment and a polymer containing a group having an unsaturated double bond A monomer, the near-infrared absorbing dye is a compound having a π-conjugated plane containing a monocyclic or condensed aromatic ring, and the content of the near-infrared absorbing dye in the total solid content of the curable composition is 10 mass % Or more, the content of the polymerizable monomer containing at least one group selected from an acid group and a hydroxyl group and a group having an unsaturated double bond in the total mass of the above-mentioned polymerizable monomer is 50% by mass or less.

[Patent Document 1] International Publication No. 2018/142799

The problem to be solved by one embodiment of the present invention is to provide a near-infrared absorbing composition having excellent storage stability. In addition, a problem to be solved by another embodiment of the present invention is to provide a film, an optical filter and a method of manufacturing the same, a solid-state imaging element, an infrared sensor, a camera module, and a spray using the above-mentioned near-infrared absorbing composition. Ink ink.

The mechanisms used to solve the above-mentioned problems include the following aspects.

<1> A near-infrared absorbing composition comprising a near-infrared absorbing pigment, a resin having a base, and other than the above-mentioned resin having a base, the SP value is 19.7MPa ^1/2 to 21.2MPa ^1/2 and the acid value It is a binder resin of 70mgKOH/g～105mgKOH/g.

<2> The near-infrared absorbing composition as described in <1>, wherein The binder resin contains a structural unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring in a ratio of 50 mol% to 90 mol% relative to the total structural unit of the binder resin之resin. <3> The near-infrared absorbing composition as described in <2>, wherein The aforementioned aliphatic ring system is bicyclic or tricyclic. <4> The near-infrared absorbing composition as described in <2> or <3>, wherein The above-mentioned aromatic ring is a benzene ring, a naphthalene ring or a nitrogen-containing heteroaromatic ring.

<5> The near-infrared absorbing composition according to any one of <1> to <4>, wherein The said binder resin is a resin which contains the structural unit which has an acid group in 10 mol%-40 mol% with respect to the total structural unit of the said binder resin. <6> The near-infrared absorbing composition according to any one of <1> to <5>, wherein The weight average molecular weight of the above-mentioned binder resin is 20,000 or less.

<7> The near-infrared absorbing composition according to any one of <1> to <6>, wherein The above-mentioned base-containing resin is at least one selected from the group consisting of a resin having a tertiary amine group in the side chain and a resin having a nitrogen atom in the main chain. <8> The near-infrared absorbing composition as described in <7>, wherein The above-mentioned resin system having a tertiary amine group on the side chain and further a resin having a quaternary ammonium salt group on the side chain.

<9> The near-infrared absorbing composition according to any one of <1> to <8>, wherein The above-mentioned near-infrared absorbing pigment is a pyrrolopyrrole compound or a squaraine compound. <10> The near-infrared absorbing composition according to any one of <1> to <9>, wherein The content of tin is 1 ppm to 15 ppm with respect to the total solid content of the near-infrared absorbing composition.

<11> The near-infrared absorbing composition according to any one of <1> to <10>, which further contains a polymerizable compound and a polymerization initiator. <12> A film consisting of the near-infrared absorbing composition described in any one of <1> to <11> or hardening the near-infrared absorbing composition. <13> An optical filter having the film described in <12>. <14> The filter as described in <13>, which is an infrared cut filter or an infrared transmission filter. <15> A solid-state imaging device having the film described in <12>. <16> An infrared sensor having the film described in <12>. <17> A method of manufacturing an optical filter, which includes: The step of applying the near-infrared absorbing composition described in <11> to the support to form a composition layer; The step of exposing the above composition layer in a pattern; and The step of developing and removing the unexposed parts to form a pattern. <18> A method of manufacturing an optical filter, which includes: The step of applying the near-infrared absorbing composition described in <11> to the support to form a composition layer, and hardening it to form a layer; The step of forming a photoresist layer on the above-mentioned layer; The step of patterning the photoresist layer by exposure and development to obtain a photoresist pattern; and The step of dry etching the above-mentioned layer using the above-mentioned photoresist pattern as an etching mask. <19> A camera module having a solid-state imaging element and the filter described in <13> or <14>. <20> An inkjet ink comprising the near-infrared absorption composition described in <11>. [Effects of the invention]

According to an embodiment of the present invention, there is provided a near-infrared absorbing composition having excellent storage stability. In addition, according to another embodiment of the present invention, there is provided a film using the above-mentioned near-infrared absorbing composition, an optical filter and a manufacturing method thereof, a solid-state imaging element, an infrared sensor, a camera module, and an inkjet ink.

Hereinafter, the content of the present invention will be described in detail. In this specification, the "total solid content" refers to the total mass of the components after removing the solvent from all the components of the composition. In addition, the "solid component" refers to the component from which the solvent has been removed as described above, for example, it may be solid or liquid at 25°C. Regarding the label of the group (atomic group) in this specification, the label system that does not describe substituted and unsubstituted includes both those that do not have a substituent and those that have a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). As long as the "exposure" in this specification is not particularly limited, in addition to exposure with light, it also includes drawing with particle beams such as electron beams and ion beams. In addition, as the light used for exposure, there are usually actinic rays or radiations such as the bright line spectrum of a mercury lamp, and extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams. In this specification, "(meth)acrylate" means both or either of acrylate and methacrylate, and "(meth)acrylic" means both or either of acrylic acid and methacrylic acid, " "(Meth)acryloyl group" means both or any one of an acryloyl group and a methacryloyl group. In this specification, Me in the chemical formula 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" not only includes an independent process, but also includes this term if it plays the expected role of the process even when it cannot be clearly distinguished from other processes. In addition, in the present invention, the definition of "% by mass" is the same as that of "% by weight", and the definition of "parts by mass" is the same as that of "parts by weight". Furthermore, in the present invention, a combination of two or more preferable aspects is a more preferable aspect. In addition, unless otherwise specified, the transmittance in the present invention is the transmittance at 25°C.

In this specification, the weight average molecular weight and number average molecular weight of the resin are defined as polystyrene conversion values measured by gel permeation chromatography (GPC). In the present invention, when the content of the "structural unit" in the resin is limited by molar ratio, the meaning of the "structural unit" is the same as the meaning of the "monomer unit". However, the "monomer unit" in the present invention may be modified by polymer reaction or the like after polymerization.

<Near-infrared absorption composition> The near-infrared absorption composition of the present invention (hereinafter also referred to as "composition") includes a near-infrared absorption pigment, a resin having a basic group, and an SP value system other than the above-mentioned resin having a basic group 19.7MPa ^1/2 to 21.2MPa ^1/2 and an acid value of 70mgKOH/g～105mgKOH/g binder resin (hereinafter, also referred to as "specific binder resin").

A near-infrared absorbing composition containing a near-infrared absorbing pigment, a dispersant as a resin having a base, and a binder resin, specifically, for example, in the curable composition described in Patent Document 1, the viscosity is found to increase over time. The storage stability may decrease. The reason for this can be presumed as follows. The base possessed by the dispersant has adsorption performance for the near-infrared absorbing pigment and improves the dispersibility of the near-infrared absorbing pigment. However, the binder resin coexisting in the composition adsorbs to the base of the dispersant, which causes the dispersant to peel off from the near-infrared absorbing pigment. As a result, it is considered that it is difficult to express the dispersibility of the near-infrared absorbing pigment based on a resin having a base, and the near-infrared absorbing pigment aggregates over time, and the storage stability is reduced. Therefore, as a result of intensive research on the problem of improving storage stability, it was found that the above problem can be solved by using a binder resin having a specific SP value and a specific acid value.

That is, in the near-infrared absorbing composition of the present invention, an SP value of 19.7 MPa ^1/2 to 21.2 MPa ^1/2 and an acid value of 70 mgKOH/ g～105mgKOH/g specific binder resin. It can be presumed that by using such a composition, the dispersibility of the near-infrared absorbing pigment based on the resin having a base is not impaired, and the dispersion of the near-infrared absorbing pigment is maintained. As a result, a near-infrared absorbing composition with excellent storage stability is obtained Things. In addition, when a film is formed from the near-infrared absorbing composition of the present invention, it is possible to maintain a high dispersion state of the near-infrared absorbing pigment in the film. It is presumed that, as a result, when a part of the formed film is removed by development or the like, the generation of residues from the aggregation of the near-infrared absorbing pigment is reduced.

Hereinafter, the details of each component contained in the composition of the present invention will be described.

<Specific binder resin> The composition of the present invention contains a binder having an SP value of 19.7 MPa ^1/2 to 21.2 MPa ^1/2 and an acid value of 70 mgKOH/g to 105 mgKOH/g, except for the resin having a base described later. Resin. That is, the specific binder resin in the present invention is a resin that does not have a base in the molecule and does not belong to the "resin having a base". The specific binder resin is a component that contributes to film formation. By including the specific binder resin, a film can be formed from the composition of the present invention.

Among them, the SP value (unit: MPa ^1/2 ) of the specific binder resin in the present invention is a solubility parameter obtained by the Okizu method. One of the methods for calculating the SP value known in the Okitsu method, for example, is the method detailed in the Journal of the Japanese Society of Adhesion, Vol.29, No.6 (1993), pages 249-259, the specific adhesive in the present invention The SP value of the resin is also calculated by this method.

In addition, the acid value of the specific binder resin in the present invention means the mass of potassium hydroxide required for neutralizing acid groups per 1 g of the specific binder resin. The acid value of the specific binder resin is measured as follows. That is, the measurement sample is dissolved in a mixed solvent of tetrahydrofuran/water = 9/1 (mass ratio), and the obtained is obtained by using a potentiometric titrator (product name: AT-510, manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD.) The solution was neutralized and titrated with 0.1 mol/L sodium hydroxide aqueous solution at 25°C. With the inflection point of the titration pH curve as the titration end point, the acid value is calculated by formula (I). Formula (I): A: Acid value (mgKOH/g)=56.11×Vs×0.5×f/w In formula (I), A represents the acid value (mgKOH/g), Vs represents the usage amount (mL) of the 0.1mol/L sodium hydroxide aqueous solution required for titration, and f represents the titration amount of the 0.1mol/L sodium hydroxide aqueous solution , W represents the mass of the measured sample (g) (conversion of solid content).

From the viewpoint of improving storage stability, the SP value in the specific binder resin is preferably ^{20.0 MPa 1/2} to 21.0 MPa ^1/2. From the viewpoint of improving storage stability, as the acid value in the specific binder resin, 72 mgKOH/g～102mgKOH is preferred, and 90mgKOH/g～100mgKOH is more preferred.

As long as the specific binder resin satisfies the above-mentioned SP value and acid value, there is no particular limitation on the structure. Examples of specific binder resins include acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polyether resins, polyether tertene resins, polyphenylene resins, and polyarylene ethers. Phosphine oxide resin, polyimide resin, polyimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, silicone resin, polyurethane resin, etc. Among them, acrylic resins are preferred from the viewpoint of easy control of the SP value and acid value and the viewpoint that the alkali developability of the formed film is good.

From the viewpoint of controlling the SP value and the acid value (especially the SP value) within the above range, the specific binder resin system contains 50 mol% to 90 mol% with respect to the total constituent units of the specific binder resin. A resin including a structural unit of at least one ring structure in the group of an aromatic ring and an aliphatic ring is preferable. The content of the constituent unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring is preferably 55 mol% to 90 mol% relative to the total constituent unit of the specific binder resin. 60 mol%～88 mol% is more preferable.

When the specific binder resin contains a structural unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring, the aliphatic ring system is preferably a bicyclic ring or a tricyclic ring, and the aromatic ring system is benzene Ring, naphthalene ring or nitrogen-containing heteroaromatic ring are preferred.

Examples of the above-mentioned bicyclic ring include bicyclo[2,2,1]heptane and a ring into which a substituent such as an alkyl group is introduced (for example, an isobornyl ring). Examples of the above-mentioned tricyclic ring include adamantane (also referred to as tricyclic [3.3.1.1 ^{3 , 7} ] decane) and a ring in which a substituent such as an alkyl group is introduced.

Examples of the nitrogen-containing heteroaromatic ring include a carbazole ring, a ring into which a substituent such as an alkyl group is introduced, and the like. Furthermore, substituents such as alkyl groups may be introduced into the benzene ring and naphthalene ring.

The structural unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring is preferably a structural unit represented by the following formula (a).

[Chemical formula 1]

In formula (a), R ¹ represents a hydrogen atom or a methyl group, L ¹ represents a single bond or -C(=O)O-, and X ¹ represents at least one selected from the group consisting of aromatic rings and aliphatic rings A group of ring structure.

In formula (a), X ¹ is preferably an isobornyl group, adamantyl group, benzyl group, naphthyl group or carbazolyl group.

The specific binder resin may individually contain one structural unit (preferably a structural unit represented by formula (a)) having at least one ring structure selected from the group consisting of aromatic rings and aliphatic rings, or Contains more than two kinds.

From the viewpoint of controlling the SP value and the acid value (especially the acid value) within the above range, the specific binder resin system contains 10 mol% to 40 mol% with respect to the total constituent units of the specific binder resin. The resin of the constituent unit is preferable. The content of the structural unit having an acid group is preferably 10 mol% to 38 mol%, and more preferably 12 mol% to 38 mol% relative to the total structural unit of the specific binder resin.

Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among them, the carboxyl group is preferred from the viewpoint of achieving both the stability with time of the composition of the present invention and the alkali developability of the formed film.

The structural unit having an acid group is preferably a structural unit represented by the following formula (b).

[Chemical formula 2]

In the formula (b), R ² represents a hydrogen atom or a methyl group, L ² represents a divalent linking group having a single bond of 2 to 10 carbon atoms, and X ² represents an acid group.

In formula (b), L ² is preferably a divalent linking group with 2 to 10 carbon atoms including an alkylene and an ester bond, and a divalent link consisting of an alkylene and an ester bond with 2 to 10 carbons is preferred. The base is better. In formula (b), X ² is preferably a carboxyl group.

The specific binder resin may include one type of structural unit having an acid group (preferably a structural unit represented by formula (b)) alone, or may include two or more types.

In addition to a structural unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring, and a structural unit having an acid group, the specific binder resin may also include other structural units. As other structural units, there are no particular restrictions as long as the SP value and the acid value can be controlled within the above-mentioned ranges, and a structural unit formed from a (meth)acrylate compound is preferably mentioned. The alkyl (meth)acrylate compound is preferred, and 2-hydroxyethyl (meth)acrylate, isobutyl (meth)acrylate, methyl (meth)acrylate, etc. are more preferred.

The other structural unit is preferably a structural unit represented by the following formula (c).

[Chemical formula 3]

In the formula (c), R ³ represents a hydrogen atom or a methyl group, L ³ represents -C(=O)O-, and X ³ represents an alkyl group.

In the formula (c), X ³ is preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and more preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. In addition, ^{examples of the substituent introduced into the alkyl group represented by X 3} include a hydroxyl group and an allyl group.

The specific binder resin may contain one type of other structural unit (preferably a structural unit represented by formula (c)) alone, or two or more types.

The weight average molecular weight (Mw) of the specific binder resin is preferably 20,000 or less, more preferably 15,000 or less, more preferably 12,000 or less, and particularly preferably 10,000 or less. The lower limit of the weight average molecular weight (Mw) of the specific binder resin is preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more.

As specific examples of the specific binder resin, resins 1 to 6 shown below may be mentioned, but they are not limited to these. In addition, in resins 1 to 6, the numerical value of each structural unit appended to the main chain is the molar ratio.

[Chemical formula 4]

The composition of the present invention may include one type of specific binder resin alone, or may include two or more types.

The content of the specific binder resin in the composition of the present invention may be appropriately determined according to the purpose of use, application, and the like of the composition of the present invention. The specific binder resin can be used, for example, by 1 to 30 times (preferably 1.5 to 27 times, more preferably 2 to 25 times) on a mass basis with respect to the resin having a base described later.

[Other adhesive resin] The composition of the present invention may contain other binder resins other than the specific binder resin within a range that does not impair the aforementioned effect of excellent storage stability. Other binder resins are resins whose SP value and acid value do not satisfy the above-mentioned range, and are resins that do not have a base in the molecule and do not belong to the "base-containing resin". In the case of using other binder resins, the content of other binder resins relative to the total binder resin contained in the composition of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and 0% by mass % Is particularly good.

<Near infrared absorbing pigment> The composition of the present invention contains a near infrared absorbing pigment. In the present invention, "near infrared light" refers to infrared light having a wavelength of 700 nm to 2,500 nm, and "near infrared light absorbing pigment" refers to a pigment having a maximum absorption wavelength in the wavelength range of 750 nm to 2,500 nm. The near-infrared absorbing pigment is preferably a pigment having a maximum absorption wavelength in the wavelength range of 750 nm to 1,800 nm. Absorbance A ¹ and the maximum absorption wavelength and near-infrared absorption pigments based wavelength of 500nm absorbance ratio of A ¹ A ² / A ² is preferably 0.08 or less based, it is more preferably 0.04 or less. In addition, the pigment in the present invention refers to a pigment that is insoluble in a solvent. Here, incompatible with solvent means that the solubility of the target substance in 100 mg of solvent at 25°C is 0.1 g or less. Here, as the solvent, propylene glycol monomethyl ether acetate or water may be mentioned, and it may be any solvent and having the above-mentioned solubility may be used as a pigment.

Examples of near-infrared absorbing pigments include pyrrolopyrrole compounds, squaraine compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanidin compounds, and crotonium Compounds, oxocyanine compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, methine azo compounds, anthraquinone compounds, bisbenzofuranone compounds, metal oxides, metals Borides, etc. Among them, from the viewpoint of durability, a pyrrolopyrrole compound or a squaraine compound is particularly preferred as a near-infrared absorbing pigment.

[Pyrrolopyrrole compound] As the pyrrolopyrrole compound, a compound represented by formula (PP) is preferred.

[Chemical formula 5]

In formula (PP), R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ may be bonded to each other. To form a ring, R ⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B or a metal atom, and R ⁴ can be combined with at least one ^{selected from R 1a} , R ^1b and R ³ Covalent bonding or coordinate bonding, R ^4A and R ^4B each independently represent a substituent.

For details of the formula (PP), please refer to paragraphs 0017 to 0047 of Japanese Patent Application Publication No. 2009-263614, paragraphs 0011 to 0036 of Japanese Patent Application Publication No. 2011-068731, and paragraphs 0010 to 0024 of International Publication No. 2015/166873. Paragraphs, these contents are incorporated into this manual.

In the formula (PP), it ^{is preferable that R 1a} and R ^1b each independently be an aryl group or a heteroaryl group, and an aryl group is more preferable. In addition, the alkyl group, aryl group, and heteroaryl group represented ^{by R 1a} and R ^{1b may have a substituent or may be unsubstituted.} As a substituent, the substituent T mentioned later can be mentioned.

