JPWO2019107015A1 - Compositions, films, infrared transmission filters, solid-state image sensors and optical sensors - Google Patents

Abstract

Provided are a composition, a film, an infrared transmission filter, a solid-state image sensor, and an optical sensor capable of producing a film having high film thickness uniformity and suppressing the occurrence of foreign matter defects in a high temperature and high humidity environment. The composition comprises a particular metal azo pigment, a coloring material having an absorption maximum in the wavelength range of 400-700 nm, a compound having an ethylenically unsaturated bond group and / or a compound having a cyclic ether group. The composition has an A / B of 4.5 or more, which is the ratio 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. The above-mentioned 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 thereof, two or more kinds of metal ions, and a melamine compound.

Description

The present invention relates to a composition used for producing an infrared transmission filter or the like, and a film using the above-mentioned composition. The present invention also relates to an infrared transmission filter having the above-mentioned film, a solid-state image sensor, and an optical sensor.

The yellow pigment is used as a coloring material for producing a basic color or a complementary color in a color filter or the like. As one kind of yellow pigment, a nickel azobarbiturate complex such as Color Index (CI) Pigment Yellow 150 is known.

Further, Patent Documents 1 to 4 describe inventions relating to 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 are said to have improved coloring performance with respect to conventional nickel azobarbiturate complexes and the like.

Japanese Unexamined Patent Publication No. 2017-171912 Japanese Unexamined Patent Publication No. 2017-171913 JP-A-2017-171914 JP-A-2017-171915

The present inventor has diligently studied a film using a metal azo pigment containing azobarbituric acid, two or more metal ions and a melamine compound, and when this film is exposed to a high temperature and high humidity environment, It was found that foreign matter defects tend to occur.

Further, when a film is produced using a composition containing a coloring material containing azobarbituric acid, two or more kinds of metal ions and a melamine compound, the film thickness is increased when the composition is applied to form a coating film. It was found that variations are likely to occur.

Therefore, an object of the present invention is to provide a composition capable of producing a film having high film thickness uniformity and suppressing the occurrence of foreign matter defects in a high temperature and high humidity environment. Another object of the present invention is to provide a film, an infrared transmission filter, a solid-state image sensor, and an optical sensor using this composition.

式中、Ｒ^１およびＲ^２はそれぞれ独立して、ＯＨまたはＮＲ^５Ｒ^６であり、
Ｒ^３およびＲ^４はそれぞれ独立して、＝Ｏまたは＝ＮＲ^７であり、
Ｒ^５〜Ｒ^７はそれぞれ独立して、水素原子またはアルキル基である。
＜２＞ 金属アゾ顔料は、上記アニオンと、Ｚｎ^２＋およびＣｕ^２＋を少なくとも含む金属イオンと、メラミン化合物とを含む、＜１＞に記載の組成物。
＜３＞ 金属アゾ顔料中の全金属イオンの１モルを基準として、Ｚｎ^２＋およびＣｕ^２＋を合計で９５〜１００モル％含有する、＜２＞に記載の組成物。
＜４＞ 金属アゾ顔料中のＺｎ^２＋とＣｕ^２＋とのモル比が、Ｚｎ^２＋：Ｃｕ^２＋＝１９９：１〜１：１５である、＜２＞または＜３＞に記載の組成物。
＜５＞ 金属アゾ顔料におけるメラミン化合物が、下記式（ＩＩ）で表される化合物である、＜１＞〜＜４＞のいずれかに記載の組成物；

式中Ｒ^１１〜Ｒ^１３は、それぞれ独立して水素原子またはアルキル基である。
＜６＞ 波長４００〜７００ｎｍの範囲に吸収極大を有する色材は、青色着色剤および紫色着色剤から選ばれる少なくとも１種を含む、＜１＞〜＜５＞のいずれかに記載の組成物。
＜７＞ 更に、近赤外線吸収色素を含む、＜１＞〜＜６＞のいずれかに記載の組成物。
＜８＞ 近赤外線吸収色素は波長８００〜９００ｎｍの範囲に吸収極大を有する、＜７＞に記載の組成物。
＜９＞ 近赤外線吸収色素はピロロピロール化合物、シアニン化合物、スクアリリウム化合物、フタロシアニン化合物、ナフタロシアニン化合物、および、クロコニウム化合物から選ばれる少なくとも１種である、＜７＞または＜８＞に記載の組成物。
＜１０＞ 赤外線透過フィルタ用である、＜１＞〜＜９＞のいずれかに組成物。
＜１１＞ ＜１＞〜＜１０＞のいずれかに記載の組成物を用いて得られる膜。
＜１２＞ ＜１１＞に記載の膜を有する赤外線透過フィルタ。
＜１３＞ ＜１１＞に記載の膜を有する固体撮像素子。
＜１４＞ ＜１１＞に記載の膜を有する光センサ。According to the study of the present inventor, it has been found that the above object can be achieved by using the composition described later, and the present invention has been completed. The present invention provides:
<1> A metal azo pigment containing at least one anion selected from an azo compound represented by the following formula (I) and an azo compound having a telecommunication structure thereof, two or more metal ions, and a melamine compound. ,
Color materials other than the above metal azo pigments, which have an absorption maximum in the wavelength range of 400 to 700 nm, and
A composition comprising a compound having an ethylenically unsaturated bond group and at least one compound selected from a compound having a cyclic ether group.
A composition having an A / B of 4.5 or more, which is the ratio of the minimum absorbance A in the wavelength range of 400 to 600 nm to the maximum absorbance B in the wavelength range of 1000 to 1300 nm.

