TWI770314B - Composition, film, infrared transmission filter, solid-state imaging element, and optical sensor - Google Patents

Abstract

The present invention provides a composition, a film, an infrared transmission filter, a solid-state imaging element, and an optical sensor capable of producing a film with high film thickness uniformity and suppressed occurrence of foreign matter defects in a high-temperature and high-humidity environment. The composition contains: a specific metal azo pigment; a colorant with a maximum absorption in the wavelength range of 400-700 nm; and a compound with an ethylenically unsaturated bond group and/or a compound with a cyclic ether group. Furthermore, the ratio A/B of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm and the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm of the composition is 4.5 or more. The aforementioned metal azo pigment contains at least one anion selected from the azo compound represented by the formula (I) and the azo compound having a tautomeric structure, two or more metal ions, and a melamine compound.

Description

Composition, film, infrared transmission filter, solid-state imaging element, and optical sensor

The present invention relates to a composition used in the manufacture of infrared transmission filters and the like, and a film using the composition. Furthermore, it relates to an infrared transmission filter, a solid-state imaging device, and an optical sensor having the above-mentioned film.

Yellow pigments are used as colorants for expressing basic colors or complementary colors in color filters and the like. A nickel azobarbiturate complex such as a color index (C.I.) Pigment Yellow 150 is known as one of the yellow pigments.

In addition, Patent Documents 1 to 4 describe inventions about metal azo pigments containing azobarbituric acid, two or more kinds of metal ions, and a melamine compound. The metal azo pigments described in Patent Documents 1 to 4 have improved coloring performance compared to conventional nickel azobarbiturate complexes and the like. [Prior Art Literature] [Patent Literature]

[Patent Document 1] JP 2017-171912 A Bulletin No.

The inventors of the present invention have intensively studied films using metal azo pigments containing azobarbituric acid, two or more types of metal ions, and melamine compounds, and as a result, have found that the film has a high performance in exposing the film to a high temperature and high humidity environment. In this case, foreign matter defects tend to occur.

In addition, it was found that when a film is produced using a composition containing azobarbituric acid, two or more kinds of metal ions, and a colorant of a melamine compound, when the composition is applied to form a coating film, the film thickness tends to occur. Uneven facts.

Accordingly, an object of the present invention is to provide a composition capable of producing a film with high uniformity of film thickness and suppressed occurrence of foreign matter defects in a high-temperature and high-humidity environment. Furthermore, it is to provide a film, an infrared transmission filter, a solid-state imaging element, and an optical sensor using the composition.

式中，R¹ 及R² 分別獨立，為OH或NR⁵ R⁶ ， R³ 及R⁴ 分別獨立，為=O或=NR⁷ ， R⁵ ～R⁷ 分別獨立，為氫原子或烷基。 ＜2＞如＜1＞所述之組成物，其中金屬偶氮顏料含有上述陰離子、至少含有Zn²⁺ 及Cu²⁺ 之金屬離子、及三聚氰胺化合物。 ＜3＞如＜2＞所述之組成物，其中以金屬偶氮顏料中的總金屬離子的1莫耳為基準，合計含有95～100莫耳%的Zn²⁺ 及Cu²⁺ 。 ＜4＞如＜2＞或＜3＞所述之組成物，其中金屬偶氮顏料中的Zn²⁺ 與Cu²⁺ 的莫耳比為Zn²⁺ :Cu²⁺ =199:1～1:15。 ＜5＞如＜1＞至＜4＞中任一項所述之組成物，其中金屬偶氮顏料中之三聚氰胺化合物為由下述式（II）表示之化合物； [化學式2]

式中R¹¹ ～R¹³ 分別獨立，為氫原子或烷基。 ＜6＞如＜1＞至＜5＞中任一項所述之組成物，其中在波長400～700nm的範圍具有吸收極大之色料含有選自藍色著色劑及紫色著色劑之至少1種。 ＜7＞如＜1＞至＜6＞中任一項所述之組成物，其還含有近紅外線吸收色素。 ＜8＞＞如＜7＞所述之組成物，其中近紅外線吸收色素在波長800～900nm的範圍具有吸收極大。 ＜9＞如＜7＞或＜8＞所述之組成物，其中近紅外線吸收色素為選自吡咯并吡咯化合物、花菁化合物、方酸菁化合物、酞菁化合物、萘酞菁化合物及克酮鎓化合物之至少1種。 ＜10＞如＜1＞至＜9＞中任一項所述之組成物，其用於紅外線透射濾波器。 ＜11＞一種膜，其使用＜1＞至＜10＞中任一項所述之組成物而獲得。 ＜12＞一種紅外線透射濾波器，其具有＜11＞所述之膜。 ＜13＞一種固體攝像元件，其具有＜11＞所述之膜。 ＜14＞一種光學感測器，其具有＜11＞所述之膜。 [發明效果]According to the research of the present inventors, it was found that the above-mentioned object can be achieved by using the composition described later, and the present invention has been completed thereby. The present invention provides the following. <1> A composition comprising: a metal azo pigment containing at least one anion and two or more metals selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure thereof Ionic and melamine compounds; colorants other than the above-mentioned metal azo pigments, and having an absorption maximum in the range of wavelengths from 400 to 700 nm; and at least one compound selected from compounds having ethylenically unsaturated bonding groups and a compound having a cyclic ether group, the ratio A/B of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm and the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm of the composition is 4.5 or more, [chemical formula 1]

In the formula, R ¹ and R ² are independently OH or NR ⁵ R ⁶ , R ³ and R ⁴ are independently =O or =NR ⁷ , and R ⁵ to R ⁷ are independently hydrogen atoms or alkyl groups. <2> The composition according to <1>, wherein the metal azo pigment contains the above-mentioned anion, a metal ion containing at least Zn ²⁺ and Cu ²⁺ , and a melamine compound. <3> The composition according to <2>, which contains 95 to 100 mol % of Zn ²⁺ and Cu ²⁺ in total based on 1 mol of total metal ions in the metal azo pigment. <4> The composition according to <2> or <3>, wherein the molar ratio of Zn ²⁺ to Cu ²⁺ in the metal azo pigment is Zn ²⁺ :Cu ²⁺ =199:1～1: 15. <5> The composition according to any one of <1> to <4>, wherein the melamine compound in the metal azo pigment is a compound represented by the following formula (II); [Chemical formula 2]

In the formula, R ¹¹ to R ¹³ are each independently and represent a hydrogen atom or an alkyl group. <6> The composition according to any one of <1> to <5>, wherein the colorant having an absorption maximum in the wavelength range of 400 to 700 nm contains at least one selected from a blue colorant and a purple colorant . <7> The composition according to any one of <1> to <6>, which further contains a near-infrared absorbing dye. <8>> The composition according to <7>, wherein the near-infrared absorbing dye has an absorption maximum in a wavelength range of 800 to 900 nm. <9> The composition according to <7> or <8>, wherein the near-infrared absorbing dye is selected from the group consisting of pyrrolopyrrole compounds, cyanine compounds, squaraine compounds, phthalocyanine compounds, naphthalocyanine compounds and ketones At least one of the onium compounds. <10> The composition according to any one of <1> to <9>, which is used for an infrared transmission filter. <11> A film obtained using the composition according to any one of <1> to <10>. <12> An infrared transmission filter having the film described in <11>. <13> A solid-state imaging element having the film described in <11>. <14> An optical sensor having the film described in <11>. [Inventive effect]

According to the present invention, it is possible to provide a composition, a film, an infrared transmission filter, a solid-state imaging device, and an optical sensor capable of producing a film with high uniformity of film thickness and suppressed occurrence of foreign matter defects in a high-temperature and high-humidity environment.

Hereinafter, the content of the present invention will be described in detail. In this specification, "-" is used to include the numerical value described before and after it as a lower limit value and an upper limit value. In the notation of groups (atomic groups) in this specification, the notation of unsubstituted and unsubstituted references includes groups without substituents and groups (atomic groups) with substituents. For example, "alkyl" means not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). In this specification, "exposure" means not only exposure using light, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Further, examples of the light used for exposure include the bright line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams and other actinic rays and radiation. In this specification, "(meth)acrylate" means both or either of acrylate and methacrylate, "(meth)acrylic" means both or either of acrylic acid and methacrylic acid, "(meth)acrylate" "base) acryl" means both or either of acryl and methacryl. In this specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values measured by gel permeation chromatography (GPC). In this specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, infrared rays refer to light (electromagnetic waves) having a wavelength of 700 to 2500 nm. In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total components of the composition. In this specification, the word "step" not only refers to an independent step, but even if it cannot be clearly distinguished from other steps, as long as the intended function of the step is achieved, it is also included in this term.

<Composition> The composition of the present invention is characterized in that it contains a metal azo pigment, at least one anion selected from the group consisting of an azo compound represented by the formula (I) and azo compounds having a tautomeric structure described later, Two or more kinds of metal ions and melamine compounds; colorants, which are colorants other than the above-mentioned metal azo pigments, and have an absorption maximum in the wavelength range of 400-700 nm; and at least one compound selected from ethylenically unsaturated The compound with a bonding group and a compound with a cyclic ether group, the ratio A/B of the minimum value A of the absorbance within the wavelength range of 400 to 600 nm and the maximum value B of the absorbance within the wavelength range of 1000 to 1300 nm is: 4.5 and above.

The inventors of the present invention have conducted intensive studies on metal azo pigments containing azobarbituric acid, two or more metal ions, and melamine compounds. As a result, it was found that the metal azo pigments tend to have low hardness and are easy to micronize. However, there will be a tendency to generate active surfaces and to aggregate easily. In addition, it is presumed that when the content of nickel ions (Ni ²⁺ ) in the metal azo pigment is small or the metal azo pigment does not contain nickel ions, the metal azo pigment is in an energetically unstable state, and it is presumed that the metal azo pigment has Tendency to coalesce more easily. In addition, the metal azo pigment contains two or more kinds of metal ions, but the configuration of the metal azo compound (metal complex) composed of the anion and the metal ion is different depending on the type of the metal ion. For example, when it is Cu ²⁺ , it forms a metal complex with a planar configuration, and when it is Zn ²⁺ , it forms a metal complex with a regular octahedral configuration. Therefore, it is presumed that the above-mentioned metal azo pigment exists in an unstable state. Therefore, it is presumed that the above-mentioned metal azo pigment tends to promote aggregation easily in a high-temperature and high-humidity environment. According to the research of the present inventors, the above-mentioned metal azo pigments are used in combination with colorants other than the above-mentioned metal azo pigments that have a maximum absorption in the wavelength range of 400 to 700 nm (hereinafter also referred to as other colorants). To prepare a composition in which the ratio A/B of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm and the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm is 4.5 or more, it was surprisingly found that even if this composition is used The film obtained from the material is exposed to high temperature and high humidity environment, and it is not easy to produce foreign matter defects. As a reason why such an effect can be obtained, it is presumed that other colorants other than the metal azo pigment interact with the azo site of the metal azo pigment, thereby improving the stability of the metal azo pigment.

On the other hand, it was found that when a composition containing the above-mentioned metal azo pigment and other colorants is applied to form a film, unevenness in film thickness tends to occur easily. The reason for this is considered to be that the dispersion state of the metal azo pigment in the composition becomes unstable due to the influence of other colorants and the like. In addition, it was found that the composition having the above-described spectral characteristics tends to contain a large amount of colorant, and therefore, the dispersion state is more likely to become unstable than the metal azo pigment, and the film thickness unevenness tends to be easily generated. However, the composition of the present invention further contains at least one compound selected from the group consisting of compounds having an ethylenically unsaturated bond group and compounds having a cyclic ether group, in addition to the above-mentioned metallic azo pigments and other colorants, thereby also Such unevenness in film thickness can be effectively suppressed. The following points are presumed as the reason why such an effect can be obtained. That is, it is presumed that when a compound having an ethylenically unsaturated bond group is contained in the composition, the compound having an ethylenically unsaturated bond group interacts with the pigment active surface (especially the azo site) of the metal azo pigment, The compound having an ethylenically unsaturated bond group is adsorbed on the surface of the metal azo pigment, so that the metal azo pigment can be stabilized. In addition, it is presumed that when a compound having a cyclic ether group is contained in the composition, the cyclic ether group is coordinated to the metal azo pigment to function as a chelating agent, and as a result, it is presumed that the metal azo pigment can become Stablize. Therefore, it is presumed that the uniformity of the film thickness is optimized by the composition of the present invention.

Therefore, according to the composition of the present invention, it is possible to produce a film with high uniformity of film thickness and suppressed occurrence of foreign matter defects in a high-temperature and high-humidity environment. Moreover, since the film obtained using this composition has high light shielding property for light with a wavelength of 400 to 600 nm and excellent transmittance for light with a wavelength of 1000 to 1300 nm, it can be preferably used for an infrared transmission filter or the like. Moreover, the said metal azo pigment contained in the composition of this invention is a coloring material with high coloring power. Therefore, by using the composition of the present invention, it is possible to form a film having a thin film thickness but high light-shielding properties in the range of wavelengths of 400 to 600 nm. In addition, since the content of the colorant in the composition can be reduced, the flexibility of formulation design is also excellent.

The composition of the present invention has a ratio A/B of the minimum absorbance value A in the wavelength range of 400 to 600 nm to the absorbance maximum value B in the wavelength range of 1000 to 1300 nm A/B is 4.5 or more, preferably 7.5 or more, and 15 or more More preferably, 30 or more is more preferable. As long as the above-mentioned absorbance ratio is 4.5 or more, it is possible to form a film having high light shielding properties for light having a wavelength of 400 to 600 nm and excellent transmittance for light having a wavelength of 1000 to 1300 nm.

The absorbance Aλ at a wavelength λ is defined by the following formula (1). Aλ=-log(Tλ/100) ... (1) Aλ is the absorbance at wavelength λ, and Tλ is the transmittance (%) at wavelength λ. In the present invention, the value of absorbance may be a value measured in a solution state, or may be a value of a film formed using the composition. When measuring the absorbance in the state of a film, it is preferable to measure using a film obtained by coating the composition on a glass substrate by a method such as spin coating and drying with a hot plate or the like at 100° C. for 120 seconds.

In addition, the absorbance can be measured using a conventionally known spectrophotometer. The measurement conditions of the absorbance are not particularly limited, but it is preferable to measure the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm under the condition that the minimum value A of the absorbance in the wavelength range of 400 to 600 nm becomes 0.1 to 3.0. . By measuring the absorbance under such conditions, the measurement error can be further reduced. It does not specifically limit as a method of adjusting so that the minimum value A of the absorbance in the wavelength range of 400-600 nm may become 0.1-3.0. For example, when measuring the absorbance in a solution state, a method of adjusting the optical path length of the sample cell can be cited. Moreover, when measuring absorbance in the state of a film, the method of adjusting a film thickness, etc. are mentioned.

The composition of the present invention preferably satisfies any one of the following spectroscopic properties (1) to (3), and satisfies ( The spectroscopic properties of 2) or (3) are more preferable, and the spectroscopic properties satisfying (3) are further preferable. The reason why such an effect can be obtained is presumed to be as follows. A film capable of blocking light on the longer wavelength side can be formed in the order of (1), (2), and (3), but in order to block light with a longer wavelength, a film that absorbs longer wavelengths is sometimes used as another colorant. The coloring material may further contain a near-infrared absorbing coloring matter. It is presumed that many of these materials have a wide conjugated system and tend to easily interact with metal azo pigments. Therefore, it is presumed that the metal azo pigment can be further stabilized, and as a result, a film in which the occurrence of foreign matter defects in a high-temperature and high-humidity environment can be further suppressed can be produced.

(1): The ratio A1/B1 of the minimum absorbance value A1 in the wavelength range of 400 to 600 nm and the absorbance maximum value B1 in the wavelength range of 800 to 1300 nm is 4.5 or more, preferably 7.5 or more, and more preferably 15 or more. Preferably, more than 30 is more preferable. According to this aspect, it is possible to form a film that blocks light in the range of wavelengths of 400 to 600 nm and can transmit light exceeding wavelengths of 650 nm. (2): The ratio A2/B2 of the minimum value A2 of the absorbance within the wavelength range of 400 to 720 nm and the maximum value B2 of the absorbance within the wavelength range of 900 to 1300 nm is 4.5 or more, preferably 7.5 or more, and more preferably 15 or more. Preferably, more than 30 is more preferable. According to this aspect, it is possible to form a film that blocks light in a wavelength range of 400 to 750 nm and can transmit light exceeding a wavelength of 800 nm. (3): The ratio A3/B3 of the minimum absorbance value A3 in the wavelength range of 400 to 830 nm and the maximum absorbance value B3 in the wavelength range of 1000 to 1300 nm is 4.5 or more, preferably 7.5 or more, and more preferably 15 or more. Preferably, more than 30 is more preferable. According to this aspect, it is possible to form a film that blocks light in a wavelength range of 400 to 830 nm and can transmit light exceeding a wavelength of 900 nm.

The film thickness after drying to produce the composition of the present invention is 10.0 μm or less (preferably 5.0 μm or less, more preferably 3.0 μm or less, further preferably 2.5 μm or less, still more preferably 2.0 μm or less, particularly preferably Also, the lower limit can be 0.4 μm or more, 0.5 μm or more, 0.6 μm or more, 0.7 μm or more, 0.8 μm or more, or 0.8 μm or more. In the case of a film having a thickness of 0.9 μm or more, the maximum value within the wavelength range of 400 to 600 nm at which the at least one film thickness satisfies the transmittance of light in the thickness direction of the film is 20% or less (preferably 15% or less). , more preferably 10% or less) and the minimum value within the wavelength range of 1000 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more) Spectral characteristics are preferred.

In addition, the composition of the present invention preferably satisfies any one of the following spectroscopic properties (11) to (13), and from the viewpoint of easily producing a film that suppresses the occurrence of foreign matter defects in a high-temperature and high-humidity environment, it satisfies ( The spectral characteristics of 12) or (13) are more preferred, and the spectral characteristics satisfying (13) are further preferred.

(11): An aspect that uses the composition of the present invention to produce a film thickness after drying of 0.4 to 3.0 μm (preferably 0.5 to 2.5 μm, more preferably 0.6 to 2.0 μm, further preferably 0.7 to 3.0 μm) 1.5 μm), the maximum value of the transmittance of light in the thickness direction of the film in the wavelength range of 400 to 600 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the The minimum value of the transmittance of light in the thickness direction within the wavelength range of 800 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). (12): An aspect that uses the composition of the present invention to produce a film having a thickness of 0.5 to 5.0 μm (preferably 0.6 to 3.0 μm, more preferably 0.7 to 2.5 μm, further preferably 0.8 to 5.0 μm) after drying. 2.0 μm), the maximum value of the transmittance of light in the thickness direction of the film in the wavelength range of 400 to 720 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the The minimum value of the transmittance of light in the thickness direction within the wavelength range of 900 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). (13): An aspect wherein the film thickness after drying is 0.6 to 10 μm (preferably 0.7 to 5.0 μm, more preferably 0.8 to 3.0 μm, further preferably 0.9 to 2.5 μm) using the composition of the present invention ), the maximum value of the transmittance of light in the thickness direction of the film in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the thickness direction of the film The minimum value in the wavelength range of 1000-1300 nm of the transmittance of the light above is 70% or more (preferably 75% or more, more preferably 80% or more).

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

<<Metal Azo Pigment A>> The composition of the present invention contains at least one kind of anion and two or more kinds of metal ions selected from the azo compound represented by the following formula (I) and the azo compound of the tautomeric structure thereof And metal azo pigment A of melamine compound. [Chemical formula 3]

In the formula, R ¹ and R ² are independently OH or NR ⁵ R ⁶ , R ³ and R ⁴ are independently =O or =NR ⁷ , and R ⁵ to R ⁷ are independently hydrogen atoms or alkyl groups. The number of carbon atoms of the alkyl group represented by R ⁵ to R ⁷ is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The alkyl group may be any of straight chain, branched chain and cyclic chain, straight chain or branched chain is preferred, straight chain is more preferred. The alkyl group may have a substituent. As a substituent, the substituent T mentioned later is mentioned, and a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, and an amine group are preferable.

In formula (I), R ¹ and R ² are preferably OH. Moreover, R ³ and R ⁴ are preferably =0.

The melamine compound in the metal azo pigment A is preferably a compound represented by the following formula (II). [Chemical formula 4]

In the formula, R ¹¹ to R ¹³ are each independently and represent a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1-10, more preferably 1-6, and even more preferably 1-4. The alkyl group may be any of straight chain, branched chain and cyclic chain, straight chain or branched chain is preferred, straight chain is more preferred. The alkyl group may have a substituent. As a substituent, the substituent T mentioned later can be mentioned, and a hydroxyl group is preferable. It is preferable that at least one of R ¹¹ to R ¹³ is a hydrogen atom, and it is more preferable that all of R ¹¹ to R ¹³ are hydrogen atoms.

In the metal azo pigment A, at least one anion selected from the azo compound represented by the formula (I) and the azo compound having a tautomeric structure contains 0.05 to 4 mol of melamine compound (compared to 1 mol). It is preferably a compound represented by formula (II)), more preferably 0.5 to 2.5 mol, and still more preferably 1.0 to 2.0 mol.

The specific surface area of the metal azo pigment A is preferably 20 to 200 m ² /g. The lower limit is preferably 60 m ² /g or more, and more preferably 90 m ² /g or more. The upper limit is preferably 160 m ² /g or less, more preferably 150 m ² /g or less. The value of the specific surface area of the metal azo pigment A is based on the BET (Brunauer, Emmett and Teller (Buett method)) method, according to DIN 66131: determination of the specific surface area of solids by gas adsorption. measurement of the specific surface area of a solid).

(Substituent T) As said substituent T, the following groups are mentioned. Alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), aryl group (preferably an aryl group having 6 to 30 carbon atoms), an amine group (preferably an amine group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group group (preferably aryloxy with 6 to 30 carbon atoms), heteroaryloxy, acyl group (preferably with 1 to 30 carbon atoms), alkoxycarbonyl (preferably with 2 to 30 carbon atoms) alkoxycarbonyl), aryloxycarbonyl (preferably aryloxycarbonyl having 7 to 30 carbon atoms), heteroaryloxycarbonyl, acyloxy (preferably aryloxy having 2 to 30 carbons), acylamino ( It is preferably an amide group with 2-30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group with a carbon number of 2-30), an aryloxycarbonylamino group (preferably with a carbon number of 7-30). aryloxycarbonylamino group), sulfamoyl group (preferably sulfasulfonyl group with 0-30 carbon atoms), aminocarbamoyl group (preferably carbamidocarboxylate group with 1-30 carbon atoms), Alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), and a heteroarylthio group (preferably having 1 to 30 carbon atoms) , alkylsulfonyl group (preferably carbon number 1-30), arylsulfonyl group (preferably carbon number 6-30), heteroarylsulfonyl group (preferably carbon number 1-30), Alkylsulfinyl (preferably having 1 to 30 carbon atoms), arylsulfinyl (preferably having 6 to 30 carbon atoms), and heteroarylsulfinyl (preferably having 1 to 30 carbon atoms) ), urea group (preferably carbon number from 1 to 30), hydroxyl group, carboxyl group, sulfo group, phosphoric acid group, carboxylic acid amine group, sulfonic acid amine group, imidic acid group, mercapto group, halogen atom, cyano group, alkane sulfinic acid group, arylsulfinic acid group, hydrazine group, imino group, heteroaryl group (preferably carbon number 1-30). When these groups are further substitutable groups, they may further have a substituent. As other substituents, the groups described in the above-mentioned substituent T can be exemplified.