-Substituent T- As the substituent T, halogen atoms, cyano groups, nitro groups, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, -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 . 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 be bonded to form a ring.

In formula (PP), R ² and R ³ each independently represent a hydrogen atom or a substituent. As a substituent, the substituent T mentioned later can be mentioned. At least one of R ² and R ³ is preferably an electron attracting group, cyano group, carboxyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aminomethanyl group, alkylcarbonyl group, arylcarbonyl group, alkyl group Sulfonyl or arylsulfonyl is more preferred, and cyano is even more preferred.

In the formula (PP), R ² represents an electron attracting group (preferably a cyano group), and R ³ represents a heteroaryl group. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. In addition, the heteroaryl group is preferably a monocyclic ring or a condensed ring, a monocyclic ring or a condensed ring having a condensation number of 2 to 8 is preferred, and a monocyclic ring or a condensed ring having a condensation number of 2 to 4 is more preferred. The number of heteroatoms constituting the heteroaryl group is preferably 1-3, more preferably 1-2. As a hetero atom, a nitrogen atom, an oxygen atom, and a sulfur atom can be illustrated, for example. The heteroaryl group preferably has one or more nitrogen atoms. ^{Two R 2} in formula (PP) may be the same or different from each other. In addition, the two R ³ in formula (PP) may be the same or different from each other.

In the formula (PP), R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a group represented by -BR ^4A R ^4B , and a hydrogen atom, an alkyl group, an aryl group or a group represented by -BR ^4A R ^4B shows the group is more preferred, a group represented by the sum -BR ^4A R ^4B is further preferred. R ^4A and R ^4B are halogen atoms, alkyl groups, alkoxy groups, aryl groups or heteroaryl groups are preferred, alkyl groups, aryl groups or heteroaryl groups are more preferred, and aryl groups are particularly preferred. These groups may also have substituents. ^{Two R 4} in the formula (PP) may be the same or different from each other. R ^4A and R ^4B may be bonded to each other to form a ring.

The pyrrolopyrrole compound may be a compound represented by formula (PP-1).

[Chemical formula 6]

Formula (PP-1) in the R ^1a, R ^2, R ³ and R ⁴ in the meaning of each of formula ^{(PP) R 1a, R 2} , the same meaning as R ³ and R ⁴ are, R ^1b represents an alkylene group , Aryl group or hetero aryl group, L is a group represented by the following formula (L1) or the following formula (L2).

Formula (PP-1) in ^{R 1a, R 1b, R 2} , R meanings ³ and R ⁴ are ^2, the same as the formula R (PP) of ^1a, R ^1b, R R ³ and R meaning ^4, The preferred aspect is also the same.

*-X ¹ -A ¹ -X ² -* Formula (L1) In the above formula (L1), X ¹ and X ² each independently represent a single bond, -O-, -S-, -NR ^1A -, -CO -, -COO-, -OCOO-, -SO ₂ NR ^1A -, -CONR ^1A -, -OCONR ^1A -or -NR ^1A CONR ^1A -, R ^1A each independently represents a hydrogen atom, an alkyl group or an aryl group, A ¹ represents a single bond, aliphatic ring structure, aromatic ring structure or heterocyclic structure, * represents ^{the connection position to R 1b} , but when A ¹ is a single bond, both X ¹ and X ² will not be single bonds at the same time .

*-X ³ -A ² -L ² -A ³ -X ⁴ -* Formula (L2) In the above formula (L2), X ³ and X ⁴ each independently represent a single bond, -O-, -S-,- NR ^2A -, -CO-, -COO-, -OCOO-, -SO ₂ NR ^2A -, -CONR ^2A -, -OCONR ^2A -or -NR ^2A CONR ^2A -, R ^2A represents a hydrogen atom or an alkyl group, L ² means single bond, -O-, -S-, -NR ^2B -, -CO-, -COO-, -OCOO-, -SO ₂ NR ^2B -, -CONR ^2B -, -OCONR ^2B -, -NR ^2B CONR ^2B -, C1-C6 alkylene, alkenyl, alkynyl, aromatic ring structure or a combination of these groups, R ^2B each independently represents a hydrogen atom or an alkyl group, A ² and A ³ each independently represents an aliphatic ring structure, an aromatic ring structure, or a heterocyclic structure.

Specific examples of the pyrrolopyrrole compound include the following compounds. In the following structural formula, Me represents a methyl group and Ph represents a phenyl group. In addition, examples of the pyrrolopyrrole compound include the compounds described in paragraphs 0016 to 0058 of JP 2009-263614 A, the compounds described in paragraphs 0037 to 0052 of JP 2011-068731, and the like. These contents are incorporated into this manual.

[Chemical formula 7]

[Squaraine compound] As the squaraine compound, a compound represented by the following formula (SQ) is preferred. [Chemical formula 8]

In the formula (SQ), A ¹ and A ² each independently represent an aryl group, a heteroaryl group or a group represented by the formula (A-1);

[Chemical formula 9]

In the formula (A-1), Z ¹ represents a non-metal atomic group forming a nitrogen-containing heterocyclic ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents a connecting bond. For details of the formula (SQ), refer to paragraphs 0020 to 0049 of Japanese Patent Application Publication No. 2011-208101, paragraphs 0043 to 0062 of Japanese Patent Publication No. 6065169, and paragraphs 0024 to 0040 of International Publication No. 2016/181987. Records, these contents are incorporated into this manual.

In addition, the cation in the formula (SQ) exists in a non-localized manner as follows.

[Chemical formula 10]

The squaraine compound is preferably a compound represented by the following formula (SQ-1).

[Chemical formula 11]

(SQ-1) In the formula, rings A and B each independently represent an aromatic ring, ^X-A and X ^B each independently represent a substituent group, G ^A and G ^B independently represents a substituent group, denotes 0 ~ n kA _{An integer of A} , kB represents an integer from 0 to n _B , n _A and n _B respectively represent the largest integer that can be substituted with ring A or ring B, X ^A and G ^A , X ^B and G ^B , X ^A and X ^B They may be bonded to each other to form a ring, and when ^{there are plural G A and G B} , respectively, they may be bonded to each other to form a ring structure.

As the substituent represented by G ^A and G ^B , the aforementioned substituent T can be mentioned.

As the substituents represented by X ^A and X ^B , groups having active hydrogen are preferred, and -OH, -SH, -COOH, -SO ₃ H, -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -NHSO ₂ R ^X1 , -B(OH) ₂ and -PO(OH) ₂ are more preferred, and -OH, -SH and -NR ^X1 R ^X2 are further preferred . R ^X1 and R ^X2 each independently represent a hydrogen atom or a substituent. ^Examples of the substituents R ^X1 and R ^X2 in X ^A and X B include an alkyl group, an aryl group, or a heteroaryl group, and an alkyl group is preferred.

Ring A and ring B each independently represent an aromatic ring. The aromatic ring may be a single ring or a condensed ring. Specific examples of aromatic rings include benzene ring, naphthalene ring, pentylene ring, indene ring, azulene ring, heptene ring, indene ring, perylene ring, fused pentabenzene ring, acenaphthylene ring, phenanthrene ring Ring, anthracene ring, fused tetraphenyl ring, tetraphenyl ring, terphenylene ring, pyrrolidine ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyridine ring, pyridine ring Ring, pyrimidine ring, pyridine ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, phthalimidine ring, naphthyridine ring , Quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthracene ring, chromene ring, stellar ring, phenanthrene ring, The phenanthrene ring and the phenanthrene ring, benzene ring or naphthalene ring are preferred. The aromatic ring may be unsubstituted or may have a substituent. As a substituent, the substituent T mentioned later can be mentioned.

X ^A and G ^A , X ^B and G ^B , X ^A and X ^B may be bonded to each other to form a ring, and when ^{there are plural G A and G B} , they may be bonded to each other to form a ring. As the ring, a 5-membered ring or a 6-membered ring is preferable. The ring may be a single ring or a condensed ring. When X ^A and G ^A , X ^B and G ^B , X ^A and X ^B , G ^A or G ^B are bonded to each other to form a ring, these can be directly bonded to form a ring, or through alkylation , -CO-, -O-, -NH-, -BR- and divalent linking groups including these combinations are bonded to form a ring. R represents a hydrogen atom or a substituent. As the substituent, the aforementioned substituent T can be mentioned, and an alkyl group or an aryl group is preferred.

kA represents an integer from 0 to n _A , kB represents an integer from 0 to n _B , n _A represents the largest integer that can be substituted on ring A, and n _B represents the largest integer that can be substituted on ring B. kA and kB each independently indicate that 0-4 is preferable, 0-2 is more preferable, and 0-1 is particularly preferable.

The squaraine compound is preferably a compound represented by the following formula (SQ-2).

[Chemical formula 12]

In the formula (SQ-2), Rs ¹¹⁹ and Rs ¹²⁰ each independently represent a substituent, A ¹ and A ² each independently represent an oxygen atom or NRs ¹²⁵ , and Rs ¹²¹ to Rs ¹²⁵ each independently represent a hydrogen atom or a substituent, X ³⁰ and X ³¹ each independently represent a carbon atom, a boron atom, or C (=O). When X ³⁰ is a carbon atom, ns32 is 2, and X ³⁰ is a boron atom. ns32 is 1, and X ³⁰ is In the case of C (=O), ns32 is 0, X ³¹ is carbon atom, ns33 is 2, X ³¹ is boron atom, ns33 is 1, X ³¹ is C (=O) , NS33 Department 0, NS30 and ns31 each independently represent an integer of 0 to 5, NS30 based at 2 or more, plural Rs ¹¹⁹ may be the same can also be different, a plurality of Rs ¹¹⁹ in which two Rs ¹¹⁹ may be bonded to each other When forming a ring, when ns31 is 2 or more, the plurality of Rs ¹²⁰ may be the same or different. ^{Two Rs 120} of the plurality of Rs ¹²⁰ can be bonded to each other to form a ring. When ns32 is 2, two Rs ¹²¹ can be the same or different. Two Rs ¹²¹ can be bonded to each other to form a ring. When ns33 is 2, the two Rs ¹²² can be the same or different. Two Rs ¹²² can be bonded to each other to form a ring. Ar ¹⁰⁰ It represents an aryl group or a heteroaryl group, and ns100 represents an integer of 0-2.

The squaraine compound is preferably a compound represented by the following formula (SQ-3).

[Chemical formula 13]

In the formula (SQ-3), X ¹ , X ² , Y ¹ and Y ² each independently represent an alkylene group, an alkynylene group, a cycloalkylene group, an aryl group, a heteroaryl group, or a bonding of these 2 A divalent group consisting of more than one, Z ¹ and Z ² each independently represent a single bond, -O-, a carbonyl group, -S-, -N(R ^N1 )-, -S(=O)-or,- S(=O) ₂ -, A ¹ and A ² each independently represent -O- or -N(R ^N2 )-, R ^N1 and R ^N2 each independently represent a hydrogen atom, an alkyl group or an aryl group, R ⁷ And R ⁸ each independently represent a substituent, and n1 and n2 each independently represent an integer of 0-5. However, when X ¹ , X ² , Y ¹ and Y ² represent an alkylene group, and A ¹ and A ² represent -N(R ^N2 )- ^{, at least one of Z 1} and Z ² represents -O-, a carbonyl group , -S-, -N(R ^N1 )-, -S(=O)-or, -S(=O) ₂ -.

The squaraine compound is preferably a compound represented by the following formula (SQ-4).

[Chemical formula 14]

In the formula (SQ-4), Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a carbon atom or a nitrogen atom. When Q ¹ , Q ² , Q ³ and Q ⁴ are nitrogen atoms, X ¹ , X ⁴ , X ⁵ and X ^{8 are} regarded as not present. R ¹ to R ⁵ each independently represent a hydrogen atom, an alkyl group, a sulfonic acid group, -SO ₃ -M ⁺ or a halogen atom. M ⁺ represents an inorganic or organic cation. X ¹ to X ⁸ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, and an optionally substituted group Alkoxy, optionally substituted aryloxy, hydroxyl, amino, -NR ⁶ R ⁷ , sulfonic acid group, -SO ₂ NR ⁸ R ⁹ , -COOR ¹⁰ , -CONR ¹¹ R ¹² , nitro, cyano Radical or halogen atom. X ¹ to X ⁸ may be bonded to each other to form a ring. R ⁶ to R ¹² each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted acyl group, or an optionally substituted pyridyl group. R ² and R ³ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ¹¹ and R ¹² may be bonded to each other to form a ring.

As specific examples of the squarylium compound, the following compounds [SQ-1 to SQ-61] can be given. In addition, examples of the squaraine compounds include the compounds described in paragraphs 0044 to 0049 of JP 2011-208101, the compounds described in paragraphs 0060 to 0061 of Japanese Patent Publication No. 6065169, and International Publication No. The compound described in paragraph 0040 of No. 2016/181987, the compound described in International Publication No. 2013/133099, the compound described in International Publication No. 2014/088063, and the compound described in Japanese Patent Application Publication No. 2014-126642 The compound described in Japanese Patent Application Publication No. 2016-146619, the compound described in Japanese Patent Application Publication No. 2015-176046, the compound described in Japanese Patent Application Publication No. 2017-025311, International Publication No. 2016/ The compound described in 154782, the compound described in Japanese Patent No. 5884953, the compound described in Japanese Patent No. 6036689, the compound described in Japanese Patent No. 5810604, and the compound described in Japanese Patent Application Publication No. 2017-068120 The described compounds, etc., are incorporated into this specification.

[Chemical formula 15]

[Chemical formula 16]

[Chemical formula 17]

[Chemical formula 18]

[Chemical formula 19]

In the composition of the present invention, the near-infrared absorbing pigment may be contained singly or two or more kinds.

The content of the near-infrared absorbing pigment in the composition of the present invention may be appropriately determined according to the purpose of use, application, and the like of the composition of the present invention. For example, from the viewpoint of expressing the functions required in the near-infrared absorbing pigment, the content of the near-infrared absorbing pigment relative to the total solid content of the composition is preferably 1% by mass or more and 80% by mass or less, and 5 mass% or more and It is more preferably 50% by mass or less.

＜Resin with bases＞ The composition of the present invention includes a resin having a base. Among them, as the base, a functional group exhibiting properties as a base and a group containing a nitrogen atom is preferred. More specifically, a primary amino group or a salt thereof, a secondary amino group or a salt thereof, and a tertiary amino group Or its salt, quaternary ammonium base, etc. are more preferable. The base in the resin with base can be neutralized with the acid group of the specific binder resin to form a salt. That is, the composition of the present invention may be a composition containing a near-infrared absorbing pigment, a specific binder resin, and a resin having a salt neutralized with an acid group of the specific binder resin as a base.

As the resin having a basic group, for example, at least one selected from the group consisting of a resin having a tertiary amine group in the side chain and a resin having a nitrogen atom in the main chain is preferable. Particularly, from the viewpoint of improving the dispersibility of the near-infrared absorbing pigment, the above-mentioned resin system having a tertiary amine group in the side chain and further a resin having a quaternary ammonium salt group in the side chain is preferable. That is, as the resin having a basic group, a resin having a tertiary amine group and a quaternary ammonium salt group in the side chain is preferable.

[Resin with tertiary amine group on the side chain] Resins with tertiary amino groups on the side chains are preferably resins containing structural units with tertiary amino groups, and resins containing structural units with tertiary amino groups and structural units with quaternary ammonium salt groups are more preferred. good. In addition, the resin having a tertiary amino group on the side chain may contain other structural units in addition to the structural unit having the tertiary amino group and the structural unit having the quaternary ammonium salt group. Moreover, it is also preferable that the resin which has a tertiary amine group in a side chain has a block structure.

In the case of resins with tertiary amine groups and quaternary ammonium salt groups on the side chain, the amine value is 10mgKOH/g～250mgKOH/g and the quaternary ammonium salt value is 10mgKOH/g～90mgKOH/g. It is more preferable that the value is 50mgKOH/g～200mgKOH/g and the quaternary ammonium salt value is 10mgKOH/g～50mgKOH/g.

Here, the above-mentioned amine value is a value obtained by using a 0.1N hydrochloric acid aqueous solution and converted to an equivalent of potassium hydroxide from the amine value obtained by the potentiometric titration method. In addition, the above-mentioned quaternary ammonium salt value is obtained by titrating a 5% potassium chromate aqueous solution as an indicator with a 0.1N silver nitrate aqueous solution to convert the amine value to the equivalent of potassium hydroxide.

The weight average molecular weight (Mw) of the resin having a tertiary amine group on the side chain is preferably 3,000 to 300,000, and more preferably 5,000 to 30,000.

Resins with tertiary amine groups on the side chains are copolymerized with ethylenically unsaturated compounds with quaternary ammonium groups and other ethylenically unsaturated compounds as needed by copolymerizing ethylenically unsaturated compounds with tertiary amine groups as needed And get. In addition, after synthesizing a polymer using an ethylenically unsaturated compound with tertiary amine in advance, a halogenated hydrocarbon compound such as benzyl chloride can be reacted with the polymer to partially modify the tertiary amine group into a quaternary ammonium salt Group, thereby introducing a quaternary ammonium group.

Examples of ethylenically unsaturated compounds having tertiary amino groups include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethyl (meth)acrylate Aminopropyl, diethylaminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylamide, etc. Examples of ethylenically unsaturated compounds having a quaternary ammonium salt group include (meth)acrylamidopropyltrimethylammonium chloride and (meth)acryloxyethyltrimethylchloride Ammonium, (meth)acryloyloxyethyl triethylammonium chloride, (meth)acryloyloxyethyl (4-benzylbenzyl)dimethylammonium bromide, (meth)propylene Acrylic oxyethyl benzyl dimethyl ammonium chloride, (meth)acrylic oxyethyl benzyl diethyl ammonium chloride, etc. Regarding ethylenically unsaturated compounds having tertiary amine groups and ethylenically unsaturated compounds having quaternary ammonium salt groups, those described in paragraphs 0150 to 0170 of International Publication No. 2018/230486 can also be cited. Incorporated into this manual. Examples of other ethylenically unsaturated compounds include alkyl (meth)acrylates. Alkyl (meth)acrylates having an alkyl group having 1 to 10 carbon atoms are preferred, and an alkyl group having 1 to 5 carbon atoms is preferred. Alkyl (meth)acrylate is more preferred. Specifically, examples of other ethylenically unsaturated compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, propyl iso(meth)acrylate, and Butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, etc.

As a specific example of the resin which has a tertiary amine group in a side chain, the following compounds can be mentioned. In the following compounds, the numerical value of each constituent unit appended to the main chain is the molar ratio.