In the equation, R ¹ and R ² are independently OH or NR ⁵ R ⁶ , respectively.
R ³ and R ⁴ are independently = O or = NR ⁷ , respectively.
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 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 all metal ions in the metal azo pigment.
<4> The composition according to <2> or <3>, wherein the molar ratio of Zn ²⁺ and 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);

In the formula, R ^{11 to} R ¹³ are independently hydrogen atoms or alkyl groups.
<6> The composition according to any one of <1> to <5>, wherein the coloring material 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>, further containing a near-infrared absorbing dye.
<8> The composition according to <7>, wherein the near-infrared absorbing dye has an absorption maximum in the wavelength range of 800 to 900 nm.
<9> The composition according to <7> or <8>, wherein the near-infrared absorbing dye is at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, and a croconium compound. ..
<10> The composition according to any one of <1> to <9>, which is for an infrared transmission filter.
<11> A film obtained by using the composition according to any one of <1> to <10>.
<12> An infrared transmission filter having the film according to <11>.
<13> A solid-state image sensor having the film according to <11>.
<14> An optical sensor having the film according to <11>.

According to the present invention, there are provided a composition, a film, an infrared transmission filter, a solid-state image sensor, and an optical sensor capable of producing a film having high film thickness uniformity and suppressing the occurrence of foreign matter defects in a high temperature and high humidity environment. be able to.

It is a schematic diagram which shows one Embodiment of an optical sensor.

The contents of the present invention will be described in detail below.
In the present specification, "~" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either. ) Acryloyl "represents both acryloyl and / or methacryloyl.
In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-equivalent values in gel permeation chromatography (GPC) measurements.
In the present 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 the present specification, infrared rays refer to light (electromagnetic waves) having a wavelength of 700 to 2500 nm.
In the present specification, the total solid content means the total mass of all the components of the composition excluding the solvent.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..

<Composition>
The composition of the present invention comprises at least one anion selected from an azo compound represented by the formula (I) described later and an azo compound having a tautomeric structure thereof, two or more metal ions, and a melamine compound. Including metal azo pigments and
Color materials other than the above metal azo pigments, which have an absorption maximum in the wavelength range of 400 to 700 nm, and
A composition comprising a compound having an ethylenically unsaturated bond group and at least one compound selected from a compound having a cyclic ether group.
The composition is characterized in that A / B, which is the ratio 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.

When the present inventor diligently studied a metal azo pigment containing azobarbituric acid, two or more kinds of metal ions and a melamine compound, the metal azo pigment tends to have low hardness and is easy to be finely divided. It was found that an active surface was formed and tended to aggregate easily. Further, when the content of nickel ion (Ni ²⁺ ) in the metal azo pigment is low, or when the metal azo pigment does not contain nickel ion, it is presumed that the metal azo pigment is in an energetically unstable state, and the metal azo pigment is present. It is presumed that they tend to aggregate more easily. Further, although this metal azo pigment contains two or more kinds of metal ions, the arrangement of the metal azo compound (metal complex) composed of the above-mentioned anion and the metal ion differs depending on the type of the metal ion. For example, in the case of Cu ²⁺ , a metal complex having a planar conformation is formed, and in the case of Zn ²⁺ , a metal complex having a regular octahedral conformation is formed. 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 pigments tend to promote aggregation in a high temperature and high humidity environment.
According to the study of the present inventor, a color material other than the above-mentioned metal azo pigment and the above-mentioned metal azo pigment having an absorption maximum in the wavelength range of 400 to 700 nm (hereinafter, also referred to as other color materials). In combination with, a composition having an A / B of 4.5 or more, which is the ratio of the minimum absorbance A in the wavelength range of 400 to 600 nm and the maximum absorbance B in the wavelength range of 1000 to 1300 nm. As a result of preparation, it was surprisingly found that even if the film obtained by using this composition is exposed to a high temperature and high humidity environment, foreign matter defects are unlikely to occur. It is speculated that the reason why such an effect was obtained is that the coloring material other than the metal azo pigment was able to interact with the azo site of the metal azo pigment to improve the stability of the metal azo pigment. it is conceivable that.

On the other hand, it was found that when a composition containing the above-mentioned metal azo pigment and another coloring material is applied to form a film, the film thickness tends to vary. It is considered that the cause is that the dispersed state of the metal azo pigment in the composition is destabilized due to the influence of other coloring materials and the like. Further, it was found that the composition having the above-mentioned spectral characteristics tends to contain a relatively large amount of coloring material, so that the dispersed state of the metal azo pigment tends to be more unstable and the film thickness tends to vary. It was. However, the composition of the present invention is at least one selected from the above-mentioned metal azo pigment, other coloring materials, a compound having an ethylenically unsaturated bond group, and a compound having a cyclic ether group. By containing the seed compound, such variation in film thickness could be effectively suppressed. It is presumed that the reason why such an effect is obtained is as follows. That is, when the composition contains a compound having an ethylenically unsaturated bond group, the compound having an ethylenically unsaturated bond group interacts with the pigment active surface (particularly the azo site) of the metal azo pigment to form ethylene. It is presumed that the compound having a sex unsaturated bond group is adsorbed on the surface of the metal azo pigment, and the metal azo pigment can be stabilized. Further, when the composition contains a compound having a cyclic ether group, it is presumed that the cyclic ether group coordinates with the metal azo pigment and acts as a chelating agent, and as a result, the metal azo pigment is stabilized. It is speculated that it can be done. Therefore, according to the composition of the present invention, it is presumed that the uniformity of the film thickness is improved.