In the metal azo pigment A, it is preferable that at least one anion selected from the azo compound represented by the formula (I) and the azo compound having a tautomeric structure form a metal complex with a metal ion. For example, in the case of a divalent metal ion Me, a metal complex having a structure represented by the following formula (Ia) can be formed from the above-mentioned anion and the metal ion Me. In addition, the metal ion Me can form a complex by bonding via the nitrogen atom in the tautomeric label of formula (Ia). [Chemical formula 5]

As a preferable aspect of the metal azo pigment A, the metal azo pigments of the following aspects (Az1) to (Az4) are exemplified, since it is easy to obtain a more pronounced effect of the present invention and further improve the spectroscopic characteristics. For this reason, the metal azo pigment in the form of (Az1) is preferable.

(Az1) A metal azo pigment of one aspect, which contains at least one anion selected from the above-mentioned azo compounds represented by formula (I) and azo compounds having tautomeric structures thereof, at least Zn ²⁺ and Cu ²⁺ metal ions, melamine compounds. In this aspect, based on 1 mol of the total metal ions of the metal azo pigment, it is preferable to contain 95-100 mol % of Zn ²⁺ and Cu ²⁺ in total, more preferably 98-100 mol % Preferably, it contains 99.9 to 100 mol %, more preferably, 100 mol % is particularly preferred. In addition, the molar ratio of Zn ²⁺ and Cu ²⁺ in the metal azo pigment is preferably Zn ²⁺ :Cu ²⁺ =199:1～1:15, more preferably 19:1～1:1, 9:1 to 2:1 is more preferable. In addition, in this aspect, the metal azo pigment may further contain divalent or trivalent metal ions (hereinafter, also referred to as metal ions Me1 ) other than Zn ²⁺ and Cu ²⁺ . Examples of the metal ion Me1 include Ni ²⁺ , Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ²⁺ , Nd ³⁺ . , Sm ²⁺ , Sm ³⁺ , Eu ²⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Yb ²⁺ , Yb ³⁺ , Er ³⁺ , Tm ³⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Mn ²⁺ , Y ³⁺ , Sc ³⁺ , Ti ²⁺ , Ti ³⁺ , Nb ³⁺ , Mo ²⁺ , Mo ³⁺ , V ²⁺ , V ³⁺ , Zr ²⁺ , Zr ³⁺ , Cd ²⁺ , Cr ³⁺ , Pb ²⁺ , Ba ²⁺ , selected from Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Yb ³⁺ , Er ³⁺ , Tm ³⁺ , Mg Preferably, at least one of ²⁺ , Ca ²⁺ , Sr ²⁺ , Mn ²⁺ and Y ³⁺ is selected from Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , La ³ At least one of ⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Tb ³⁺ , Ho ³⁺ and Sr ²⁺ is further preferred, selected from Al ³⁺ , Fe ²⁺ , Fe ³ At least one of ⁺ , Co ²⁺ and Co ³⁺ is particularly preferred. The content of the metal ion Me1 is preferably 5 mol% or less based on 1 mol of the total metal ions of the metal azo pigment, more preferably 2 mol% or less, and further preferably 0.1 mol% or less.

(Az2) A metal azo pigment of one aspect, which contains at least one anion, a metal ion, and a melamine compound selected from the above-mentioned azo compounds represented by the formula (I) and azo compounds having a tautomeric structure thereof, a metal The ion contains Ni ²⁺ , Zn ²⁺ and at least one other metal ion Me2, the metal ion Me2 is selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ²⁺ , Nd ³⁺ , Sm ²⁺ , Sm ^{3 +} , Eu ²⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm ³⁺ , Yb ²⁺ , Yb ³⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ²⁺ , Ti ³⁺ , Zr ²⁺ , Zr ³⁺ , V ²⁺ , V ³⁺ , Nb ³⁺ , Cr ³⁺ , Mo ² At least one of ⁺ , Mo ³⁺ , Mn ²⁺ , Cd ²⁺ and Pb ²⁺ . The metal ion Me2 is selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Preferably at least one of Tm ³⁺ , Yb ³⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Y ³⁺ and Mn ²⁺ is selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd More preferably, at least one of ³⁺ , Sm ³⁺ , Tb ³⁺ , Ho ³⁺ and Sr ²⁺ . In this aspect, based on 1 mol of the total metal ions of the metal azo pigment, 75 to 99.5 mol % of Zn ²⁺ and Ni ²⁺ are contained in total, and 0.5 to 25 mol % of the metal ion Me2 is contained as Preferably, it contains 78-95 mol% of Zn ²⁺ and Ni ²⁺ in total and 5-22 mol% of metal ions Me2 is more preferably, and contains 82-90 mol% of Zn ²⁺ and Ni ² in total ⁺ and it is more preferable to contain 10-18 mol% of metal ions Me2. In addition, the molar ratio of Zn ²⁺ and Ni ²⁺ in the metal azo pigment is preferably Zn ²⁺ :Ni ²⁺ =90:3～3:90, more preferably 80:5～5:80, 60:33～33:60 is more preferable.

(Az3) A metal azo pigment of one aspect, which contains at least one anion, a metal ion, and a melamine compound selected from the azo compound represented by the formula (I) and the azo compound having a tautomeric structure above, a metal The ions contain Ni ²⁺ , Cu ²⁺ and at least one other metal ion Me3, the metal ion Me3 is selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ²⁺ , Nd ³⁺ , Sm ²⁺ , Sm ^{3 +} , Eu ²⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Yb ²⁺ , Yb ³⁺ , Er ³⁺ , Tm ³⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Mn ²⁺ , Y ³⁺ , Sc ³⁺ , Ti ²⁺ , Ti ³⁺ , Nb ³⁺ , Mo ²⁺ , Mo ³⁺ , V ²⁺ , V ³⁺ , Zr ²⁺ , Zr ³ At least one of ⁺ , Cd ²⁺ , Cr ³⁺ , Pb ²⁺ and Ba ²⁺ . The metal ion Me3 is selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Yb ³⁺ , At least one of Er ³⁺ , Tm ³⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Mn ²⁺ and Y ³⁺ is preferably selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd More preferably, at least one of ³⁺ , Sm ³⁺ , Tb ³⁺ , Ho ³⁺ and Sr ²⁺ . In this aspect, based on 1 mol of the total metal ions of the metal azo pigment, Cu ²⁺ and Ni ²⁺ are contained in a total of 70 to 99.5 mol % and 0.5 to 30 mol % of the metal ion Me3 are contained as Preferably, Cu 2+ and Ni ²⁺ are contained in a total of 75-95 mol %, and metal ions Me3 are contained in a total of 5-25 mol %, and Cu ²⁺ and Ni ² are contained in a total of 80-90 mol ^% . ⁺ and it is further preferable to contain 10-20 mol% of metal ions Me3. In addition, the molar ratio of Cu ²⁺ and Ni ²⁺ in the metal azo pigment is preferably Cu ²⁺ :Ni ²⁺ =42:1～1:42, more preferably 10:1～1:10, 3:1 to 1:3 is more preferable.

(Az4) A metal azo pigment of one aspect, which contains at least one anion, a metal ion and a melamine compound selected from the above-mentioned azo compounds represented by the formula (I) and azo compounds having a tautomeric structure thereof, a metal The ion contains Ni ²⁺ and metal ion Me4a, the metal ion Me4a is selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ²⁺ , Nd ³⁺ , Sm ²⁺ , Sm ³⁺ , Eu ²⁺ , Eu ³ At least one of ⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm ³⁺ , Yb ²⁺ and Yb ³⁺ . The metal ion Me4a is selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , At least one of Tm ³⁺ and Yb ³⁺ is preferably at least one selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Tb ³⁺ and Ho ³⁺ . better. In this aspect, based on 1 mol of the total metal ions of the metal azo pigment, it is preferable to contain 95-100 mol % of Ni ²⁺ and metal ion Me4a in total, more preferably 98-100 mol % Preferably, it contains 99.9 to 100 mol %, which is further preferred, and 100 mol % is particularly preferred. In addition, the molar ratio of Ni ²⁺ and metal ion Me4a in the metal azo pigment is preferably Ni ²⁺ : metal ion Me4a=1:1～19:1, more preferably 2:1～4:1, 2.3:1～3:1 is more preferable. In addition, in this aspect, the metal azo pigment may further contain metal ions other than Ni ²⁺ and metal ions Me4a (hereinafter, also referred to as metal ions Me4b). Examples of the metal ion Me4b include Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ²⁺ , Ti ³⁺ , Zr ²⁺ , Zr ³⁺ , V ²⁺ , V ³⁺ , Nb ³⁺ , Cr ³⁺ , Mo ²⁺ , Mo ³⁺ , Mn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Cu ²⁺ , Zn ²⁺ , Cd ²⁺ , Al ³⁺ and Pb ²⁺ , selected from Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Y ³⁺ , Mn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Cu At least one of ²⁺ , Zn ²⁺ and Al ³⁺ is preferably selected from Sr ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Cu ²⁺ , Zn ²⁺ and Al ³ At least one of ⁺ is better. In addition, the content of the metal ion Me4b is preferably 5 mol% or less based on 1 mol of the total metal ions of the metal azo pigment, more preferably 2 mol% or less, and further preferably 0.1 mol% or less. .

The metal azo pigment A is preferably an adduct formed of a metal azo compound and a melamine compound (preferably a compound represented by the above formula (II)), wherein the metal azo compound is represented by the above-mentioned formula (I) It consists of at least one anion and a metal ion in the azo compound and its tautomeric azo compound. Adducts can be understood as molecular aggregates. Such intermolecular bonds may be based on, for example, intermolecular interactions, Lewis acid-base interactions, or coordinative bonds or chain bonds. In addition, the adduct may have a structure such as a crystal dragon compound (clathrate) in which a guest molecule is inserted into a crystal lattice constituting a host molecule. In addition, the adduct may have a structure such as a composite interlayer crystal (including an interlattice compound). The composite interlayer crystal refers to a chemically non-stoichiometric crystalline compound composed of at least two elements. In addition, the adduct may be, for example, a mixed substituted crystal in which a common crystal is formed from two substances and the atoms of the second component are located in the regular lattice of the first component.

The metallic azo pigments used in the present invention may be physical mixtures or chemical composite compounds. A physical mixture is preferred.

The following (Az1-1) and (Az1-2) are mentioned as a preferable example of the physical mixture in the case of the metal azo pigment of the aspect of said (Az1). Moreover, when the metal azo pigment of the aspect of (Az1) is a chemical composite compound, it is preferable that Zn ²⁺ , Cu ²⁺ , and any other metal ion Me1 are embedded in a common crystal lattice. ( ^Az1-1 ) ^Physical Properties Sexual mixture. (Az1-2) The physical mixture of (Az1-1) further contains a physical mixture of an adduct 1c of a metal azo compound and a melamine compound composed of the above-mentioned anion and a metal ion Me1.

The following (Az2-1) is mentioned as a preferable example of the physical mixture in the case of the metal azo pigment of the aspect of said (Az2). Moreover, when the metal azo pigment of the aspect of (Az2) is a chemical composite compound, it is preferable that Ni ²⁺ , Zn ²⁺ and the metal ion Me 2 are embedded in a common crystal lattice. (Az2-1) contains the adduct 2a of a metal azo compound composed of the above anion and Ni ²⁺ and a melamine compound, an adduct 2b of a metal azo compound composed of the above anion and Zn ²⁺ and a melamine compound, A physical mixture of the adduct 2c of a metal azo compound and a melamine compound composed of the above-mentioned anion and metal ion Me2.

The following (Az3-1) is mentioned as a preferable example of the physical mixture in the case of the metal azo pigment of the aspect of said (Az3). Moreover, when the metal azo pigment of the aspect of (Az3) is a chemical composite compound, it is preferable that Ni ²⁺ , Cu ²⁺ and metal ion Me3 are embedded in a common crystal lattice. (Az3-1) Adduct 3a comprising a metal azo compound composed of the above anion and Ni ²⁺ and a melamine compound, an adduct 3b of a metal azo compound composed of the above anion and Cu ²⁺ and a melamine compound, The physical mixture of the adduct 3c of the metal azo compound and the melamine compound composed of the above-mentioned anion and the metal ion Me3.

The following (Az4-1) and (Az4-2) are mentioned as a preferable example of the physical mixture in the case of the metal azo pigment of the aspect of the said (Az4). Moreover, when the metal azo pigment of the aspect of (Az4) is a chemical composite compound, it is preferable that Ni ²⁺ , the metal ion Me4a, and any other metal ion Me4b are embedded in a common crystal lattice. ( ^Az4-1 ) Physical Properties Sexual mixture. (Az4-2) The physical mixture of (Az4-1) further contains a physical mixture of an adduct 4c of a metal azo compound and a melamine compound composed of the above-mentioned anion and a metal ion Me4b.

The metal azo pigment of the aspect of the above (Az1) can be obtained by mixing the compound of the formula (III) or its tautomer with the compound of the formula (III) or a tautomer thereof in the presence of a melamine compound (preferably a compound represented by the formula (II)). A zinc salt, a copper salt, and any one of the salts of the above-mentioned metal ion Me1 are further reacted and produced. The amount of zinc salt used is preferably 0.05-0.995 mol, preferably 0.05-0.5 mol, and more preferably 0.1-0.3 mol, relative to 1 mol of the compound of formula (III) or its tautomer. good. In addition, the amount of the copper salt used is preferably 0.005 to 0.95 mol, more preferably 0.49 to 0.95 mol, and 0.7 to 0.9 mol per 1 mol of the compound of formula (III) or its tautomer. Further preferred. Further, the amount of the salt of the metal ion Me1 to be used is preferably 0.05 mol or less, more preferably 0.01 mol or less, relative to 1 mol of the compound of formula (III) or its tautomer. In addition, the total amount of the zinc salt, the copper salt, and the salt of the metal ion Me1 is preferably 1 mol relative to 1 mol of the compound of the formula (III). In addition, the amount of the melamine compound used is preferably 0.05 to 4 mol, more preferably 0.5 to 2.5 mol, and 1.0 to 2.0 mol per 1 mol of the compound of formula (III) or its tautomer. Further preferred.

[Chemical formula 6]

In the formula, X ¹ and X ² are independently hydrogen atoms or alkali metal ions, and at least one of X ¹ and X ² is an alkali metal ion. R ¹ and R ² are each independently, and are OH or NR ⁵ R ⁶ . R ³ and R ⁴ are each independently and are =O or =NR ⁷ , and R ⁵ to R ⁷ are each independently a hydrogen atom or an alkyl group. R ¹ to R ⁷ have the same meanings as R ¹ to R ⁷ in formula (I), and the preferred ranges are also the same. As the alkali metal ions represented by X ¹ and X ² , Na ⁺ and K ⁺ are preferred.

Moreover, the metal azo pigment of the aspect of the said (Az1) can be manufactured by mixing the said adduct 1a, the adduct 1b, and the adduct 1c.

The metal azo pigment of the aspect of (Az2), the metal azo pigment of the aspect of (Az3), and the metal azo pigment of the aspect of (Az4) can also be produced by the same method as the method described above.

Regarding the above-mentioned metal azo pigments, reference can be made to paragraph numbers 0011 to 0062 and 0137 to 0276 of JP 2017-171912 A, paragraph numbers 0010 to 0062, 0138 to 0295 of JP 2017-171913 A, and JP 2017-171913 A. The descriptions in paragraph numbers 0011 to 0062 and 0139 to 0190 of JP 2017-171914 A, and paragraphs 0010 to 0065 and 0142 to 0222 of JP 2017-171915 A, and these contents are incorporated into the present specification.

In the composition of the present invention, the content of the metal azo pigment A is preferably 1 to 50% by mass in the total solid content of the composition of the present invention. The lower limit is preferably 2 mass % or more, and more preferably 3 mass % or more. The upper limit is preferably 45 mass % or less, more preferably 40 mass % or less. When the composition of the present invention contains two or more metal azo pigments A, it is preferable that the total amount of these is within the above-mentioned range.

<<Other coloring materials>> The composition of the present invention contains a coloring material other than the above-mentioned metal azo pigment A, and the coloring material is a coloring material having a maximum absorption in the wavelength range of 400 to 700 nm (hereinafter, also referred to as other coloring materials. ). As other colorants, chromatic colorants, black colorants, etc. are mentioned. The colorant used as another colorant is not particularly limited as long as it is a colorant other than the above-mentioned metal azo pigment A, and examples thereof include red colorants, green colorants, blue colorants, yellow colorants, Purple colorant, orange colorant, etc. The composition of the present invention preferably contains two or more other colorants. According to this aspect, the metal azo pigment A can be further stabilized, and the occurrence of foreign matter defects in a high-temperature and high-humidity environment can be suppressed more effectively. Moreover, when the composition of this invention contains 2 or more types of other color materials, it is preferable to contain 2 or more types of color materials of different hues.

It is preferable that the composition of this invention contains at least 1 sort(s) chosen from a blue coloring agent and a purple coloring agent as another coloring material. The colorant of these hues has an absorption maximum on the longer wavelength side of the visible light wavelength region, and therefore has a relatively wide conjugated system. Therefore, these colorants easily interact with the metal azo pigment A, and the metal azo pigment A can be further stabilized to more effectively suppress the occurrence of foreign matter defects in a high-temperature and high-humidity environment. In addition, it is easy to obtain a composition having a spectral characteristic in which the ratio A/B of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to the maximum value B of the absorbance in the wavelength range of 1000 to 1300 nm is 4.5 or more. As a blue colorant, a triarylmethane compound, a phthalocyanine compound, etc. are mentioned, and a phthalocyanine compound is preferable because it is easy to acquire the effect of this invention more prominently. Examples of the purple colorant include xanthene compounds, triarylmethane compounds, anthraquinone compounds, oxazine compounds, quinacridone compounds, benzimidazolone compounds, and the like, from which the effect of the present invention is more pronounced easily. For this reason, an oxazine compound is considered to be preferable.

When the composition of the present invention contains at least one selected from a blue colorant and a purple colorant as other colorants, the content of the blue colorant in the total amount of the other colorants is preferably 5% by mass or more, 10% by mass or more. It is more preferable that it is more than 20 mass %, and it is more preferable that it is more than 20 mass %. The upper limit is not particularly limited. It can be 100 mass %, 90 mass % or less, and 80 mass % or less. In addition, the content of the purple colorant in the total amount of other colorants is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is not particularly limited. It can be 100 mass %, 90 mass % or less, and 80 mass % or less. Moreover, the total content of the blue colorant and the purple colorant in the total amount of other colorants is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. The upper limit is not particularly limited. It can be 100 mass %, 90 mass % or less, and 80 mass % or less.

(Colorful Colorant) The colorant used for other colorants can be either pigments or dyes, and pigments are preferred. Examples of the pigment include organic pigments and inorganic pigments, and organic pigments are preferred. The following are mentioned as an organic pigment.

Color Index (C.I.) PigMent Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. (the above are yellow pigments), C.I.PigMent Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (the above are orange pigments), C.I.PigMent Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc. (the above are red pigments), C.I.PigMent Green 7, 10, 36, 37, 58, 59, etc. (the above are green pigments), C.I.PigMent Violet 1, 19, 23, 27, 32, 37, 42, etc. (the above are purple pigments), C.I.PigMent Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6 , 16, 22, 60, 64, 66, 79, 80, etc. (the above are blue pigments),

Moreover, as a red pigment, the compound which has the structure which the aromatic ring group which introduce|transduced the group which couple|bonded with an oxygen atom, a sulfur atom, or a nitrogen atom, and a diketopyrrolopyrrole skeleton can also be used. As such a compound, the compound represented by the formula (DPP1) is preferable, and the compound represented by the formula (DPP2) is more preferable. [Chemical formula 7]

In the above formula, R ¹¹ and R ¹³ each independently represent a substituent, R ¹² and R ¹⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and n11 and n13 each independently represent an integer of 0 to 4 , X ¹² and X ¹⁴ respectively independently represent an oxygen atom, a sulfur atom or a nitrogen atom, when X ¹² is an oxygen atom or a sulfur atom, m12 represents 1, when X ¹² is a nitrogen atom, m12 represents 2, and X ¹⁴ is an oxygen atom or When a sulfur atom is used, m14 represents 1, and when X ¹⁴ is a nitrogen atom, m14 represents 2. Examples of the substituents represented by R ¹¹ and R ¹³ include those listed for the aforementioned substituent T, and preferred specific examples include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, and an aryloxy group. Carbonyl, heteroaryloxycarbonyl, amine, cyano, nitro, trifluoromethyl, arylene, sulfo, etc.

The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo series, anilino azo series, triarylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole series can be used , pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole methine azo, mouth Yamaguchi galaxy, phthalocyanine series, benzopyran series, indigo series, pyrrolomethylene (Pyrromethene) dyes, etc.

Moreover, a dye multimer can also be used as another coloring agent. The dye multimer is preferably a dye that is dissolved in a solvent. The dye multimer can form particles. When the dye multimer is in the form of particles, it is usually used in a state of being dispersed in a solvent. The dye multimer in the particle state can be obtained, for example, by emulsion polymerization, and specific examples thereof include the compounds and production methods described in JP-A No. 2015-214682. As the dye multimer, compounds described in JP 2011-213925 A, JP 2013-041097 A, JP 2015-028144 A, JP 2015-030742 A, and the like can also be used.