[Chemical formula 20]

[Resin containing nitrogen atoms in the main chain] The resin containing a nitrogen atom in the main chain (hereinafter, also referred to as an oligomeric imine resin) preferably contains a poly(lower alkyleneimine)-based structural unit. Among them, the lower alkyleneimine in the present invention means an alkyleneimine having 1 to 5 carbon atoms. From the viewpoint of improving the dispersibility of near-infrared absorbing pigments, as an oligomeric imine resin, a poly(lower alkyleneimine) system having a side chain X containing a functional group with a pKa14 or less bonded to a nitrogen atom The constitutional unit of and a resin having a poly(lower alkyleneimine)-based constitutional unit containing an oligomer chain or a polymer chain with a number of atoms of 40 to 10,000 or a side chain Y of the polymer chain are preferred. In addition, the oligoimine resin includes at least one selected from the group consisting of a primary amine group or its salt, a secondary amine group or its salt, a tertiary amine group or its salt, and a quaternary ammonium salt group For better.

As the oligoimine resin, a resin having a structural unit represented by the formula (OI-1) and a structural unit represented by the formula (OI-2) is preferable.

[Chemical formula 21]

In the formulas (OI-1) and (OI-2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group, a each independently represents an integer from 1 to 5, and * represents the distance between the constituent units In the linking part, X represents a side chain containing a functional group of pKa14 or less, and Y represents a side chain containing an oligomer chain or a polymer chain having 40 to 10,000 atoms.

Examples of the functional groups having pKa14 or less contained in the side chain represented by X include the following. In addition, "pKa" in the present invention is the definition described in the Handbook of Chemistry (II) (Revised 4th edition, 1993, The Chemical Society of Japan, MARUZEN Co., Ltd.). The structure of the "functional group with pKa 14 or less" is not particularly limited. Examples include well-known functional groups that satisfy the pKa system of 14 or less. In particular, functional groups with a pKa system of 12 or less are more preferred, and functional groups with a pKa system of 11 or less are more preferred. Better. Specifically, for example, carboxylic acid groups (approximately pKa3 to 5), sulfonic acid groups (approximately pKa-3 to -2), _{-COCH 2} CO- (approximately pKa8 to 10), _{-COCH 2} CN (pKa8 to approximately About 11), -CONHCO-, phenolic hydroxyl, -R ^F CH ₂ OH or -(R ^F ) ₂ CHOH (wherein, R ^F represents a perfluoroalkyl group. pKa9 to about 11), sulfonamide group (pKa9 to 11) etc., especially carboxylic acid group, sulfonic acid group or -COCH ₂ CO- is preferred.

In addition to the structural unit represented by the formula (OI-1) and the structural unit represented by the formula (OI-2), it is preferable that the oligoimine-based resin further has a structural unit represented by the formula (OI-3).

[Chemical formula 22]

In the formula (OI-3), *, R ¹ , R ² and a have the same meanings as in the general formula (OI-1). Y'represents a side chain containing an oligomer chain or a polymer chain having an anion group with 40 to 10,000 atoms.

Among them, the structural unit represented by the formula (OI-3) can be oligomerized by adding a group that reacts with an amine to form a salt to a resin containing a structural unit having a primary or secondary amine group on the main chain. It is formed by the reaction of a substance or polymer.

In formula (OI-1), formula (OI-2) and formula (OI-3), from the viewpoint of obtaining raw materials, R ¹ and R ² are preferably hydrogen atoms, and a is 2 preferably.

In addition to the structural units represented by the formula (OI-1), the formula (OI-2), and the formula (OI-3), the oligoimine-based resin may also contain poly(lower alkyleneimines) as the structural unit. In the same manner as described above, the lower alkyleneimine means an alkyleneimine having 1 to 5 carbon atoms. In addition, one or more of the side chains represented by the aforementioned X, Y or Y'may be further bonded to the nitrogen atom in the poly(lower alkyleneimine).

Regarding the oligoimine-based resin, reference can be made to the description in paragraphs 0102 to 0166 of JP 2012-255128 A, and this content is incorporated in this specification.

As a specific example of the resin containing a nitrogen atom in the main chain (oligomeric imine resin), the following three compounds can be mentioned. In the following compounds, the numerical value of each constituent unit of the main chain is the molar ratio, and the numerical value of the side chain is the number of repeating units.

[Chemical formula 23]

In the present invention, the resin having a base may be used singly or in combination of two or more kinds.

The content of the resin having a basic group in the composition of the present invention may be appropriately set depending on the type and content of the near-infrared absorbing pigment. For example, the content of the resin having a base relative to the total amount of the near-infrared absorbing pigment (preferably the total amount of the near-infrared absorbing pigment and the pigment other than the near-infrared absorbing pigment) is preferably 15% to 90% by mass , 25% by mass to 70% by mass is more preferable, and 30% by mass to 50% by mass is still more preferable.

(The content of tin) The composition of the present invention may include tin (Sn) used when synthesizing the resin with a base, depending on the type of resin having a base used. Therefore, the content of tin (Sn) in the composition of the present invention is preferably 1 ppm to 15 ppm with respect to the total solid content of the composition, for example. In the present invention, "ppm", "ppb" and "ppt" mentioned later are all quality standards. As a resin having a basic group used in order to satisfy the above-mentioned tin content, for example, a resin containing a nitrogen atom in the main chain can be exemplified.

The content of tin in the composition of the present invention is measured by the following method. The content of tin is measured according to a known method and a calibration curve is made by gas chromatography.

(Other ingredients) The composition of the present invention is preferably a composition that obtains a film, and preferably a curable composition that obtains a cured film by final curing. In addition, the composition of the present invention contains a specific binder resin having a specific acid value. Therefore, for example, a curable composition capable of forming a pattern of a cured film by pattern exposure and developing and removing unexposed parts is preferable. That is, the composition of the present invention is preferably a negative curable composition. When the composition of the present invention is a negative curable composition, in addition to the aforementioned near-infrared absorbing pigment, specific binder resin, and resin having a base, it also includes a polymerization initiator and a polymerizable compound. For better. In addition, the composition of the present invention may contain a dispersant other than the aforementioned resin having a basic group and a pigment other than the near-infrared absorbing pigment within a range that does not impair the effect of the composition of the present invention.

[Curable composition] The composition of the present invention is preferably a so-called curable composition containing a polymerizable compound and a polymerization initiator in addition to a near-infrared absorbing pigment, a specific binder resin, and a resin having a base. The curable composition described above contains the composition of the present invention, and therefore it is possible to maintain a high dispersion state of the near-infrared absorbing pigment in a film formed of the curable composition. As a result, according to the curable composition described above, when a part of the formed film is removed by development, it is difficult to generate residues derived from the aggregation of the near-infrared absorbing pigments, thereby reducing development residues. Hereinafter, the case where the composition of the present invention is a negative curable composition is described in detail.

The content of the near-infrared absorbing pigment in the curable composition of the present invention is preferably 1% to 30% by mass relative to the total solid content of the curable composition, more preferably 5 to 30% by mass, and 5 The mass %-20 mass% is more preferable. If the content of the near-infrared absorbing pigment is within the above-mentioned range, the function based on the near-infrared absorbing pigment will be fully expressed.

The content of the specific binder resin in the curable composition of the present invention is preferably 10% to 50% by mass relative to the total solid content of the curable composition, more preferably 10% to 40% by mass, 15 Mass% to 35% by mass is more preferable. If the content of the specific binder resin is within the above-mentioned range, excellent film forming properties are obtained.

The content of the resin having a base in the curable composition of the present invention is preferably 0.5% by mass to 20% by mass relative to the total solid content of the curable composition, and more preferably 1% by mass to 20% by mass, 5 to 15% by mass is more preferable. If the content of the resin having a base is within the above range, the storage stability is improved.

[Polymerizable compound] The curable composition in the present invention preferably contains a polymerizable compound. As the polymerizable compound, an ethylenically unsaturated compound is more preferable, and a compound having a terminal ethylenic unsaturated group is particularly preferable. As these compound groups, well-known ones can be used without particular limitation. The polymerizable compound has, for example, a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer, and an oligomer, or these mixtures, and these copolymers.

Examples of polymerizable compounds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters and their amides , Esters of unsaturated carboxylic acids and aliphatic polyol compounds, amides of unsaturated carboxylic acids and aliphatic polyamine compounds can be preferably used. As examples of polymerizable compounds, esters or amides of unsaturated carboxylic acids having nucleophilic substituents such as hydroxyl groups, amine groups, and mercapto groups, and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used. The addition reactants of, and the dehydration condensation reactants of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl groups, amino groups, and mercapto groups, and monofunctional or polyfunctional carboxylic acids. Also, as examples of polymerizable compounds, esters or amides of unsaturated carboxylic acids having electrophilic substituents such as isocyanate groups and epoxy groups, and monofunctional or polyfunctional alcohols, amines, and thiols Addition reactants of, and esters or amides of unsaturated carboxylic acids with detachable substituents such as halogen atoms, toluene sulfonyloxy groups, and monofunctional or polyfunctional alcohols, amines, and thiols Substitution reactants are also preferred. In addition, as another example of the polymerizable compound, a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether, etc., in place of the above-mentioned unsaturated carboxylic acid can be given.

Specific examples of monomers of esters of aliphatic polyol compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and acrylic acid esters. Tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene oxypropyl) ether, trihydroxyl Methylethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, neopentaerythritol diacrylate, neopentaerythritol triacrylate , Neopentyl erythritol tetraacrylate, dineopentaerythritol diacrylate, dineopentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbose Alcohol hexaacrylate, tris(acryloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid EO modified triacrylate, etc.

As specific examples of monomers of esters of aliphatic polyol compounds and unsaturated carboxylic acids, as methacrylates, there are tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and new Pentylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethyl Alkyl acrylate, hexanediol dimethacrylate, neopentyl erythritol dimethacrylate, neopentyl erythritol trimethacrylate, neopentyl erythritol tetramethacrylate, dine pentaerythritol dimethyl acrylate Base acrylate, dineopentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, double [p-(3-methacryloyloxy-2-hydroxypropane) Oxy)phenyl]dimethylmethane, bis-[p-(methacryloxyethoxy)phenyl]dimethylmethane, etc.

Moreover, as the polymerizable compound, a urethane-based addition polymerizable compound produced by the addition reaction of an isocyanate group and a hydroxyl group is also preferable. As such specific examples, for example, Japanese Patent Publication No. 48-041708 can be cited. The polyisocyanate compound having two or more isocyanate groups in one molecule described in the No. Bulletin is added to a vinyl monomer containing a hydroxyl group represented by the following general formula (I). It contains in one molecule Two or more polymerizable vinyl vinyl carbamate compounds, etc.

CH ₂ =C(R)COOCH ₂ CH(R')OH (I) (where R and R'represent H or CH ₃ .)

In addition, for example, the urethane acrylates described in Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 2-032293, and Japanese Patent Publication No. 2-016765, or Japanese Patent Publication No. 58-049860, Japanese Patent The urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferable. In addition, by using the addition polymerizability described in JP-A 63-277653, JP-A 63-260909, and JP-A 1-105238, which has an amino group structure or a sulfide structure in the molecule Compounds can obtain compositions with very excellent photosensitivity.

In addition, examples of the polymerizable compound include compounds described in paragraphs 0178 to 0190 of JP 2007-277514 A. Moreover, as a polymerizable compound, the epoxy compound described in JP 2015-187211 A can also be used.

In the curable composition of the present invention, the polymerizable compound may be used singly or in combination of two or more kinds.

The content of the polymerizable compound in the curable composition of the present invention is preferably 1% to 90% by mass relative to the total solid content of the curable composition, more preferably 5% to 80% by mass, 10% by mass to 70% by mass is more preferable. When the content of the polymerizable compound is within the above range, the curable composition has excellent curability.

[Polymerization initiator] The curable composition in the present invention preferably contains a polymerization initiator. As the polymerization initiator, a photopolymerization initiator is particularly preferred. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and it can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light from the ultraviolet region to the visible region is preferred. In addition, the photopolymerization initiator may be a compound that has some effect with a light-excited sensitizer to generate active free radicals. Among them, a photopolymerization initiator-based photoradical polymerization initiator is particularly preferred.

As the photopolymerization initiator, for example, halogenated hydrocarbon derivatives (for example, compounds having a triazole skeleton, compounds having a diazole skeleton, etc.), phosphine compounds, hexaarylbisimidazoles, oxime compounds, organic Peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, α-amino ketone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyl tris compound, a benzyl dimethyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, an phosphine compound, and a phosphine oxide. Compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, haloforms Amino acid diazole compounds and 3-aryl substituted coumarin compounds are preferred, and compounds selected from the group consisting of oxime compounds, α-hydroxy ketone compounds, α-amino ketone compounds and phosphine compounds are more preferred, and oxime compounds To be further preferred. Regarding the photopolymerization initiator, the descriptions in paragraphs 0065 to 0111 of JP 2014-130173 A and paragraphs 0274 to 0306 of JP 2013-029760 can be referred to, and these contents are incorporated into the present invention.

Commercial products of α-hydroxy ketone compounds include DAROCUR 1173 manufactured by BASF, IRGACURE 500, Omnirad 184 (old IRGACURE 184) manufactured by IGM Resins BV, Omnirad 2959 (old IRGACURE 2959), Omnirad 127 (old IRGACURE) -127) etc. Commercial products of α-amino ketone compounds include Omnirad 907 (old IRGACURE-907), Omnirad 369 (old IRGACURE 369), Omnirad 379 (old IRGACURE 379) and Omnirad 379 (old IRGACURE) manufactured by IGM Resins BV. -379EG) and so on. Examples of commercially available products of the phosphine compound include Omnirad 819 (former IRGACURE 819) manufactured by IGM Resins B.V., Omnirad TPO H (former IRGACURE TPO) manufactured by BASF, and the like.

As the oxime compound, for example, the compound described in JP 2001-233842 A, the compound described in JP 2000-080068 A, the compound described in JP 2006-342166, The compound described in JCSPerkin II (1979, pp.1653-1660), the compound described in JCSPerkin II (1979, pp.156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), the compound described in Japanese Patent Application Publication No. 2000-066385, the compound described in Japanese Patent Application Publication No. 2000-080068, the compound described in Japanese Patent Application Publication No. 2004-534797 The compound, the compound described in Japanese Patent Application Publication No. 2006-342166, the compound described in Japanese Patent Application Publication No. 2017-019766, the compound described in Japanese Patent No. 6065596, International Publication No. 2015/152153 The described compounds, the compounds described in International Publication No. 2017/051680, etc. As specific examples of the oxime compound, for example, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propanyloxy 2-acetiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzene Methoxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyloxyimino -1-Phenylpropan-1-one and so on. As a commercially available product of the oxime compound, IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE03, and IRGACURE OXE04 manufactured by BASF can also be preferably used. In addition, as commercial products of oxime compounds, TRONLY TR-PBG-304, TRONLY TR-PBG-309, manufactured by Changzhou Tronly New Electronic Materials Co., Ltd. (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) can be mentioned. TRONLY TR-PBG-305, ADEKA ARKLSNCI-930 manufactured by ADEKA Corporation, ADEKA OPTOMER N-1919 (equivalent to photopolymerization initiator 2 in JP 2012-014052 A).

In addition, as the oxime compound other than the above, the compound described in Japanese Patent Application Publication No. 2009-519904 in which an oxime is linked to the N-position of the carbazole ring, and a compound having a heterosubstituent introduced at the benzophenone site can also be used. The compound described in the specification of U.S. Patent No. 7626957, the compound described in Japanese Patent Laid-Open No. 2010-015025 and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced into the pigment site, International Publication No. 2009/131189 The ketoxime compound described in the specification, the compound described in the specification of U.S. Patent No. 7556910, which contains a three-frame and an oxime skeleton in the same molecule, has a great absorption at 405nm and has good sensitivity to g-ray light sources. The compounds described in JP 2009-221114 A, etc.

As the photopolymerization initiator, an oxime compound having a sulphur ring can also be used. As a specific example of the oxime compound which has a sulphur ring, the compound described in Unexamined-Japanese-Patent No. 2014-137466 is mentioned, and this content is incorporated in this invention.

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

As the photopolymerization initiator, an oxime compound having at least one benzene ring in the carbazole ring as a skeleton of a naphthalene ring can also be used. As a specific example of this oxime compound, the compound described in International Publication No. 2013/083505 can be mentioned.

As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include the compounds described in JP 2010-262028 A, the compounds 24, 36-40, and the compounds described in JP 2014-500852 A The compound (C-3) and the like described in the 2013-164471 Bulletin are included in the present invention.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably used as a dimer. Specific examples of oxime compounds having a nitro group include those described in paragraphs 0031 to 0047 of JP 2013-114249, paragraphs 0008 to 0012, and paragraphs 0070 to 0079 of JP 2014-137466. The compound, the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARKLSNCI-831 (manufactured by ADEKA Corporation), etc.

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

[Chemical formula 24]

[Chemical formula 25]

The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, and a compound having a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm is more preferred. In addition, the oxime compound is preferably a compound having a large absorbance at wavelengths of 365 nm and 405 nm.

From the viewpoint of sensitivity, the molar absorption 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 even more preferably 5,000 to 200,000. The molar absorption coefficient of the compound can be measured using a known method. For example, it is better to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) and use an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photopolymerization initiator, a difunctional or trifunctional or higher photopolymerization initiator can also be used. As specific examples of such photopolymerization initiators, Japanese Special Publication No. 2010-527339, Japanese Special Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Special Publication No. 2016-532675 may be mentioned. Paragraphs 0417 to 0412, dimers of oxime compounds described in paragraphs 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compound (G) described in JP 2013-522445, Cmpd1~7 etc. described in International Publication No. 2016/034963.

In the curable composition of the present invention, the polymerization initiator may be used singly or in combination of two or more kinds.

The content of the polymerization initiator in the curable composition of the present invention is preferably 0.1% by mass to 50% by mass relative to the total solid content of the curable composition, more preferably 0.5% by mass to 30% by mass , Particularly preferably 1% by mass to 20% by mass. When the content of the polymerization initiator is within the above range, good sensitivity and pattern formability can be obtained.

(Other ingredients) The curable composition in the present invention may contain other components in addition to the aforementioned components. Examples of other components include pigment derivatives, polymerization inhibitors, solvents, sensitizers, co-sensitizers, and other additives.

(Pigment Derivatives) The curable composition in the present invention preferably contains a pigment derivative. As the pigment derivative, a compound 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 is exemplified. Examples of the acid group include a sulfonic acid group, a carboxyl group, a phosphoric acid group, a boronic acid group, a sulfonamide group, a sulfonamide group, these salts, and the desalination structure of these salts. Examples of 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. Ions, phosphonium ions, etc. Moreover, as a desalination structure of the said salt, the group which detached the atom or atomic group from the said salt to form a salt is mentioned. For example, the structure desalting salt of carboxyl group is a carboxylate group (-COO ^-). As a basic group, an amino group, a pyridyl group, these salts, and the desalination structure of these salts are mentioned. Examples of atoms or atomic groups constituting the salt include hydroxide ions, halide ions, carboxylate ions, sulfonate ions, and phenol ions. Moreover, as a desalination structure of the said salt, the group which detached the atom or atomic group from the said salt to form a salt is mentioned. The hydrogen-bonding group refers to a group that interacts via a hydrogen atom. Specific examples of the hydrogen-bonding group include an amido group, a hydroxyl group, -NHCONHR, -NHCOOR, -OCONHR, and the like. Among them, R-based alkyl groups and aryl groups are preferred.