Therefore, according to the composition of the present invention, it is possible to produce a film having high film thickness uniformity and suppressing the occurrence of foreign matter defects in a high temperature and high humidity environment. Further, the film obtained by using this composition has a high light-shielding property of light having a wavelength of 400 to 600 nm and an excellent light transmission property having a wavelength of 1000 to 1300 nm, and therefore can be preferably used as an infrared transmission filter or the like. .. Further, the metal azo pigment contained in the composition of the present invention is a coloring material having high coloring power. Therefore, by using the composition of the present invention, it is possible to form a film having a high light-shielding property in the wavelength range of 400 to 600 nm even if the film thickness is thin. Further, since the content of the coloring material in the composition can be reduced, the degree of freedom in formulation design is also excellent.

The composition of the present invention has an A / B of 4.5 or more, which is the ratio of the minimum absorbance A in the wavelength range of 400 to 600 nm to the maximum absorbance B in the wavelength range of 1000 to 1300 nm. It is preferably .5 or more, more preferably 15 or more, and even more preferably 30 or more. When the above-mentioned absorbance ratio is 4.5 or more, it is possible to form a film having a high light-shielding property of light having a wavelength of 400 to 600 nm and an excellent light transmission property having a wavelength of 1000 to 1300 nm.

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

In addition, the absorbance can be measured using a conventionally known spectrophotometer. The measurement condition of the absorbance is not particularly limited, but the absorbance in the wavelength range of 1000 to 1300 nm is adjusted so that the minimum value A of the absorbance in the wavelength range of 400 to 600 nm is 0.1 to 3.0. It is preferable to measure the maximum value B. By measuring the absorbance under such conditions, the measurement error can be further reduced. The method of adjusting the minimum absorbance A in the wavelength range of 400 to 600 nm to be 0.1 to 3.0 is not particularly limited. For example, when measuring the absorbance in the state of a solution, a method of adjusting the optical path length of the sample cell can be mentioned. Further, when measuring the absorbance in the state of a film, a method of adjusting the film thickness and the like can be mentioned.

The composition of the present invention preferably satisfies any of the following spectral characteristics (1) to (3), and produces a film in which the occurrence of foreign matter defects is further suppressed in a high temperature and high humidity environment. For the reason that it is easy, it is more preferable to satisfy the spectral characteristics of (2) or (3), and it is further preferable to satisfy the spectral characteristics of (3). It is presumed that the reason why such an effect is obtained is as follows. A film capable of blocking light up to a longer wavelength side can be formed in the order of (1), (2), and (3), but in order to block light up to a longer wavelength side, another coloring material can be formed. A coloring material that absorbs light at a longer wavelength may be used, or a near-infrared absorbing dye may be contained. It is presumed that such a material often has a broad conjugated system and tends to easily interact with the metal azo pigment. Therefore, it is presumed that the metal azo pigment can be more stabilized, and as a result, a film in which the generation of foreign matter defects in a high temperature and high humidity environment is further suppressed can be produced.

(1): A1 / B1, which is the ratio of the minimum absorbance A1 in the wavelength range of 400 to 600 nm and the maximum absorbance B1 in the wavelength range of 800 to 1300 nm, is 4.5 or more and 7.5 or more. Is more preferable, 15 or more is more preferable, and 30 or more is further more preferable. According to this aspect, it is possible to block light in the wavelength range of 400 to 600 nm to form a film capable of transmitting light having a wavelength exceeding 650 nm.
(2): A2 / B2, which is the ratio of the minimum absorbance A2 in the wavelength range of 400 to 720 nm and the maximum absorbance B2 in the wavelength range of 900 to 1300 nm, is 4.5 or more and 7.5 or more. Is more preferable, 15 or more is more preferable, and 30 or more is further more preferable. According to this aspect, it is possible to block light in the wavelength range of 400 to 750 nm and form a film capable of transmitting light having a wavelength exceeding 800 nm.
(3): A3 / B3, which is the ratio of the minimum absorbance A3 in the wavelength range of 400 to 830 nm and the maximum absorbance B3 in the wavelength range of 1000 to 1300 nm, is 4.5 or more and 7.5 or more. Is more preferable, 15 or more is more preferable, and 30 or more is further more preferable. According to this aspect, it is possible to block light in the wavelength range of 400 to 830 nm and form a film capable of transmitting light having a wavelength exceeding 900 nm.

The composition of the present invention has a film thickness after drying of 10.0 μm or less (preferably 5.0 μm or less, more preferably 3.0 μm or less, still more preferably 2.5 μm or less, and even more preferably. Is 2.0 μm or less, particularly preferably 1.5 μm or less, and the lower limit value can be 0.4 μm or more, 0.5 μm or more, and 0.6 μm or more. It can be 0.7 μm or more, 0.8 μm or more, 0.9 μm or more.) When the film is formed, at least the above-mentioned film thickness is at least. In one case, the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 600 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the wavelength is 1000 to 1300 nm. It is preferable that the minimum value in the range satisfies the spectral characteristics of 70% or more (preferably 75% or more, more preferably 80% or more).