(Black Colorant) Examples of the black colorant used as other colorants include organic black colorants such as bisbenzofuranone compounds, methaneimine compounds, perylene compounds, and azo compounds. The black colorant is preferably a bisbenzofuranone compound or a perylene compound. Examples of compounds described in JP 2010-534726 A, JP 2012-515233 A, JP 2012-515234 A, etc. can be obtained as "Irgaphor Black" manufactured by BASF Corporation, for example. As a perylene compound, CI Pigment Black 31, 32, etc. are mentioned. Examples of the methimine compound include compounds described in JP-A-1-170601, JP-A-2-034664, etc. For example, "CHROMOFINEBLACK A1103" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. can be used. " and obtained. The bisbenzofuranone compound is preferably a compound represented by the following formula and a mixture thereof. [Chemical formula 8]

In the formula, R ¹ and R ² each independently represent a hydrogen atom or a substituent, R ³ and R ⁴ each independently represent a substituent, a and b each independently represent an integer of 0 to 4, and when a is 2 or more, a plural number R ³ may be the same or different, and a plurality of R ³ may be bonded to form a ring. When b is 2 or more, a plurality of R ⁴ may be the same or different, and a plurality of R ⁴ may also be bonded to form a ring. form a ring. The substituents represented by R ¹ to R ⁴ represent halogen atoms, cyano groups, nitro groups, alkyl groups, alkenyl groups, alkynyl groups, aralkyl groups, aryl groups, heteroaryl groups, -OR ³⁰¹ , -COR ³⁰² , - COOR ³⁰³ , -OCOR ³⁰⁴ , -NR ³⁰⁵ R ³⁰⁶ , -NHCOR ³⁰⁷ , -CONR ³⁰⁸ R ³⁰⁹ , -NHCONR ³¹⁰ R ³¹¹ , -NHCOOR ³¹² , -SR ³¹³ , -SO ₂ R ³¹⁴ , -SO ₂ OR ³¹⁵ , - NHSO ₂ R ³¹⁶ or -SO ₂ NR ³¹⁷ R ³¹⁸ , and R ³⁰¹ to R ³¹⁸ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. Details of the bisbenzofuranone compound can be referred to the descriptions in paragraphs 0014 to 0037 of JP 2010-534726 A, which are incorporated in the present specification.

In the composition of the present invention, it is preferable to combine the metallic azo pigment A and other colorants to form black color. The following (C1)-(C6) are mentioned as a preferable combination of the metal azo pigment A and another coloring material. In the case of the combination of the following (C1), the composition having the spectral characteristics of the above (1) can be easily obtained. In the case of a combination of the following (C2) to (C6), the composition having the spectral characteristics of the above (2) is easily obtained.

(C1) An aspect containing metallic azo pigment A and a purple colorant. Moreover, you may contain a yellow coloring agent as another coloring material. (C2) An aspect containing metal azo pigment A, red colorant, blue colorant, and purple colorant. Moreover, you may contain a yellow coloring agent as another coloring material. (C3) An aspect containing metal azo pigment A, a red colorant, and a blue colorant. Moreover, you may contain a yellow coloring agent as another coloring material. (C4) An aspect containing metallic azo pigment A, a blue colorant, and a purple colorant. Moreover, you may contain a yellow coloring agent as another coloring material. (C5) An aspect containing metallic azo pigment A, a purple colorant, and a black colorant. Moreover, you may contain a yellow coloring agent as another coloring material. (C6) An aspect containing metallic azo pigment A, a blue colorant, and a black colorant. Moreover, you may contain a yellow coloring agent as another coloring material.

As the metal azo pigment A, the metal azo pigment of the aspect of the above-mentioned (Az1) is preferable. As the purple colorant, C.I. Pigment Violet 23 is preferred. As the yellow colorant, C.I. Pigment Yellow 139, 150, and 185 are preferable, C.I. Pigment Yellow 139 and 150 are more preferable, and C.I. Pigment Yellow 139 is further preferable. As the red colorant, Pigment Red 122, 177, 224, 254, and 264 are preferable, Pigment Red 122, 177, 254, and 264 are more preferable, and Pigment Red 254 is further preferable. As the blue colorant, C.I. Pigment Blue 15:6 and 16 are preferred. As the black colorant, Irgaphor Black (BASF Corporation) and C.I. Pigment Black 31 and 32 are preferable.

In the combination of the above (C1), it is preferable to contain 50 to 500 parts by mass of the purple colorant relative to 100 parts by mass of the metallic azo pigment A, more preferably to contain 75 to 400 parts by mass, and to contain 100 to 350 parts by mass of Further preferred. Furthermore, when a yellow colorant as another colorant is further contained, the content of the yellow colorant as another colorant is preferably 10 to 200 parts by mass, preferably 20 to 150 parts by mass with respect to 100 parts by mass of the metal azo pigment A for better. The aspect which does not contain the yellow coloring agent which is another coloring material can also be set.

In the combination of the above (C2), it is preferable to contain 100 to 800 parts by mass of the red colorant with respect to 100 parts by mass of the metal azo pigment A, and more preferably 200 to 700 parts by mass. Moreover, it is preferable to contain 100-1000 mass parts of blue coloring agents, and it is more preferable to contain 200-800 mass parts. Moreover, it is preferable to contain 50-500 mass parts of purple coloring agents, and it is more preferable to contain 70-400 mass parts. Furthermore, when a yellow colorant as another colorant is further contained, the content of the yellow colorant as another colorant is preferably 10 to 200 parts by mass, preferably 20 to 150 parts by mass with respect to 100 parts by mass of the metal azo pigment A for better. The aspect which does not contain the yellow coloring agent which is another coloring material can also be set.

In the combination of the above (C3), it is preferable to contain 100 to 800 parts by mass of the red colorant with respect to 100 parts by mass of the metal azo pigment A, and more preferably 200 to 700 parts by mass. Moreover, it is preferable to contain 100-1000 mass parts of blue coloring agents, and it is more preferable to contain 200-800 mass parts. Furthermore, when a yellow colorant as another colorant is further contained, the content of the yellow colorant as another colorant is preferably 10 to 200 parts by mass, preferably 20 to 150 parts by mass with respect to 100 parts by mass of the metal azo pigment A for better. The aspect which does not contain the yellow coloring agent which is another coloring material can also be set.

In the combination of the above (C4), it is preferable to contain 100 to 1000 parts by mass of the blue colorant with respect to 100 parts by mass of the metal azo pigment A, and it is more preferable to contain 200 to 800 parts by mass. Moreover, it is preferable to contain 50-500 mass parts of purple coloring agents, and it is more preferable to contain 75-400 mass parts. Furthermore, when a yellow colorant as another colorant is further contained, the content of the yellow colorant as another colorant is preferably 10 to 200 parts by mass, preferably 20 to 150 parts by mass with respect to 100 parts by mass of the metal azo pigment A for better. The aspect which does not contain the yellow coloring agent which is another coloring material can also be set.

In the combination of the above (C5), it is preferable to contain 50 to 500 parts by mass of the purple colorant with respect to 100 parts by mass of the metal azo pigment A, and it is more preferable to contain 75 to 400 parts by mass. Moreover, it is preferable to contain 50-1000 mass parts of black coloring agents, and it is more preferable to contain 100-800 mass parts. Furthermore, when a yellow colorant as another colorant is further contained, the content of the yellow colorant as another colorant is preferably 10 to 200 parts by mass, preferably 20 to 150 parts by mass with respect to 100 parts by mass of the metal azo pigment A for better. The aspect which does not contain the yellow coloring agent which is another coloring material can also be set.

In the combination of the above (C6), it is preferable to contain 100 to 1000 parts by mass of the blue colorant with respect to 100 parts by mass of the metal azo pigment A, and it is more preferable to contain 200 to 800 parts by mass. Moreover, it is preferable to contain 50-1000 mass parts of black coloring agents, and it is more preferable to contain 100-800 mass parts. Furthermore, when a yellow colorant as another colorant is further contained, the content of the yellow colorant as another colorant is preferably 10 to 200 parts by mass, preferably 20 to 150 parts by mass with respect to 100 parts by mass of the metal azo pigment A for better. The aspect which does not contain the yellow coloring agent which is another coloring material can also be set.

In the composition of the present invention, the content of other colorants is preferably 10 to 80% by mass in the total solid content of the composition of the present invention. The lower limit is preferably 20% by mass or more, and more preferably 30% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less. Moreover, it is preferable that content of other coloring material is 50-1000 mass parts with respect to 100 mass parts of metal azo pigments A. The lower limit is preferably 70 parts by mass or more, and more preferably 100 parts by mass or more. The upper limit is preferably 500 parts by mass or less. Moreover, it is preferable that the total content of the metal azo pigment A and other coloring materials is 10-70 mass % in the total solid content of the composition of this invention. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. When the composition of the present invention contains two or more other colorants, it is preferable that the total amount of these is within the above range.

<<Near-infrared absorbing dye>> The composition of the present invention can contain a near-infrared absorbing dye. In the infrared transmissive filter, the near-infrared absorbing dye has the function of limiting the transmitted light (infrared rays) to the longer wavelength side. When the composition of the present invention contains a near-infrared absorbing dye, it is easy to obtain a composition having the spectral characteristics of the above (3). In particular, when the metal azo pigment A and other colorants are contained in a combination of the above (C2) to (C6), the composition having the spectral characteristics of the above (3) can be easily obtained by further containing a near-infrared absorbing dye. In addition, when the composition of the present invention contains a near-infrared absorbing dye, the occurrence of foreign matter defects in a high temperature and high humidity environment can be effectively suppressed.

In the present invention, as the near-infrared absorbing dye, a compound having a maximum absorption in the range of the near-infrared region (preferably a wavelength of 700 to 1100 nm, more preferably a wavelength of 700 to 1000 nm, and still more preferably a wavelength of 800 to 900 nm) can be mentioned. The near-infrared absorbing dye may be a pigment or a dye.

As the near-infrared absorbing dye, a compound having a π-conjugated plane containing a monocyclic or condensed aromatic ring can be preferably used. The number of atoms other than hydrogen constituting the π-conjugated plane of the near-infrared absorbing dye is preferably 14 or more, more preferably 20 or more, further preferably 25 or more, and particularly preferably 30 or more. For example, the upper limit is preferably 80 or less, and more preferably 50 or less. In addition, the π-conjugated plane possessed by the near-infrared absorbing dye preferably contains two or more monocyclic or condensed aromatic rings, more preferably three or more of the above-mentioned aromatic rings, and four or more of the above-mentioned aromatic rings. An aromatic ring is more preferable, and it is especially preferable that it contains 5 or more of the said aromatic rings. The upper limit is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less. Examples of the above-mentioned aromatic ring include a benzene ring, a naphthalene ring, an indene ring, an azulene ring, a heptavine ring, an indene ring, a perylene ring, a condensed pentabenzene ring, a quartane ring, an ethanenaphthalene ring, a phenanthrene ring. Ring, anthracene ring, fused tetraphenyl ring, triphenyl ring, biextended triphenyl ring, perylene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzo Thiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzoxazole ring, imidazoline ring, pyrazine ring, quinoxaline ring, pyrimidine ring, quinazoline ring, pyridazine ring, three An oxazine ring, a pyrrole ring, an indole ring, an isoindole ring, a carbazole ring, and a fused ring having these rings.

The near-infrared absorbing dye is selected from the group consisting of pyrrolopyrrole compounds, cyanine compounds, squaraine compounds, phthalocyanine compounds, naphthalocyanine compounds, quartane compounds, merocyanine compounds, ketonium compounds, oxa compounds, Preferably, at least one of diimmonium compounds, dithiol compounds, triarylmethane compounds, pyrromethine compounds, methaneimine compounds, anthraquinone compounds, indigo compounds and dibenzofuranone compounds is selected from pyrrolopyrrole Compounds, cyanine compounds, squaraine compounds, phthalocyanine compounds, naphthalocyanine compounds, ketonium compounds and indigo compounds are preferably at least one selected from the group consisting of pyrrolopyrrole compounds, cyanine compounds and squaraine compounds At least one of them is more preferred, and a pyrrolopyrrole compound is particularly preferred. As a diimmonium compound, the compound described in Unexamined-Japanese-Patent No. 2008-528706 is mentioned, for example, and the content is incorporated in this specification. Examples of the phthalocyanine compound include compounds described in paragraph No. 0093 of JP 2012-077153 A, titanium phthalocyanine described in JP 2006-343631 A, and compounds described in JP 2013-195480 A. The compounds described in Paragraph Nos. 0013 to 0029, the vanadium phthalocyanine described in Japanese Patent No. 6081771, and these contents are incorporated into the present specification. As a naphthalocyanine compound, the compound described in the paragraph No. 0093 of Unexamined-Japanese-Patent No. 2012-077153 is mentioned, for example, and the content is incorporated in this specification. Preferably, the indigo compound is an indigo boron complex compound. Examples of the indigo compound include compounds described in Japanese Patent No. 5642013, and the contents thereof are incorporated into the present specification. In addition, as the near-infrared absorbing dye, the compound described in JP 2016-146619 A, the compound described in JP 2016-079331 A, the compound described in JP 2017-082029 A, the The compound described in Kokai Publication No. 2015-040176 and the compound described in Japanese Patent Publication No. 5539676. Moreover, the compound of the following structure can also be used for a near-infrared absorption dye. [Chemical formula 9]

式中，R^1a 及R^1b 分別獨立地表示烷基、芳基或雜芳基，R² 及R³ 分別獨立地表示氫原子或取代基，R² 及R³ 亦可以相互鍵結而形成環，R⁴ 分別獨立地表示氫原子、烷基、芳基、雜芳基、-BR^4A R^4B 或金屬原子，R⁴ 亦可以與選自R^1a 、R^1b 及R³ 之至少一個共價鍵結或配位鍵結，R^4A 及R^4B 分別獨立地表示取代基。關於式（PP）的詳細內容，能夠參閱日本特開2009-263614號公報的段落號0017～0047、日本特開2011-068731號公報的段落號0011～0036、國際公開WO2015/166873號公報的段落號0010～0024中的記載，且該等內容被併入本說明書中。As the pyrrolopyrrole compound, a compound represented by the formula (PP) is preferable. [Chemical formula 10]

In the formula, 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 can also be bonded to each other to form a ring. , R ⁴ independently represents hydrogen atom, alkyl group, aryl group, heteroaryl group, -BR ^4A R ^4B or metal atom, R ⁴ can also be selected from R ^1a , R ^1b and R ³ at least one covalent bond A bond or a coordinate bond, R ^4A and R ^4B each independently represent a substituent. For details of formula (PP), refer to paragraphs 0017 to 0047 of JP 2009-263614 A, paragraphs 0011 to 0036 of JP 2011-068731 A, and paragraphs of International Publication WO2015/166873 Nos. 0010 to 0024, and these contents are incorporated into this specification.

In formula (PP), it is preferable that R ^1a and R ^1b each independently represent 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 not be substituted. Examples of the substituent include the substituents described in paragraphs 0020 to 0022 of JP-A No. 2009-263614, and the above-mentioned substituent T. In addition, when the alkyl group, aryl group, and heteroaryl group represented by R ^1a and R ^1b have two or more substituents, the substituents may be bonded to each other to form a ring.

Specific examples of the groups represented by R ^1a and R ^1b include an aryl group having an alkoxy group as a substituent, an aryl group having a hydroxyl group as a substituent, and an aryl group having an alkoxy group as a substituent.

In formula (PP), R ² and R ³ each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent T. Preferably, at least one of R ² and R ³ is an electron withdrawing group. A substituent having a positive Hammett substituent constant σ value (sigma value) acts as an electron withdrawing group. Here, a σp value and a σm value exist in the substituent constant obtained by Hammett's law. Such equivalents can be found in many general publications. In the present invention, as the electron withdrawing group, a substituent having a Hammett substituent constant σ value of 0.2 or more can be exemplified. The σ value is preferably 0.25 or more, more preferably 0.3 or more, and even more preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80 or less. Specific examples of the electron withdrawing group include a cyano group (-CN: σp value=0.66), a carboxyl group (-COOH: σp value=0.45), an alkoxycarbonyl group (for example, -COOMe: σp value=0.45), an aryloxy group Carbonyl (eg, -COOPh:σp value=0.44), Aminocarboxy (eg, -CONH ₂ :σp value=0.36), Alkylcarbonyl (eg, -COMe:σp value=0.50), Arylcarbonyl (eg, -COMe:σp value=0.50) For example, -COPh: σp value = 0.43), alkylsulfonyl group (eg, -SO ₂ Me: σp value = 0.72), arylsulfonyl group (eg, -SO ₂ Ph: σp value = 0.68), etc., Cyano is preferred. Here, Me represents a methyl group, and Ph represents a phenyl group. In addition, regarding the value of the Hammett substituent constant σ, for example, paragraph numbers 0017 to 0018 of Japanese Patent Laid-Open No. 2011-068731 can be referred to, and the contents thereof are incorporated into the present specification.

In formula (PP), R ² represents an electron withdrawing group (preferably a cyano group), and R ³ preferably 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 or fused ring, preferably a monocyclic or a fused ring with a condensation number of 2 to 8, and more preferably a single ring or a fused ring with a condensation number of 2 to 4. The number of hetero atoms 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 are illustrated, for example. The heteroaryl group preferably has one or more nitrogen atoms. The two R ² in the 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 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 , a hydrogen atom, an alkyl group, an aryl group or a group represented by -BR ^4A R The group represented by ^4B is more preferable, and the group represented by -BR ^4A R ^4B is further preferable. As the substituent represented by R ^4A and R ^4B , a halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group is preferable, an alkyl group, an aryl group or a heteroaryl group is more preferable, and an aryl group is particularly preferable . These groups may further have a substituent. The 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.

Specific examples of the compound represented by the formula (PP) 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 2011-68731 A, and international publications. Compounds and the like described in Paragraph Nos. 0010 to 0033 of WO2015/166873, and these contents are incorporated into the present specification. [Chemical formula 11]

式（SQ）中，A¹ 及A² 分別獨立地表示芳基、雜芳基或由式（A-1）表示之基團； [化學式13]

式（A-1）中，Z¹ 表示形成含氮雜環之非金屬原子團，R² 表示烷基、烯基或芳烷基，d表示0或1，波浪線表示連接鍵。關於式（SQ）的詳細內容，能夠參閱日本特開2011-208101號公報的段落號0020～0049、日本專利第6065169號公報的段落號0043～0062、國際公開WO2016/181987號公報的段落號0024～0040中的記載，且該等內容被併入本說明書中。As the squaraine compound, a compound represented by the following formula (SQ) is preferable. [Chemical formula 12]

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 13]

In formula (A-1), Z ¹ represents a non-metallic atomic group forming a nitrogen-containing heterocycle, 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 formula (SQ), refer to paragraphs 0020 to 0049 of Japanese Patent Laid-Open No. 2011-208101, paragraphs 0043 to 0062 of Japanese Patent No. 6065169, and paragraph 0024 of International Publication WO2016/181987 ~0040, and these contents are incorporated into this specification.

In addition, the cation in the formula (SQ) exists in the following delocalized manner. [Chemical formula 14]

As a squaraine compound, the compound of the following structure is mentioned. In addition, the compounds described in paragraphs 0044 to 0049 of JP 2011-208101 A, the compounds described in paragraphs 0060 to 0061 of Japanese Patent No. 6065169, and the paragraphs of International Publication WO2016/181987 Compounds described in 0040, compounds described in International Publication WO2013/133099 A, compounds described in International Publication WO2014/088063, compounds described in JP 2014-126642 A, JP 2016-146619 A Compounds described in the publications, compounds described in JP 2015-176046 A, compounds described in JP 2017-025311 A, compounds described in International Publication WO 2016/154782, JP 5884953 The compounds described in, the compound described in Japanese Patent No. 6036689, the compound described in Japanese Patent No. 5810604, the compound described in Japanese Patent Laid-Open No. 2017-068120, etc., and the contents of which are incorporated into this specification middle. [Chemical formula 15]

式中，Z¹ 及Z² 分別獨立地為形成可以縮環的5員或6員的含氮雜環之非金屬原子團， R¹⁰¹ 及R¹⁰² 分別獨立地烷基、烯基、炔基、芳烷基或芳基， L¹ 表示具有奇數個次甲基之次甲鏈， a及b分別獨立，為0或1， a為0時，碳原子與氮原子以雙鍵形式鍵結，b為0時，碳原子與氮原子以單鍵形式鍵結， 式中由Cy表示之部位為陽離子部時，X¹ 表示陰離子，c表示用於確保電荷的平衡所需的數，式中由Cy表示之部位為陰離子部時，X¹ 表示陽離子，c表示用於確保電荷的平衡所需的數，式中由Cy表示之部位的電荷在分子內中和時，c為0。The cyanine compound is preferably a compound represented by formula (C). Formula (C) [Chemical Formula 16]

In the formula, Z ¹ and Z ² are respectively independently a non-metallic atomic group that forms a 5-membered or 6-membered nitrogen-containing heterocyclic ring that can be condensed, and R ¹⁰¹ and R ¹⁰² are independently alkyl, alkenyl, alkynyl, aryl, respectively. Alkyl or aryl, L ¹ represents a methine chain with an odd number of methine groups, a and b are independently 0 or 1, when a is 0, a carbon atom and a nitrogen atom are bonded in the form of double bonds, and b is When it is 0, the carbon atom and the nitrogen atom are bonded by a single bond, and when the part represented by Cy in the formula is a cation part, X ¹ represents an anion, and c represents a number required to ensure the balance of electric charges, and in the formula, it is represented by Cy When the moiety is an anion moiety, X ¹ represents a cation, and c represents a number necessary for securing the balance of charges. In the formula, when the charges of the moiety represented by Cy are neutralized in the molecule, c is 0.

Examples of the cyanine compound include compounds described in paragraphs 0044 to 0045 of JP 2009-108267 A, compounds described in paragraphs 0026 to 0030 of JP 2002-194040 A, and JP 2015- The compound described in JP 172004 A, the compound described in JP 2015-172102 A, the compound described in JP 2008-088426 A, the compound described in JP 2017-031394 A, etc., and the and the like are incorporated into this specification.

In this invention, a commercial item can also be used for a near-infrared absorption dye. For example, SDO-C33 (manufactured by ARIMOTO CHEMICAL Co., Ltd.), EXcolor IR-14, EXcolor IR-10A, EXcolor TX-EX-801B, EXcolor TX-EX-805K (manufactured by Nippon Shokubai Co., Ltd.) , ShigenoxNIA-8041, ShigenoxNIA-8042, ShigenoxNIA-814, ShigenoxNIA-820, ShigenoxNIA-839 (manufactured by Kyowa Hakko Chemical Co., Ltd.), EpoliteV-63, Epolight3801, Epolight3036 (manufactured by Epolin, Inc.), PRO-JET825LDI (manufactured by Epolin, Inc.) Fujifilm Corporation), NK-3027, NK-5060 (manufactured by HAYASHIBARA CO., LTD.), YKR-3070 (manufactured by Mitsui Chemicals, Inc.), FDN-003 (manufactured by YAMADA CHEMICAL CO., LTD.), and the like.