The pigment derivative has at least one group selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphoric acid group, a boric acid group, a sulfonamide group, an amino group, a pyridyl group, a salt thereof, or a desalted structure thereof The group is preferred, and it is more preferred to have a sulfonic acid group, a carboxyl group, or an amino group. The pigment derivative has such a group, whereby the dispersibility of the near-infrared absorbing pigment can be further improved.

As a pigment derivative, the compound represented by formula (B1) can be mentioned.

[Chemical formula 26]

In formula (B1), P represents the pigment skeleton, L represents a single bond or a linking group, X represents an acid group, a basic group or a hydrogen bonding group, m represents an integer of 1 or more, n represents an integer of 1 or more, and m is 2 In the above case, 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.

The pigment skeleton represented by P is selected from the group consisting of squaraine pigment structure, pyrrolopyrrole pigment skeleton, diketopyrrolopyrrole pigment skeleton, quinacridone pigment skeleton, anthraquinone pigment skeleton, dianthraquinone pigment skeleton, benzo Isoindole pigment skeleton, thiocyanindigo pigment skeleton, azo pigment skeleton, quinoline yellow pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, bis-indole pigment skeleton, perylene pigment skeleton, pyrenone pigment skeleton, benzene At least one of the bisimidazolone pigment skeleton, the benzothiazole pigment skeleton, the benzimidazole pigment skeleton, and the benzoxazole pigment skeleton is preferred. From the viewpoint of affinity with the aforementioned near-infrared absorber, squaric acid The cyanine pigment skeleton or the pyrrolopyrrole pigment skeleton is particularly preferred.

As the linking group represented by L, a group composed 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 preferred , May be unsubstituted, or may further have a substituent. As a substituent, the substituent T mentioned later can be mentioned.

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

The dissolution amount of the pigment derivative in 100 g of propylene glycol methyl ether acetate at 25°C is preferably 0.01 mg to 10 g. The upper limit is preferably 7.5 g or less, and more preferably 5 g or less. The lower limit is preferably 0.05 mg or more, and more preferably 0.1 mg or more. According to this aspect, the dispersibility of the near-infrared absorbing pigment in the composition of the present invention can be further improved.

The molecular weight of the pigment derivative is preferably 160 to 4500. The upper limit of the molecular weight of the pigment derivative is preferably 4000 or less, and more preferably 3500 or less. The lower limit of the molecular weight of the pigment derivative is preferably 200 or more, and more preferably 250 or more. If the molecular weight of the pigment derivative is within the above range, the effect of improving the dispersibility of the near-infrared absorbing pigment can be expected.

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 is more preferable, and has a maximum absorption wavelength in the wavelength range of 700 nm to 1,000 nm. Compounds that absorb wavelengths are further preferred. In the pigment derivative with a maximum absorption wavelength in the above-mentioned wavelength range, the extension of the π-conjugated plane can be easily close to the near-infrared absorbing pigment, and the absorption of the near-infrared absorbing pigment is improved, so that more excellent dispersion stability can be easily obtained. Sex.

In addition, the pigment derivative is preferably a compound containing an aromatic ring, and a compound having a structure formed by condensing two or more aromatic rings is also more preferred. In addition, the pigment derivative is preferably a compound having a π-conjugated plane, and a compound having the same structure as the π-conjugated plane contained in the near-infrared absorbing pigment is also more preferred. Among them, the number series of π electrons contained in the π conjugate plane of the pigment derivative is preferably 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.

The pigment derivative is preferably a compound having a π-conjugated plane including a partial structure represented by the following formula (SQ-a) or a π-conjugated plane including a partial structure represented by the following formula (CR-a) . In the following formulas (SQ-a) and (CR-a), wavy lines represent bonding bonds.

[Chemical formula 27]

It is also preferable that the pigment derivative is at least one selected from a compound represented by the following formula (Syn1) and a compound represented by the following formula (Syn2).

[Chemical formula 28]

In the 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 sulfonic acid group, a carboxyl group, a phosphoric acid group, a boronic acid group, and a sulfonic acid group. Amino group, sulfonamide group, amino group, pyridyl group, a group selected from these salts or these desalination structures, 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.

In the formula (Syn2), Rsy ³ and Rsy ⁴ each independently represent an organic group, L ² represents a single bond or a p2+1 valent group, and A ² represents a sulfonic acid group, a carboxyl group, a phosphoric acid group, a boronic acid group, and a sulfonate group. Amino group, sulfonamido group, amino group, pyridyl group, a group selected from the salt or the desalting structure, p2 and q2 each independently represent an integer of 1 or more. When p2 is 2 or more, a plurality of A ² may be the same or different. When q2 is 2 or more, a plurality of L ² and A ² may be the same or different.

Examples of the organic groups represented by Rsy ¹ and Rsy ^{2 of formula (Syn1) and the organic groups represented by Rsy 3} and Rsy ^{4 of} formula (Syn2) include aryl groups, heteroaryl groups, and the following formula (R1) Represents the group.

[Chemical formula 29]

In formula (R1), R ¹ to R ³ each independently represent a hydrogen atom or a substituent, As ³ represents a heteroaryl group, nr1 represents an integer of 0 or more, R ¹ and R ² may be bonded to each other to form a ring, R ¹ And As ³ can be bonded to each other to form a ring, R ² and R ³ can be bonded to each other to form a ring, when n _r1 is 2 or more, plural R ² and R ³ may be the same or different, respectively, * means Bonding key.

The carbon number system of the aryl group represented by Rsy ¹ to Rsy ⁴ is preferably from 6 to 48, more preferably from 6 to 22, and particularly preferably from 6 to 12. The number of carbon atoms constituting the ring of the heteroaryl group represented by Rsy ¹ to Rsy ^{4 is preferably 1-30, and more preferably 1-12.} Examples of the types of heteroatoms constituting the ring of the heteroaryl group include a nitrogen atom, an oxygen atom, and a sulfur atom. As the number of heteroatoms constituting the heteroaryl group, 1 to 3 are preferred, and 1 to 2 are more preferred. The heteroaryl group is preferably a single ring or a condensed ring, a single ring or a condensed ring having a condensation number of 2 to 8 is more preferred, and a single ring or a condensed ring having a condensation number of 2 to 4 is even more preferred. The aryl group and heteroaryl group represented by Rsy ¹ to Rsy ^{4 may have a substituent.} Examples of the substituent include the aforementioned substituent T, a group represented by the following formula (R-SQ), and the like.

[Chemical formula 30]

In the formula (R-SQ), Rsq ¹ represents an organic group. The organic group represented by Rsq ¹ includes an aryl group, a heteroaryl group, a group represented by the formula (R1), a group represented by the formula (1) mentioned later, a group represented by the formula (10), The group represented by the formula (20), the group represented by the formula (30), and the group represented by the formula (40).

^{R 1} to R ³ in formula (R1) each independently represent a hydrogen atom or a substituent. As a substituent, the substituent T mentioned later can be mentioned. The substituent represented by R ¹ to R ³ is preferably an alkyl group. The carbon number of the alkyl group is preferably 1-20, more preferably 1-15, and still more preferably 1-8. The alkyl group may be any of straight chain, branched chain, and cyclic, and straight chain or branched chain is preferred. R ¹ to R ³ are preferably hydrogen atoms. ^{As 3} in the formula (R1) represents a heteroaryl group. Examples of the heteroaryl group represented by As ^{3 are the} same as the heteroaryl groups represented ^{by Rsy 1} to Rsy ^{4, and preferred aspects are also the same.}

In formula (R1), R ¹ and R ² may be bonded to each other to form a ring, R ¹ and As ³ may be bonded to each other to form a ring, and R ² and R ³ may be bonded to each other to form a ring. As the linking group when forming the above-mentioned ring, a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, -CH- and combinations thereof is preferred.

_{N r1} in formula (R1) represents an integer of 0 or more. n _r1 is an integer of 0-2, preferably 0 or 1, and even more preferably 0. In the formula (R1), when n _r1 is 2 or more, a plurality of R ² and R ³ may be the same or different.

As the organic group represented by Rsy ¹ and Rsy ² of formula (Syn1) ^{and the organic group represented by Rsy 3} and Rsy ^{4 of} formula (Syn2), the group represented by the following formula (1) is preferable.

[Chemical formula 31]

In the formula (1), ring Z ¹ represents a condensed ring containing an aromatic heterocycle or aromatic heterocycle ^{that may have one or more substituents, and ring Z 2} represents 4 to 4 that may have one or more substituents When a 9-membered hydrocarbon ring or a heterocyclic ring, and ring Z ¹ and ring Z ² have plural substituents, the plural substituents may be the same or different, and * represents a bonding bond.

In the formula (1), the ring Z ¹ represents a condensed ring including an aromatic heterocyclic ring or an aromatic heterocyclic ring which may have one or more substituents. Examples of the aromatic heterocyclic ring include imidazole ring, azole ring, thiazole ring, pyridine ring, pyridine ring, pyrrole ring, furan ring, thiophene ring, pyrazole ring, isoazole ring, isothiazole ring, and pyrazole ring. Ring, pyrimidine ring, etc., imidazole ring, azole ring, thiazole ring, pyridine ring, pyridine ring, and pyrrole ring are preferred. Examples of condensed rings containing aromatic heterocycles include those selected from the group consisting of imidazole ring, azole ring, thiazole ring, pyridine ring, pyridine ring, pyrrole ring, furan ring, thiophene ring, pyrazole ring, isoazole ring, One or more rings of isothiazole ring, pyrimidine ring, and pyrimidine ring (in the case of two or more, they may be the same type of ring or different types of rings) and selected from benzene ring, naphthalene ring, anthracene ring , Tetracene ring, phenanthrene ring, triphenylene ring, tetraphenol ring, pyrene ring (preferably benzene ring, naphthalene ring) condensed ring; selected from imidazole ring, azole ring, thiazole Ring, pyridine ring, pyridine ring, pyrrole ring, furan ring, thiophene ring, pyrazole ring, isooxazole ring, isothiazole ring, pyridine ring, pyrimidine ring at least 2 rings (in the case of 2 or more , May be the same type of ring, or a different type of ring) condensed ring, etc. For the reason that it is easy to obtain more excellent spectroscopic characteristics, the condensation number system of the condensed ring is preferably 2-6, and more preferably 2-4.

In formula (1), ring Z ² represents a 4- to 9-membered hydrocarbon ring or heterocyclic ring which may have one or more substituents. The hydrocarbon ring and heterocyclic ring represented by the ring Z ² are preferably a 5- to 7-membered ring, and more preferably a 5- or 6-membered ring. Specific examples of the hydrocarbon ring include cyclobutene ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, cyclohexadiene ring, cycloheptane ring, cycloheptadiene ring, and cycloheptane ring. Cycloolefin rings such as ene ring, cyclononane ring, cyclononadiene ring, cyclononatriene ring, cyclononene ring, cyclononadiene ring, cyclononatriene ring, cyclonontetraene ring, etc., cyclopentene ring , Cyclohexene ring, cycloheptane ring and cyclononane ring are preferred, and cyclopentene ring and cyclohexene ring are more preferred. The heterocyclic ring system represented by ring Z ² is preferably a nitrogen-containing heterocyclic ring.

Examples of the substituent that the ring Z ¹ and the ring Z ² may have include the aforementioned substituent T. Furthermore, it is also preferable that the substituent which the ring Z ¹ may have is an electron withdrawing group. Hammett's substituent constant σ value (sigma value) is a positive substituent that functions as an electron withdrawing group. Among them, the substituent constant calculated by the Hammett equation has a σp value and a σm value. Equivalent values can be found in many common books. In the present invention, a substituent whose Hammett's substituent constant σ value is 0.1 or more can be exemplified as the electron withdrawing group. The σ value is preferably 0.15 or more, more preferably 0.2 or more, and more preferably 0.3 or more. The upper limit is not particularly limited, but it is preferably 1.0 or less. Specific examples of electron withdrawing groups include halogen atoms, alkyl groups in which at least part of hydrogen atoms are substituted with halogen atoms, aryl groups, nitro groups, cyano groups, and cyanomethyl groups in which at least part of hydrogen atoms are substituted with halogen atoms. Base, -CH=C(CN) ₂ , -C(CN)=C(CN) ₂ , -P(CN) ₂ , -N=NCN, -COR ^z , -COOR ^z , -OCOR ^z , -NHCOR ^z , -CONHR ^z , -SOR ^z , -SO ₂ R ^z , -SO ₂ OR ^z , -NHSO ₂ R ^z or SO ₂ NHR ^z . R ^z represents an alkyl group in which at least a part of hydrogen atoms may be substituted with fluorine atoms, and an aryl group, an amine group, a halogen atom, a cyano group, or a cyanomethyl group in which at least part of the hydrogen atoms may be substituted with a fluorine atom. Among them, cyanomethyl includes monocyanomethyl (-CH ₂ CN), dicyanomethyl (-CH(CN) ₂ ), and tricyanomethyl (-C(CN) ₃ ). In the alkyl group in which at least a part of hydrogen atoms may be substituted with fluorine atoms, the carbon number is preferably 1 to 6, more preferably 1 to 5, and even more preferably 1 to 4. In the aryl group in which at least a part of the hydrogen atoms may be substituted with fluorine atoms, the carbon number is preferably 6-14, and the carbon number is 6-10. In these alkyl groups and aryl groups, all of the hydrogen atoms may be substituted with fluorine atoms, only a part of them may be substituted with fluorine atoms, or they may not be substituted with fluorine atoms.

The group represented by formula (1) is preferably a group represented by formula (1-1) or formula (1-2). [Chemical formula 32]

In the formula (1-1), Z ^1a represents a ring having one or a plurality of substituents of azetidin having many aromatic ring containing 5 or 6-membered ring, the ring represented by Z ^2a or may have a plurality of A 4- to 9-membered hydrocarbon ring or heterocyclic ring of each substituent. When ring Z ^1a and ring Z ^2a have plural substituents, the plural substituents may be the same or different. R ⁵ and R ⁷ each independently represent a hydrogen atom or a substituent.

In the formula (1-1), as the ^{polycyclic aromatic ring represented by ring Z 1a} , examples include those selected from the group consisting of imidazole ring, azole ring, thiazole ring, pyridine ring, pyridine ring, pyrrole ring, furan ring, Condensed rings of 5- or 6-membered nitrogen-containing heterocyclic rings of thiophene ring, pyrazole ring, isoazole ring, isothiazole ring, pyrimidine ring, and pyrimidine ring, including one selected from the aforementioned nitrogen-containing heterocyclic rings The above rings (in the case of two or more, they may be the same type of nitrogen-containing heterocyclic ring, or different types of nitrogen-containing heterocyclic ring) and a fused ring of a benzene ring or a naphthalene ring; selected from 2 of the aforementioned nitrogen-containing heterocyclic rings Condensed rings of more than one ring (the same type of nitrogen-containing heterocyclic ring or different types of nitrogen-containing heterocyclic ring), etc. For the reason that it is easy to obtain more excellent spectroscopic properties, the number of rings contained in the polycyclic aromatic ring (the number of condensed rings) is preferably 2-6, and more preferably 2-4.

In the formula (1-1), the 4- to 9-membered hydrocarbon ring and heterocyclic ring represented ^{by the ring Z 2a} include those described in the term of ^{the ring Z 2 of the formula (1).}

In the formula (1-1), ^{the substituents that the ring Z 1a} and the ring Z ^2a may have and the substituents represented by R ⁵ and R ⁷ include the aforementioned substituent T. Moreover, it is also preferable that the substituent which the ring Z ^1a may have is an electron withdrawing group. Examples of the electron withdrawing group include the above-mentioned electron withdrawing group as a substituent that the ^{ring Z 1 may have.}

In formula (1-2), ring Z ^1b represents a polycyclic aromatic ring with a 5- or 6-membered nitrogen-containing heterocyclic ring that may have one or more substituents, and ring Z ^2b represents that may have one or more substituents When a nitrogen-containing heterocyclic ring with 4 to 9 members of ^{each substituent has a plurality of substituents in the ring Z 1b} and the ring Z ^2b , the plurality of substituents may be the same or different.

In the formula (1-2), as the ^{polycyclic aromatic ring represented by ring Z 1b} , examples include those selected from the group consisting of imidazole ring, azole ring, thiazole ring, pyridine ring, pyrrole ring, pyrrole ring, furan ring, Condensed rings of 5- or 6-membered nitrogen-containing heterocyclic rings of thiophene ring, pyrazole ring, isoazole ring, isothiazole ring, pyrimidine ring, and pyrimidine ring, including one selected from the aforementioned nitrogen-containing heterocyclic rings The above rings (in the case of two or more, they may be the same type of nitrogen-containing heterocyclic ring, or different types of nitrogen-containing heterocyclic ring) and a fused ring of a benzene ring or a naphthalene ring; selected from 2 of the aforementioned nitrogen-containing heterocyclic rings Condensed rings of more than one ring (the same type of nitrogen-containing heterocyclic ring or different types of nitrogen-containing heterocyclic ring), etc. For the reason that it is easy to obtain more excellent spectroscopic properties, the number of rings contained in the polycyclic aromatic ring (the number of condensed rings) is preferably 2-6, and more preferably 2-4.

In the formula (1-2), ^{the nitrogen-containing heterocyclic ring represented by ring Z 2b} is preferably a 5- to 7-membered ring, and more preferably a 5- or 6-membered ring.

In the formula (1-2), ^{examples of the substituent that the ring Z 1b} and the ring Z ^2b may have include the aforementioned substituent T. Moreover, it is also preferable that the substituent which the ring Z ^1b may have is an electron withdrawing group. Examples of the electron withdrawing group include the above-mentioned electron withdrawing group as a substituent that the ^{ring Z 1 may have.}

As the organic group represented by Rsy ¹ and Rsy ^{2 of formula (Syn1) and the organic group represented by Rsy 3} and Rsy ^{4 of} formula (Syn2), a group represented by the following formula (10) is also preferable.

[Chemical formula 33]

In formula (10), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a substituent, ^{two adjacent groups in R 11} to R ¹⁴ may be bonded to each other to form a ring, and R ²⁰ represents an aryl group or For heteroaryl, R ²¹ represents a substituent, and X ¹⁰ represents -CO- or -SO ₂ -.