Further, the composition of the present invention preferably satisfies any of the following spectral characteristics (11) to (13), and provides a film in which the generation of foreign matter defects is further suppressed in a high temperature and high humidity environment. It is more preferable that the spectral characteristics of (12) or (13) are satisfied, and it is further preferable that the spectral characteristics of (13) are satisfied because it is easy to manufacture.

(11): The film thickness after drying using the composition of the present invention is 0.4 to 3.0 μm (preferably 0.5 to 2.5 μm, more preferably 0.6 to 2.0 μm, still more preferably. When a film of 0.7 to 1.5 μm) is produced, the maximum value of the light transmittance 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 minimum value of the light transmittance in the thickness direction of the film in the wavelength range of 800 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
(12): The film thickness after drying using the composition of the present invention is 0.5 to 5.0 μm (preferably 0.6 to 3.0 μm, more preferably 0.7 to 2.5 μm, still more preferably. When a film of 0.8 to 2.0 μm is produced, the maximum value of the light transmittance 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 minimum value of the light transmittance in the thickness direction of the film in the wavelength range of 900 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
(13): The film thickness after drying using the composition of the present invention is 0.6 to 10 μm (preferably 0.7 to 5.0 μm, more preferably 0.8 to 3.0 μm, still more preferably 0. When a film of 9 to 2.5 μm) is produced, the maximum value of the light transmittance 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%). The minimum value of the light transmittance in the thickness direction of the film in the wavelength range of 1000 to 1300 nm 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 anion selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure thereof, two or more metal ions, and a melamine compound. Contains metal azo pigment A.

In the equation, R ¹ and R ² are independently OH or NR ⁵ R ⁶ , R ³ and R ⁴ are independent, = O or = NR ⁷ , and R ^{5 to} R ⁷ are respectively. Independently, it is a hydrogen atom or an alkyl group. The alkyl group represented by R ^{5 to} R ⁷ preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear. The alkyl group may have a substituent. Examples of the substituent include a substituent T described later, and a halogen atom, a hydroxy group, an alkoxy group, a cyano group and an amino group are preferable.

In formula (I), R ¹ and R ² are preferably OH. Further, it is preferable that R ³ and R ⁴ are = O.

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

In the formula, R ^{11 to} R ¹³ are independently hydrogen atoms or alkyl groups. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear. The alkyl group may have a substituent. Examples of the substituent include the Substituent T described later, and a hydroxy group is preferable. Preferably, at least one of R ¹¹ to R ¹³ is a hydrogen ^atom, more preferably all of R 11 ^{to R 13} is a hydrogen atom.

The metal azo pigment A is represented by a melamine compound (preferably represented by the formula (II)) per mole of at least one anion selected from the azo compound represented by the formula (I) and the azo compound having a telecommunication structure thereof. Compound) is preferably contained in an amount of 0.05 to 4 mol, more preferably 0.5 to 2.5 mol, and even 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, and more preferably 150 m ² / g or less. The specific surface area value of the metal azo pigment A is measured according to the BET (Brunauer, Emmet and Teller) method and according to the DIN 66131: determination of the special surface area of solids by gas adsorption (gas adsorption). Is the value.

(Substituent T)
Examples of the above-mentioned substituent T include the following groups. Alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms), alkenyl groups (preferably alkenyl groups having 2 to 30 carbon atoms), alkynyl groups (preferably alkynyl groups having 2 to 30 carbon atoms), aryl groups (preferably aryl groups). Aryl groups with 6 to 30 carbon atoms), amino groups (preferably amino groups with 0 to 30 carbon atoms), alkoxy groups (preferably alkoxy groups with 1 to 30 carbon atoms), aryloxy groups (preferably 6 to 30 carbon atoms). 30 aryloxy groups), heteroaryloxy groups, acyl groups (preferably acyl groups having 1 to 30 carbon atoms), alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 30 carbon atoms), aryloxycarbonyl groups (preferably aryloxycarbonyl groups). Is an aryloxycarbonyl group having 7 to 30 carbon atoms), a heteroaryloxycarbonyl group, an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), and an alkoxy. A carbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoyl group (preferably having 0 to 30 carbon atoms). Sulfamoyl group), carbamoyl group (preferably carbamoyl group having 1 to 30 carbon atoms), alkylthio group (preferably alkylthio group having 1 to 30 carbon atoms), arylthio group (preferably arylthio group having 6 to 30 carbon atoms), hetero Arylthio groups (preferably 1 to 30 carbon atoms), alkylsulfonyl groups (preferably 1 to 30 carbon atoms), arylsulfonyl groups (preferably 6 to 30 carbon atoms), heteroarylsulfonyl groups (preferably 1 to 1 carbon atoms). 30), alkylsulfinyl groups (preferably 1 to 30 carbon atoms), arylsulfinyl groups (preferably 6 to 30 carbon atoms), heteroarylsulfinyl groups (preferably 1 to 30 carbon atoms), ureido groups (preferably carbon atoms). 1-30), hydroxy group, carboxyl group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imic acid group, mercapto group, halogen atom, cyano group, alkylsulfino group, arylsulfino group , Hydradino group, imino group, heteroaryl group (preferably 1 to 30 carbon atoms). These groups may have additional substituents if they are further substitutable groups. As a further substituent, the group described in Substituent T described above can be mentioned.

The metal azo pigment A preferably has a metal complex formed by at least one anion selected from the azo compound represented by the formula (I) and the azo compound having a tautomeric structure thereof and a metal ion. For example, in the case of a divalent metal ion Me, the above anion and the metal ion Me can form a metal complex having a structure represented by the following formula (Ia). The metal ion Me may be bonded via a nitrogen atom in the tautomerization notation of the formula (Ia) to form a complex.