When the composition of the present invention contains a near-infrared absorbing dye, the content of the near-infrared absorbing dye is preferably 1 to 30% by mass in the total solid content of the composition of the present invention. The upper limit is preferably 20 mass % or less, more preferably 10 mass % or less. The lower limit is preferably 3 mass % or more, and more preferably 5 mass % or more. Moreover, the content of the near-infrared absorbing dye is preferably 5 to 50 parts by mass relative to 100 parts by mass of the total of the metal azo pigment A and other colorants. The upper limit is preferably 45 mass % or less, more preferably 40 mass % or less. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more. Moreover, it is preferable that the total content of the metal azo pigment A, other coloring materials, and a near-infrared absorbing dye is 10-70 mass % in the total solid content of the composition of this invention. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. The composition of the present invention may contain one type of near-infrared absorbing dye, or may contain two or more types. When two or more types of near-infrared absorbing dyes are contained, it is preferable that the total amount of these is in the above-mentioned range.

<<hardenable compound>> The composition of this invention contains at least 1 sort(s) of compound chosen from the compound which has an ethylenically unsaturated bond group, and the compound which has a cyclic ether group. Hereinafter, both are also collectively referred to as a curable compound. A vinyl group, a (meth)allyl group, a (meth)acryloyl group, etc. are mentioned as an ethylenically unsaturated bond group. As a cyclic ether group, an epoxy group, an oxetanyl group, etc. are mentioned.

(Compound having an ethylenically unsaturated bond group) The compound having an ethylenically unsaturated bond group used in the present invention may be a monomer or a polymer. Hereinafter, the monomer having an ethylenically unsaturated bond group is also referred to as a polymerizable monomer. Moreover, the polymer which has an ethylenically unsaturated bond group can also be called a polymerizable polymer.

The molecular weight of the polymerizable monomer is preferably less than 3000. The upper limit is more preferably 2000 or less, and further more preferably 1500 or less. The lower limit is preferably 100 or more, more preferably 150 or more, and still more preferably 250 or more. The polymerizable monomer is preferably a compound containing 3 or more ethylenically unsaturated bond groups, more preferably a compound containing 3-15 ethylenically unsaturated bond groups, and preferably a compound containing 3-6 ethylenically unsaturated bond groups The compound of an unsaturated bond group is more preferable. Moreover, the (meth)acrylate compound whose polymerizable monomer is 3-15 functional is more preferable, and the (meth)acrylate compound which is 3-6 functional is more preferable. Specific examples of the polymerizable monomer include paragraphs 0095 to 0108 of JP 2009-288705 A, paragraph 0227 of JP 2013-029760 A, and paragraph 0254 of JP 2008-292970 A ~0257, and the contents are incorporated into this specification.

The C=C equivalent of the polymerizable monomer (the molecular weight of the polymerizable monomer [g/mol]/the number of ethylenically unsaturated bond groups contained in the polymerizable monomer) is preferably 50 to 1,000. The lower limit is preferably 60 or more, and more preferably 70 or more. The upper limit is preferably 700 or less, more preferably 500 or less, further more preferably 200 or less, still more preferably 150 or less, and particularly preferably 140 or less. When the C=C equivalent of the polymerizable monomer is in the above range, it can be effectively adsorbed on the active surface of the pigment, and the aggregation of the metal azo pigment A can be suppressed more significantly.

As a polymerizable monomer, dipeotaerythritol triacrylate (a commercial item: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipeotaerythritol tetraacrylate (a commercial item) can be mentioned. It is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), two Neotaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin Nakamura Chemical Co., Ltd.) and the like (Meth)acryloyl group bonded via ethylene glycol and/or propylene glycol residues ), KAYARAD RP-1040, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.), etc. In addition, as the polymerizable monomer, trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide modified Trifunctional (meth)acrylate compounds such as mass tri(meth)acrylate, isocyanurate-modified ethylene oxide tri(meth)acrylate, and pentaerythritol tri(meth)acrylate are also preferred. As a commercial item of a trifunctional (meth)acrylate compound, ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 are mentioned , M-305, M-303, M-452, M-450 (manufactured by TOAGOSEI CO., LTD.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A- TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (NIPPON KAYAKU CO., LTD.), TMPEOTA (DAICEL-ALLNEX LTD.), etc.

As the polymerizable monomer, it is also preferable to use a polymerizable monomer having an acid group. By using a polymerizable monomer having an acid group, the composition layer of the unexposed portion can be easily removed during development, and the occurrence of development residues can be effectively suppressed. As an acid group, a carboxyl group, a sulfo group, a phosphoric acid group, etc. are mentioned, A carboxyl group is preferable. As a commercial item of the polymerizable monomer which has an acid group, aronix M-510, M-520, aronix TO-2349 (made by TOAGOSEI CO., LTD.) etc. are mentioned. The acid value of the polymerizable monomer having an acid group is preferably 0.1 to 40 mgKOH/g, more preferably 5 to 30 mgKOH/g. As long as the acid value of the polymerizable monomer is 0.1 mgKOH/g or more, the solubility to a developing solution is good, and more excellent developability can be obtained. As long as the acid value of the polymerizable monomer is 40 mgKOH/g or less, production and handling are favorable.

It is also preferable to use compounds represented by the following formulae (MO-1) to (MO-6) as the polymerizable monomer. In addition, in the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

[Chemical formula 17]

In the above formula, n is 0-14, and m is 1-8. A plurality of R and T may be the same or different from each other in one molecule. In each of the compounds represented by the above formulae (MO-1) to (MO-6), at least one of the plurality of R represents -OC(=O)CH=CH ₂ , -OC(=O)C(CH ₃ )=CH ₂ , -NHC(=O)CH=CH ₂ or -NHC(=O)C(CH ₃ )=CH ₂ . Specific examples of the polymerizable compounds represented by the above formulae (MO-1) to (MO-6) include compounds described in paragraphs 0248 to 0251 of JP 2007-269779 A.

Moreover, it is also preferable to use the compound which has a caprolactone structure as a polymerizable monomer. The compound having a caprolactone structure is not particularly limited to those having a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, Ditrimethylolpropane, pentaerythritol, dipeptaerythritol, tripentaerythritol, glycerol, diglycerol, trimethylolmelamine and other polyols are esterified with (meth)acrylic acid and ε-caprolactone, ε -Caprolactone-modified polyfunctional (meth)acrylates. The compound having a caprolactone structure is preferably a compound represented by the following formula (Z-1).

[Chemical formula 18]

In formula (Z-1), 6 Rs are all groups represented by formula (Z-2) or 1 to 5 of 6 Rs are groups represented by formula (Z-2), and the rest are groups represented by formula (Z-2) (Z-3) represents a group, an acid group or a hydroxyl group.

式（Z-2）中，R¹ 表示氫原子或甲基，m表示1或2的整數，“*”表示鍵結鍵。[Chemical formula 19]

In formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 or 2, and "*" represents a bond.

式（Z-3）中，R¹ 表示氫原子或甲基，“*”表示鍵結鍵。[Chemical formula 20]

In formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond.

As a polymerizable monomer, the compound represented by formula (Z-4) or (Z-5) can also be mentioned.

[Chemical formula 21]

In formulas (Z-4) and (Z-5), E each independently represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, and y each independently Each independently represents an integer of 0 to 10, and X each independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxyl group. In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, m each independently represents an integer of 0 to 10, and each m is an integer of 0 to 40 in total. In formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, n each independently represents an integer of 0 to 10, and each n is an integer of 0 to 60 in total.

In formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. In addition, each m is preferably an integer of 2 to 40 in total, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8. In formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. In addition, each n is preferably an integer of 3 to 60 in total, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12. In addition, E in formula (Z-4) or formula (Z-5), that is, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- is oxygen The form in which the terminal on the atom side is bonded to X is preferable.

As the polymerizable monomer, a compound having an alkyleneoxy group can also be used. The polymerizable monomer having an alkyleneoxy group is preferably a compound having an ethylideneoxy group and/or a propylideneoxy group, more preferably a compound having an ethylideneoxy group, and has 4 to 20 extension groups. The 3- to 6-functional (meth)acrylate compound of an ethyloxy group is more preferable. As a commercial item of the polymerizable monomer which has an alkyleneoxy group, the SR-494 which has a tetrafunctional (meth)acrylate which has 4 vinyloxy groups made by SARTOMER, the SR-494 which has 3 isobutenyloxy groups is mentioned, for example The KAYARAD TPA-330 of the 3-functional (meth)acrylate, etc.

Examples of the polymerizable monomer include urethanes described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 2-032293, and Japanese Patent Publication No. 2-016765. Acrylates and those having ethylene oxide-based skeletons described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 Amine ester compounds, described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. Hei 1-105238, have an amine structure and a thioether structure in the molecule, and these compounds are used Also better. Commercially available products include UA-7200 (manufactured by Shin Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH- 600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like. In addition, as the polymerizable monomer, 8UH-1006, 8UH-1012 (the above are manufactured by Taisei Fine Chemical Co., Ltd.), LIGHT ACRYLATE POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. are also preferably used. Moreover, as a polymerizable monomer, the compound described in Unexamined-Japanese-Patent No. 2017-048367, Unexamined-Japanese-Patent No. 6057891, and Unexamined-Japanese-Patent No. 6031807 can also be used.

The weight average molecular weight of the polymerizable polymer is preferably 3,000 or more, more preferably 5,000 or more, further preferably 7,000 or more, and particularly preferably 10,000 or more. In addition, the weight average molecular weight of the polymerizable polymer is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less.

The C=C equivalent of the polymerizable polymer (the molecular weight of the polymerizable polymer/the number of ethylenically unsaturated bond groups contained in the polymerizable polymer) is preferably 100 to 5,000. The lower limit is preferably 150 or more, and more preferably 200 or more. The upper limit is preferably 4500 or less, and more preferably 4000 or less. As long as the C=C equivalent of the polymerizable polymer is in the above range, it can be effectively adsorbed to the active surface of the pigment, and the aggregation of the metal azo pigment A can be suppressed more significantly.

式（A-1-1）中，X¹ 表示重複單元的主鏈，L¹ 表示單鍵或2價的連結基，Y¹ 表示乙烯性不飽和鍵結基。The polymerizable polymer preferably contains a repeating unit having an ethylenically unsaturated bond group in a side chain, and more preferably contains a repeating unit represented by the following formula (A-1-1). In addition, the polymerizable polymer preferably contains 10 mol% or more of repeating units having an ethylenically unsaturated bond group in the total repeating units of the polymerizable polymer, more preferably 10 to 80 mol%, including 20-70 mol% is more preferable. [Chemical formula 22]

In formula (A-1-1), X ¹ represents the main chain of the repeating unit, L ¹ represents a single bond or a divalent linking group, and Y ¹ represents an ethylenically unsaturated linking group.

In formula (A-1-1), the main chain of the repeating unit represented by X ¹ is not particularly limited. There is no particular limitation as long as it is a known linking group formed from a polymerizable monomer. For example, a poly(meth)acrylic-based linking group, a polyalkyleneimide-based linking group, a polyester-based linking group, a polyurethane-based linking group, a polyurea-based linking group, a polyamide-based linking group, and a polyether From the viewpoints of availability of raw materials and suitability for production, poly(meth)acrylic acid-based linking groups and polyalkyleneimine-based linking groups are preferred as linking groups, polystyrene-based linking groups, and the like. A poly(meth)acrylic linking group is more preferable.

In the formula (A-1-1), the divalent linking group represented by L ¹ includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkylene group having 1 to 12 carbon atoms). alkylene oxy with 1 to 12 carbon atoms), oxyalkylenecarbonyl (preferably oxyalkylene carbonyl with 1 to 12 carbons), aryl extended (preferably aryl extended with 6 to 20 carbons) ), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of them.

In the formula (A-1-1), examples of the ethylenically unsaturated bond group represented by Y ¹ include vinyl, (meth)allyl, (meth)acryloyl, and the like, (methyl) Acryloyl group is preferable, and acryl group is more preferable.

It is preferable that the polymerizable polymer further contains repeating units having a graft chain. When the polymerizable polymer includes a repeating unit having a graft chain, aggregation of the metal azo pigment A and the like can be more effectively suppressed by the steric hindrance effect based on the graft chain. The polymerizable polymer preferably contains 1.0 to 60 mol% of repeating units having a graft chain in the total repeating units of the polymerizable polymer, more preferably 1.5 to 50 mol%. As the dispersing agent, a polymerizable polymer containing a repeating unit having a graft chain is preferably used.

In the present invention, the graft chain refers to a polymer chain branched and extended from the main chain of the repeating unit. The length of the graft chain is not particularly limited, but when the graft chain becomes longer, the steric repulsion effect is enhanced, and the dispersibility of the metal azo pigment A and the like can be improved. As the graft chain, the number of atoms other than hydrogen atoms is preferably 40 to 10,000, the number of atoms other than hydrogen atoms is more preferably 50 to 2,000, and the number of atoms other than hydrogen atoms is preferably 60 to 500. Further preferred.

Preferably, the graft chain of the polymerizable polymer comprises at least one structure selected from the group consisting of polyester structure, polyether structure, poly(meth)propylene structure, polyurethane structure, polyurea structure and polyamide structure, including At least one structure selected from a polyester structure, a polyether structure and a poly(meth)propylene structure is more preferable, and it is further preferable to include a polyester structure. As a polyester structure, the structure represented by following formula (G-1), formula (G-4), or formula (G-5) is mentioned. Moreover, as a polyether structure, the structure represented by following formula (G-2) is mentioned. Moreover, as a poly(meth)propylene structure, the structure represented by following formula (G-3) is mentioned. [Chemical formula 23]

In the above formula, R ^G1 and R ^G2 each represent an alkylene group. The alkylene group represented by R ^G1 and R ^G2 is not particularly limited, but a linear or branched alkylene group having 1 to 20 carbon atoms is preferable, and a linear or branched alkyl group having 2 to 16 carbon atoms is preferable. A linear or branched alkylene group having 3 to 12 carbon atoms is more preferable. In the above formula, R ^G3 represents a hydrogen atom or a methyl group. In the above formula, Q ^G1 represents -O- or -NH-, and L ^G1 represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkylene group having 1 to 12 carbon atoms), an oxyalkylene group. Alkenylcarbonyl (preferably oxyalkylenecarbonyl with 1 to 12 carbons), aryl extended (preferably with 6 to 20 carbons), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, -S- and groups formed by combining two or more of them. In the above formula, R ^G4 represents a hydrogen atom or a substituent. As a substituent, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio ether group, an arylthio ether group, a heteroarylthio ether group, etc. are mentioned.

The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. As a substituent, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio ether group, an arylthio ether group, a heteroarylthio ether group, etc. are mentioned. Among them, from the viewpoint of improving the dispersibility of the color material and the like, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched is preferred.

In the present invention, as the graft chain, the structure represented by the following formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a) or formula (G-5a) is: better. [Chemical formula 24]

In the above formula, R ^G1 and R ^G2 respectively represent an alkylene group, R ^G3 represents a hydrogen atom or a methyl group, Q ^G1 represents -O- or -NH-, L ^G1 represents a single bond or a divalent linking group, and R ^G4 represents A hydrogen atom or a substituent, W ¹⁰⁰ represents a hydrogen atom or a substituent. n1 to n5 each independently represent an integer of 2 or more. R ^G1 to R ^G4 , Q ^G1 , and L ^G1 have the same meanings as R ^G1 to R ^G4 , Q ^G1 , and L ^G1 described in the formulae (G-1) to (G-5), and the preferred ranges are also the same.

In the formulae (G-1a) to (G-5a), it is preferable that W ¹⁰⁰ is a substituent. As a substituent, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio ether group, an arylthio ether group, a heteroarylthio ether group, etc. are mentioned. Among them, from the viewpoint of improving the dispersibility of the color material and the like, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched is preferred.

In the formulae (G-1a) to (G-5a), n1 to n5 each independently represent an integer of 2 or more, more preferably 3 or more, and even more preferably 5 or more. For example, the upper limit is preferably 100 or less, more preferably 80 or less, and even more preferably 60 or less.

As a repeating unit which has a graft chain, the repeating unit represented by following formula (A-1-2) is mentioned. [Chemical formula 25]

In formula (A-1-2), X ² represents the main chain of the repeating unit, L ² represents a single bond or a divalent linking group, and W ¹ represents a graft chain.

As the main chain of the repeating unit represented by X ² in the formula (A-1-2), the structures described for X ¹ in the formula (A-1-1) can be mentioned, and the preferred range is also the same. Examples of the divalent linking group represented by L ² in the formula (A-1-2) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylidene group (preferably a carbon 6-20 aryl groups), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, -S-, and combinations of two or more of these the group. Examples of the graft chain represented by W ¹ in the formula (A-1-2) include the above-mentioned graft chains.

When the polymerizable polymer contains a repeating unit having a graft chain, the weight average molecular weight (Mw) of the repeating unit having a graft chain is preferably 1,000 or more, more preferably 1,000 to 10,000, and even more preferably 1,000 to 7,500. Moreover, in this invention, the weight average molecular weight of the repeating unit which has a graft chain is a value calculated based on the weight average molecular weight of the raw material monomer used for the polymerization of this repeating unit. For example, repeating units with grafted chains can be formed by polymerizing macromonomers. Here, the macromonomer refers to a polymer compound having a polymerizable group introduced into a polymer terminal. When a macromonomer is used to form a repeating unit having a graft chain, the weight average molecular weight of the macromonomer corresponds to the weight average molecular weight of the repeating unit having a graft chain.

It is also preferable that the polymerizable polymer further contains a repeating unit having an acid group. When the polymerizable polymer further includes a repeating unit having an acid group, the dispersibility of the metal azo pigment A and the like can be further improved. In addition, developability can also be improved. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group.

As a repeating unit which has an acid group, the repeating unit represented by following formula (A-1-3) is mentioned. [Chemical formula 26]

In formula (A-1-3), X ³ represents the main chain of the repeating unit, L ³ represents a single bond or a divalent linking group, and A ¹ represents an acid group.

As the main chain of the repeating unit represented by X ³ in the formula (A-1-3), the structures described for X ¹ in the formula (A-1-1) can be exemplified, and the preferred range is also the same. Examples of the divalent linking group represented by L ³ in the formula (A-1-3) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkylene group having 1 to 12 carbon atoms). is an alkyleneoxy group having 2 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an alkylene group having 1 to 12 carbon atoms) oxyalkylene carbonyl), aryl extended (preferably aryl extended with 6 to 20 carbon atoms), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO -, -S-, and a group formed by combining two or more of these. The alkylene group in the alkylene group, the alkylene group in the alkylene groupoxy, and the alkylene group in the oxyalkylene carbonyl group can be any one of straight chain, branched chain and cyclic, and the straight chain or branched chain is relatively good. In addition, the alkylene group in the alkylene group, the alkylene group in the alkylene groupoxy, and the alkylene group in the oxyalkylene carbonyl group may have a substituent or may not be substituted. As a substituent, a hydroxyl group etc. are mentioned. Examples of the acid group represented by A ¹ in the formula (A-1-3) include a carboxyl group, a sulfo group, and a phosphoric acid group.

The acid value of the polymerizable polymer is preferably 20 to 150 mgKOH/g. The upper limit is more preferably 100 mgKOH/g or less. The lower limit is preferably 30 mgKOH/g or more, and more preferably 35 mgKOH/g or more. As long as the acid value of the polymerizable polymer is within the above-mentioned range, particularly excellent dispersibility can be easily obtained. In addition, excellent developability is easily obtained.

In addition, the polymerizable polymer can contain, as another repeating unit, a repeating unit derived from a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, sometimes These compounds are also referred to as "ether dimers".) monomer components.

[Chemical formula 27]

式（ED2）中，R表示氫原子或碳數1～30的有機基團。作為式（ED2）的具體例，能夠參閱日本特開2010-168539號公報中的記載。In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms. [Chemical formula 28]

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of Formula (ED2), the description in Unexamined-Japanese-Patent No. 2010-168539 can be referred to.

As a specific example of the ether dimer, for example, paragraph No. 0317 of JP 2013-029760 A can be referred to, the content of which is incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.

Specific examples of the polymerizable polymer include the following. [Chemical formula 29]

(Compound which has a cyclic ether group) As a compound which has a cyclic ether group used for this invention, the compound which has two or more cyclic ether groups in 1 molecule is mentioned. The number of cyclic ether groups contained in the compound having a cyclic ether group is preferably 100 or less, more preferably 10 or less, and even more preferably 5 or less. As a cyclic ether group, an epoxy group, an oxetanyl group, etc. are mentioned, An epoxy group is preferable. That is, it is preferable that the compound having a cyclic ether group is a compound having an epoxy group (hereinafter, also referred to as an epoxy compound).

The epoxy equivalent of the epoxy compound (=the molecular weight of the compound having an epoxy group/the number of epoxy groups) is preferably 500 or less, more preferably 100 to 400, and even more preferably 100 to 300. The epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 1000) or a macromolecule compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, the weight average molecular weight is 1000 or more). The molecular weight of the epoxy compound (in the case of a polymer, the weight average molecular weight) is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the molecular weight (in the case of a polymer, the weight average molecular weight) is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,500 or less.

As the epoxy compound, the paragraph numbers 0034 to 0036 of JP 2013-011869 A, the paragraph numbers 0147 to 0156 of JP 2014-043556 A, and the paragraph numbers 0085 to 0092 of JP 2014-089408 A can be used. Compounds described. These contents are incorporated into this specification. Commercially available epoxy compounds include jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (the above are manufactured by DIC CORPORATION), etc. As bisphenol F type epoxy resins, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (the above are manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 ( The above are made by DIC CORPORATION), LCE-21, RE-602S (the above are made by NIPPON KAYAKU CO., LTD.), etc., as phenol novolak epoxy resins, jER152, jER154, jER157S70, jER157S65 (the above are Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (the above are manufactured by DIC CORPORATION), etc., as cresol novolak epoxy resins, EPICLON N-660, EPICLON N-665, EPICLON N As fatty epoxy resin , for ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (made by ADEKA CORPORATION), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (the above are Nagase Ch emtex Corporation), etc. In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (the above are manufactured by ADEKA CORPORATION), NC-2000, NC-3000, NC-7300, XD-1000 , EPPN-501, EPPN-502 (the above are manufactured by ADEKA CORPORATION), jER1031S (manufactured by Mitsubishi Chemical Corporation), MARPROOF G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G -1010S, G-2050M, G-01100, G-01758 (the above are NOF CORPORATION. manufactured, epoxy group-containing polymers) and the like.

In the composition of the present invention, the content of the compound having an ethylenically unsaturated bond group is preferably 1 to 50% by mass in the total solid content of the composition. The lower limit is preferably 3 mass % or more, and more preferably 5 mass % or more. The upper limit is preferably 45 mass % or less, more preferably 40 mass % or less. In addition, the content of the compound having an ethylenically unsaturated bond group is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and still more preferably 50 parts by mass or more with respect to 100 parts by mass of the metal azo pigment A. good. The upper limit is preferably 750 parts by mass or less, more preferably 700 parts by mass or less, more preferably 650 parts by mass or less, and particularly preferably 600 parts by mass or less. As long as the ratio of the metal azo pigment A to the compound having an ethylenically unsaturated bond group is within the above range, the effect of the present invention can be more remarkably obtained. Furthermore, when a polymerizable monomer and a polymerizable polymer are used in combination as a compound having an ethylenically unsaturated bond group, the content of the polymerizable polymer is preferably 5 to 500 parts by mass relative to 100 parts by mass of the polymerizable monomer. good. The lower limit is preferably 8 parts by mass or more, and more preferably 10 parts by mass or more. The upper limit is preferably 450 parts by mass or less, more preferably 400 parts by mass or less.