In the formula (10), examples of the substituent represented ^{by R 11} to R ^{14 include the aforementioned substituent T.}

In formula (10), R ²⁰ represents an aryl group or a heteroaryl group, and an aryl group is preferred. The carbon number of the aryl group is preferably from 6 to 48, more preferably from 6 to 22, and particularly preferably from 6 to 12. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 1-30, and more preferably 1-12. Examples of the types of heteroatoms constituting the ring of the heteroaryl group include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of heteroatoms constituting the heteroaryl group is preferably 1-3, more preferably 1-2. The heteroaryl group is preferably a single ring or a condensed ring, a single ring or a condensed ring having a condensation number of 2 to 8 is more preferred, and a single ring or a condensed ring having a condensation number of 2 to 4 is even more preferred. The aryl group and heteroaryl group may have a substituent. As a substituent, the substituent T mentioned later can be mentioned. It is preferable that the aryl group and the heteroaryl group do not have a substituent.

In formula (10), R ²¹ represents a substituent. Examples of the substituent represented by R ²¹ include the aforementioned substituent T, and an alkyl group, an aryl group, a heteroaryl group, -OCORt ¹ or -NHCORt ¹ is preferred. Rt ¹ is preferably an alkyl, aryl or heteroaryl group, and more preferably an alkyl group.

As the ^{organic group represented by Rsy 1} and Rsy ^{2 of formula (Syn1) and the organic group represented by Rsy 3} and Rsy ^{4 of} formula (Syn2), the group represented by the following formula (20) is also preferable.

[Chemical formula 34]

In formula (20), R ²⁰ and R ²¹ each independently represent a hydrogen atom or a substituent, R ²⁰ and R ²¹ may be bonded to each other to form a ring, and X ²⁰ represents an oxygen atom, a sulfur atom, -NR ²² -, a selenium atom Or tellurium atom, R ²² represents a hydrogen atom or a substituent, when X ²⁰ is NR ²² , R ²² and R ²⁰ may be bonded to each other to form a ring, n _r2 represents an integer from 0 to 5, and n _r2 is one of 2 or more In this case, the plurality of R ²⁰ may be the same or different. ^{Two R 20} of the plurality of R ²⁰ may be bonded to each other to form a ring, and * represents a bonding bond.

In formula (20), examples of the substituent represented ^{by R 20} and R ^{21 include the aforementioned substituent T.} R ²⁰ is preferably an alkyl group, a halogenated alkyl group (preferably a fluorinated alkyl group), an aryl group or a halogen atom, an alkyl group or a halogenated alkyl group is more preferred, and a halogenated alkyl group is even more preferred. R ²¹ is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

In the formula (20), X ²⁰ is preferably an oxygen atom, a sulfur atom, and -NR ²² -, and -NR ²² -is more preferably. R ²² represents a hydrogen atom or a substituent. Examples of the substituent include the aforementioned substituent T, and an alkyl group is preferred. When X ²⁰ is NR ²² , R ²² and R ²⁰ may be bonded to each other to form a ring. Examples of the ring formed by bonding R ²² and R ²⁰ include 4 to 9 membered hydrocarbon ring or heterocyclic ring, 5 to 7 membered hydrocarbon ring or heterocyclic ring is preferred, 5 to 6 membered hydrocarbon ring or heterocyclic ring The ring is more preferred, a 5- to 6-membered hydrocarbon ring is further preferred, and a 6-membered hydrocarbon ring is particularly preferred.

In formula (20), n _r2 represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably an integer of 1-2. the case where n _r2 system of 2 or more, plural R ²⁰ may be the same, it can also be different, a plurality of two 2 R ²⁰ R ²⁰ may be bonded to each other to form a ring. The ring formed by bonding R ^{20 to} each other may be a hydrocarbon ring or a heterocyclic ring. In addition, the ring formed by bonding these groups to each other may be a monocyclic ring or a condensed ring.

As an organic group represented by Rsy ¹ and Rsy ^{2 of formula (Syn1) and an organic group represented by Rsy 3} and Rsy ^{4 of} formula (Syn2), a group represented by the following formula (30) or a group represented by formula (40) The group is also preferred.

[Chemical formula 35]

In formula (30), R ³⁵ to R ³⁸ each independently represent a hydrogen atom or a substituent, R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ may be bonded to each other to form a ring, and * represents bonding key. In formula (40), R ³⁹ to R ⁴⁵ each independently represent a hydrogen atom or a substituent, R ³⁹ and R ⁴⁵ , R ⁴⁰ and R ⁴¹ , R ⁴⁰ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ and R ⁴⁴ , R ⁴⁴ and R ⁴⁵ can be bonded to each other to form a ring, and * represents a bonding bond.

^{Examples of the substituents represented by R 35} to R ^{38 in} formula (30) and the substituents represented by R ³⁹ to R ^{45 in} formula (40) include the aforementioned substituents T. The alkyl group or the aryl group is more Preferably, the alkyl group is more preferable.

In formula (30), R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , and R ³⁷ and R ³⁸ may be bonded to each other to form a ring. In addition, in formula (40), R ³⁹ and R ⁴⁵ , R ⁴⁰ and R ⁴¹ , R ⁴⁰ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ and R ⁴⁴ , R ⁴⁴ and R ⁴⁵ may be bonded to each other to form a ring . The ring formed by bonding these groups to each other includes a hydrocarbon ring and a heterocyclic ring, and a hydrocarbon ring is preferred. In addition, the ring formed by the bonding of these groups may be a monocyclic ring or a condensed ring, and a condensed ring is preferred.

In formula (30), R ³⁵ and R ³⁶ are preferably bonded to form a ring. In the formula (40), it ^{is preferable that R 40} and R ⁴¹ and R ⁴⁴ and R ⁴⁵ are respectively bonded to form a ring.

The group represented by the formula (30) is preferably a group represented by the following formula (30a). In addition, the group represented by the formula (40) is preferably a group represented by the following formula (40a).

[Chemical formula 36]

In the formula (30a), R ³⁵ , R ³⁶ , and R ¹⁰¹ to R ¹⁰⁶ each independently represent a hydrogen atom or a substituent, and * represents a bonding bond. In the formula (40a), R ³⁹ , R ⁴² , R ⁴³ , and R ²⁰¹ to R ²¹² each independently represent a hydrogen atom or a substituent, and * represents a bonding bond. The substituents represented by R ³⁵ , R ³⁶ , and R ¹⁰¹ to R ^{106 and} the substituents represented by R ³⁹ , R ⁴² , R ⁴³ , and R ²⁰¹ to R ²¹² include the aforementioned substituent T, alkyl or aryl. The group is preferable, and the alkyl group is more preferable.

Examples of the p1+1 valent group represented by L ^{1 of the formula (Syn1) and the p2+1 valent group represented by L 2 of the} formula (Syn2) include a hydrocarbon group, a heterocyclic group, -O-, -S-, -CO-, -COO-, -OCO-, -SO ₂ -, -NR ^L -, -NR ^L CO-, -CONR ^L -, -NR ^L SO ₂ -, -SO ₂ NR ^L- And groups formed by these combinations. ^RL 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 an alkylene group, an arylene group, and a group obtained by removing one or more hydrogen atoms from these groups. The carbon number of the alkylene group is preferably 1-30, more preferably 1-15, and still more preferably 1-10. The alkylene group may be any of linear, branched, and cyclic. In addition, the cyclic alkylene group may be monocyclic or polycyclic. The carbon number of the arylene group is preferably 6-18, more preferably 6-14, and still more preferably 6-10. The heterocyclic group is preferably a monocyclic ring or a condensed ring having a condensation number of 2 to 4. The number of heteroatoms in the ring constituting the heterocyclic group is preferably 1 to 3. The hetero atom 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 3-30, more preferably 3-18, and still more preferably 3-12. The hydrocarbon group and heterocyclic group may have a substituent. As a substituent, the substituent T mentioned later can be mentioned.

And by R ^L represents an alkyl group of from 1 to 20 carbon atoms is preferred based, more preferably 1 to 15, 1 to 8 is further preferred. The alkyl group may be any of straight chain, branched chain, and cyclic, and straight chain or branched chain is preferred, and straight chain is more preferred. The alkyl group represented by the R ^L may further have a substituent. Examples of the substituent include the aforementioned substituent T. Carbon atoms represented by the R ^L of the aryl group having 6 to 30 lines is preferred, more preferably 6 to 20, 6 to 12 are more preferred. Aryl group represented by the sum R ^L may further have a substituent. Examples of the substituent include the aforementioned substituent T.

^{Preferably, L 1} of the formula (Syn1) is a group having a valence of p1+1. ^{Furthermore, L 2} of the formula (Syn2) is preferably a group having a valence of p2+1. In addition, the compound represented by the formula (Syn1) is preferably separated from the group represented ^{by A 1} by 1 atom or more by the p1+1 valent group represented ^{by L 1 and 3 atoms} The above is better. Further, the mother nucleus compound is represented by the formula of (SYN2) and a group represented by the sum of A ² by the + p2 L ² represents a monovalent group separated by one or more atoms are preferred, spaced three atoms The above is better. According to this structure, it is easy to obtain more excellent dispersibility of the near-infrared absorbing pigment.

As specific examples of pigment derivatives, compounds of the following structures [BP-1 to BP-4, B-1 to B-17] can be given. Also, Japanese Patent Application Publication No. 56-118462, Japanese Patent Application Publication No. 63-264674, Japanese Patent Application Publication No. 1-217077, Japanese Patent Application Publication No. 3-009961, Japanese Patent Application Publication No. 3-026767 Bulletin, Japanese Patent Application Publication No. 3-153780, Japanese Patent Application Publication No. 3-045662, Japanese Patent Application Publication No. 4-285669, Japanese Patent Application Publication No. 6-145546, Japanese Patent Application Publication No. 6-212088, Japanese Patent Application Publication No. 6-212088 6-240158, Japanese Patent Application Publication No. 10-030063, Japanese Patent Application Publication No. 10-195326, International Publication No. 2011/024896, paragraphs 0086 to 0098, International Publication No. 2012/102399, paragraphs 0063 to 0094, etc. The compounds described in. In addition, as the pigment derivative, Japanese Patent Application Publication No. 2015-172732 (metal salt of quinophthalone compound having sulfonic acid group), Japanese Patent Application Publication No. 2014-199308, and Japanese Patent Application Publication No. 2014-085562 , Japanese Unexamined Patent Publication No. 2014-035351 or Japanese Unexamined Patent Publication No. 2008-081565, the contents of which are incorporated in this specification.

[Chemical formula 37]

[Chemical formula 38]

[Chemical formula 39]

[Chemical formula 40]

[Chemical formula 41]

In the curable composition of the present invention, the pigment derivative may be used singly, or two or more of them may be used in combination.

The content of the pigment derivative in the curable composition of the present invention is preferably 1% to 30% by mass relative to the total amount of all pigments including the near-infrared absorbing pigment, and more preferably 5% to 30% by mass , 10% by mass to 30% by mass is more preferable.

(Polymerization inhibitor) From the viewpoint of storage stability, the curable composition in the present invention preferably contains a polymerization inhibitor. The polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, gallic phenol, tertiary butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tertiary butyl phenol), 2,2'-methylene bis (4-methyl-6-tertiary butyl phenol), N-nitrosophenyl hydroxylamine salt ( Ammonium salt, cerium salt, etc.), 2,2,6,6-tetramethylpiperidine-1-oxyl, etc. In addition, the polymerization inhibitor can also function as an antioxidant.

In the curable composition of the present invention, the polymerization inhibitor may be used singly or in combination of two or more kinds.

From the viewpoint of storage stability, the content of the polymerization inhibitor in the curable composition of the present invention is preferably 0.1 ppm to 1,000 ppm relative to the total solid content of the curable composition, and more preferably 1 ppm to 500 ppm. 1ppm～100ppm is particularly preferred.

(Solvent) The curable composition in the present invention preferably contains a solvent. Examples of solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyric acid Ethyl, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, 3-oxopropionic acid alkyl esters such as butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxopropionate and ethyl 3-oxopropionate (for example, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate) and methyl 2-oxopropionate, 2- Alkyl 2-oxypropionate such as ethyl oxypropionate and propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2-methylpropionate Ethyl pyruvate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate) and methyl pyruvate, ethyl pyruvate, propyl pyruvate, Methyl acetoxyacetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellulose acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, two Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc.; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; Aromatic hydrocarbons such as toluene and xylene. Among them, for environmental reasons, etc., there are cases where the aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) that are organic solvents are reduced (for example, relative to the total mass of the organic solvent, it can also be It can be set to 50 ppm or less, can also be set to 10 ppm or less, or can be set to be 1 mass ppm or less.).

Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, etc. are preferred. The solvent may be used alone or in combination of two or more kinds.

In the present invention, it is preferable to use an organic solvent with a small metal content, and the metal content of the organic solvent is preferably 10 ppb or less, for example. According to needs, ppt grade organic solvents can also be used, such organic solvents are provided by Toyo Gosei Co., Ltd (Chemical Industry Daily, November 13, 2015), for example.

As a method of removing impurities such as metals from organic solvents, for example, distillation (molecular distillation, thin-film distillation, etc.) or filtration using a filter can be cited. As the filter pore size of the filter used for filtration, 10 μm or less is preferable, 5 μm or less is more preferable, and 3 μm or less is still more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

Organic solvents can contain isomers (compounds with the same number of atoms but different structures). In addition, the isomer may include only one type, or may include a plurality of types.

The content rate of the peroxide in the organic solvent is preferably 0.8 mmol/L or less, and it is more preferred that the peroxide is not contained substantially.

In the curable composition of the present invention, the solvent may be used singly or in combination of two or more kinds.

The solid content of the curable composition in the present invention varies depending on the coating method and the presence or absence of a solvent. For example, 1% by mass to 100% by mass is preferable, 5% by mass to 50% by mass is more preferable, and 10% by mass to 10% by mass. 30% by mass is more preferable. That is, in the curable composition of the present invention, a solvent may be used so that the solid content falls within the above-mentioned range.

〔Sensitizer〕 The curable composition in the present invention may also contain a sensitizer for the purpose of enhancing the effect of polymerization initiators such as radicals and cations of the polymerization initiator and increasing the photosensitive wavelength. As a sensitizer, it is preferable to sensitize the above-mentioned photopolymerization initiator using an electron transfer mechanism or an energy transfer mechanism.

As the sensitizer, a compound that belongs to the compounds exemplified below and has an absorption wavelength in a wavelength region from a wavelength of 300 nm to a wavelength of 450 nm can be mentioned. As an example of a preferable sensitizer, a compound belonging to the following compounds and having an absorption wavelength in a wavelength region from a wavelength of 330 nm to a wavelength of 450 nm can be cited. Examples of sensitizers include polynuclear aromatics (e.g., phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), stellar (e.g., fluorescent Yellow, Eosin, Chizaoxin, Rose Red B, Bengal Rose Red), 9-oxysulfur (isopropyl 9-oxythio), diethyl thioxanthone, chlorine 9-oxy Thiocyanines), cyanines (for example, thiocarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbocyanine), phthalocyanines, thiocarbocyanines (For example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavin), anthraquinones (for example, anthraquinone), squaraines (for example, Squaraine), acridine orange, coumarins (for example, 7-diethylamino-4-methylcoumarin), coumarin ketones, phenothione, phenanthrene, styryl Benzene, azo compound, diphenylmethane, triphenylmethane, stilbene benzene, carbazole, porphyrin, spiro compound, quinacridone, indigo, styrene, pyrylium compound, pyrrole Aromatic ketone compounds such as methyl compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, and Michelone , N-aryl oxazolidinone and other heterocyclic compounds. Examples of sensitizers include European Patent No. 568,993, U.S. Patent No. 4,508,811, U.S. Patent No. 5,227,227, Japanese Patent Application Publication No. 2001-125255, Japanese Patent Application Publication No. 11-271969, etc. The compounds described in

A sensitizer may be used individually by 1 type, and may use 2 or more types together. From the viewpoint of the light absorption effect in the deep part and the effect of starting decomposition, when the curable composition of the present invention contains a sensitizer, the content of the sensitizer is 0.1% by mass relative to the total solid content of the curable composition -20% by mass is preferable, and 0.5% by mass to 15% by mass is more preferable.

(Co-sensitizer) The curable composition in the present invention may also contain a co-sensitizer. The co-sensitizer has the effects of further improving the sensitivity of the sensitizing dye or the active radiation of the initiator or inhibiting the inhibition of the polymerization of the polymerizable compound by oxygen.

In addition, examples of the co-sensitizer include the compounds described in paragraphs 0233 to 0241 of JP 2007-277514 A.

A co-sensitizer may be used individually by 1 type, and may use 2 or more types together. From the viewpoint of improving the curing rate based on the balance of polymerization growth rate and chain transfer, when the curable composition of the present invention contains a co-sensitizer, the content of the co-sensitizer is relative to the total amount of the curable composition. The solid content is preferably in the range of 0.1% by mass to 30% by mass, more preferably in the range of 0.5% by mass to 25% by mass, and more preferably in the range of 1% by mass to 20% by mass.

(Other additives) If necessary, the curable composition of the present invention can contain various additives such as coloring agents, adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation inhibitors other than surfactants and near-infrared absorbing pigments.

As other components, for example, the compounds described in paragraphs 0238 to 0249 of JP 2007-277514 A can be cited.

[Preparation of curable composition] The curable composition in the present invention can be prepared by mixing the above-mentioned components. In addition, for the purpose of removing impurities or reducing defects, it is better to filter with a filter. As the filter, if it is a filter previously used for filtering purposes, etc., it can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (for example, nylon-6, nylon-6, 6), and polyolefins such as polyethylene and polypropylene (PP) are used. Resin (including high-density, ultra-high molecular weight) and other filters. Among these raw materials, polypropylene (including high-density polypropylene) or nylon is preferred. The aperture of the filter is preferably 0.01 μm to 7.0 μm, more preferably 0.01 μm to 3.0 μm, and even more preferably 0.05 μm to 0.5 μm. By setting the aperture of the filter in this range, it is possible to reliably remove fine impurities that hinder the preparation of a uniform and smooth composition in the subsequent step. Alternatively, it is also preferable to use a fibrous filter material. Examples of the filter material include polypropylene fiber, nylon fiber, glass fiber, etc. Specifically, SBP type series (SBP008 etc.) manufactured by ROKI TECHNO CO., LTD., TPR can be used Type series (TPR002, TPR005, etc.), SHPX type series (SHPX003, etc.) filter elements. When using filters, different filters can also be combined. At this time, the filtration using the first filter may be performed once, or may be performed twice or more. In addition, it is also possible to combine first filters having different pore diameters within the above-mentioned range. Here, the pore size can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, various filters can be provided from NIHON PALL LTD. (DFA4201NIEY etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris KK (formerly Japan Microlis Co., Ltd.) or KITZ MICRO FILTER CORPORATION, etc. Choose.