Preferred embodiments of the metal azo pigment A include the metal azo pigments of the following aspects (Az1) to (Az4), in which the effect of the present invention can be more remarkably obtained and the spectral characteristics can be further improved. For this reason, it is preferable that the metal azo pigment according to the embodiment (Az1).

(Az1) An at least one anion selected from the azo compound represented by the above formula (I) and an azo compound having a reciprocal structure thereof, a metal ion containing at least Zn ²⁺ and Cu ²⁺ , and a melamine compound. A metal azo pigment in an embodiment. In this aspect, it is preferable to contain Zn ²⁺ and Cu ²⁺ in a total amount of 95 to 100 mol%, more preferably 98 to 100 mol%, based on 1 mol of all metal ions of the metal azo pigment. It is more preferably contained in an amount of 99.9 to 100 mol%, and particularly preferably 100 mol%. The molar ratio of Zn ²⁺ to Cu ²⁺ in the metal azo pigment is preferably Zn ²⁺ : Cu ²⁺ = 199: 1-1: 15, more preferably 19: 1 to 1: 1. , 9: 1 to 2: 1, more preferably. Further, in this embodiment, the metal azo pigment may further contain divalent or trivalent metal ions other than Zn ²⁺ and Cu ²⁺ (hereinafter, also referred to as metal ion Me1). As the metal ion Me1 ^{is, 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⁺ , 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 2+, Ca 2+, Sr 2+, Mn 2+ And Y ^3+, preferably at least one selected from Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Tb ³⁺ , Ho ^3+. And at least one selected from Sr ^2+, and particularly preferably at least one selected from Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ and Co ³⁺ . The content of the metal ion Me1 is preferably 5 mol% or less, more preferably 2 mol% or less, and 0.1 mol% or less, based on 1 mol of all metal ions of the metal azo pigment. It is more preferable to have.

(Az2) The metal ion contains at least one anion selected from the azo compound represented by the above formula (I) and the azo compound having a telecommunication structure thereof, a metal ion, and a melamine compound, and the metal ion is Ni ^2+. , Zn ²⁺ and at least one additional metal ion Me2, the metal ion Me2 is 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⁺ , Mo ³⁺ , Mn ²⁺ , Cd ²⁺ , and Pb ²⁺ , which are at least one metal azo pigment. Metal ions Me2 ^{is, La 3+, Ce 3+, Pr} 3+, Nd 3+, Sm 3+, Eu 3+, Gd 3+, Tb 3+, Dy 3+, Ho 3+, Er 3+, Tm 3+, Yb 3+, Mg 2+, Ca 2+, It is preferably at least one selected from Sr ²⁺ , Y ³⁺ , and Mn ²⁺ , and at least one selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Tb ³⁺ , Ho ³⁺ , and Sr ^2+. More preferably it is a seed. In this embodiment, Zn ²⁺ and Ni ²⁺ are contained in a total amount of 75 to 99.5 mol% and the metal ion Me2 is 0.5 to 25 mol% based on 1 mol of all metal ions of the metal azo pigment. preferably contains contains 78 to 95 mol% of ^{Zn 2+} and ^{Ni 2+} in total, and a metal ion Me2 more preferably contains 5 to 22 mol%, the ^{Zn 2+} and ^{Ni 2+} in total 82 to It is more preferable to contain 90 mol% and 10 to 18 mol% of the metal ion Me2. The molar ratio of Zn ²⁺ to Ni ²⁺ in the metal azo pigment is preferably Zn ²⁺ : Ni ²⁺ = 90: 3 to 3:90, more preferably 80: 5 to 5:80. , 60:33 to 33:60, more preferably.

(Az3) The metal ion contains at least one anion selected from the azo compound represented by the above formula (I) and the azo compound having a telecommunication structure thereof, a metal ion, and a melamine compound, and the metal ion is Ni ^2+. , Cu ²⁺ and at least one additional metal ion Me3, the metal ion Me3 is 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+, A metal azo pigment of the embodiment which is at least one selected from Mo ³⁺ , V ²⁺ , V ³⁺ , Zr ²⁺ , Zr ³⁺ , Cd ²⁺ , Cr ³⁺ , Pb ²⁺ and Ba ²⁺ . Metal ions Me3 ^{is, 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 2+, Ca 2+, It is preferably at least one selected from Sr ²⁺ , Mn ²⁺ , and Y ³⁺ , and at least one selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Tb ³⁺ , Ho ³⁺ , and Sr ^2+. More preferably it is a seed. In this embodiment, Cu ²⁺ and Ni ²⁺ are contained in a total amount of 70 to 99.5 mol% and metal ion Me3 is 0.5 to 30 mol% based on 1 mol of all metal ions of the metal azo pigment. preferably contains contains 75-95 mol% of ^{Cu 2+} and ^{Ni 2+} in total, and 80 it is more preferable to contain a metal ion Me3 5 to 25 mol%, the ^{Cu 2+} and ^{Ni 2+} in total It is more preferable to contain 90 mol% and 10 to 20 mol% of the metal ion Me3. The molar ratio of Cu ²⁺ to Ni ²⁺ in the metal azo pigment is preferably Cu ²⁺ : Ni ²⁺ = 42: 1-1: 42, more preferably 10: 1 to 1:10. It is more preferably 3: 1 to 1: 3.