In the composition of the present invention, the content of the compound having a cyclic ether group is preferably 1 to 50% by mass in the total solid content of the composition. The lower limit is preferably 3 mass % or more, and more preferably 5 mass % or more. The upper limit is preferably 45 mass % or less, more preferably 40 mass % or less. The content of the compound having a cyclic ether group is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and even more preferably 50 parts by mass or more, relative to 100 parts by mass of the metal azo pigment A. The upper limit is preferably 750 parts by mass or less, more preferably 700 parts by mass or less, more preferably 650 parts by mass or less, and particularly preferably 600 parts by mass or less. As long as the ratio of the metal azo pigment A to the compound having a cyclic ether group is within the above range, the effects of the present invention can be more remarkably obtained.

In the composition of the present invention, the total content of the compound having an ethylenically unsaturated bond group and the compound having a cyclic ether group is preferably 1 to 50% by mass in the total solid content of the composition. The lower limit is preferably 3 mass % or more, and more preferably 5 mass % or more. The upper limit is preferably 45 mass % or less, more preferably 40 mass % or less. In addition, the total content of the compound having an ethylenically unsaturated bond group and the compound having a cyclic ether group is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, with respect to 100 parts by mass of the metal azo pigment A. Preferably, 50 parts by mass or more is further preferable. The upper limit is preferably 750 parts by mass or less, more preferably 700 parts by mass or less, more preferably 650 parts by mass or less, and particularly preferably 600 parts by mass or less. As long as the content is within the above-mentioned range, the effect of the present invention can be obtained more remarkably. Furthermore, when the composition of the present invention contains a compound having an ethylenically unsaturated bond group and a compound having a cyclic ether group, it contains 1 to 50 parts by mass relative to 100 parts by mass of the compound having an ethylenically unsaturated bond group. Compounds having a cyclic ether group are preferred. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. The lower limit is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and still more preferably 10 parts by mass or more.

<<Other resins>> The composition of the present invention can further contain resins other than the above-mentioned curable compounds (hereinafter, also referred to as other resins). Other resins are blended, for example, for the purpose of dispersing particles such as pigments in the composition or for the purpose of a binder. In addition, resins used mainly for dispersing particles such as pigments are also referred to as dispersants. However, the application such as resin is an example, and resin can be used for purposes other than such applications.

The weight average molecular weight (Mw) of other resins is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more.

Examples of other resins include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polyarylene resins, polyether resins, polyphenylene resins, polyarylenes Ether phosphine oxide resin, polyimide resin, polyimide imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, etc. One type of these resins may be used, or two or more types may be mixed and used. In addition, the resin described in the examples of International Publication WO2016/088645, the resin described in JP 2017-057265 A, the resin described in JP 2017-032685 A, JP 2017 A can be used as the resin. - Resin described in Gazette No. 075248, and resin described in JP-A No. 2017-066240. Moreover, resin which has a skeleton can also be used. As resins having a pyrene skeleton, resins having the following structures are exemplified. In the following structural formula, A is the residue of carboxylic acid two selected from pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and diphenyl ether tetracarboxylic dianhydride group, M is phenyl or benzyl. Regarding the resin having a pyrene skeleton, the description in US Patent Application Publication No. 2017/0102610 can be referred to, and the content is incorporated into the present specification. [Chemical formula 30]

Other resins may have acid groups. As an acid group, a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group etc. are mentioned, for example, A carboxyl group is preferable. Only one type of these acid groups may be used, or two or more types may be used. Resins having acid groups can also be used as alkali-soluble resins.

As the resin having an acid group, a polymer having a carboxyl group in a side chain is preferable. Specific examples include alkali-soluble phenol resins such as methacrylic acid copolymers, acrylic acid copolymers, itonic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolak resins. , Acidic cellulose derivatives with carboxyl groups on the side chain, resins with acid anhydrides added to polymers with hydroxyl groups. Copolymers of (meth)acrylic acid and other monomers which can be copolymerized therewith are particularly preferred as alkali-soluble resins. As another monomer which can be copolymerized with (meth)acrylic acid, an alkyl (meth)acrylate, an aryl (meth)acrylate, a vinyl compound, etc. are mentioned. Examples of alkyl (meth)acrylate and aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (Meth)acrylate, Isobutyl (meth)acrylate, Amyl (meth)acrylate, Hexyl (meth)acrylate, Octyl (meth)acrylate, Phenyl (meth)acrylate ester, benzyl (meth)acrylate, tolyl (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl (meth)acrylate, etc. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, and polymethyl methacrylate macromonomer body etc. In addition, maleimide monomers such as N-phenylmaleimide and N-cyclocyclohexylmaleimide can also be used as other monomers. Only 1 type may be sufficient as the other monomer which can be copolymerized with these (meth)acrylic acid, and 2 or more types may be sufficient as it.

For resins with acid groups, benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth)acrylic acid can be preferably used. base) acrylate copolymer, a multi-component copolymer composed of benzyl (meth)acrylate/(meth)acrylic acid/other monomers. In addition, 2-hydroxypropyl (meth)acrylate/polyphenylene described in Japanese Patent Laid-Open No. 7-140654 obtained by copolymerizing 2-hydroxyethyl (meth)acrylate can also be preferably used. Ethylene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methyl methacrylate acrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer /benzyl methacrylate/methacrylic acid copolymer, etc.

It is also preferable that the resin having an acid group is a polymer containing repeating units derived from the above-mentioned ether dimer-containing monomer component.

式（X）中，R₁ 表示氫原子或甲基，R₂ 表示碳數為2～10的伸烷基，R₃ 表示氫原子或可以包含苯環之碳數為1～20的烷基。n表示1～15的整數。The resin having an acid group may contain repeating units derived from a compound represented by the following formula (X). [Chemical formula 31]

In formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer of 1-15.

Regarding resins having an acid group, reference can be made to the descriptions in paragraphs 0558 to 0571 of JP-A No. 2012-208494 (corresponding to paragraphs 0685-0700 of the specification of U.S. Patent Application Laid-Open No. 2012/0235099 ), JP-A The descriptions in paragraph numbers 0076 to 0099 of Gazette No. 2012-198408 are incorporated into the present specification. Moreover, a commercial item can also be used for resin which has an acid group.

The acid value of the resin having an acid group is preferably 30 to 200 mgKOH/g. The lower limit is preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more. The upper limit is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less.

As resin which has an acid group, the resin etc. of the following structure are mentioned, for example. [Chemical formula 32]

The composition of the present invention can also contain a resin as a dispersant. The dispersing agent includes an acidic dispersing agent (acidic resin) and a basic dispersing agent (basic resin). Here, the acidic dispersant (acidic resin) means a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is a resin in which the amount of the acid group accounts for 70 mol% or more, when the total amount of the amount of the acid group and the amount of the basic group is 100 mol%, and is substantially A resin composed of only acid groups is more preferable. It is preferable that the acid group which the acidic dispersant (acidic resin) has is a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH/g, more preferably 50 to 105 mgKOH/g, and even more preferably 60 to 105 mgKOH/g. In addition, the basic dispersant (basic resin) refers to a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol % when the total amount of the amount of acid groups and the amount of basic groups is 100 mol %. Preferably, the basic group of the basic dispersant is an amine group.

It is preferable that the resin used as a dispersant contains a repeating unit having an acid group. By including a repeating unit having an acid group in the resin used as a dispersant, it is possible to further reduce the residues generated on the substrate of the pixel when patterning is performed by the photolithography method.

The resin used as a dispersant is preferably a resin containing a repeating unit having a graft chain in a side chain (hereinafter, also referred to as a graft resin). According to this aspect, the dispersibility of the metal azo pigment A and the like can be further improved. Here, the graft chain means a polymer chain that is branched and extended from the main chain of the repeating unit. The length of the graft chain is not particularly limited, but when the graft chain becomes longer, the steric repulsion effect is enhanced, and the dispersibility of pigments and the like can be improved. In the graft chain, the number of atoms other than hydrogen atoms is preferably 40 to 10,000, the number of atoms other than hydrogen atoms is more preferably 50 to 2,000, and the number of atoms other than hydrogen atoms is 60 to 500. Further preferred.

Preferably, the graft chain includes at least one structure selected from polyester chain, polyether chain, poly(meth)propylene chain, polyurethane chain, polyurea chain and polyamide chain, and includes a structure selected from polyester chain, polyamide chain and polyamide chain. At least one structure of an ether chain and a poly(meth)propylene chain is more preferable, and it is more preferable to include a polyester chain.

The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. As a substituent, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio ether group, an arylthio ether group, a heteroarylthio ether group, etc. are mentioned. Among them, from the viewpoint of improving the dispersibility of the metal azo pigment A and the like, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched is preferred.

As a graft resin, the resin etc. of the following structures are mentioned, for example. In addition, the details of the graft resin can be referred to the descriptions in paragraph numbers 0025 to 0094 of JP 2012-255128 A, and the contents are incorporated in the present specification. [Chemical formula 33]

It is also preferable that the resin used as the dispersant is an oligoimine-based resin containing a nitrogen atom in at least one of the main chain and the side chain. The oligoimine-based resin is preferably a resin having the following structural unit and side chain, and having a basic nitrogen atom in at least one of the main chain and the side chain, wherein the structural unit has a functional group having a pKa of 14 or less. In the partial structure X, the aforementioned side chain includes a side chain Y having 40 to 10,000 atoms. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. Regarding the oligoimine-based resin, the descriptions in paragraph numbers 0102 to 0166 of JP 2012-255128 A can be referred to, and the above-mentioned contents are incorporated in the present specification. As a specific example of an oligoimine-type resin, the following are mentioned, for example. In addition, the resins described in paragraphs 0168 to 0174 of Japanese Patent Laid-Open No. 2012-255128 can be used. [Chemical formula 34]

The dispersant can also be obtained in the form of a commercial item, and as such specific examples, the Disperbyk series (for example, Disperbyk-111, etc.) manufactured by BYK-Chemie GmbH, and the Solsperse series (for example, the Solsperse series manufactured by Boyd & Moore Executive Search K.K.) Solsperse76500 etc.) etc. In addition, the pigment dispersants described in paragraphs 0041 to 0130 of JP 2014-130338 A can also be used, and the contents are incorporated in this specification. Moreover, the resin which has the said acid group, a polymerizable polymer, etc. can also be used as a dispersing agent. Moreover, the resin demonstrated as the said dispersing agent can also be used for the application other than a dispersing agent. For example, it can also be used as an adhesive.

When the composition of the present invention contains other resins, the content of the other resins is preferably 1 to 50% by mass in the total solid content of the composition of the present invention. The upper limit is preferably 45 mass % or less, more preferably 40 mass % or less. The lower limit is preferably 2 mass % or more, more preferably 3 mass % or more, and even more preferably 5 mass % or more. Moreover, when containing 2 or more types of other resins, it is preferable that these total amounts fall into the said range. Moreover, the composition of this invention can also contain other resin substantially. When the composition of the present invention does not substantially contain other resins, the content of the other resins in the total solid content of the composition of the present invention is preferably 0.1 mass % or less, more preferably 0.05 mass % or less, and does not contain Excellent. Moreover, it is preferable that the total content of the said compound which has a curable property and other resin is 5-50 mass % in the total solid content of the composition of this invention. The lower limit is preferably 8% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 45 mass % or less, more preferably 40 mass % or less. Moreover, when 2 or more types of other resins are contained, it is preferable that the total amount of these is in the said range.

<<Solvent>> The composition of the present invention contains a solvent. The solvent is preferably an organic solvent. The solvent is not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition.

As an example of an organic solvent, the following organic solvent is mentioned, for example. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. , butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g. methyl methoxyacetate, methoxyacetate) Ethoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxypropionate (such as methyl 3-oxypropionate, Ethyl 3-oxypropionate, etc. (eg methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate etc.), alkyl 2-oxypropionate (such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (such as 2-methoxypropionate) Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-oxopropionate Methyl-2-methylpropanoate and ethyl 2-oxy-2-methylpropanoate (such as methyl 2-methoxy-2-methylpropanoate, 2-ethoxy-2-methylpropanoate ethyl propionate, etc.), methyl pyruvate (methyl pyruvate), ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate (Methyl 2 -oxobutanoate), ethyl 2-oxobutanoate, etc. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. As ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are mentioned, for example. As aromatic hydrocarbons, toluene, xylene, etc. are mentioned preferably, for example. In addition, 3-methoxy-N,N-dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide are also preferred from the viewpoint of improving solubility. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

In the present invention, it is preferable to use a solvent with a small metal content as the solvent. It is preferable that the metal content in a solvent is 10 mass ppb (parts per billion) or less, for example. A solvent with a metal content of parts per trillion (parts per trillion) can be used as needed, such a high-purity solvent is provided by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015). As a method of removing impurities such as metals from the solvent, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter can be mentioned. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may also contain isomers (compounds with the same number of atoms but different structures). In addition, only one type of isomer may be contained, or a plurality of types may be contained.

The content of peroxide in the organic solvent used in the present invention is preferably 0.8 mmol/L or less, and it is more preferably substantially free of peroxide.

The content of the solvent is preferably such an amount that the solid content concentration (total solid content) of the composition is 5 to 50% by mass. The upper limit is preferably 45 mass % or less, more preferably 40 mass % or less. The lower limit is preferably 8% by mass or more, and more preferably 10% by mass or more.

Moreover, it is preferable that the composition of this invention does not contain an environmental regulation substance substantially from a viewpoint of environmental regulation. In addition, in the present invention, substantially no environmental regulation substance means that the content of the environmental regulation substance in the composition is 50 mass ppm or less, preferably 30 mass ppm or less, more preferably 10 mass ppm or less, and 1 mass ppm or less Excellent. Examples of the environmental regulation substances include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, and the like. These works are based on REACH (Registration Evaluation Authorization and Restriction of Chemicals) rules, PRTR (Pollutant Release and Transfer Register) law, VOC (Volatile Organic Compounds) regulations, etc. and are recorded in them, and strictly stipulate the dosage and usage. These compounds may be used as a solvent in the production of each component and the like used in the composition of the present invention, and may be mixed into the composition as a residual solvent. From the viewpoint of human safety and environmental protection, it is better to reduce these substances as much as possible. As a method of reducing the environmental regulation substance, there is a method of reducing the amount of the environmental regulation substance by distilling off the environmental regulation substance from the reaction system by heating and depressurizing the reaction system so as to be equal to or higher than the boiling point of the environmental regulation substance. In addition, when a small amount of environmental regulation substances are distilled off, it is also useful to boil together with a solvent having the same boiling point as the solvent in order to improve the efficiency. In addition, when a compound having radical polymerizability is contained, in order to suppress intermolecular crosslinking due to radical polymerization reaction during the removal by distillation under reduced pressure, a polymerization inhibitor or the like may be added and removed by distillation under reduced pressure. These distillation removal methods can be performed at any stage of the stage of raw materials, the stage of products obtained by reacting the raw materials (for example, the resin solution after polymerization and the polyfunctional monomer solution), or the stage of mixing these compounds to obtain a composition. implement.

<<Photopolymerization initiator>> The composition of the present invention can further contain a photopolymerization initiator. In particular, when the composition of the present invention contains a compound having an ethylenically unsaturated bond group, it is preferable to contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light from the ultraviolet region to the visible region are preferred. Preferably, the photopolymerization initiator is a photoradical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a three-hole skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, etc. Oxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, α-amino ketone compounds, and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is selected from the group consisting of trihalomethyl three well compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine compounds, Phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyl compounds The compounds among the oxadiazole compounds and the 3-aryl-substituted coumarin compounds are preferred, and the compounds selected from the group consisting of oxime compounds, α-hydroxy ketone compounds, α-amino ketone compounds and acylphosphine compounds are more preferred, Oxime compounds are further preferred. Excellent hardenability can be obtained by using an oxime compound as a photopolymerization initiator. In addition, even when the composition is stored for a long time in a low temperature environment, a film in which defects are further suppressed can be produced. The reason why such an effect can be obtained is presumed to be as follows. The metal azo pigment A contained in the composition of the present invention contains two or more types of metal ions, but depending on the type of metal ions, the configuration of the metal azo compound (metal complex) composed of the above-mentioned anions and metal ions different. For example, when it is Cu ²⁺ , it forms a metal complex with a planar configuration, and when it is Zn ²⁺ , it forms a metal complex with a regular octahedral configuration. Therefore, in a composition containing a solvent or the like, the metal azo pigment A is presumed to exist in an unstable state with little association, and it is presumed that the metal azo pigment A tends to aggregate easily when the composition is stored. In addition, in particular, when the content of nickel ions (Ni ²⁺ ) in the metal azo pigment A is small or the metal azo pigment A does not contain nickel ions, it is presumed that the state is unstable in terms of energy, and it is presumed that the composition is stored. Metal azo pigment A tends to aggregate more easily. However, it is presumed that by blending the oxime compound, the oxime compound functions as a chelating agent by coordinating with the metal azo pigment A, and as a result, it is presumed that the metal azo pigment A can be stabilized, thereby being more effective. Agglomeration of metal azo pigment A and the like are suppressed. Therefore, even when the composition is stored in a low temperature environment for a long period of time, it is estimated that a film in which defects are suppressed can be produced.

Commercially available products of the α-hydroxyketone compound include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (the above, manufactured by BASF Corporation). As a commercial item of an α-amino ketone compound, IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (the above are manufactured by BASF Corporation), etc. are mentioned. As a commercial item of an acylphosphine compound, IRGACURE-819, DAROCUR-TPO (the above are manufactured by BASF Corporation), etc. are mentioned.

Examples of the oxime compound include compounds described in JP 2001-233842 A, compounds described in JP 2000-080068 A, compounds described in JP 2006-342166 A, J.C.S. Perkin II ( Compounds described in J.C.S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232) , the compound described in JP 2000-066385 A, the compound described in JP 2000-080068 A, the compound described in JP 2004-534797 A, JP 2006-342166 A The compounds described in JP 2017-019766 A, the compounds described in JP 6065596 A, the compounds described in International Publication WO2015/152153, the compounds described in International Publication WO2017/051680 compounds, etc. Specific examples of the oxime compound include, for example, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-acetoxyiminobutane-2-one. Aminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzyl Oxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyloxyimino-1 -Phenylpropan-1-one, etc. Commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (the above, manufactured by BASF), TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR- PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arkls NCI-930, Adeka OptoMer N-1919 (from photopolymerization of Japanese Patent Laid-Open No. 2012-014052) Starter 2) (above, manufactured by ADEKA CORPORATION).

In addition, as the oxime compound other than the above, the compounds described in JP-A No. 2009-519904 in which the oxime is linked to the N-position of the carbazole ring, and the U.S. Patent No. Compounds described in Gazette 7626957, compounds described in JP 2010-015025 A and U.S. Patent Publication No. 2009-292039 in which nitro groups are introduced into pigment sites, ketoximes described in International Publication WO 2009/131189 Compounds, compounds described in U.S. Patent No. 7,556,910 that contain a triple-well skeleton and an oxime skeleton in the same molecule, and Japanese Patent Laid-Open No. 2009-221114 having a maximum absorption at 405 nm and good sensitivity to a g-ray light source compounds, etc.

In the present invention, an oxime compound having a perylene ring can also be used as a photopolymerization initiator. As a specific example of the oxime compound which has a perylene ring, the compound described in Unexamined-Japanese-Patent No. 2014-137466 is mentioned.

In the present invention, an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples include compounds OE-01 to OE-75 described in International Publication WO2015/036910.

In the present invention, as a photopolymerization initiator, an oxime compound having at least one benzene ring of a carbazole ring serving as a skeleton of a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication WO2013/083505.

In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include the compounds described in JP 2010-262028 A, compound 24 and compounds 36 to 40 described in JP 2014-500852 A, and JP 2013-A Compound (C-3) and the like described in Gazette No. 164471.

In the present invention, an oxime compound having a nitro group can also be used as a photopolymerization initiator. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include those described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012, and paragraphs 0070 to 0079 of JP 2014-137466 A The compounds described, the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION), and the like.

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

[化學式36]

[Chemical formula 35]

[Chemical formula 36]

The oxime compound is preferably a compound having an absorption maximum in the wavelength range of 350-500 nm, and more preferably a compound having an absorption maximum in the wavelength range of 360-480 nm. In addition, the oxime compound is preferably a compound having high absorbance at 365 nm and 405 nm.

From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferable to measure at a concentration of 0.01 g/L by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Corporation) using an ethyl acetate solvent.

In the present invention, a bifunctional or trifunctional or more photopolymerization initiator can also be used. By using such a photopolymerization initiator, two or more radicals are generated from one molecule of the photopolymerization initiator, so that good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the solubility in a solvent or the like is improved due to the decrease in crystallinity, and precipitation is not easy to occur over time, so that the temporal stability of the composition can be improved. Specific examples of the bifunctional or trifunctional or more than trifunctional photopolymerization initiators include JP 2010-527339 A, JP 2011-524436 A, International Publication WO 2015/004565 A, JP 2016-A Dimers of oxime compounds described in paragraphs 0417 to 0412 of Japanese Patent Publication No. 532675, paragraphs 0039 to 0055 of International Publication No. WO2017/033680, and compounds (E) and compounds described in Japanese Patent Application Publication No. 2013-522445 (G), Cmpd1 to 7 described in International Publication WO2016/034963, the oxime ester-based photoinitiator described in paragraph No. 0007 of JP 2017-523465 A, and JP 2017-167399 A. The photoinitiators described in paragraphs 0020 to 0033, the photopolymerization initiators (A) described in paragraphs 0017 to 0026 of JP-A No. 2017-151342, and the like.

When the composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator A is preferably 0.1 to 30% by mass in the total solid content of the composition. The lower limit is, for example, more preferably 0.5 mass % or more, and even more preferably 1 mass % or more. For example, the upper limit is more preferably 20 mass % or less, and even more preferably 10 mass % or less. Moreover, it is preferable that content of a photopolymerization initiator is 1-200 mass parts with respect to 100 mass parts of said metal azo pigments. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 100 parts by mass or less, and more preferably 80 parts by mass or less. Moreover, when an oxime compound is used as a photopolymerization initiator, it is preferable that content of an oxime compound is 1-200 mass parts with respect to 100 mass parts of said metal azo pigments A. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 100 parts by mass or less, and more preferably 80 parts by mass or less. In this aspect, the effect of the present invention described above tends to be obtained more remarkably. The composition of the present invention may contain one type of photopolymerization initiator, or may contain two or more types. When two or more types of photopolymerization initiators are contained, it is preferable that the total amount of them is in the above-mentioned range.