[Use of curable composition] The curable composition in the present invention can be formed into a liquid state. Therefore, for example, the curable composition in the present invention can be applied to a substrate or the like and dried to easily produce a film. In the case of forming a film by coating, from the viewpoint of coating properties, the curable composition in the present invention preferably has a viscosity of 1 mPa·s to 100 mPa·s at 23°C. 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. Using a viscometer (product name: VISCOMETER TV-22) manufactured by TOKI SANGYO CO., LTD., the viscosity in the present invention was measured at 23°C.

The use of the curable composition in the present invention is not particularly limited. For example, it can be preferably used in the formation of an infrared cut filter and the like. For example, it can be preferably used for infrared cut filters on the light receiving side of solid-state imaging devices (for example, infrared cut filters for wafer-level lenses, etc.), and the back side of solid-state imaging devices (the side opposite to the light-receiving side) Infrared cut filter and so on. In particular, it can be suitably used as an infrared cut filter on the light-receiving side of a solid-state imaging element. In addition, with respect to the curable composition of the present invention, a coloring agent that shields visible light is further contained, thereby forming an infrared transmission filter capable of transmitting a part of infrared rays having a specific wavelength or more. For example, it is also possible to form an infrared transmission filter that shields to a wavelength of 400 nm to 850 nm and can transmit infrared rays having a wavelength of 850 nm or more.

In addition, the curable composition in the present invention is preferably stored in a storage container. In addition, for the purpose of preventing impurities from mixing into the raw material or composition as the container, it is also preferable to use a multi-layered bottle in which the inner wall of the container is formed by 6 kinds of 6-layer resins or a bottle in which 6 kinds of resins are formed into a 7-layer structure. Examples of these containers include those described in JP 2015-123351 A.

＜Membrane＞ The film of the present invention is composed of the curable composition of the present invention or is formed by curing the curable composition of the present invention. In addition, when the curable composition in the present invention contains a solvent, it may be dried. The film of the present invention can be preferably used as an infrared cut filter. In addition, it can also be used as a heat ray shielding filter and an infrared transmission filter. The film of the present invention may be laminated on a support and used, or it may be peeled off from the support and used. The film of the present invention may have a pattern or a film without a pattern (flat film). The "drying" in the present invention only needs to remove at least a part of the solvent, and it is not necessary to completely remove the solvent. The removal amount of the solvent can be set as desired. In addition, the above-mentioned curing may increase the hardness of the film, and curing by polymerization is preferable.

The thickness of the film of the present invention can be appropriately adjusted according to 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 more preferably 0.3 μm or more.

The film of the present invention preferably has a maximum absorption wavelength in the wavelength range of 650 nm to 1,500 nm, more preferably has a maximum absorption wavelength in the wavelength range of 680 nm to 1,300 nm, and more preferably has a maximum absorption wavelength in the wavelength range of 700 nm to 850 nm .

When the film of the present invention is used as an infrared cut filter, it is preferable that the film of the present invention satisfies at least one of the following conditions (1) to (4), and satisfies all the conditions (1) to (4): Further better. (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 particularly 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 particularly 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 particularly 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 particularly preferably 95% or more.

The film of the present invention can also be used in combination with color filters containing color colorants. Among them, the color filter can be manufactured using a coloring composition containing a color colorant. As the color coloring agent, a conventionally known color coloring agent can be mentioned. The coloring composition can contain a resin, a polymerizable compound, a polymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber, etc., in addition to the color colorant. As each component contained in the coloring composition, in addition to the previously known components, the aforementioned components can be appropriately used.

When the film of the present invention is used in combination with a color filter, it is preferable to arrange the color filter on the optical path of the light passing through the film of the present invention. For example, the film of the present invention and the color filter can be laminated and used as a laminated body. In the laminate, the film of the present invention and the color filter may be adjacent to each other in the thickness direction, or may not be adjacent. When the film of the present invention and the color filter are not adjacent in the thickness direction, the film of the present invention may be formed on a support body different from the support body on which the color filter is formed, or it may be a solid-state imaging element. Other components (for example, microlens, planarization layer, etc.) are between the film and the color filter of the present invention.

In addition, in the present invention, the infrared cut filter refers to a filter that transmits light with a wavelength in the visible region (visible light) and shields at least a part of light with a wavelength in the infrared region (infrared). The infrared cut filter may be one that completely transmits light of a wavelength in the visible region, or one that transmits light of a specific wavelength region among light of a wavelength of the visible region and shields light of a specific wavelength region. In addition, in the present invention, the color filter refers to a filter that transmits light in a specific wavelength region among light of wavelengths in the visible region and shields light in a specific wavelength region. In addition, in the present invention, the infrared transmission filter refers to a filter that blocks visible light and transmits at least a part of infrared rays.

The film of the present invention can be used in various devices such as solid-state imaging devices such as CCD (Charge Coupled Device) or CMOS (Complementary Metal Oxide Semiconductor), infrared sensors, and image display devices.

＜Method of manufacturing film＞ Next, the manufacturing method of the film of this invention is demonstrated. The film of the present invention can be manufactured through the step of applying the composition of the present invention.

In the method of manufacturing the film of the present invention, it is preferable to coat the composition on the support. As the support, for example, a substrate formed of a material such as silicone, alkali-free glass, soda glass, Pyrex glass (registered trademark) glass, and quartz glass can be cited. Organic films, inorganic films, etc. can be formed on these substrates. As a material of the organic film, the above-mentioned resin can be mentioned, for example. Moreover, as a support body, the board|substrate formed with the said resin can also be used. In addition, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. can be formed on the support. In addition, a black matrix that isolates each pixel is sometimes formed on the support. In addition, the support may be provided with an undercoat layer as needed, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface of the support such as a substrate. Moreover, when using a glass substrate as a support body, it is preferable to form an inorganic film on a glass substrate, or to perform a dealkalization process on a glass substrate and use. According to this aspect, it is possible to easily manufacture a film that further suppresses the generation of impurities.

As the coating method of the composition, a known method can be used. For example, the dropping method (drop casting); the slit coating method; the spray method; the roll coating method; the spin coating method (spin coating); the casting coating method; the slit spin coating method; the pre-wet method ( For example, the method described in Japanese Patent Laid-Open No. 2009-145395); inkjet (for example, on-demand, piezoelectric, thermal), nozzle jet and other jet printing, flexographic printing, screen printing, gravure printing , Reverse offset printing, metal mask printing and other printing methods; transfer method using molds, etc.; nano imprinting method, etc. The application method in inkjet is not particularly limited. For example, "Inkjet that can be promoted and used-Unlimited Possibilities in Patent-Issued in February 2005, Sumitbe Techon Research Co., Ltd." (Especially pages 115 to 133) or Japanese Patent Application Publication No. 2003-262716, Japanese Patent Application Publication No. 2003-185831, Japanese Patent Application Publication No. 2003-261827, Japanese Patent Application Publication No. 2012-126830, The method described in JP 2006-169325 A, etc.

The composition layer formed by coating the composition can be dried (pre-baked). When the pattern is formed by a low-temperature process, pre-baking may not be performed. When performing pre-baking, the pre-baking 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 preferably 50°C or higher, and more preferably 80°C or higher. By performing the pre-baking temperature below 150° C., for example, when the photoelectric conversion film of the image sensor is formed from an organic material, these characteristics can be maintained more effectively. The pre-baking time is preferably from 10 seconds to 3,000 seconds, more preferably from 40 seconds to 2,500 seconds, and even more preferably from 80 seconds to 220 seconds. Drying can be performed with a hot plate, oven, etc.

The method of manufacturing the film of the present invention may further include a step of forming a pattern. As the pattern formation method, a pattern formation method using a photolithography method or a pattern formation method using a dry etching method can be cited. In addition, when the film of the present invention is used as a flat film, the step of forming a pattern may not be performed. Hereinafter, the steps of forming a pattern will be described in detail.

-The use of photolithography to form patterns- The pattern forming method using photolithography method preferably includes the following steps, namely the exposure step, the composition layer formed by coating the composition of the present invention is exposed in a pattern; the development step is to develop and remove the unexposed part The composition layer is used to form a pattern. If necessary, you can set the step of baking the developed pattern (post-baking step). Hereinafter, each step will be described.

<<Exposure process>> In the exposure step, the composition layer is exposed in a pattern. For example, by exposing the composition layer through a mask having a predetermined mask pattern using an exposure device such as a stepper, the composition layer can be pattern-exposed. Thereby, the exposed part can be hardened. As the radiation (light) that can be used for exposure, ultraviolet rays such as g-rays and i-rays are preferred, and i-rays are more preferred. Irradiation amount (exposure amount) based e.g. ^{0.03J / cm 2 ~ 2.5J / cm} 2 is ^{preferred, 0.05J / cm 2 ~ 1.0J /} cm 2 is more ^{preferred, 0.08J / cm 2 ~ 0.5J /} cm 2 of Especially good. Regarding the oxygen concentration during exposure, it can be appropriately selected. In addition to performing it in the atmosphere, for example, it can be performed in a low-oxygen environment with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, and substantially no oxygen). Exposure can also be performed in a high-oxygen environment with an oxygen concentration greater than 21% by volume (for example, 22% by volume, 30% by volume, and 50% by volume). Further, the exposure illuminance can be appropriately set, so as to be preferably from ^{1,000W / m 2 ~ 100,000W / m} 2 ( ^{e.g., 5,000W / m 2, 15,000W /} m 2, 35,000W / m 2) range selection. The oxygen concentration and the exposure illuminance can be appropriately combined with conditions. For example, the oxygen concentration can be 10% by volume and the illuminance is 10,000 W/m ² , the oxygen concentration is 35% by volume and the illuminance is 20,000 W/m ² .

＜＜Development step＞＞ Next, the unexposed part of the composition layer in the unexposed part of the exposed composition layer is developed and removed to form a pattern. The development and removal of the composition layer of the unexposed part can be performed using a developer. Thereby, the composition layer of the unexposed part in the exposure step is eluted by the developing solution, and only the photohardened part remains on the support. As the developer, an alkaline developer that does not damage the solid-state imaging element or circuit of the substrate or the like is preferable. The temperature of the developing solution is preferably 20°C to 30°C, for example. The development time is preferably 20 seconds to 180 seconds. In addition, in order to improve the residue removal performance, the following steps can be repeated several times, that is, the developer is shaken off every 60 seconds, and then a new developer is supplied.

As the alkali agent used in the developer, for example, ammonia, ethylamine, diethylamine, dimethylethanolamine, diethylene glycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, Piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene and other organic basic compounds, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, metasilica Inorganic alkaline compounds such as sodium sulfate. The developer can preferably use an alkaline aqueous solution diluted with pure water. The concentration of the alkali 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. In addition, a surfactant can also be used in the developer. As an example of a surfactant, the conventionally well-known surfactant used in a developer can be mentioned, and a nonionic surfactant is preferable. From the viewpoint of convenient transportation or storage, the developer can be temporarily made into a concentrated solution and diluted to the desired concentration during use. The dilution ratio is not particularly limited, and can be set in the range of 1.5 times to 100 times, for example. In addition, when using a developer containing these alkaline aqueous solutions, it is better to wash (rinse) with pure water after development.

After development, heat treatment (post-baking) can be performed after drying. Post-baking is a heat treatment after development to completely harden the film. In the case of post-baking, the post-baking temperature is preferably 100°C to 240°C, for example. From the viewpoint of film curing, 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 an image sensor is formed from organic materials, the post-baking temperature is preferably 150°C or less, and 120°C or less More preferably, 100°C or less is more preferred, and 90°C or less is particularly preferred. The lower limit can be set to 50°C or higher, for example. Regarding post-baking, the developed film can be post-baked continuously or intermittently by using heating mechanisms such as heating plates, convection ovens (hot air circulation dryers), and high-frequency heaters to meet the above-mentioned conditions. . In addition, when the pattern is formed by a low-temperature process, post-baking may not be performed, and a step of re-exposure (post-exposure step) may be added.

-When the pattern is formed by dry etching- The pattern formation by the dry etching method can be performed by a method of hardening a composition layer formed by coating the composition on a support to form a hardened layer, and then forming a hardened layer on the hardened layer. The patterned photoresist layer is then used as a mask and the hardened layer is subjected to dry etching using an etching gas. When forming the photoresist layer, it is better to further perform a pre-baking treatment. In particular, as a photoresist forming process, it is preferable to perform heat treatment after exposure and heat treatment after development (post-baking treatment). Regarding pattern formation by the dry etching method, reference can be made to the description in paragraphs 0010 to 0067 of JP 2013-064993 A, and the content is incorporated into this specification.

＜Filter＞ The optical filter of the present invention has the film of the present invention. The filter of the present invention can be preferably used as an infrared cut filter or an infrared transmission filter, and can be more preferably used as an infrared cut filter. In addition, the aspect having the film of the present invention and the pixels selected from the group including red, green, blue, magenta, yellow, cyan, black, and colorless are also preferred aspects of the optical filter of the present invention .

The infrared cut filter of the present invention has the film of the present invention. In addition, the infrared cut filter of the present invention may be a filter that cuts only a part of the wavelength of the infrared region, or may be a filter that cuts off the entire infrared region. As a filter that cuts off only a part of the wavelength of the infrared region, for example, a near-infrared cut filter can be cited. In addition, examples of near-infrared rays include infrared rays having a wavelength of 750 nm to 2,500 nm. In addition, the infrared cut filter of the present invention is preferably a filter with a cut-off wavelength in the range of 750nm to 1,000nm, and a filter with a cutoff wavelength in the range of 750nm to 1,200nm is more preferable, with a cut-off wavelength of 750nm to 1,500nm The infrared filter is further preferred. In addition to the above-mentioned films, the infrared cut filter of the present invention may have a layer containing copper, a dielectric multilayer film, an ultraviolet absorbing layer, and the like. The infrared cut filter of the present invention also has at least a copper-containing layer or a dielectric multilayer film, whereby an infrared cut filter with a wide viewing area and excellent infrared shielding properties can be easily obtained. In addition, the infrared cut filter of the present invention further has an ultraviolet absorbing layer, whereby an infrared cut filter having excellent ultraviolet shielding properties can be formed. As the ultraviolet absorbing layer, for example, the absorbing layer described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/099060 can be referred to, and the content can be incorporated in this specification. As the dielectric multilayer film, the dielectric multilayer film described in paragraphs 0255 to 0259 of JP 2014-041318 A can be referred to, and this content is incorporated in this specification. As the copper-containing layer, a glass substrate (copper-containing glass substrate) or a copper-containing complex layer (copper-containing complex layer) formed of copper-containing glass may also be used. Examples of copper-containing glass substrates include copper-containing phosphate glass and copper-containing fluorophosphate glass. Commercial products of glass containing copper include NF-50 (manufactured by AGC TECHNO GLASS CO., LTD.), BG-60, BG-61 (manufactured by Schott AG above), CD5000 (manufactured by HOYA GROUP), etc. .

The infrared cut filter of the present invention can be used in various devices such as solid-state imaging devices such as CCD (Charge Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor), infrared sensors, and image display devices.

The infrared cut filter of the present invention has pixels (patterns) of a film obtained by using the composition of the present invention and at least selected from the group consisting of red, green, blue, magenta, yellow, cyan, black, and colorless The aspect of a pixel (pattern) is also preferable.

The method for manufacturing the optical filter of the present invention is not particularly limited, but it sequentially includes a step of applying the composition of the present invention to a support to form a composition layer, a step of exposing the composition layer in a pattern, and The method of developing and removing the unexposed part to form a pattern is preferable. In addition, as a method of manufacturing the optical filter of the present invention, it includes the steps of applying the composition of the present invention to a support to form a composition layer and curing it to form a layer, and forming a photoresist layer on the layer. The step, the step of patterning the photoresist layer by exposure and development to obtain a photoresist pattern, and the step of dry etching the layer using the photoresist pattern as an etching mask are also preferable. As each step in the method of manufacturing the optical filter of the present invention, reference can be made to the steps in the method of manufacturing the film of the present invention.

＜Solid-state imaging device＞ The solid-state imaging device of the present invention has the film of the present invention. The structure of the solid-state imaging element is not particularly limited as long as it has the structure of the film of the present invention and can function as a solid-state imaging element. For example, the following structure can be mentioned.

The structure is as follows: on the support there is a transfer electrode composed of a plurality of photodiodes and polysilicon constituting the light-receiving area of the solid-state imaging element, and the photodiode and the transfer electrode have only the photodiode light-receiving A light-shielding film including tungsten, etc. is provided on the light-shielding film, and a device protective film including silicon nitride, etc., formed to cover the entire light-shielding film and the photodiode light-receiving part is provided on the light-shielding film, and the device protective film has the device protection film of the present invention. membrane. Furthermore, it may be a structure having a light-concentrating mechanism (for example, a microlens, etc.) on the device protection film and on the lower side of the film of the present invention (the side close to the support), and the film of the present invention has a condensing mechanism. The composition of the light mechanism, etc. In addition, the color filter used in the solid-state imaging device may have a structure in which a film forming each pixel is buried in a space divided into, for example, a grid shape by a partition. In this case, the refractive index of the partition wall is preferably lower than the refractive index of each pixel system. Examples of solid-state imaging elements having such a structure include devices described in Japanese Patent Application Publication No. 2012-227478 and Japanese Patent Application Publication No. 2014-179577.

＜Image display device＞ The image display device of the present invention has the film of the present invention. Examples of the image display device include a liquid crystal display device, an organic electroluminescence (organic EL) display device, and the like. The definition or details of image display devices are described in, for example, "Electronic Display Devices (by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd. in 1990)", "Display Devices (by Ibuki Junzhang, Sangyo Tosho Publishing Co.) ., Ltd. issued in the first year of Heisei)” etc. In addition, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd. in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology". The image display device may have a white organic EL element. As a white organic EL element, a tandem structure is preferable. Regarding the tandem structure of organic EL elements, it is described in Japanese Patent Laid-Open No. 2003-045676, Supervised by Akoyoshi Mikami, "The front line of organic EL technology development-high brightness, high precision, long life, and technical secret collection -", technology Information Association, 326-328 pages, 2008, etc. The spectrum of the white light emitted by the organic EL element has a strong maximum emission peak in the blue region (430nm～485nm), the green region (530nm～580nm) and the yellow region (580nm～620nm). In addition to these luminous peaks, it is better to have a very large luminous peak in the red region (650nm～700nm).

＜Infrared sensor＞ The infrared sensor of the present invention has the film of the present invention. The structure of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. Hereinafter, an embodiment of the infrared sensor of the present invention will be described with reference to the drawings.

In FIG. 1, reference numeral 110 is a solid-state imaging element. The imaging area provided on the solid-state imaging element 110 has an infrared cut filter 111 and an infrared transmission filter 114. In addition, a color filter 112 is laminated on the infrared cut filter 111. A micro lens 115 is arranged on the incident light hν side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed to cover the microlens 115.

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

The color filter 112 is a color filter formed with pixels that transmit and absorb light of a specific wavelength in the visible region, and is not particularly limited, and a previously known color filter for pixel formation can be used. For example, a color filter formed with pixels of red (R), green (G), and blue (B) can be used. For example, it is possible to refer to the description in paragraphs 0214 to 0263 of JP 2014-043556 A, and incorporate the content into this specification.