(Az4) The metal ion contains at least one anion selected from the azo compound represented by the above formula (I) and the azo compound having a telecommunication structure thereof, a metal ion, and a melamine compound, and the metal ion is Ni ^2+. and it comprises a metal ion Me4a, metal ions Me4a is ^{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+, A metal azo pigment of the embodiment which is at least one selected from 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⁺ , Tm ³⁺ and Yb ^3+. It is preferably at least one selected from La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Tb ³⁺ and Ho ³⁺ . In this embodiment, Ni ²⁺ and metal ion Me4a are preferably contained in a total amount of 95 to 100 mol%, more preferably 98 to 100 mol%, based on 1 mol of all metal ions of the metal azo pigment. , 99.9 to 100 mol% is more preferable, and 100 mol% is particularly preferable. The molar ratio of Ni ²⁺ to the metal ion Me4a in the metal azo pigment is preferably Ni ²⁺ : metal ion Me4a = 1: 1 to 19: 1, preferably 2: 1 to 4: 1. More preferably, it is 2.3: 1-3: 1. Further, in this embodiment, the metal azo pigment may further contain a metal ion other than Ni ²⁺ and the metal ion Me4a (hereinafter, also referred to as a metal ion Me4b). Metal ion Me4b includes 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⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Y ³⁺ , Mn It is preferably at least one selected from ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Cu ²⁺ , Zn ²⁺ and Al ^3+, and is preferably Sr ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Cu. More preferably, it is at least one selected from ²⁺ , Zn ²⁺ and Al ³⁺ . The content of the metal ion Me4b is preferably 5 mol% or less, more preferably 2 mol% or less, and 0.1 mol% based on 1 mol of all metal ions of the metal azo pigment. The following is more preferable.

The metal azo pigment A is a metal azo compound composed of at least one anion and a metal ion selected from the azo compound represented by the above formula (I) and the azo compound having a remutable structure thereof, and a melamine compound. It is preferable that an adduct is formed with (preferably the compound represented by the above formula (II)). The accretionary prism is understood to mean a molecular assembly. The bonds between these molecules may be, for example, by intermolecular interaction, by Lewis acid-base interaction, or by coordination bond or chain bond. Further, the adduct may have a structure such as an inclusion compound (clathrate) in which the guest molecule is incorporated in the lattice constituting the host molecule. Further, the adduct may have a structure such as a composite interlayer crystal (including an interstitial compound). A composite interlayer crystal is a chemical non-stoichiometric crystal compound consisting of at least two elements. Further, the adduct may be a mixed substitution crystal in which the two substances form a co-crystal and the atom of the second component is located at the position of the regular lattice of the first component.

The metal azo pigment used in the present invention may be a physical mixture or a chemical composite compound. Preferably, it is a physical mixture.

Preferred examples of the physical mixture in the case of the metal azo pigment of the above-mentioned aspect (Az1) include the following (Az1-1) and (Az1-2). Further, when the metal azo pigment of the aspect (Az1) is a chemical composite compound, it is preferable that Zn ²⁺ , Cu ²⁺ and any additional metal ion Me1 are incorporated in a common crystal lattice.
(Az1-1) An adduct 1a of a metal azo compound composed of the anion and Zn ²⁺ and a melamine compound, an adduct of a metal azo compound composed of the anion and Cu ²⁺ , and a melamine compound. 1b physical mixture.
(Az1-2) In the physical mixture of (Az1-1), a physical mixture further containing an adduct 1c of a metal azo compound composed of the anion and the metal ion Me1 and a melamine compound.

Preferred examples of the physical mixture in the case of the metal azo pigment of the above-mentioned aspect (Az2) include the following (Az2-1). When the metal azo pigment of the aspect (Az2) is a chemical composite compound, it is preferable that Ni ²⁺ , Zn ²⁺ and the metal ion Me2 are incorporated in a common crystal lattice.
(Az2-1) An adduct 2a of a metal azo compound composed of the anion and Ni ²⁺ and a melamine compound, an adduct of a metal azo compound composed of the anion and Zn ²⁺ , and a melamine compound. A physical mixture containing 2b, an adduct 2c of a metal azo compound composed of the anion and the metal ion Me2, and a melamine compound.

Preferred examples of the physical mixture in the case of the metal azo pigment of the above-mentioned aspect (Az3) include the following (Az3-1). Further, when the metal azo pigment of the aspect (Az3) is a chemical composite compound, it is preferable that Ni ²⁺ , Cu ²⁺ and the metal ion Me3 are incorporated in a common crystal lattice.
(Az3-1) An adduct 3a of a metal azo compound composed of the anion and Ni ²⁺ and a melamine compound, an adduct of a metal azo compound composed of the anion and Cu ²⁺ , and a melamine compound. A physical mixture containing 3b, an adduct 3c of a metal azo compound composed of the anion and the metal ion Me3, and a melamine compound.

Preferred examples of the physical mixture in the case of the metal azo pigment of the above-mentioned aspect (Az4) include the following (Az4-1) and (Az4-2). Further, when the metal azo pigment of the aspect (AZ4) is a chemical composite compound, it is preferable that Ni ²⁺ , the metal ion Me4a and any additional metal ion Me4b are incorporated in a common crystal lattice.
(Az4-1) Addition of a metal azo compound composed of the anion and Ni ²⁺ , an adduct 4a of the melamine compound, a metal azo compound composed of the anion and the metal ion Me4a, and a melamine compound. Physical mixture of body 4b.
(Az4-2) A physical mixture containing an adduct 4c of a metal azo compound composed of the anion, a metal ion Me4b, and a melamine compound in the physical mixture of (Az4-1).