<<Polyfunctional thiol>> The composition of the present invention can contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups. The polyfunctional thiol is used together with the above-mentioned photopolymerization initiator to function as a chain transfer agent in the radical polymerization process after irradiation with light to generate a sulfur group that is not easily hindered by oxygen polymerization, so that the composition can be improved. sensitivity. In particular, the SH group is preferably a polyfunctional aliphatic thiol bonded to an aliphatic group such as a methylene group or an ethylene group.

Examples of polyfunctional thiols include hexyl dithiol, decane dithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithioacetate, and ethylene glycol dithioacetate. Thioacetate, ethylene glycol dithiopropionate, trimethylolpropane trithioacetate, trimethylolpropane trithiopropionate, trimethylolethane tris(3-mercaptobutyrate) ), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), neotaerythritol tetrathioacetate, neotaerythritol tetrathiopropionic acid Esters, neotaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), trimercaptopropionate tris(2-hydroxyethyl) isocyanurate, 1,4- Dimethylmercaptobenzene, 2､4､6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. Moreover, the compound of the following structure can also be mentioned.

[Chemical formula 37]

The content of the polyfunctional thiol is preferably 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.1 to 10% by mass relative to the total solid content of the composition of the present invention. The composition of this invention may contain 1 type of polyfunctional thiol, and may contain 2 or more types. When two or more types of polyfunctional thiols are contained, it is preferable that the total amount of these be in the above-mentioned range.

式（syn1）中，P表示色素結構，L表示單鍵或連結基，X表示酸基、鹼性基或鄰苯二甲醯亞胺基，m表示1以上的整數，n表示1以上的整數，m為2以上時，複數個L及X可以彼此不同，n為2以上時，複數個X可以彼此不同。<<Pigment Derivative>> The composition of the present invention can contain a pigment derivative. According to this aspect, it is possible to form a film in which spectral fluctuations with respect to temperature changes are suppressed. Examples of the pigment derivatives include compounds having a structure in which a part of the pigment is substituted with an acid group, a basic group, a phthalimide group, or the like. The pigment derivative is preferably a compound represented by the following formula (syn1). [Chemical formula 38]

In formula (syn1), P represents a pigment structure, L represents a single bond or a linking group, X represents an acid group, a basic group or a phthalimide group, m represents an integer of 1 or more, and n represents an integer of 1 or more , when m is 2 or more, a plurality of L and X may be different from each other, and when n is 2 or more, a plurality of X may be different from each other.

The pigment structure represented by P in the formula (syn1) is selected from the group consisting of pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, quinoline pigment structure, quinacridone pigment structure, isoindoline pigment structure, isoindoline pigment structure Dolinone pigment structure, anthraquinone pigment structure, dianthraquinone pigment structure, benzoisoindole pigment structure, thiazine indigo pigment structure, azo pigment structure, quinoline yellow pigment structure, phthalocyanine pigment structure, naphthalocyanine At least one of pigment structure, dioxazine pigment structure, perylene pigment structure, peronene pigment structure, benzimidazolone pigment structure, benzothiazole pigment structure, benzimidazole pigment structure and benzoxazole pigment structure is compared Preferably, at least one selected from the group consisting of pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, quinacridone pigment structure and benzimidazolone pigment structure is further preferred, and pyrrolopyrrole pigment structure is particularly preferred.

In the formula (syn1), the linking group represented by L includes a hydrocarbon group, a heterocyclic group, -NR-, -SO ₂ -, -S-, -O-, -CO-, -COO-, - OCO- or a group consisting of these combinations. R 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. Moreover, it may be a group combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 10. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a single ring or a fused ring. The condensation number of the fused ring is preferably 2-8, more preferably 2-4. A nitrogen atom, a sulfur atom, and an oxygen atom are mentioned as a hetero atom of the ring which comprises a heterocyclic group, A nitrogen atom is preferable.

In formula (syn1), X represents an acid group, a basic group or a phthalimide group. As an acid group represented by X, a carboxyl group, a sulfo group, a carboxylic acid amine group, a sulfonic acid amine group, an imidic acid group, etc. are mentioned. As the carboxylic acid amine group, a group represented by -NHCOR ^X1 is preferable. As the sulfonic acid amine group, a group represented by -NHSO ₂ R ^X2 is preferable. As the imidic acid group, a group represented by -SO ₂ NHSO ₂ R ^X3 , -CONHSO ₂ R ^X4 , -CONHCOR ^X5 or -SO ₂ NHCOR ^X6 is preferable. R ^X1 to R ^X6 each independently represent a hydrocarbon group or a heterocyclic group. The hydrocarbon group and the heterocyclic group represented by R ^X1 to R ^X6 may have a substituent. As a substituent, the above-mentioned substituent T is mentioned, a halogen atom is preferable, and a fluorine atom is more preferable. An amino group is mentioned as a basic group represented by X. The amine group is preferably a group represented by -NR ¹⁰⁰ R ¹⁰¹ . R ¹⁰⁰ and R ¹⁰¹ each independently represent a hydrogen atom, a hydrocarbon group or a heterocyclic group. The hydrocarbon group and the heterocyclic group represented by R ¹⁰⁰ and R ¹⁰¹ may have a substituent. As a substituent, the above-mentioned substituent T can be mentioned. The phthalimide group represented by X may be unsubstituted or may have a substituent. As a substituent, the above-mentioned substituent T can be mentioned.

In formula (syn1), m is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 2. In formula (syn1), n is preferably 1 to 4, more preferably 1 to 3, and further preferably 1 to 2.

As a pigment derivative, the compound of the following structure is mentioned. In the following structural formula, Me represents a methyl group, and Ph represents a phenyl group. In addition, as pigment derivatives, Japanese Patent Laid-Open No. 56-118462, Japanese Patent Laid-Open No. 63-264674, Japanese Patent Laid-Open No. 1-217077, Japanese Patent Laid-Open No. 3-009961, Japanese Patent Laid-Open No. 3-009961, Japanese Patent Laid-Open No. 3-026767, Japanese Patent Laid-Open No. 3-153780, Japanese Patent Laid-Open No. 3-045662, Japanese Patent Laid-Open No. 4-285669, Japanese Patent Laid-Open No. 6-145546, Japanese Patent Laid-Open No. 6-212088 , Japanese Patent Laid-Open No. 6-240158, Japanese Patent Laid-Open No. 10-30063, Japanese Patent Laid-Open No. 10-195326, Paragraph Nos. 0086 to 0098 of International Publication WO2011/024896, and International Publication No. WO2012/102399 Paragraph Nos. 0063 to 0094, Paragraph No. 0082 of International Publication WO2017/038252, and Japanese Patent No. 5299151. [Chemical formula 39]

When the composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass relative to 100 parts by mass of the pigment contained in the composition. Moreover, it is preferable that content of a pigment derivative is 1-30 mass parts with respect to 100 mass parts of metal azo pigments A, and 3-20 mass parts is more preferable. The composition of the present invention may contain only one type of pigment derivative, or may contain two or more types. When two or more kinds of pigment derivatives are contained, it is preferable that the total amount of these is in the above-mentioned range.

<<surfactant>> The composition of the present invention can contain a surfactant. Regarding the surfactant, the descriptions in Paragraph Nos. 0238 to 0245 of International Publication WO2015/166779 can be referred to, and the contents are incorporated in the present specification. Examples of the surfactant include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants, and the like, and fluorine-based surfactants are preferred. The composition of the present invention contains a fluorine-based surfactant, whereby the liquid properties (especially, fluidity) are improved, so that the liquid saving property can be further improved. Moreover, a film with small thickness unevenness can also be formed.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass. The fluorine-based surfactant having the fluorine content in this range is effective in terms of uniformity of the thickness of the coating film and liquid saving.

Examples of the fluorine-based surfactant include those described in paragraphs 0060 to 0064 of JP-A No. 2014-041318 (corresponding to paragraphs 0060-0064 of International Publication WO 2014/017669), Japanese Patent Laid-Open Publication No. 0060-0064 The surfactants and the like described in paragraphs 0117 to 0132 of the 2011-132503 publication. Moreover, as a commercial item of a fluorine-based surfactant, MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS-330 (above, manufactured by DIC CORPORATION), FLUORAD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC-1068 , SC-381, SC-383, S-393, KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA SOLUTIONS INC.), etc.

In addition, as the fluorine-based surfactant, an acrylic compound having a molecular structure of a functional group containing a fluorine atom can be used, and when the acrylic compound is heated, the portion of the functional group containing a fluorine atom is cleaved and the fluorine atom is volatilized. Examples of such fluorine-based surfactants include MEGAFACE DS series (for example, MEGAFACE DS-21) manufactured by DIC CORPORATION.

Further, as the fluorine-based surfactant, a copolymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound can be used. Regarding such a fluorine-based surfactant, the description in JP 2016-216602 A can be referred to, and the content thereof is incorporated into the present specification.

上述化合物的重量平均分子量較佳為3,000～50,000，例如為14,000。上述化合物中表示重複單元的比例之%為莫耳%。As the fluorine-based surfactant, a block polymer can be used. As a block polymer, the compound described in Unexamined-Japanese-Patent No. 2011-089090 is mentioned, for example. In addition, as the fluorine-based surfactant, a fluorine-containing copolymer can be used, and the fluorine-containing copolymer includes: a repeating unit derived from a (meth)acrylate compound having a fluorine atom; (meth)acrylate compound repeating unit of more than one) alkeneoxy group (preferably ethylideneoxy group, propylideneoxy group). The following compounds are also exemplified as the fluorine-based surfactant used in the present invention. [Chemical formula 40]

The weight average molecular weight of the above-mentioned compound is preferably 3,000 to 50,000, for example, 14,000. The % representing the ratio of the repeating unit in the above compound is mol%.

Moreover, the fluorine-containing copolymer containing the repeating unit which has an ethylenically unsaturated group in a side chain can be used as a fluorine-type surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP 2010-164965 A, MEGAFACE RS-101, RS-102, RS-718K, RS- 72-K et al. In addition, the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A can also be used as the fluorine-based surfactant.

Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate) compound, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilauryl ether acid ester, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF Corporation), Solsperse 20000 (manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W , D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

The content of the surfactant is preferably 0.001 to 5% by mass in the total solid content of the composition. The upper limit is preferably 3 mass % or less, more preferably 1 mass % or less. The lower limit is preferably 0.05 mass % or more, and more preferably 0.01 mass % or more. The composition of the present invention may contain only one type of surfactant, or may contain two or more types. When two or more types of surfactants are contained, it is preferable that the total amount of these be in the above-mentioned range.

<<Ultraviolet absorber>> The composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triazine compounds, indole compounds can be used. compounds, triazine compounds, etc. For details of these, refer to paragraph numbers 0052 to 0072 of JP 2012-208374 A, paragraph numbers 0317 to 0334 of JP 2013-068814 A, and paragraph numbers of JP 2016-162946 A 0061 to 0080, and these contents are incorporated into this specification. As a specific example of an ultraviolet absorber, the compound etc. of the following structures are mentioned. As a commercial item of an ultraviolet absorber, UV-503 (made by DAITO CHEMICAL CO., LTD.) etc. are mentioned, for example. Moreover, as a benzotriazole compound, the MYUA series (Chemical Industry Daily, February 1, 2016) manufactured by MIYOSHI OIL & FAT CO., LTD. can be mentioned. [Chemical formula 41]

When the composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber in the total solid content of the composition is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly 0.1 to 3% by mass good. The composition of this invention may contain 1 type of ultraviolet absorber, and may contain 2 or more types. When two or more types of ultraviolet absorbers are contained, it is preferable that the total amount of these be in the above-mentioned range.

<<Silane coupling agent>> The composition of the present invention can contain a silane coupling agent. In the present invention, the silane coupling agent refers to a silane compound having a hydrolyzable group and a functional group other than that. In addition, the hydrolyzable group refers to a substituent which can be directly linked to a silicon atom and generate a siloxane bond by at least any one of a hydrolysis reaction and a condensation reaction. As a hydrolyzable group, a halogen atom, an alkoxy group, an acyloxy group, etc. are mentioned, for example, An alkoxy group is preferable. That is, it is preferable that the silane coupling agent is a compound having an alkoxysilyl group. Moreover, as a functional group other than a hydrolyzable group, a vinyl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amine group, a urea group, a thioether group, an isocyanate group, etc. are mentioned, for example , (meth)acryloyl and epoxy groups are preferred. Examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP-A No. 2009-288703 and the compounds described in paragraphs 0056-0066 of JP-A 2009-242604, and these contents are combined. into this manual.

The content of the silane coupling agent is preferably 0.001 to 20 mass %, more preferably 0.01 to 10 mass %, and particularly preferably 0.1 to 5 mass % in the total solid content of the composition of the present invention. The composition of the present invention may contain only one type of silane coupling agent, or may contain two or more types. When two or more types of silane coupling agents are contained, it is preferable that the total amount of these be within the above-mentioned range.

<<Polymerization inhibitor>> It is preferable that the composition of the present invention contains a polymerization inhibitor. The composition of the present invention contains a polymerization inhibitor, whereby even when the composition is stored in a low temperature environment for a long period of time, a film with further suppressed defects can be produced. Although the detailed reason why such an effect can be obtained is not clear, the following reason is presumed. That is, the metal azo pigment A contained in the composition of the present invention contains two or more kinds of metal ions. Therefore, when the composition is stored, it is presumed that the metal azo compounds composed of the above-mentioned anions and metal ions undergo metal exchange with each other. It is presumed that the precipitates are formed, however, by including a polymerization inhibitor, the activation degree of the metal azo compounds is lowered, and metal exchange between the metal azo compounds is less likely to occur. As a result, it is presumed that the above-mentioned effects are obtained.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, tertiary butyl catechol, p-benzoquinone, 4,4' - Thiobis(3-methyl-6-tertiarybutylphenol), 2,2'-methylenebis(4-methyl-6-tertiarybutylphenol), N-nitrosophenyl Hydroxylamine salts (ammonium salts, cerium salts, etc.), etc., 2,2,6,6-tetramethylpiperidine 1-oxyl, etc. When the composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor in the composition is preferably 0.0001 to 1% by mass. The lower limit is preferably 0.0005 mass % or more, and more preferably 0.001 mass % or more. The upper limit is preferably 0.5 mass % or less, more preferably 0.1 mass % or less. The composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more kinds of polymerization inhibitors are contained, it is preferable that the total amount of these be within the above-mentioned range.

<<Other additives>> The composition of the present invention can incorporate various additives, for example, fillers, adhesion promoters, antioxidants, latent antioxidants, thermal polymerization initiators, and the like as necessary. Regarding these additives, reference can be made to the description in paragraph No. 0183 of JP 2012-003225 A (corresponding to paragraph No. 0237 in the specification of US Patent Application Laid-Open No. 2013/0034812 ) and the description in JP 2008-250074 A The descriptions in paragraph numbers 0101 to 0104, 0107 to 0109, etc., and these contents are incorporated into this specification. Moreover, as an antioxidant, a phenol compound, a phosphorus compound (for example, the compound described in the paragraph No. 0042 of Unexamined-Japanese-Patent No. 2011-090147), a thioether compound, etc. can be used, for example. Examples of commercially available products include Adekastab series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-330 manufactured by ADEKA CORPORATION) Wait). Examples of potential antioxidants include compounds whose sites that function as antioxidants are protected by protective groups, and the compounds are heated at 100 to 250°C or heated at 80 to 200°C in the presence of an acid/salt-based catalyst, whereby A compound in which the protective group is removed to function as an antioxidant. Examples of potential antioxidants include compounds described in International Publication No. WO2014/021023, International Publication No. WO2017/030005, and JP 2017-008219 A. As a commercial item, ADEKA ARKLS GPA-5001 (made by ADEKA CORPORATION) etc. are mentioned. As a thermal polymerization initiator, a pinacol compound, an organic peroxide, an azo compound, etc. are mentioned, A pinacol compound is preferable. Examples of the pinacol compound include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diethoxy-1,1,2, 2-Tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4- Methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetrakis(4-methoxyphenyl)ethane, 1,2-bis(trimethylsiloxy) )-1,1,2,2-tetraphenylethane, 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tertiary Butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1 -Hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2- Tetraphenylethane, etc. In addition, regarding the pinacol compound, reference can be made to the descriptions in JP 2014-521772 A, JP 2014-523939 A, and JP 2014-521772 A, and these contents are incorporated into this specification .

The solid content concentration of the composition of the present invention is preferably 5 to 50 mass %. The upper limit is preferably 45 mass % or less, more preferably 40 mass % or less. The lower limit is preferably 8% by mass or more, and more preferably 10% by mass or more.

The viscosity (23° C.) of the composition of the present invention is preferably 1 to 100 mPa·s when, for example, a film is formed by coating. 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.

It does not specifically limit as a container of the composition of this invention, A well-known container can be used. In addition, as the container, it is also preferable to use a multilayer bottle in which the inner wall of the container is constituted by 6 types of 6-layer resins or a bottle in which 6 types of resins have a 7-layer structure for the purpose of suppressing the contamination of impurities into the raw material or the composition. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

The composition of the present invention can be preferably used as a composition for forming an infrared transmission filter

<Method for preparing composition> The composition of the present invention can be prepared by mixing the aforementioned components. When preparing a composition, the composition can be prepared by dissolving or dispersing all the components in a solvent at the same time, or a solution or dispersion in which two or more components of each component are appropriately blended can be prepared in advance as required. These are then mixed to prepare a composition.

In addition, when preparing the composition, it is preferable to include the process of dispersing the pigment. In the process of dispersing pigments, compression, pressing, impact, shearing, cavitation, etc. may be mentioned as the mechanical force used in the dispersion of pigments. Specific examples for carrying out these processes include ball milling, sand milling, roller milling, ball milling, paint stirring, micro-jet, high-speed impeller, sand mixing, jet mixing, high-pressure wet micronization, ultrasonic dispersion, and the like. In addition, in the grinding of the pigment in the sand mill (ball mill), it is preferable to carry out the treatment under the conditions that the grinding efficiency is improved by using beads with a small diameter, increasing the filling rate of the beads, and the like. In addition, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. Also, regarding the process of dispersing pigments and the dispersing machine, the "Encyclopedia of Dispersion Technology, Published by JOHOKIKO CO., LTD., July 15, 2005" and "Suspension (solid/liquid dispersion system) as the center" can be used. The process and dispersing machine described in the actual comprehensive data collection of dispersion technology and industrial application, issued by the Publishing Department of the Management Development Center, October 10, 1978", Japanese Patent Application Laid-Open No. 2015-157893, Paragraph No. 0022. In addition, in the process of dispersing the pigment, the micronization treatment of the pigment may be performed in the salt milling step. For materials, machines, processing conditions and the like used in the salt milling step, for example, the descriptions in Japanese Patent Application Laid-Open No. 2015-194521 and Japanese Patent Application Laid-Open No. 2012-046629 can be referred to.

When preparing the composition, it is preferable to filter the composition with a filter for the purpose of removing foreign matter and reducing defects. The filter can be used without particular limitation as long as it is an existing filter used for filtering purposes or the like. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (for example, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) are used ( Including high-density, ultra-high molecular weight polyolefin resin) and other materials of the filter. Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. When the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For filter pore size values, you can refer to the filter manufacturer's nominal value. As the filter, various filters provided by NIHON PALL LTD. (DFA4201NIEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (for Merly Nippon Mykrolis Corporation), or KITZ MICROFILTER CORPORATION can be used.

Moreover, a filter using a fibrous filter medium as a filter is also preferable. As a fibrous filter medium, polypropylene fiber, nylon fiber, glass fiber, etc. are mentioned, for example. Commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by ROKI TECHNO CO., LTD.

When using filters, you can combine different filters (eg, 1st filter vs. 2nd filter, etc.). At this time, the filtration using each filter may be performed only once, or may be performed twice or more. Also, filters of different pore sizes may be combined within the above-mentioned range. Moreover, the filtration using the 1st filter may be performed only with respect to the dispersion liquid, and after mixing other components, filtration may be performed using the 2nd filter.

<Film> Next, the film of this invention is demonstrated. The film of the present invention is obtained from the composition of the present invention described above. The film of the present invention can be preferably used as an infrared transmission filter.

The film of the present invention satisfies the maximum value within the wavelength range of 400 to 600 nm for the transmittance of light in the thickness direction of the film is 20% or less (preferably 15% or less, more preferably 10% or less) and wavelength 1000 to 1300 nm The minimum value within the range of 70% or more (preferably 75% or more, more preferably 80% or more) is better for spectral characteristics:

More preferably, the film of the present invention satisfies any one of the spectroscopic properties in the following (111) to (113). (111): The maximum value of the transmittance of light in the thickness direction of the film in the wavelength range of 400 to 600 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the film thickness direction The minimum value in the wavelength range of 800-1300nm of the transmittance|permeability of the light above is the aspect which is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, it can be set as a film which can block the light of the range of wavelength 400-600nm, and can transmit the light exceeding a wavelength of 650nm. (112): The maximum value of the transmittance of light in the thickness direction of the film in the wavelength range of 400 to 720 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the film thickness direction The minimum value in the wavelength range of 900-1300nm of the transmittance|permeability of the light above is an aspect which is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, it can be set as a film which can block the light of the range of wavelength 400-750nm, and can transmit the light exceeding wavelength 800nm. (113): The maximum value of the transmittance of light in the thickness direction of the film in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less) in the thickness direction of the film The minimum value in the wavelength range of 1000-1300nm of the transmittance|permeability of light is an aspect which is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, it can be set as a film which can block the light of the range of wavelength 400-830nm, and can transmit the light exceeding wavelength 900nm.

The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. 10.0 μm or less is preferred, 5.0 μm or less is more preferred, 3.0 μm or less is further preferred, 2.5 μm or less is still more preferred, 2.0 μm or less is further preferred, and 1.5 μm or less is particularly preferred. The lower limit of the film thickness is preferably 0.4 μm or more, more preferably 0.5 μm or more, still more preferably 0.6 μm or more, still more preferably 0.7 μm or more, still more preferably 0.8 μm or more, and especially 0.9 μm or more. good.

<The manufacturing method of a film> Next, the manufacturing method of the film of this invention is demonstrated. The film of the present invention can be produced through a step of coating the composition of the present invention.

In the manufacturing method of the film of this invention, it is preferable that a composition is apply|coated on a support body. Examples of the support include substrates made of materials such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, and quartz glass. An organic film, an inorganic film, etc. may be formed on these substrates. As a material of an organic film, the resin demonstrated in the column of the said composition is mentioned, for example. Moreover, the board|substrate which consists of resins can also be used for a support body. In addition, a charge coupled element (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, and the like may be formed on the support. Moreover, the black matrix which isolate|separates each pixel may be formed in a support body. In addition, an undercoat layer may be provided on the support as necessary for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the surface of the 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 it.