The characteristics of the infrared transmission filter 114 can be selected according to the emission wavelength of the infrared LED used. For example, when the emission wavelength of the infrared LED is 850 nm, the maximum light transmittance in the thickness direction of the film of the infrared transmission filter 114 in the wavelength range of 400 nm to 650 nm is preferably 30% or less, and 20% or less is More preferably, 10% or less is even more preferable, and 0.1% or less is particularly preferable. It is preferable that the transmittance satisfies the above conditions in all regions in the wavelength range of 400 nm to 650 nm.

The light transmittance of the infrared transmission filter 114 in the thickness direction of the film has a minimum value of at least 70% in the wavelength range of 800 nm or more (preferably 800 nm to 1,300 nm), and more preferably 80% or more, 90 % Or more is more preferable. The above-mentioned transmittance preferably satisfies the above-mentioned condition in a part of the wavelength range of 800 nm or more, and it is more preferable that the above-mentioned condition is satisfied at the 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 particularly preferably 1 μm or less. The lower limit is preferably 0.1 μm. As long as the film thickness is within the above-mentioned range, it can be a film satisfying the above-mentioned spectral characteristics. The method of measuring the spectral characteristics, film thickness, and the like of the infrared transmission filter 114 is shown below. Regarding the film thickness, a probe-type surface profile measuring device (DEKTAK150 manufactured by ULVAC, INC.) was used to measure the dried substrate with the film. The spectroscopic properties of the film are values obtained by measuring the transmittance in the wavelength range of 300 nm to 1,300 nm using an ultraviolet-visible-near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

Also, for example, when the emission wavelength of the infrared LED is 940 nm, the transmittance of light in the thickness direction of the infrared transmission filter 114 is 20% or less at the maximum value in the range of wavelengths from 450 nm to 650 nm. The transmittance of light with a wavelength of 835nm is 20% or less, and the minimum value of the transmittance of light in the thickness direction of the film in the wavelength range of 1,000nm to 1,300nm is preferably 70% or more.

In the infrared sensor shown in FIG. 1, an infrared cut filter (other infrared cut filter) different from the infrared cut filter 111 may be further disposed on the planarization layer 116. Examples of other infrared cut filters include a layer containing copper or a layer having at least a dielectric multilayer film. Regarding these details, the above can be cited. In addition, as another infrared cut filter, a dual band pass filter can be used. In addition, the absorption wavelengths of the infrared transmission filter and the infrared cut filter used in the present invention can be appropriately combined and used in accordance with the light source used.

＜Camera Module＞ The camera module of the present invention has a solid-state imaging element and the optical filter of the present invention. Furthermore, it is preferable that the camera module of the present invention further has a lens and a circuit for processing the image obtained from the solid-state image sensor. The solid-state image sensor used in the camera module of the present invention may be the above-mentioned solid-state image sensor of the present invention, or may be a known solid-state image sensor. In addition, as the lens used in the camera module of the present invention and the circuit for processing the imaging obtained from the solid-state imaging element described above, known ones can be used. As an example of a camera module, refer to the camera module described in Japanese Patent Application Publication No. 2016-006476 or Japanese Patent Application Publication No. 2014-197190, and these contents are incorporated in this manual.

＜Inkjet ink and other uses＞ The inkjet ink of the present invention contains the curable composition of the present invention. In addition, the curable composition in the present invention can also be used for paints, anti-counterfeiting inks, and the like. In addition, the curable composition in the present invention can also be used as a heat shielding material, a heat storage material, or a light-to-heat conversion material. [Example]

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to these. Unless otherwise specified, "%" and "parts" in this embodiment refer to "mass %" and "parts by mass" respectively. In addition, in the polymer compound, unless otherwise specified, the molecular weight is the weight average molecular weight (Mw), and the ratio of the structural unit is the molar percentage. The weight average molecular weight (Mw) is the value measured by the polystyrene conversion value based on the gel permeation chromatography (GPC) method.

[Examples 1 to 68, Comparative Examples 1 to 6] ＜Preparation of curable composition＞ The raw materials described in the following Tables 1 to 6 were mixed and filtered using a nylon filter (manufactured by NIHON PALL Corporation) with a pore size of 0.45 μm to prepare a curable composition. In addition, the dispersion liquid prepared as follows was used for the dispersion liquid. The near-infrared absorbing pigments (marked as "pigment" in the table) of the types described in the dispersion column of Tables 1 to 6 below were mixed in the amounts described in the dispersion column of Tables 1 to 6 below. , Pigment derivative, dispersant and solvent A, and 230 parts by mass of zirconia beads with a diameter of 0.3 mm were added, and a dispersion treatment was carried out for 5 hours using a paint stirrer, and the beads were separated by filtration to prepare a dispersion.

[Table 1] Dispersions Adhesive resin Polymeric compound Polymerization initiator UV absorber Surfactant Polymerization inhibitor Solvent B pigment Pigment derivatives Dispersant Solvent A species Share SP value Acid value species Share species Share species Share species Share species Share species Share species Share species Share species Share species Share Example 1 Pigment PP1 2.5 Pigment Derivatives 1 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 2 Pigment PP1 2.5 Pigment Derivatives 1 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 2 5.5 21.2 88 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 3 Pigment PP1 2.5 Pigment Derivatives 1 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 3 5.5 20.2 91 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 4 Pigment PP1 2.5 Pigment Derivatives 1 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 4 5.5 19.7 102 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 5 Pigment PP1 2.5 Pigment Derivatives 1 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 5 5.5 21.1 72 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 6 Pigment PP1 2.5 Pigment Derivatives 1 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 6 5.5 21.0 101 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 7 Pigment PP2 2.5 Pigment derivatives 2 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 8 Pigment PP2 2.5 Pigment derivatives 2 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 2 5.5 21.2 88 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 9 Pigment PP2 2.5 Pigment derivatives 2 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 3 5.5 20.2 91 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 10 Pigment PP2 2.5 Pigment derivatives 2 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 4 5.5 19.7 102 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 11 Pigment PP2 2.5 Pigment derivatives 2 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 5 5.5 21.1 72 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 12 Pigment PP2 2.5 Pigment derivatives 2 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 6 5.5 21.0 101 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7

[Table 2] Dispersions Adhesive resin Polymeric compound Polymerization initiator UV absorber Surfactant Polymerization inhibitor Solvent B pigment Pigment derivatives Dispersant Solvent A species Share SP value Acid value species Share species Share species Share species Share species Share species Share species Share species Share species Share species Share Example 13 Pigment PP3 2.5 Pigment derivatives 3 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 14 Pigment PP3 2.5 Pigment derivatives 3 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 2 5.5 21.2 88 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 15 Pigment PP3 2.5 Pigment derivatives 3 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 3 5.5 20.2 91 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 16 Pigment PP3 2.5 Pigment derivatives 3 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 4 5.5 19.7 102 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 17 Pigment PP3 2.5 Pigment derivatives 3 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 5 5.5 21.1 72 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 18 Pigment PP3 2.5 Pigment derivatives 3 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 6 5.5 21.0 101 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 19 Pigment PP4 2.5 Pigment derivatives 4 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 20 Pigment PP4 2.5 Pigment derivatives 4 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 2 5.5 21.2 88 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 21 Pigment PP4 2.5 Pigment derivatives 4 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 3 5.5 20.2 91 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 22 Pigment PP4 2.5 Pigment derivatives 4 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 4 5.5 19.7 102 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 23 Pigment PP4 2.5 Pigment derivatives 4 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 5 5.5 21.1 72 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 24 Pigment PP4 2.5 Pigment derivatives 4 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 6 5.5 21.0 101 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7

[table 3] Dispersions Adhesive resin Polymeric compound Polymerization initiator UV absorber Surfactant Polymerization inhibitor Solvent B pigment Pigment derivatives Dispersant Solvent A species Share SP value Acid value species Share species Share species Share species Share species Share species Share species Share species Share species Share species Share Example 25 Pigment SQ1 2.5 Pigment derivatives 5 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 26 Pigment SQ1 2.5 Pigment derivatives 5 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 2 5.5 21.2 88 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 27 Pigment SQ1 2.5 Pigment derivatives 5 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 3 5.5 20.2 91 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 28 Pigment SQ1 2.5 Pigment derivatives 5 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 4 5.5 19.7 102 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 29 Pigment SQ1 2.5 Pigment derivatives 5 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 5 5.5 21.1 72 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 30 Pigment SQ1 2.5 Pigment derivatives 5 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 6 5.5 21.0 101 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 31 Pigment SQ2 2.5 Pigment derivatives 6 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 32 Pigment SQ2 2.5 Pigment derivatives 6 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 2 5.5 21.2 88 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 33 Pigment SQ2 2.5 Pigment derivatives 6 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 3 5.5 20.2 91 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 34 Pigment SQ2 2.5 Pigment derivatives 6 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 4 5.5 19.7 102 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 35 Pigment SQ2 2.5 Pigment derivatives 6 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 5 5.5 21.1 72 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 36 Pigment SQ2 2.5 Pigment derivatives 6 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 6 5.5 21.0 101 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7

[Table 4] Dispersions Adhesive resin Polymeric compound Polymerization initiator UV absorber Surfactant Polymerization inhibitor Solvent B pigment Pigment derivatives Dispersant Solvent A species Share SP value Acid value species Share species Share species Share species Share species Share species Share species Share species Share species Share species Share Example 37 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 38 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 2 5.5 21.2 88 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 39 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 3 5.5 20.2 91 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 40 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 4 5.5 19.7 102 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 41 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 5 5.5 21.1 72 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 42 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 6 5.5 21.0 101 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 43 Pigment PP1 2.5 Pigment Derivatives 1 0.5 Dispersant 2 1.8 Solvent 1 39 Resin 2 5.5 21.2 88 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 44 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 3 1.8 Solvent 1 39 Resin 3 5.5 20.2 91 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 45 Pigment SQ3 3.0 Pigment derivatives 7 0.5 Dispersant 1 1.3 Solvent 1 39 Resin 4 5.5 19.7 102 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 46 Pigment SQ3 2.0 Pigment derivatives 7 0.5 Dispersant 1 2.3 Solvent 1 39 Resin 5 5.5 21.1 72 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 47 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 1 2.4 Solvent 1 39 Resin 4 4.9 19.7 102 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 48 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 1 1.4 Solvent 1 39 Resin 5 5.9 21.1 72 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 49 Pigment SQ2 2.5 Pigment derivatives 7 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 4 5.5 19.7 102 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 50 Pigment SQ2 2.5 Pigment derivatives 7 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 5 5.5 21.1 72 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 51 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 2 1.8 Solvent 1 39 Resin 4 5.5 19.7 102 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 52 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 5 5.5 21.1 72 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 2 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7

[table 5] Dispersions Adhesive resin Polymeric compound Polymerization initiator UV absorber Surfactant Polymerization inhibitor Solvent B pigment Pigment derivatives Dispersant Solvent A species Share SP value Acid value species Share species Share species Share species Share species Share species Share species Share species Share species Share species Share Example 53 SQ-1 2.5 B-2 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 54 SQ-14 2.5 B-2 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 55 SQ-13 2.5 B-2 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 56 SQ-15 2.5 B-6 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 19.7 20.7 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 57 SQ-17 2.5 B-14 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 58 SQ-33 2.5 B-14 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 59 SQ-24 2.5 B-1 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 60 SQ-25 2.5 B-1 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 61 SQ-27 2.5 B-1 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 62 SQ-30 2.5 B-1 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 63 SQ-21 2.5 B-3 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 64 SQ-37 2.5 B-17 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 65 SQ-43 2.5 B-17 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 66 SQ-52 2.5 B-2 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 67 SQ-56 2.5 B-2 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Example 68 SQ-60 2.5 B-2 0.5 Dispersant 1 1.8 Solvent 1 39 Resin 1 5.5 20.7 96 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7

[Table 6] Dispersions Adhesive resin Polymeric compound Polymerization initiator UV absorber Surfactant Polymerization inhibitor Solvent B pigment Pigment derivatives Dispersant Solvent A species Share SP value Acid value species Share species Share species Share species Share species Share species Share species Share species Share species Share species Share Comparative example 1 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 3 1.8 Solvent 1 39 Resin 7 5.5 19.3 91 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Comparative example 2 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 3 1.8 Solvent 1 39 Resin 8 5.5 20.7 107 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Comparative example 3 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 3 1.8 Solvent 1 39 Resin 9 5.5 21.1 217 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Comparative example 4 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 3 1.8 Solvent 1 39 Resin 10 5.5 20.9 69 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Comparative example 5 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 3 1.8 Solvent 1 39 Resin 11 5.5 19.6 64 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7 Comparative example 6 Pigment SQ3 2.5 Pigment derivatives 7 0.5 Dispersant 3 1.8 Solvent 1 39 Resin 12 5.5 21.3 91 Monomer 1 monomer 2 3.2 3.2 Polymerization initiator 1 1 UV absorber 1 1.6 Surfactant 1 0.025 Polymerization inhibitor 1 0.003 Solvent 1 41.7

The raw materials used for each curable composition are as follows. -Near infrared absorbing pigment (marked as "pigment" in the table)- Pigments PP1～PP4 and SQ1～SQ3: compounds with the following structures SQ-1, SQ-14, SQ-13, SQ-15, SQ-17, SQ-33, SQ-24, SQ-25, SQ-27, SQ-30, SQ-21, SQ-37, SQ- 43. SQ-52, SQ-56 and SQ-60: The compounds mentioned as specific examples of squaraine compounds [SQ-1, SQ-14, SQ-13, SQ-15, SQ-17 , SQ-33, SQ-24, SQ-25, SQ-27, SQ-30, SQ-21, SQ-37, SQ-43, SQ-52, SQ-56 and SQ-60]

[Chemical formula 42]

-Pigment Derivatives- Pigment Derivatives 1-7: Compounds with the following structures B-1, B-2, B-3, B-6, B-14, and B-17: The compounds mentioned as specific examples of pigment derivatives [B-1, B-2, B- 3. B-6, B-14 and B-17]

[Chemical formula 43]

-Dispersant- Dispersant 1 (resin with base): Resin with the following structure (the value of each constituent unit attached to the main chain is the molar ratio, and the value attached to the side chain is the number of repeating units. Mw=21,000, acid value =36.0mgKOH/g, amine value=47.0mgKOH/g)

[Chemical formula 44]

Dispersant 2 (resin with base): Resin with the following structure (the value of each constituent unit in the main chain is the molar ratio, and the value in the side chain is the number of repeating units. Mw=23,000, acid value =32.3mgKOH/g, amine value=45.0mgKOH/g) [Chemical formula 45]

Dispersant 3 (resin with base): Resin with the following structure (the value of each constituent unit attached to the main chain is the molar ratio, and the value attached to the side chain is the number of repeating units. Mw=10,000, acid value =44.3mgKOH/g, amine value=40.0mgKOH/g) [Chemical formula 46]

-Binder resin- Resins 1 to 6 (specific binder resins): Resins 1 to 6 described in the specific examples of specific binder resins Resins 7-12 (comparative binder resins): Resins with the following structure (the value of each constituent unit attached to the main chain is the molar ratio)

[Chemical formula 47]

-Polymerizable compound- Monomer 1: A mixture of compounds of the following structure (M-1) (containing 55 mol% to 63 mol% of the left compound) Monomer 2: The compound of the following structure (M-2) Monomer 3: The compound of the following structure (M-3) Monomer 4: The compound of the following structure (M-4)

[Chemical formula 48]

-Polymerization initiator- Polymerization initiator 1 (photopolymerization initiator): a compound of the following structure (I-1) (IRGACURE OXE-01, manufactured by BASF Corporation) Polymerization initiator 2 (photopolymerization initiator): a compound of the following structure (I-2)

[Chemical formula 49]

-Ultraviolet absorber- Ultraviolet absorber 1: The compound of the following structure (UV1)

[Chemical formula 50]

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

[Chemical formula 51]

-Polymerization inhibitor- Polymerization inhibitor 1: p-methoxyphenol (manufactured by Sanritsu chemy)

-Solvent A and B- Solvent 1: Propylene glycol monomethyl ether acetate (PGMEA)

[Measurement of tin content] Regarding the content of tin in the curable composition, it is measured by the aforementioned method. The results are shown in Table 7.

[Evaluation of storage stability] The storage stability of the curable composition was evaluated as follows. The viscosity of the curable composition immediately after the production was measured (it was set as the initial viscosity A). After storing the curable composition whose viscosity was measured in a thermostat at 45° C. for 72 hours, the viscosity was measured again (referred to as the viscosity after storage B). In addition, the temperature of the curable composition was adjusted to 23°C to measure the viscosity. In addition, the viscosity increase rate was calculated from the following calculation formula, and the storage stability was evaluated by the viscosity increase rate. Viscosity increase rate (%)=[(Viscosity after storage B/Initial viscosity A)-1]×100

The storage stability was evaluated based on the following criteria. The results are shown in Table 7. -Benchmark- 5: The viscosity increase rate of the curable composition is 5% or less. 4: The viscosity increase rate of the curable composition exceeds 5% and is 7.5% or less. 3: The viscosity increase rate of the curable composition exceeds 7.5% and is 10% or less. 2: The viscosity increase rate of the curable composition exceeds 10% and is 20% or less. 1: The viscosity increase rate of the curable composition exceeds 20%.

[Preparation and evaluation of cured film] A spin coater (manufactured by MIKASA CO., LTD) was used to coat the curable composition on a silicon wafer to form a coating film so that the film thickness after post-baking became 1.0 μm. Next, using a hot plate, it was heated at 100°C for 2 minutes. Next, using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), ^{exposure was performed at an exposure amount of 1000 mJ/cm 2} through a mask having a 1 μm square Bayer pattern. Next, a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used to perform spin immersion development at 23° C. for 60 seconds. Then, it was rinsed with a rotary shower, and further rinsed with pure water. Next, using a hot plate, heating (post-baking) was performed at 200°C for 5 minutes, thereby forming a pattern. Regarding any 10 locations between the patterns (unexposed portions), residues were confirmed and observed using a scanning electron microscope, and the development residues were evaluated based on the following criteria. The results are shown in Table 7. -Reference-5: No residue was confirmed in 10 places in the unexposed part. 4: In 10 locations in the unexposed portion, the average number of residues having a size of 5 nm to 200 nm in diameter exceeds 0 and is 1 or less. 3: In 10 locations in the unexposed portion, the average number of residues of a size of 50 nm to 200 nm in diameter exceeds 1 and is 5 or less. 2: The average value of the number of residues having a size of 5 nm to 200 nm in diameter exceeds 5 in 10 locations in the unexposed part. 1: Residues with a size of 200 nm or more in diameter exist in 10 places in the unexposed part, or the unexposed part is almost insoluble.