The metal azo pigment according to the embodiment (Az1) described above is a compound of formula (III) or a mutant thereof, in the presence of a melamine compound (preferably a compound represented by formula (II)), a zinc salt and a zinc salt. It can be produced by reacting with a copper salt and optionally a salt of the metal ion Me1 described above. The amount of the zinc salt used is preferably 0.05 to 0.995 mol, preferably 0.05 to 0.5 mol, relative to 1 mol of the compound of formula (III) or its tautomer. More preferably, it is more preferably 0.1 to 0.3 mol. The amount of the copper salt used is preferably 0.005 to 0.95 mol, preferably 0.49 to 0.95 mol, based on 1 mol of the compound of the formula (III) or its tautomer. It is more preferable that the amount is 0.7 to 0.9 mol. The amount of the salt of the metal ion Me1 to be used is preferably 0.05 mol or less, preferably 0.01 mol or less, with respect to 1 mol of the compound of the formula (III) or its tautomer. Is more preferable. Further, the total amount of the zinc salt, the copper salt and the salt of the metal ion Me1 is preferably 1 mol with respect to 1 mol of the compound of the formula (III). The amount of the melamine compound used is preferably 0.05 to 4 mol, preferably 0.5 to 2.5 mol, with respect to 1 mol of the compound of the formula (III) or its tautomer. More preferably, it is more preferably 1.0 to 2.0 mol.

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 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, respectively. For R ¹ to R ⁷ have the same meanings as those ^R 1 to R ⁷ of formula (I), preferred ranges are also the same. As the alkali metal ions represented by X ¹ and X ² , Na ⁺ and K ⁺ are preferable.

Further, the metal azo pigment according to the above-mentioned aspect (Az1) can also be produced by mixing the above-mentioned adduct 1a, the adduct 1b, and the adduct 1c.

The metal azo pigment according to the embodiment (Az2), the metal azo pigment according to the aspect (AZ3), and the metal azo pigment according to the aspect (AZ4) can also be produced by the same method as described above.

Regarding the above metal azo pigments, paragraph numbers 0011 to 0062, 0137 to 0276 of JP-A-2017-171912, paragraph numbers 0010 to 0062, 0138-0295, JP-A-2017-171914 of JP-A-2017-171913, and JP-A-2017-171914. The descriptions of paragraph numbers 0011 to 0062 and 0139 to 0190 of Japanese Patent Application Laid-Open No. 2017-171915 and paragraph numbers 0010 to 0065 and 0142-0222 of JP-A-2017-171915 can be referred to, and these contents are incorporated in 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 based on the total solid content of the composition of the present invention. The lower limit is preferably 2% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. When the composition of the present invention contains two or more kinds of metal azo pigments A, the total amount thereof is preferably in the above range.

<< Other color materials >>
The composition of the present invention contains a color material other than the above-mentioned metal azo pigment A, which has an absorption maximum in the wavelength range of 400 to 700 nm (hereinafter, also referred to as another color material). Examples of other coloring materials include chromatic colorants and black colorants. The chromatic 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 is a red colorant, a green colorant, a blue colorant, a yellow colorant, and a purple colorant. Agents, orange colorants and the like. The composition of the present invention preferably contains two or more other coloring materials. According to this aspect, the metal azo pigment A can be more stabilized, and the occurrence of foreign matter defects in a high temperature and high humidity environment can be suppressed more effectively. Further, when the composition of the present invention contains two or more kinds of other coloring materials, it is preferable to contain two or more kinds of coloring materials having different hues.

The composition of the present invention preferably contains at least one selected from a blue colorant and a purple colorant as another colorant. Coloring materials of these hues have a relatively wide conjugated system because they have an absorption maximum on the long wavelength side in the wavelength region of visible light. Therefore, these coloring materials easily interact with the metal azo pigment A, can more stabilize the metal azo pigment A, and can more effectively suppress the occurrence of foreign matter defects in a high temperature and high humidity environment. Further, a composition having a spectral characteristic of A / B of 4.5 or more, which is the ratio 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. Easy to obtain. Examples of the blue colorant include triarylmethane compounds and phthalocyanine compounds, and phthalocyanine compounds are preferable because the effects of the present invention can be obtained more remarkably. Examples of the purple colorant include xanthene compounds, triarylmethane compounds, anthraquinone compounds, oxazine compounds, quinacridone compounds, benzimidazolone compounds and the like, and oxazine compounds are preferable because the effects of the present invention can be obtained more remarkably. ..

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 5% by mass or more. It is preferably 10% by mass or more, more preferably 20% by mass or more. The upper limit is not particularly limited. It can be 100% by mass, 90% by mass or less, or 80% by mass or less. Further, the content of the purple colorant in the total amount of the other coloring materials is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. The upper limit is not particularly limited. It can be 100% by mass, 90% by mass or less, or 80% by mass or less. The total content of the blue colorant and the purple colorant in the total amount of the other colorants is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 30% by mass or more. Is more preferable. The upper limit is not particularly limited. It can be 100% by mass, 90% by mass or less, or 80% by mass or less.

(Coloring agent)
The chromatic colorant used as another coloring material may be a pigment, a dye, and preferably a pigment. Examples of the pigment include organic pigments and inorganic pigments, and organic pigments are preferable. Examples of the organic pigment include the following.