As a coating method of the composition, a known method can be adopted. For example, drop coating method (drop casting); slot coating method; spray coating method; roll coating method; spin coating method (spin coating); , the method described in Japanese Patent Laid-Open No. 2009-145395); inkjet (such as on-demand method, piezoelectric method, thermal method), nozzle jetting and other ejection printing, flexographic printing, screen printing, gravure printing, reverse printing Various printing methods such as offset printing and metal mask printing method; transfer method using molds, etc.; nanoimprinting method, etc. It does not specifically limit as coating in inkjet, For example, the method shown in "Inkjet widely used - Unlimited possibilities in Japanese patent-, issued in February 2005, S.B. RESEARCH CO., LTD." can be mentioned. (particularly pages 115 to 133) and JP 2003-262716 A, JP 2003-185831 A, JP 2003-261827 A, JP 2012-126830 A, JP 2006-A The method described in Gazette 169325 and the like. Moreover, it is preferable to carry out the application|coating in a spin-coating method at the rotation speed of 1000-2000 rpm. In addition, regarding the coating in the spin coating method, as described in Japanese Patent Laid-Open No. 10-142603, Japanese Patent Laid-Open No. 11-302413, and Japanese Patent Laid-Open No. 2000-157922, the rotational speed can be increased during the coating process. . In addition, the spin coating process described in "Process Technology and Chemical Preparation of Advanced Color Filters", CMC Publishing Co., Ltd., January 31, 2006 can also be preferably used. Moreover, about the coating method of a composition, the method described in International Publication WO2017/030174 A and International Publication WO2017/018419 A can be exemplified, and these contents are incorporated into the present specification.

The composition layer (coating film) formed by applying the composition may be dried (pre-baking). When the film is fabricated by a low temperature process, prebaking may not be performed. When pre-baking is performed, 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 can be, for example, 50°C or higher, or 80°C or higher. The pre-baking time is preferably 10 to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 220 seconds. The prebaking can be performed using a hot plate, an oven, or the like.

In the manufacturing method of the film, it is also preferable to further include the step of forming a pattern. As a pattern formation method, the pattern formation method using a photolithography method, the pattern formation method using a dry etching method, and the pattern formation method using a photolithography method is preferable. 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 case of pattern formation by photolithography) The pattern formation method by photolithography preferably includes the following steps: the step of exposing the composition layer formed by coating the composition of the present invention in a pattern ( Exposure step); and the step of developing and removing the composition layer of the unexposed portion to form a pattern (development step). According to needs, a step of baking the developed pattern (post-baking step) can also be provided. Hereinafter, each step will be described.

<<Exposure Step>> In the exposure step, the composition layer is exposed in a pattern (exposure step). For example, pattern exposure can be performed by exposing the composition layer through a mask having a predetermined mask pattern using a stepper, a scanner, or the like. Thereby, the exposed part can be hardened. Examples of radiation (light) that can be used for exposure include g-rays, i-rays, and the like. In addition, light having a wavelength of 300 nm or less (preferably, light having a wavelength of 180 to 300 nm) can also be used. As light with a wavelength of 300 nm or less, KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), etc. are mentioned, and KrF rays (wavelength 248 nm) are preferred. The irradiation dose (exposure dose) is, for example, preferably 0.03 to 2.5 J/cm ² , more preferably 0.05 to 1.0 J/cm ² , and most preferably 0.08 to 0.5 J/cm ² . The oxygen concentration at the time of exposure can be appropriately selected. For example, exposure can be performed in the atmosphere, or in a low-oxygen atmosphere with an oxygen concentration of 19 vol % or less (eg, 15 vol %, 5 vol %, substantially oxygen-free), or an oxygen concentration exceeding 21 vol. Exposure is performed under a high oxygen atmosphere (eg, 22 vol%, 30 vol%, 50 vol%) by volume. In addition, the exposure illuminance can be appropriately set, and it is preferably selected from the range of 1000 to 100000 W/m ² . The oxygen concentration and exposure illuminance can be combined with appropriate conditions. For example, the illuminance can be 10,000 W/m ² at an oxygen concentration of 10 vol %, and 20,000 W/m ² at an oxygen concentration of 35 vol %.

<<Development Step>> Next, among the exposed composition layers, the composition layer of the unexposed portion is developed and removed to form a pattern. The development and removal of the composition layer of the unexposed portion can be performed using a developing solution. Thereby, the composition layer of the unexposed part in the exposure step is eluted in the developing solution, and only the photohardened part remains on the support. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, in order to improve the residue removal property, the step of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

The developer is preferably an alkaline aqueous solution obtained by diluting the alkaline agent with pure water. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diethylene glycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium Propylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium 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, metasilicon Inorganic basic compounds such as sodium. Alkali agents Considering the environment and safety, compounds with large molecular weights are preferred. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. In addition, the developer may further contain a surfactant. As a surfactant, the above-mentioned surfactant is mentioned, and a nonionic type surfactant is preferable. From the viewpoints of convenient transportation and storage, the developer can be temporarily manufactured as a concentrated solution, and then diluted to a desired concentration when used. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. Moreover, when an alkaline aqueous solution is used as a developing solution, it is preferable to wash (rinse) with pure water after image development. In addition, it is preferable to perform rinsing by supplying a rinse liquid to the developed composition layer while rotating the support on which the developed composition layer is formed. Moreover, it is also preferable to carry out by moving the nozzle which discharges a rinse liquid from the center part of a support body to the peripheral part of a support body. In this case, when moving from the center portion of the support body of the nozzle to the peripheral portion, the nozzle can be moved by gradually decreasing the moving speed. By rinsing in this way, unevenness in the surface of the rinse can be suppressed. In addition, even if the rotational speed of the support body is gradually decreased while moving from the center portion of the support body to the peripheral portion of the nozzle, the same effect can be obtained.

After image development, heat treatment (post-baking) can also be performed after drying. The post-baking is a heat treatment after development for completely hardening the film. When post-baking is performed, the post-baking temperature is preferably 100 to 240° C., for example. From a viewpoint of film hardening, 200-230 degreeC is more preferable. The post-baking can be carried out by using a heating mechanism such as a hot plate, a convection oven (hot air circulation type dryer), and a high-frequency heater in order to achieve the above-mentioned conditions for the film after development, in a continuous or intermittent manner. carried out.

(In the case of pattern formation by dry etching method) The pattern formation by dry etching method can be performed by a method of hardening a composition layer formed by applying the composition of the present invention on a support to form a hardening A method of forming a patterned photoresist layer on the cured material layer, and then using the patterned photoresist layer as a mask to dry-etch the cured material layer using an etching gas, etc. . Regarding the patterning by the dry etching method, the descriptions in paragraph numbers 0010 to 0067 of JP 2013-064993 A can be referred to, and the contents are incorporated in the present specification.

<Infrared transmission filter> Next, the infrared transmission filter of this invention is demonstrated. The infrared transmissive filter of the present invention has the film of the present invention described above.

The infrared transmission filter of the present invention can also be used in combination with a color filter containing a colorant. A color filter can be manufactured using the coloring composition containing a coloring agent. As the coloring agent, the coloring agent described in the composition of the present invention can be mentioned. The coloring composition can further contain a curable compound, a resin, a photopolymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber, and the like. As for the details of these, the materials described in the composition of the present invention can be listed, and these can be used.

In addition, regarding the aspect of the infrared transmission filter of the present invention, a pixel having the film of the present invention and a pixel selected from the group consisting of red, green, blue, magenta, yellow, cyan, black and colorless are also preferred.

<Solid-state imaging element> The solid-state imaging element of the present invention includes the film of the present invention described above. 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 functions as a solid-state imaging element. For example, the following structures can be mentioned.

The structure is as follows: the support body is provided with a plurality of photodiodes and polysilicon and other transfer electrodes that constitute the light receiving area of the solid-state imaging element, and the photodiode and the transfer electrode are provided with only photodiodes. The light-receiving part opening The light-shielding film composed of tungsten or the like is provided with an element protective film composed of silicon nitride or the like formed so as to cover the entire light-shielding film and the photodiode light-receiving portion, and the element protective film has the film of the present invention. . In addition, it is also possible to have a protective condensing mechanism (for example, a microlens, etc., the same below) on the element protective film, that is, under the film in the present invention (the side close to the support), and on the film in the present invention. It has a structure to protect the condensing mechanism, etc. In addition, the color filter may have a structure in which a film for forming each pixel is embedded in a space partitioned by a spacer such as a grid. In this case, it is preferable that the refractive index of the spacer is lower than that of each pixel. Examples of the imaging device having such a structure include devices described in Japanese Patent Laid-Open No. 2012-227478 and Japanese Patent Laid-Open No. 2014-179577.

<Optical Sensor> The optical sensor of the present invention includes the film of the present invention described above. The structure of the optical sensor is not particularly limited as long as it is a structure that functions as an optical sensor. Hereinafter, an embodiment of the optical 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 region provided on the solid-state imaging element 110 has a near-infrared cut filter 111 and an infrared transmission filter 114 . In addition, the color filter 112 is laminated on the near-infrared cut filter 111 . A microlens 115 is arranged on the incident light hν side of the color filter 112 and the infrared transmission filter 114 . A planarization layer 116 is formed so as to cover the microlenses 115 .

The spectral characteristics of the near-infrared cut filter 111 are selected according to the emission wavelength of the infrared light emitting diode (infrared LED) used. The color filter 112 is a color filter in which a pixel that transmits and absorbs light of a specific wavelength in a visible region is formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter or the like in which red (R), green (G), and blue (B) pixels are formed is used. For example, the descriptions in paragraph Nos. 0214 to 0263 of Japanese Patent Laid-Open No. 2014-043556 can be referred to, and the contents are incorporated into the present specification. The characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used.

In the infrared sensor shown in FIG. 1 , a near-infrared cut-off filter (other near-infrared cut-off filter) different from the near-infrared cut-off filter 111 may be further disposed on the planarization layer 116 . As another near-infrared cut filter, a layer containing copper and/or a dielectric multilayer film etc. are mentioned. As for these details, the above-mentioned ones can be mentioned. Also, as another near-infrared cut filter, a double-pass band filter may be used. [Example]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples unless it deviates from the gist of the present invention. In addition, unless otherwise specified, "part" is a mass basis.

<Measurement of Weight Average Molecular Weight> The weight average molecular weight of the resin was measured by gel permeation chromatography (GPC) under the following conditions. Type of column: Column connecting TOSOH TSkgel Super HZM-H, TOSOH TSkgel Super HZ4000 and TOSOH TSKgel Super HZ2000 Development solvent: Tetrahydrofuran Column temperature: 40°C Flow rate (sample injection amount): 1.0 μL (sample concentration 0.1 mass %) Device name: HLC-8220GPC manufactured by TOSOH CORPORATION Detector: RI (refractive index) detector calibration curve Base resin: Polystyrene resin

<Production of Metal Azo Pigment> (Production of Metal Azo Pigment 1) 46.2 g of disazobarbituric acid and 38.4 g of barbituric acid were added to 1100 g of distilled water at 85°C. Next, an aqueous potassium hydroxide solution was added to this solution to adjust the pH to approximately 5, followed by stirring for 90 minutes to produce an azobarbituric acid precursor. Next, 1500 g of distilled water at 82° C. was added to the azobarbituric acid precursor produced by the above method. Next, 10 g of 30% hydrochloric acid was added by dropwise addition. Next, 79.4 g of melamine was added. Next, a mixture of 0.282 moles of approximately 25% salted zinc solution and 0.0015 moles of approximately 30% salted copper(II) solution was added dropwise. Next, after holding the solution to which these were added at a temperature of 82° C. for 3 hours, KOH was added to adjust the pH to approximately 5.5. Next, the temperature of the solution was raised to 90°C, and 100 g of distilled water was added and diluted while maintaining the temperature of 90°C. Next, after adding 21 g of 30% hydrochloric acid to the solution by dropwise addition, heat treatment was performed at a temperature of 90° C. for 12 hours. Next, a potassium hydroxide aqueous solution was added to the solution after the heat treatment, and the pH was set to approximately 5. Next, the pigment was isolated from the solution on a suction filter, washed, dried in a vacuum oven at 80°C, and then mashed for approximately 2 minutes using a standard laboratory grinder to produce a metal coupler. Nitrogen Pigment 1.

(Production of Metal Azo Pigment 2) 154.1 g of disazobarbituric acid and 128.1 g of barbituric acid were added to 3600 g of distilled water at 85°C. Next, an aqueous potassium hydroxide solution was added to this solution to adjust the pH to approximately 5, followed by stirring for 90 minutes to produce an azobarbituric acid precursor. Next, 5000 g of distilled water at 82° C. was added to the azobarbituric acid precursor produced by the above method. Next, 252.2 g of melamine was added. Next, 0.68 moles of approximately 30% salted nickel (II) solution, 0.02 moles of approximately 30% salted copper (II) solution, and 0.200 moles of approximately 20% salted lanthanum ( III) Mixtures of solutions. Next, after holding the solution to which these were added at 82° C. for 3 hours, KOH was added to adjust the pH to approximately 5.5. Next, the temperature of the solution was raised to 90°C, and 1000 g of distilled water was added and diluted while maintaining the temperature at 90°C. Next, after adding 113 g of 30% hydrochloric acid to the solution by dropwise addition, heat treatment was performed at a temperature of 90° C. for 12 hours. Next, after the heat treatment, an aqueous potassium hydroxide solution was added to the solution to adjust the pH to approximately 5. Next, the pigment was isolated from the solution on a suction filter, washed, dried in a vacuum drying oven at 80°C, and then mashed for approximately 2 minutes using a standard laboratory grinder to produce metal azo Pigment 2.

(Production of Metal Azo Pigment 3) 154.1 g of disazobarbituric acid and 128.1 g of barbituric acid were added to 3600 g of distilled water at 85°C. Next, an aqueous potassium hydroxide solution was added to this solution to adjust the pH to approximately 5, followed by stirring for 90 minutes to produce an azobarbituric acid precursor. Next, 5000 g of distilled water at 82° C. was added to the azobarbituric acid precursor produced by the above method. Next, 252.2 g of melamine was added. Next, 0.70 moles of approximately 30% salted nickel (II) solution, 0.05 moles of approximately 30% salted zinc (II) solution, and 0.167 moles of approximately 20% salted lanthanum ( III) Mixtures of solutions. Next, after holding the solution to which these were added at 82° C. for 3 hours, KOH was added to adjust the pH to approximately 5.5. Next, the temperature of the solution was raised to 90° C., and while maintaining the temperature of 90° C., 1000 g of distilled water was added and diluted. Next, after adding 113 g of 30% hydrochloric acid to the solution by dropwise addition, heat treatment was performed at a temperature of 90° C. for 12 hours. Next, a potassium hydroxide aqueous solution was added to the solution after the heat treatment, and the pH was set to approximately 5. Next, the pigment was isolated from the solution on a suction filter, washed, dried in a vacuum drying oven at 80°C, and then mashed for approximately 2 minutes using a standard laboratory grinder to produce metal azo Pigment 3.

(Production of Metal Azo Pigment 4) 46.2 g of disazobarbituric acid and 38.4 g of barbituric acid were added to 1100 g of distilled water at 85°C. Next, an aqueous potassium hydroxide solution was added to this solution to adjust the pH to approximately 5, followed by stirring for 90 minutes to produce an azobarbituric acid precursor. Next, 5000 g of distilled water at 82° C. was added to the azobarbituric acid precursor produced by the above method. Next, 252.2 g of melamine was added. Next, a mixture of 0.285 moles of approximately 25% nickel salt solution and 0.010 moles of approximately 10% gadolinium (III) salt solution was added dropwise. Next, after holding the solution to which these were added at 82° C. for 3 hours, KOH was added to adjust the pH to approximately 5.5. Next, the temperature of the solution was raised to 90°C, and 1000 g of distilled water was added and diluted while maintaining the temperature of 90°C. Next, after adding 113 g of 30% hydrochloric acid to the solution by dropwise addition, heat treatment was performed at a temperature of 90° C. for 12 hours. Next, a potassium hydroxide aqueous solution was added to the solution after the heat treatment, and the pH was set to approximately 5. Next, the pigment was isolated from the solution on a suction filter, washed, dried in a vacuum drying oven at 80°C, and then mashed for approximately 2 minutes using a standard laboratory grinder to produce metal azo Pigment 4.

<Method of Removing Environmental Regulation Substances by Distillation> (Production Example 1) Production of Polymerizable Monomer D5 Polyfunctional acrylate (KAYARAD DPHA, Nippon Kayaku Co., Ltd.) containing 238 mass ppm of toluene was added to the flask as a residual solvent. manufactured), 50 g of propylene glycol monomethyl ether acetate (PGMEA), and 80 mg of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), and the temperature of the external equipment was set to 90°C to make The pressure inside the flask was gradually reduced from normal pressure to 68 mmHg, and was distilled off under reduced pressure over 4 hours. Then, the weight in the reaction system was adjusted with PGMEA so that it might become 100 g, and the polyfunctional acrylate solution 1 (polymerizable monomer D5) was obtained. The amount of the residual solvent (toluene) contained in the polyfunctional acrylate solution 1 was measured by gas chromatography, and it was confirmed that it was reduced to 11 mass ppm. In addition, peaks derived from polyfunctional acrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) were detected by ¹ H-NMR (nuclear magnetic resonance), and it was confirmed that no crossover caused by radical polymerization occurred. linked reaction.

(Production Example 2) Production of Dispersant C5 50 g of an acrylate compound (ARONIX M-5300, manufactured by TOAGOSEI CO., LTD.) containing 835 mass ppm of toluene, 50 g of PGMEA, and 40 mg of TEMPO were added to a flask as a residual solvent, and the external The equipment temperature was set to 90° C., the pressure inside the flask was gradually reduced from normal pressure to 66 mmHg, and the pressure was distilled off under reduced pressure over 4 hours. Then, the weight in the reaction system was adjusted to 100 g with PGMEA, and the monomer solution 1 was obtained. The amount of the residual solvent (toluene) contained in the monomer solution 1 was measured by gas chromatography analysis, and it was confirmed that it was reduced to 9 mass ppm. In addition, the peak derived from the acrylate compound (ARONIX M-5300, manufactured by TOAGOSEI CO., LTD.) was detected by ¹ H-NMR, and it was confirmed that the crosslinking reaction by radical polymerization did not occur.

Into the three-necked flask, 1044.2 g of ε-caprolactone, 184.3 g of δ-valerolactone, and 71.6 g of 2-ethyl-1-hexanol were introduced to obtain a mixture. Next, the above-mentioned mixture was stirred while blowing in nitrogen. Next, 0.61 g of monobutyltin oxide was added to the mixture, and the obtained mixture was heated to 90°C. After 6 hours, after confirming the disappearance of the peak derived from 2-ethyl-1-hexanol in the mixture using ¹ H-NMR, the mixture was heated to 110°C. After the polymerization reaction was carried out continuously at 110° C. for 12 hours under a nitrogen atmosphere, the disappearance of peaks derived from ε-caprolactone and δ-valerolactone was confirmed by ¹ H-NMR, and the obtained compound was subjected to a GPC method. Molecular weight measurement. After confirming that the molecular weight of the compound reached a desired value, 0.35 g of 2,6-di-butyl-4-methylphenol was added to the mixture containing the above-mentioned compound. After that, 87.0 g of 2-methacryloyloxyethyl isocyanate was added dropwise to the obtained mixture over 30 minutes. After 6 hours elapsed from the end of the dropwise addition, the disappearance of the peak derived from 2-methacryloyloxyethyl isocyanate (MOI) was confirmed by ¹ H-NMR, and PGMEA1387.0 g was added to the mixture to obtain a concentration of 2770 g of 50 mass % macromonomer A-1 solution. The structure of macromonomer A-1 (shown in formula (A-1)) was confirmed by ¹ H-NMR. The weight average molecular weight of the obtained macromonomer A-1 was 6,000. [Chemical formula 42]

A mixture was obtained by adding 120 g of the above-mentioned macromonomer A-1 solution, 280 g of the above-mentioned monomer solution 1, and 266.7 g of PGMEA to the three-necked flask. The above mixture was stirred while blowing in nitrogen. Next, while flowing nitrogen into the flask, the temperature of the mixture was raised to 75°C. Next, 1.65 g of dodecyl mercaptan and 0.83 g of 2,2'-azobis(methyl 2-methylpropionate) (hereinafter also referred to as "V-601") were added to the mixture, and the Polymerization. After the mixture was heated at 75°C for 2 hours, 0.83 g of V-601 was further added to the mixture. After 2 hours, a further 0.83 g of V-601 was added to the mixture. After an additional 2 hours of reaction, the mixture was warmed to 90°C and stirred for 3 hours. By the above operation, the polymerization reaction was completed. After completion of the reaction, 6.0 g of dimethyldodecylamine and 2.46 g of TEMPO were added in an air atmosphere, and then 15.7 g of glycidyl methacrylate was added. After the reaction was continuously performed at 90° C. for 24 hours in an air atmosphere, it was confirmed by the acid value measurement that the reaction was completed. After cooling to 60 degreeC, 2-isocyanatoethyl acrylate (AOI) 15.6g was further added to the obtained mixture, and it was made to react at 60 degreeC for 6 hours. The disappearance of AOI was confirmed by ¹ H-NMR measurement. By adding an appropriate amount of PGMEA to the obtained mixture, a 20 mass % solution of dispersant C-5 was obtained. The obtained resin C-5 had a weight average molecular weight of 25,000, an acid value of 80 mgKOH/mg, and a C=C valence of 0.9 mmol/g. Moreover, when the amount of toluene contained in resin C-5 was measured, it was confirmed that it was 5 mass ppm or less.

[Test Example 1] <Production of Pigment Dispersion Liquid> After mixing the raw materials described in the following Table 1, 230 parts by mass of zirconia beads having a diameter of 0.3 mm were added, and the dispersion treatment was performed by stirring with paint for 5 hours, and filtered by filtration. to separate the beads to produce a pigment dispersion. Numerical values described in the following tables are parts by mass.

[Table 1]

<Preparation of composition> The compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared by mixing the raw materials described in Tables 2 to 5 below. Numerical values described in the following tables are parts by mass.

[Table 2]

[table 3]

[Table 4]

[table 5]

The raw materials described in the above Tables 1 to 5 are as follows.