[Table 7] Tin content ppm Evaluation Tin content ppm Evaluation Storage stability Residue Storage stability Residue Example 1 7.0 5 5 Example 43 7.0 3 4 Example 2 7.0 4 5 Example 44 7.0 4 5 Example 3 7.0 5 5 Example 45 5.1 3 4 Example 4 7.0 4 5 Example 46 8.9 5 5 Example 5 7.0 5 4 Example 47 9.3 5 5 Example 6 7.0 4 5 Example 48 5.4 4 3 Example 7 7.0 5 5 Example 49 7.0 5 4 Example 8 7.0 4 5 Example 50 7.0 4 4 Example 9 7.0 5 5 Example 51 7.0 4 5 Example 10 7.0 4 5 Example 52 7.0 5 4 Example 11 7.0 5 4 Example 53 7.0 5 5 Example 12 7.0 4 5 Example 54 7.0 5 5 Example 13 7.0 5 5 Example 55 7.0 5 5 Example 14 7.0 4 5 Example 56 7.0 5 5 Example 15 7.0 5 5 Example 57 7.0 5 5 Example 16 7.0 4 5 Example 58 7.0 5 5 Example 17 7.0 5 4 Example 59 7.0 5 5 Example 18 7.0 4 5 Example 60 7.0 5 5 Example 19 7.0 5 5 Example 61 7.0 5 5 Example 20 7.0 4 5 Example 62 7.0 5 5 Example 21 7.0 5 5 Example 63 7.0 5 5 Example 22 7.0 4 5 Example 64 7.0 5 5 Example 23 7.0 5 4 Example 65 7.0 5 5 Example 24 7.0 4 5 Example 66 7.0 5 5 Example 25 7.0 5 5 Example 67 7.0 5 5 Example 26 7.0 4 5 Example 68 7.0 5 5 Example 27 7.0 5 5 Comparative example 1 7.0 2 2 Example 28 7.0 4 5 Comparative example 2 7.0 2 5 Example 29 7.0 5 4 Comparative example 3 7.0 1 5 Example 30 7.0 4 5 Comparative example 4 7.0 2 2 Example 31 7.0 5 5 Comparative example 5 7.0 2 2 Example 32 7.0 4 5 Comparative example 6 7.0 2 4 Example 33 7.0 5 5 Example 34 7.0 4 5 Example 35 7.0 5 4 Example 36 7.0 4 5 Example 37 7.0 5 5 Example 38 7.0 4 5 Example 39 7.0 5 5 Example 40 7.0 4 5 Example 41 7.0 5 4 Example 42 7.0 4 5

From the results described in Table 7, it can be seen that the curable composition of Example 1 to Example 68, which is the composition of the present invention, has excellent storage stability compared with the composition of Comparative Example 1 to Comparative Example 6, and further The development residue is also reduced. In Example 1, when the ultraviolet absorber, surfactant, and polymerization inhibitor were removed, the same results as in Example 1 were obtained. In Example 1, even if the polymerizable compound was changed to only 6.4 parts of monomer 1, the results were the same as in Example 1. In Example 1, even if the polymerization initiator was changed from polymerization initiator 1 (1 part) to a mixture of polymerization initiator 1 and polymerization initiator 2 (0.5 parts each), it was the same as in Example 1. result. In Example 1, the solvent B was changed from solvent 1 to cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.), and the results were the same as in Example 1. In Example 1, when the amount of solvent B was changed to 31.7 parts or 51.7 parts, the same results as in Example 1 were obtained.

(Example 101 to Example 168) Using the compositions of Examples 1 to 68, respectively, a 2 μm square pattern (infrared cut filter) was formed by the following method.

Using the curable compositions of Examples 1 to 68, patterns were produced by the following method. The curable composition was applied on a silicon wafer by a spin coating method so that the film thickness after film formation became 1.0 μm. Next, using a hot plate, it was heated at 100°C for 2 minutes. Next, using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed at 1,000 mJ/cm ² through a mask of a 2 μm square dot pattern. Next, a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used to perform spin immersion development at 23° C. for 60 seconds. Then, it was rinsed with a rotary shower, and further rinsed with pure water. Next, it was heated at 200° C. for 5 minutes using a hot plate, thereby forming a 2 μm square pattern (infrared cut filter).

Next, the Red composition was applied on the pattern of the infrared cut filter by a spin coating method so that the film thickness after film formation became 1.0 μm. Next, using a hot plate, it was heated at 100°C for 2 minutes. Next, using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed at 1,000 mJ/cm ² through a mask of a 2 μm square dot pattern. Next, a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used to perform spin immersion development at 23° C. for 60 seconds. Then, it was rinsed with a rotary shower, and further rinsed with pure water. Next, by heating at 200°C for 5 minutes using a hot plate, the Red composition was patterned on the pattern of the infrared cut filter. Similarly, the Green composition and the Blue composition are patterned in sequence to form colored patterns (Bayer patterns) of red, green, and blue. In addition, the Bayer pattern refers to a color filter element with one red element, two green elements, and one blue element repeated as disclosed in the specification of US Patent No. 3,971,065 2×2 array pattern, but in this embodiment, a repeating pattern with 1 red (Red) element, 1 green (Green) element, 1 blue (Blue) element and 1 infrared transmission filter is formed The Bayer pattern of a 2×2 array of element filter elements.

Next, the composition for forming an infrared transmission filter (the following composition 100 or composition 101) was applied on the patterned film by a spin coating method so that the film thickness after film formation became 2.0 μm. Next, using a hot plate, it was heated at 100°C for 2 minutes. Next, using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed at 1,000 mJ/cm ² through a 2 μm square Bayer pattern mask. Next, a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used to perform spin immersion development at 23° C. for 60 seconds. Then, it was rinsed with a rotary shower, and further rinsed with pure water. Next, by heating at 200° C. for 5 minutes using a hot plate, the missing portion of the Bayer pattern of the infrared cut filter where the colored pattern was not formed was patterned with the infrared transmission filter. It is assembled in a solid-state imaging device according to these well-known methods. In a low-illumination environment (0.001lux (Lux)), the solid-state image sensor was irradiated with infrared light by an infrared light-emitting diode (infrared LED), and the image was captured, and the image performance was evaluated. In the case of using any of the curable compositions obtained in Example 1 to Example 68, the image can be clearly recognized even in a low-illuminance environment.

The Red composition, Green composition, Blue composition, and infrared transmission filter forming composition used for the above patterning are as follows.

-Red composition- The following components were mixed and stirred, and then filtered with a nylon filter (manufactured by NIHON PALL LTD.) with a pore diameter of 0.45 μm to prepare a Red composition. Red pigment dispersion: 51.7 parts by mass Resin 4 (40% by mass PGMEA solution): 0.6 parts by mass Polymerizable compound 12: 0.6 parts by mass Photopolymerization initiator 1: 0.3 parts by mass Surfactant 2: 4.2 parts by mass PGMEA: 42.6 parts by mass

-Green composition- The following components were mixed and stirred, and then filtered with a nylon filter (manufactured by NIHON PALL LTD.) with a pore diameter of 0.45 μm to prepare a Green composition. Green pigment dispersion: 73.7 parts by mass Resin 4 (40% by mass PGMEA solution): 0.3 parts by mass Polymerizable compound 11: 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- After mixing and stirring the following components, filtration was performed with a nylon filter (manufactured by NIHON PALL LTD.) with a pore diameter of 0.45 μm to prepare a Blue composition. Blue pigment dispersion: 44.9 parts by mass Resin 4 (40% by mass PGMEA solution): 2.1 parts by mass Polymerizable compound 11: 1.5 parts by mass Polymerizable compound 12: 0.7 parts by mass Photopolymerization initiator 1: 0.8 parts by mass Surfactant 2: 4.2 parts by mass PGMEA: 45.8 parts by mass

-Composition for forming infrared transmission filter- After mixing and stirring the components in the following composition, it filtered with a 0.45 μm nylon filter (manufactured by NIHON PALL LTD.) to prepare an infrared transmission filter forming composition.

＜Composition 100＞ Pigment dispersion liquid 1-1: 46.5 parts by mass Pigment dispersion liquid 1-2: 37.1 parts by mass Polymeric compound 13: 1.8 parts by mass Resin 4: 1.1 parts by mass Photopolymerization initiator 2: 0.9 parts by mass Surfactant 2: 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 (dineopentaerythritol hexaacrylate): 50 parts by mass Resin 4: 17 parts by mass Photopolymerization initiator (1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzophenoxime)): 10 parts by mass PGMEA: 179 parts by mass Alkali-soluble polymer F-1: 17 parts by mass (35 parts by mass of solid content)

＜Synthesis example of alkali-soluble polymer F-1＞ In the 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 methyl 20 parts by mass of acrylic acid was dissolved in 200 parts by mass of propylene glycol monomethyl ether acetate, and 3 parts by mass of 2,2'-azobisisobutyronitrile and 5 parts by mass of α-methylstyrene dimer were added. After nitrogen purging in the reaction vessel, stirring and nitrogen bubbling were performed while heating at 80° C. for 5 hours to obtain a solution (solid content concentration 35% by mass) containing the alkali-soluble polymer F-1. The weight average molecular weight of this polymer in terms of polystyrene is 9,700, the number average molecular weight is 5,700, and the Mw/Mn is 1.70.

＜Pigment dispersion 2-1＞ 60 parts by mass of CI Pigment Black 32, 20 parts by mass of CI Pigment Blue 15:6, 20 parts by mass of CI Pigment Yellow 139, and 80 parts by mass of Lubrizol Japan Ltd. SOLSPERSE 76500 (solid content concentration 50% by mass), 120 parts by mass of a solution containing alkali-soluble polymer F-1 (with a solid content concentration of 35% by mass) and 700 parts by mass of propylene glycol monomethyl ether acetate were mixed and dispersed for 8 hours using a paint mixer to obtain a colorant Dispersion 2-1.

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

･Red pigment dispersion liquid is mixed with 9.6 parts by mass of CIPigment Red 254, 4.3 parts by mass of CIPigment Yellow 139, and 6.8 parts by mass of dispersant (Disperbyk-161, BYK Chemie GmbH) and 79.3 parts by mass of a mixture of PGMEA were mixed and dispersed for 3 hours to prepare a pigment dispersion. After that, a high-pressure disperser NANO-3000-10 (manufactured by Nippon Bee Chemical Co., Ltd.) with a decompression mechanism was further used ^{for dispersion treatment at a pressure of 2,000 kg/cm 3} at a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion.

･Green pigment dispersion liquid is combined with 6.4 parts by mass of CIPigment Green 36, 5.3 parts by mass of CIPigment Yellow 150, and 5.2 parts by mass of dispersant (Disperbyk-161, BYK) by a bead mill (zirconia beads with a diameter of 0.3 mm). Chemie GmbH) and 83.1 parts by mass of a mixture of PGMEA were mixed and dispersed for 3 hours to prepare a pigment dispersion. After that, a high-pressure disperser NANO-3000-10 (manufactured by Nippon Bee Chemical Co., Ltd.) with a decompression mechanism was further used ^{for dispersion treatment at a pressure of 2,000 kg/cm 3} at a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion.

･Blue pigment dispersion liquid is mixed with 9.7 parts by mass of CIPigment Blue 15:6, 2.4 parts by mass of CIPigment Violet 23, 5.5 parts of dispersant (Disperbyk-161, A mixed solution consisting of BYK Chemie GmbH) and 82.4 parts of PGMEA was mixed and dispersed for 3 hours to prepare a pigment dispersion. After that, a high-pressure disperser NANO-3000-10 (manufactured by Nippon Bee Chemical Co., Ltd.) with a decompression mechanism was further used ^{for dispersion treatment at a pressure of 2,000 kg/cm 3} at a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion liquid.

･Pigment Dispersion Liquid 1-1 Use zirconia beads with a diameter of 0.3mm, and mix the mixture of the following components with a bead mill (a high-pressure disperser NANO-3000-10 (manufactured by Nippon Bee Chemical Co., Ltd.) with a decompression mechanism) And dispersed for 3 hours, thereby preparing a pigment dispersion liquid 1-1. ･Pigment mixture composed 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 Use zirconia beads with a diameter of 0.3mm, and mix the mixture of the following components with a bead mill (a high-pressure disperser NANO-3000-10 (manufactured by Nippon Bee Chemical Co., Ltd.) with a decompression mechanism) And dispersed for 3 hours, thereby preparing a pigment dispersion liquid 1-2. ･Pigment mixture composed 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

The details of the abbreviations in the ingredients used in the above are shown below.

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

[Chemical formula 52]

･Polymerizable compound 11: KAYARAD DPHA (a mixture of dineopentaerythritol hexaacrylate and dineopentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.) ･Polymerizable compound 12: The following structure

[Chemical formula 53]

Polymeric compound 13: the following structure (a mixture of 7:3 molar ratio of the compound on the left and the compound on the right)

[Chemical formula 54]

･Resin 4: The following structure (acid value: 70mgKOH/g, Mw=11,000, and the ratio of each structural unit is molar ratio.)

[Chemical formula 55]

･Photopolymerization initiator 1: IRGACURE OXE01 (1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzophenoxime), manufactured by BASF) ･Photopolymerization initiator 2: A compound of the following structure

[Chemical formula 56]

･Surfactant 2: Same as Surfactant 1 above.

･Silane coupling agent: a compound with the following structure. In the following structural formulae, Et represents an ethyl group.

[Chemical formula 57]

(Examples 201 to 268) After mixing and stirring the following composition, filtration was performed with a nylon filter (manufactured by NIHON PALL Corporation) with a pore size of 0.45 μm to prepare a pattern forming composition of Example 201. The curable composition of Example 1: 22.67 parts by mass Pigment dispersion liquid 2-1: 51.23 parts by mass Using the pattern forming composition of Example 201, the development residue was evaluated in the same manner as in Example 1, and as a result, the same effect as in Example 1 was obtained. In addition, the cured film obtained using the pattern forming composition of Example 201 can block light of wavelengths in the visible region and transmit at least a part of light of wavelengths in the near-infrared region (near infrared rays). The pattern formation compositions of Examples 202 to 268 in which the curable composition of Examples 2 to 68 were used instead of the curable composition of Example 1 were evaluated in the same manner as in Example 201. The same effects as in Example 201 were obtained, respectively.

(Examples 301-368) After mixing and stirring the following composition, filtration was performed with a nylon filter (manufactured by NIHON PALL Corporation) with a pore diameter of 0.45 μm to prepare a pattern forming composition of Example 301. The curable composition of Example 1: 36.99 parts by mass Pigment dispersion liquid 1-1: 46.5 parts by mass Pigment dispersion liquid 1-2: 37.1 parts by mass Using the pattern formation composition of Example 301, the development residue was evaluated in the same manner as Example 1, and as a result, the same effect as Example 1 was obtained. In addition, the cured film obtained using the pattern forming composition of Example 301 can block light of wavelengths in the visible region and transmit at least a part of light of wavelengths in the near-infrared region (near infrared). The pattern formation compositions of Examples 302 to 368 in which the curable composition of Examples 2 to 68 were used instead of the curable composition of Example 1 were evaluated in the same manner as in Example 301. The same effects as in Example 301 were obtained.

(Example 400) In the above-mentioned Examples 1 to 68, Examples 101 to 168, Examples 201 to 268, and Examples 301 to 368, the silicon wafer was changed to a glass substrate and evaluated in the same manner. The same effect as the above-mentioned embodiment is achieved.

110: solid-state image sensor 111: Infrared cut filter 112: color filter 114: Infrared transmission filter 115: Microlens 116: Planarization layer

Fig. 1 is a schematic diagram showing an embodiment of the infrared sensor of the present invention.

Claims (20)

A near-infrared absorbing composition comprising: a near-infrared absorbing pigment; a resin having a base; and other than the aforementioned resin having a base, an SP value of 19.7MPa ^1/2 to 21.2MPa ^1/2 and an acid value of Binder resin of 70mgKOH/g～105mgKOH/g. The near-infrared absorbing composition according to claim 1, wherein The aforementioned binder resin contains a constituent unit having at least one ring structure selected from the group consisting of an aromatic ring and an aliphatic ring at 50 mol% to 90 mol% relative to the total constituent units of the aforementioned binder resin之resin. The near-infrared absorbing composition according to claim 2, wherein The aforementioned aliphatic ring system is bicyclic or tricyclic. The near-infrared absorbing composition according to claim 2, wherein The aforementioned aromatic ring is a benzene ring, a naphthalene ring or a nitrogen-containing heteroaromatic ring. The near-infrared absorbing composition according to any one of claims 1 to 4, wherein The aforementioned binder resin is a resin containing a structural unit having an acid group at 10 mol% to 40 mol% with respect to the total structural unit of the aforementioned binder resin. The near-infrared absorbing composition according to any one of claims 1 to 4, wherein The weight average molecular weight of the aforementioned binder resin is 20,000 or less. The near-infrared absorbing composition according to any one of claims 1 to 4, wherein The aforementioned resin having a basic group is at least one selected from the group consisting of a resin having a tertiary amine group in the side chain and a resin having a nitrogen atom in the main chain. The near-infrared absorbing composition according to claim 7, wherein The aforementioned resin system having a tertiary amine group on the side chain and further a resin having a quaternary ammonium salt group on the side chain. The near-infrared absorbing composition according to any one of claims 1 to 4, wherein The aforementioned near-infrared absorbing pigment is a pyrrolopyrrole compound or a squaraine compound. The near-infrared absorbing composition according to any one of claims 1 to 4, wherein The content of tin is 1 ppm to 15 ppm with respect to the total solid content of the near-infrared absorbing composition. The near-infrared absorbing composition according to any one of claims 1 to 4, which further includes a polymerizable compound and a polymerization initiator. A film consisting of the near-infrared absorbing composition according to any one of claims 1 to 11 or hardened the aforementioned near-infrared absorbing composition. An optical filter having the film described in claim 12. The optical filter according to claim 13, which is an infrared cut filter or an infrared transmission filter. A solid-state imaging device having the film described in claim 12. An infrared sensor having the film described in claim 12. A method for manufacturing an optical filter, which includes: The step of applying the near-infrared absorbing composition described in claim 11 to the support to form a composition layer; The step of exposing the aforementioned composition layer in a pattern; and The step of developing and removing the unexposed parts to form a pattern. A method for manufacturing an optical filter, which includes: The step of applying the near-infrared absorbing composition described in claim 11 to a support to form a composition layer, and hardening it to form a layer; The step of forming a photoresist layer on the aforementioned layer; The step of patterning the aforementioned photoresist layer by exposure and development to obtain a photoresist pattern; and The step of dry etching the aforementioned layer using the aforementioned photoresist pattern as an etching mask. A camera module having a solid-state imaging element and the filter described in claim 13 or claim 14. An inkjet ink comprising the near-infrared absorbing composition described in claim 11.

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