(Colorant) Metal Azo Pigments 1 to 4: Metal Azo Pigments 1 to 4 above C.I.Pigment Blue 16 IB: Irgaphor Black (manufactured by BASF) PBk32: C.I.Pigment Black 32

[化學式44]

(Near-infrared absorbing dyes) K1, K2, K5, K6, K7, K8, K10: compounds of the following structures. In the following formula, Me represents a methyl group, and Ph represents a phenyl group. K9: FDN-003 (manufactured by YAMADA CHEMICAL CO., LTD.) [Chemical formula 43]

[Chemical formula 44]

(Pigment Derivatives) B1, K3, K4: Compounds of the following structures. In the following structural formula, Ph represents a phenyl group, and Me represents a methyl group. [Chemical formula 45]

(Dispersant) C1: Resin of the following structure (The value noted on the main chain is molar ratio, and the value noted on the side chain is the number of repeating units. Mw=20,000) C2: Resin of the following structure (On the main chain The value of the note is the mole ratio, the value of the note on the side chain is the number of repeating units. Mw=24,000) C3: Resin of the following structure (the value of the note on the main chain is the mole ratio, and the value of the note on the side chain is Number of repeating units. Mw=20,000) C4: BYK2000 (solid content concentration 40% by mass, manufactured by BYK Japan KK) C5: Dispersant produced in Production Example 2 above C5 (solid content concentration 20% by mass) [Chemical formula 46]

(Resin) P1: Resin of the following structure (Mw=11000, the numerical value noted on the main chain is a molar ratio. Me is a methyl group.) P2: Resin of the following structure. (Mw=4400, acid value=95 mgKOH/g, in the following structural formula, M is a phenyl group, and A is a biphenyl tetracarboxylic anhydride residue.) P3: CYCLOMER ACA250 (solid content concentration 45 mass %, manufactured by Daicel Corporation) P4 : Resin with the following structure (Mw=30000, the value in the note on the main chain is molar ratio.) [Chemical formula 47]

D4：下述結構的化合物 [化學式49]

D5：上述製造例1中製造之聚合性單體D5（固體成分濃度50質量%） D6：ARONIX M-520（TOAGOSEI CO., LTD.製）(Polymerizable monomer) D1: Compound of the following structure (a+b+c=3) D2: Compound of the following structure (a+b+c=4) D3: Mixture of compounds of the following structure (a+ Compounds with b+c=5: Compounds with a+b+c=6 = 3:1 (mol ratio) [Chem. 48]

D4: Compound of the following structure [Chemical formula 49]

D5: Polymerizable monomer D5 (solid content concentration: 50% by mass) produced in Production Example 1 above D6: ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.)

(Silane coupling agent) H1: a compound of the following structure (in the following structural formula, Et is an ethyl group) [Chemical formula 50]

I6：Adeka Arkls NCI-831（ADEKA CORPORATION製、肟化合物） I7：IRGACURE-379（BASF公司製、α-胺基酮化合物） I8：日本特表2017-523465號公報的段落號0007中記載之化合物NO.12 I9：日本特開2017-151342號公報的段落號0025中記載之式（2）的化合物 I10：日本特開2017-167399號公報的段落號0031中記載之化合物6 （紫外線吸收劑） L1：下述結構的化合物 [化學式52]

(Photopolymerization initiator) I1 to I5: Compounds of the following structures (oxime compounds) [Chemical formula 51]

I6: Adeka Arkls NCI-831 (manufactured by ADEKA CORPORATION, oxime compound) I7: IRGACURE-379 (manufactured by BASF, α-amino ketone compound) I8: The compound described in paragraph No. 0007 of JP 2017-523465 A NO.12 I9: Compound of formula (2) described in paragraph No. 0025 of JP 2017-151342 A L1: Compound of the following structure [Chemical formula 52]

(polyfunctional thiol) M1: Trimethylolpropane tris(3-mercaptobutyrate)

(Surfactant) F1: The following mixture (Mw=14000). In the following formula, the % representing the ratio of the repeating unit is mol%. [Chemical formula 53]

(Epoxy compound) N1: EHPE3150 (manufactured by Daicel Corporation) (polymerization inhibitor) G1: p-p-methoxyphenol (solvent) J1: propylene glycol monomethyl ether acetate (PGMEA) J2: cyclohexanone J3: 3 -Methoxy-N,N-dimethylpropionamide J4: 3-butoxy-N,N-dimethylpropionamide

<Evaluation of spectroscopic properties> Each composition was applied on a glass substrate using a spin coater so that the film thickness after post-baking reached the film thickness described in the following table, and the composition was applied for 120 seconds using a 100° C. hot plate. Pre-baked. Next, the entire surface of the coating film after prebaking was exposed to i-rays at an exposure amount of 1000 mJ/cm ² , and then post-baking was performed at 220° C. for 5 minutes using a hot plate to form a film. The absorbance and transmittance of the obtained film at wavelengths of 400 to 1300 nm were measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation), and the maximum value of transmittance in the wavelength range of 400 to 600 nm was measured. (Transmittance T1), the minimum value of transmittance within the wavelength range of 1000 to 1300 nm (transmittance T2), the minimum value of absorbance within the wavelength range of 400 to 600 nm (absorbance A), and the minimum value of the absorbance within the wavelength range of 1000 to 1300 nm The ratio of the maximum absorbance (absorbance B), the minimum absorbance in the wavelength range of 400 to 600 nm, and the maximum absorbance in the wavelength range of 1000 to 1300 nm (absorbance A/absorbance B).

<Film thickness uniformity> Each composition was applied on an 8-inch (20.32 cm) silicon wafer by spin coating. Next, it heated at 100 degreeC for 2 minutes using a hotplate. The film thickness of the obtained film was measured using an optical film thickness meter (Filmetrics Japan, Inc., F50), and the difference between the film thickness of the thinnest part and the film thickness of the last part (hereinafter, referred to as film thickness difference) was calculated. The smaller the film thickness difference, the better the film thickness uniformity. 5: The difference in film thickness is 0.02 μm or less. 4: The difference in film thickness is greater than 0.02 μm and not more than 0.03 μm 3: The difference in film thickness is greater than 0.03 μm and not more than 0.04 μm 2: The difference in film thickness is greater than 0.04 μm and not more than 0.05 μm 1: The difference in film thickness is greater than 0.05 μm

<Moisture resistance> Each composition was coated using a spin coater, and the film thickness after post-baking was the film thickness described in the following table on the glass substrate. bake. Next, the entire surface of the pre-baked coating film was exposed to i-rays at an exposure amount of 1000 mJ/cm ² , and then post-baked at 220° C. for 5 minutes using a hot plate to form a film. The obtained film was stored for 300 hours under the conditions of a temperature of 135° C. and a humidity of 85%, and a high-temperature and high-humidity test was performed. The film after the high-temperature and high-humidity test was observed with an optical microscope at a 1 cm square portion, and the number of crystalline defects having a size of 0.5 μm or more was counted to evaluate moisture resistance. 5: The number of defects is 0 4: The number of defects is 1 to 4 3: The number of defects is 5 to 9 2: The number of defects is 10 to 15 1: The number of defects is 16 or more

[Table 6]

As shown in the above table, the examples were excellent in film thickness uniformity and moisture resistance. Moreover, the composition of the Example is excellent in the light shielding property of the light of the wavelength range of 400-600 nm, and can be used suitably as an infrared transmission filter. Moreover, the composition of Examples 1-4 can form the film which blocks the light of the range of wavelength 400-600nm, and can transmit the light exceeding the wavelength of 650nm. Moreover, the composition of Examples 5-13 can form the film which blocks the light of the wavelength range of 400-720 nm, and can transmit the light exceeding the wavelength of 800 nm. Moreover, the composition of Examples 14-25 can form the film which blocks the light of the wavelength range of 400-830 nm, and can transmit the light exceeding the wavelength of 900 nm.

In each example, even if 1 mass %, 2 mass %, 3 mass %, 4 mass % or 5 mass % of tetraphenylethanol is further contained in the total solid content of the composition, the same effect as in each example can be obtained.

[Test Example 2] The compositions of Examples 1 to 25 were applied using a spin coater so that the film thickness after post-baking was the film thickness described in Table 6, respectively, on a silicon wafer, and the composition was applied using a 100° C. hot plate. pre-bake for 120 seconds. Next, the entire surface of the pre-baked coating film was exposed to i-rays at an exposure amount of 1000 mJ/cm ² , and then post-baked at 220° C. for 5 minutes using a hot plate to form a film. Next, the following composition for absorbing layer formation was applied on the surface of the obtained film using a spin coater, and prebaking was performed for 120 seconds using a hot plate at 100°C. Next, the entire surface of the pre-baked coating film was exposed to i-rays at an exposure amount of 1000 mJ/cm ² , and then post-baked at 220° C. for 5 minutes using a hot plate to form an absorption layer, thereby forming laminated body. This laminate can block and transmit light in the same wavelength range as in Test Example 1. Furthermore, light resistance is also excellent.

(Composition for absorbing layer formation) 12 parts by mass of C.I. Pigment Yellow 150, 37 parts by mass of dispersant C5, and 51 parts by mass of PGMEA were added to 230 parts by mass of zirconia beads with a diameter of 0.3 mm, and the mixture was stirred with paint for 5 parts by mass. Dispersion treatment was carried out for 2 hours, and the Yellow Pigment Dispersion was produced by separating the beads by filtration. 35 parts by mass of the obtained Yellow pigment dispersion liquid, 12 parts by mass of resin P1, 4 parts by mass of polymerizable monomer D5, 1.8 parts by mass of photopolymerization initiator I1, and 47.2 parts by mass of PGMEA were mixed to produce absorber A composition for forming a layer.

[Test Example 3] The IR composition was applied on a silicon wafer by a spin coating method so that the film thickness after film formation was 1.0 μm. Next, it heated at 100 degreeC for 2 minutes using a hotplate. Next, exposure was performed through a mask having a Bayer pattern with a square of 2 μm at an exposure amount of 1000 mJ/cm ² using an i-ray stepper exposure apparatus (FPA-3000i5+, manufactured by Canon Inc.). Next, using a 0.3 mass % aqueous solution of tetrapotassium ammonium hydroxide (TMAH), spin immersion development was performed at 23° C. for 60 seconds. After that, 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, a Bayer pattern (near-infrared cut filter) having a square of 2 μm was formed. Next, the Red composition was applied on the Bayer pattern of the near-infrared cut filter by spin coating so that the film thickness after film formation was 1.0 μm. Next, it heated at 100 degreeC for 2 minutes using a hotplate. Next, exposure was performed with an exposure amount of 1000 mJ/cm ² using an i-ray stepper exposure apparatus (FPA-3000i5+, manufactured by Canon Inc.) through a mask having a pattern of 2 μm square. Next, spin immersion development was performed at 23° C. for 60 seconds using a 0.3 mass % aqueous solution of tetrapotassium ammonium hydroxide (TMAH). After that, it was rinsed with a rotary shower, and further rinsed with pure water. Next, patterning of the Red composition was performed on the Bayer pattern of the near-infrared cut filter by heating at 200° C. for 5 minutes using a hot plate. Similarly, patterning of the Green composition and the Blue composition was performed in this order, thereby forming colored patterns of red, green, and blue. Next, the compositions of Examples 14 to 25 were applied on the film formed in the pattern by spin coating so that the film thickness after film formation was 2.0 μm. Next, it heated at 100 degreeC for 2 minutes using a hotplate. Next, exposure was performed with an exposure amount of 1000 mJ/cm ² using an i-ray stepper exposure apparatus (FPA-3000i5+, manufactured by Canon Inc.) through a mask having a pattern of 2 μm square. Next, spin immersion development was performed at 23° C. for 60 seconds using a 0.3 mass % aqueous solution of tetrapotassium ammonium hydroxide (TMAH). After that, it was rinsed with a rotary shower, and further rinsed with pure water. Next, it heated at 200 degreeC for 5 minutes using a hotplate, and formed the film (infrared transmission filter) of the composition of Examples 14-25 in the missing part of the Bayer pattern of a near-infrared cut filter. This was assembled into a solid-state imaging element according to a known method. The obtained solid-state imaging element was irradiated with light from an infrared light emitting diode (infrared LED) light source in a low-illuminance environment (0.001 Lux) to capture an image, and the image performance was evaluated. The subject can be clearly recognized on the image. In addition, the incident angle dependence is good. In addition, the same effect can be obtained even if the infrared transmissive filter realizes the described film thickness by multilayer coating. For example, in the case of Example 14, a coating film may be formed by applying the composition by spin coating several times, and then heating the coating film at 100° C. for 120 seconds, followed by exposure and development, and then at 200° C. The film thickness was adjusted to 2.0 μm by performing a series of operations under heating for 5 minutes.

The Red composition, Green composition, Blue composition, and IR composition used in Test Example 3 are as follows.

(Red composition) The following components were mixed, and after stirring, it was filtered through a nylon filter (manufactured by Pall Corporation) having a pore diameter of 0.45 μm to prepare a Red composition. Red pigment dispersion liquid...51.7 parts by mass resin P1...0.6 parts by mass polymerizable monomer D6...0.6 parts by mass Photopolymerization initiator I1...0.4 parts by mass Surfactant F1...0.2 parts by mass UV absorber ( UV-503, manufactured by DAITO CHEMICAL CO., LTD.) ……0.3 parts by mass PGMEA ……46.6 parts by mass

(Green composition) The following components were mixed, and after stirring, it was filtered through a nylon filter (manufactured by Pall Corporation) having a pore diameter of 0.45 μm to prepare a Green composition. Green pigment dispersion liquid... 73.7 parts by mass resin P1... 0.3 parts by mass polymerizable monomer D6... 1.2 parts by mass photopolymerization initiator I1... 0.6 parts by mass Surfactant F1... 0.2 parts by mass ultraviolet absorber ( UV-503, manufactured by DAITO CHEMICAL CO., LTD.) ...... 0.5 parts by mass PGMEA ...... 23.5 parts by mass

(Blue composition) The following components were mixed, and after stirring, it was filtered through a nylon filter (manufactured by Pall Corporation) having a pore diameter of 0.45 μm to prepare a Blue composition. Blue Pigment Dispersion Liquid 44.9 parts by mass Resin P1 ...... 2.1 parts by mass Polymerizable monomer D6 ...... 2.2 parts by mass Photopolymerization initiator I1 ...... 0.8 parts by mass Surfactant F1 ...... 0.2 parts by mass Ultraviolet absorber (UV- 503, manufactured by DAITO CHEMICAL CO., LTD.) ... 0.3 parts by mass PGMEA ... 49.8 parts by mass

(IR Composition) The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Pall Corporation) having a pore diameter of 0.45 μm to prepare an IR composition. IR pigment dispersion liquid... 85 parts by mass of polymerizable monomer D6... 1.8 parts by mass of resin P1... 1.1 parts by mass of photopolymerization initiator I1... 0.9 parts by mass of surfactant F1... 0.2 parts by mass of polymerization inhibitor ( p-p-methoxyphenol) ... 0.001 parts by mass PGMEA ... 11.0 parts by mass

Pigment dispersion liquids used for the Red composition, Green composition, Blue composition and IR composition are as follows.

･Red pigment dispersion liquid was ball milled (zirconia bead diameter: 0.3 mm) into 9.6 parts by mass of CI Pigment Red 254, 4.3 parts by mass of CI Pigment Yellow 139, and 6.8 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK-Chemie GmbH) , The mixed solution of 79.3 parts by mass of PGMEA was mixed and dispersed for 3 hours. After that, dispersion treatment was further performed at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Beryu Corporation) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion liquid.

･Green pigment dispersion liquid was ball milled (zirconia bead diameter: 0.3 mm) into 6.4 parts by mass of CI Pigment Green 36, 5.3 parts by mass of CI Pigment Yellow 150, and 5.2 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK-Chemie GmbH) , PGMEA was 83.1 parts by mass of the mixed solution, which was mixed and dispersed for 3 hours. After that, dispersion treatment was further performed at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Beryu Corporation) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion liquid.

･Blue Pigment Dispersion Liquid: 9.7 parts by mass of CI Pigment Blue 15:6, 2.4 parts by mass of CI Pigment Violet 23, and 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK-Chemie GmbH) by ball milling (zirconia bead diameter: 0.3 mm). The mixed liquid containing 82.4 parts by mass of PGMEA was mixed and dispersed for 3 hours. After that, dispersion treatment was further performed at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Beryu Corporation) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion liquid.

･The IR pigment dispersion is composed of 6.25 parts by mass of near-infrared absorbing pigment K2, 1.25 parts by mass of pigment derivative K4, 6 parts by mass of dispersant C3, and 86.5 parts by mass of PGMEA by ball milling (zirconia bead diameter: 0.3 mm). The mixed solution was mixed and dispersed for 3 hours. After that, dispersion treatment was further performed at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Beryu Corporation) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain an IR pigment dispersion.

110‧‧‧Solid-state imaging element 111‧‧‧Near infrared cut-off filter 112‧‧‧Color filter 114‧‧‧Infrared transmission filter 115‧‧‧Micro lens 116‧‧‧Planarization layer hn‧‧‧Irradiation light

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

110‧‧‧Solid-state imaging element

111‧‧‧NIR cut-off filter

112‧‧‧Color Filters

114‧‧‧Infrared transmission filter

115‧‧‧Micro lens

116‧‧‧Planarization layer

hν‧‧‧Irradiation light

Claims (15)

A composition comprising: a metal azo pigment containing at least one anion, two or more metal ions and A melamine compound; a colorant, as a colorant other than the metal azo pigment, having an absorption maximum in the wavelength range of 400nm to 700nm; and at least one compound selected from compounds with ethylenically unsaturated bonds and cyclic ether groups The compound, the ratio A/B of the minimum value A of the absorbance within the wavelength range of 400nm to 600nm and the maximum value B of the absorbance within the wavelength range of 1000nm to 1300nm of the composition is 4.5 or more, and the metal azo pigment is a metal At least one of azo pigment Az1~metal azo pigment Az4, the metal azo pigment Az1 contains the anion, at least metal ions containing Zn ²⁺ and Cu ²⁺ , melamine compound, the metal azo pigment Az2 contains the anion , a metal ion containing Ni ²⁺ , Zn ²⁺ and at least one other metal ion Me2, the melamine compound, the metal ion Me2 is selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ²⁺ , Nd ³⁺ , Sm ²⁺ , Sm ³⁺ , Eu ²⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm ³⁺ , Yb ²⁺ , Yb ³⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ²⁺ , Ti ³⁺ , Zr ²⁺ , Zr ³⁺ , V ²⁺ , V ³⁺ , Nb ³⁺ At least one of , Cr ³⁺ , Mo ²⁺ , Mo ³⁺ , Mn ²⁺ , Cd ²⁺ and Pb ²⁺ , the metal azo pigment Az3 contains the anion, Ni ²⁺ , Cu ²⁺ and at least 1 A metal ion of other metal ions Me3, the melamine compound, the metal ion Me3 is selected from La ^{3 +} , Ce ³⁺ , Pr ³⁺ , Nd ²⁺ , Nd ³⁺ , Sm ²⁺ , Sm ³⁺ , Eu ²⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Yb ²⁺ , Yb ³⁺ , Er ³⁺ , Tm ³⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Mn ²⁺ , Y ³⁺ , Sc ³⁺ , Ti ²⁺ , Ti ³⁺ , Nb ³⁺ , Mo ²⁺ , Mo ³⁺ , V ²⁺ , V ³⁺ , Zr ²⁺ , Zr ³⁺ , Cd ²⁺ , at least one of Cr ³⁺ , Pb ²⁺ and Ba ²⁺ , the metal azo pigment Az4 contains the anion, the metal ion containing Ni ²⁺ and the metal ion Me4a, the melamine compound, The metal ion Me4a is selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ²⁺ , Nd ³⁺ , Sm ²⁺ , Sm ³⁺ , Eu ²⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , At least one of Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm ³⁺ , Yb ²⁺ and Yb ³⁺ ;

In the formula, R ¹ and R ² are each independently OH or NR ⁵ R ⁶ , R ³ and R ⁴ are each independently =O or =NR ⁷ , and R ⁵ to R ⁷ are each independently a hydrogen atom or an alkyl group. The composition of claim 1, wherein the metal azo pigment Az1 is based on 1 mole of the total metal ions in the metal azo pigment and contains a total of 95 mol % to 100 mol % of Zn ^{2 +} and Cu ²⁺ , the metal azo pigment Az2 contains 75 mol % to 99.5 mol % of Zn ²⁺ and Cu ²⁺ in total based on 1 mol of the total metal ions in the metal azo pigment, and contains 0.5 mol% to 25 mol% of the metal ion Me2, the metal azo pigment Az3 is based on 1 mol of the total metal ions in the metal azo pigment and contains 70 mol% to 99.5 mol% of Cu in total ²⁺ and Ni ²⁺ , and contains 0.5 mol% to 30 mol% of the metal ion Me3, the metal azo pigment Az4 is based on 1 mol of the total metal ions in the metal azo pigment, and contains a total of 95 mol% %~100 mol% of Ni ²⁺ and the metal ion Me4a, and the molar ratio of Ni ²⁺ to the metal ion Me4a is Ni ²⁺ : metal ion Me4a=1:1~19:1. The composition of claim 1, wherein the metal azo pigment is the metal azo pigment Az1. The composition of claim 1, wherein the metal ion Me2 is selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Tb ³⁺ , Ho ³⁺ and Sr At least one of ²⁺ , the metal ion Me3 is at least one selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Tb ³⁺ , Ho ³⁺ and Sr ²⁺ , The metal ion Me4a is at least one selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Tb ³⁺ and Ho ³⁺ . The composition according to claim 1, wherein the molar ratio of Zn ²⁺ to Cu ²⁺ in the metal azo pigment Az1 is Zn ²⁺ :Cu ²⁺ =199:1~1:15. The composition according to any one of items 1 to 5 of the claimed scope, wherein the melamine compound in the metal azo pigment is a compound represented by the following formula (II);

In the formula, R ¹¹ to R ¹³ are each independently a hydrogen atom or an alkyl group. The composition according to any one of items 1 to 5 of the scope of the application, wherein The colorant having an absorption maximum in the wavelength range of 400 nm to 700 nm contains at least one selected from a blue colorant and a violet colorant. The composition according to any one of claims 1 to 5 of the claimed scope, further comprising a near-infrared absorbing dye. The composition according to claim 8, wherein the near-infrared absorbing dye has an absorption maximum in the wavelength range of 800nm-900nm. The composition according to claim 8, wherein the near-infrared absorbing dye is selected from the group consisting of pyrrolopyrrole compounds, cyanine compounds, squaraine compounds, phthalocyanine compounds, naphthalocyanine compounds and ketonium compounds At least 1 species. The composition according to any one of items 1 to 5 of the claimed scope, which is used in an infrared transmission filter. A film obtained by using the composition described in any one of items 1 to 11 of the claimed scope. An infrared transmission filter having the film described in item 12 of the patent application scope. A solid-state imaging element having the film described in claim 12 of the scope of application. An optical sensor having the film described in item 12 of the patent application scope.

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