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

Further, as the red pigment, a compound having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom or a nitrogen atom bonded to the aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used. it can. As such a compound, a compound represented by the formula (DPP1) is preferable, and a compound represented by the formula (DPP2) is more preferable.

In the above formula, R ¹¹ and R ¹³ independently represent a substituent, R ¹² and R ¹⁴ independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and n ¹¹ and n ¹³ are independent of each other. And X ¹² and X ¹⁴ independently represent an oxygen atom, a sulfur atom or a nitrogen atom, and when X ¹² is an oxygen atom or a sulfur atom, m12 represents 1 and X. ^{When 12} is a nitrogen atom, m12 represents 2, m14 represents 1 when X ¹⁴ is an oxygen atom or a sulfur atom, and m14 represents 2 when X ¹⁴ is a nitrogen atom. Examples of the substituent represented by R ¹¹ and R ¹³ include the group mentioned in the above-mentioned substituent T, which includes an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a heteroaryloxycarbonyl. Preferred specific examples include a group, an amide group, a cyano group, a nitro group, a trifluoromethyl group, a sulfoxide group, a sulfo group and the like.

The dye is not particularly limited, and a known dye can be used. For example, pyrazole azo series, anilino azo series, triarylmethane series, anthraquinone series, anthrapylidene series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, xanthene series, Phthalocyanine-based, benzopyran-based, indigo-based, pyrromethene-based dyes and the like can be used.

Moreover, the dye multimer can also be used as another color material. The dye multimer is preferably a dye used by dissolving it in a solvent, but the dye multimer may form particles, and when the dye multimer is a particle, it is usually dispersed in a solvent. Used. The pigment multimer in the particle state can be obtained by, for example, emulsion polymerization, and specific examples thereof include compounds and production methods described in JP-A-2015-214682. As the dye multimer, compounds described in JP2011-213925, JP2013-041097, JP2015-028144, JP2015-030742, and the like can also be used.

(Black colorant)
Examples of the black colorant used as another colorant include organic black colorants such as bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds. The black colorant is preferably a bisbenzofuranone compound or a perylene compound. Examples of the bisbenzofuranone compound include the compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234, and the like. It is available. Examples of the perylene compound include C.I. I. Pigment Black 31, 32 and the like can be mentioned. Examples of the azomethine compound include compounds described in JP-A-1-170601 and JP-A-2-34664, and are available as, for example, "Chromofine Black A1103" manufactured by Dainichiseika. The bisbenzofuranone compound is preferably a compound represented by the following formula and a mixture thereof.

In the formula, R ¹ and R ² independently represent a hydrogen atom or a substituent, R ³ and R ⁴ each independently represent a substituent, and a and b each independently represent an integer of 0 to 4. Represented, when a is 2 or more, the plurality of R ^3s may be the same or different, and when the plurality of R ^3s are combined to form a ring, when b is 2 or more. , The plurality of R ^4s may be the same or different, and the plurality of R ^4s may be combined to form a ring. The substituents represented by R ^{1 to} R ⁴ are halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heteroaryl group, -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 Representing R ³¹⁶ or -SO ₂ NR ³¹⁷ R ³¹⁸ , R ^{301 to} R ³¹⁸ independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, respectively. For details of the bisbenzofuranone compound, the description in paragraphs 0014 to 0037 of JP-A-2010-534726 can be referred to, and the content thereof is incorporated in the present specification.

In the composition of the present invention, it is preferable that a black color is formed by a combination of the metal azo pigment A and another coloring material. Preferred combinations of the metal azo pigment A and other coloring materials include the following (C1) to (C6). In the case of the combination of (C1) below, the composition having the spectral characteristics of (1) described above can be easily obtained. In the case of the following combinations (C2) to (C6), the composition having the above-mentioned spectral characteristics of (2) can be easily obtained.

(C1) An embodiment containing a metal azo pigment A and a purple colorant. Further, a yellow colorant as another coloring material may be contained.
(C2) An embodiment containing a metal azo pigment A, a red colorant, a blue colorant, and a purple colorant. Further, a yellow colorant as another coloring material may be contained.
(C3) An embodiment containing a metal azo pigment A, a red colorant, and a blue colorant. Further, a yellow colorant as another coloring material may be contained.
(C4) An embodiment containing a metal azo pigment A, a blue colorant, and a purple colorant. Further, a yellow colorant as another coloring material may be contained.
(C5) An embodiment containing a metal azo pigment A, a purple colorant, and a black colorant. Further, a yellow colorant as another coloring material may be contained.
(C6) An embodiment containing a metal azo pigment A, a blue colorant, and a black colorant. Further, a yellow colorant as another coloring material may be contained.

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

In the combination of (C1) above, the purple colorant is preferably contained in an amount of 50 to 500 parts by mass, more preferably 75 to 400 parts by mass, and 100 to 350 parts by mass with respect to 100 parts by mass of the metal azo pigment A. It is more preferable to contain by mass. When the yellow colorant as another color material is further contained, the content of the yellow colorant as the other color material shall be 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and it is more preferably 20 to 150 parts by mass. It is also possible that the yellow colorant as another coloring material is not contained.

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. Further, it is preferable to contain 100 to 1000 parts by mass of the blue colorant, and more preferably 200 to 800 parts by mass. Further, it is preferable to contain 50 to 500 parts by mass of the purple colorant, and more preferably 70 to 400 parts by mass. When the yellow colorant as another color material is further contained, the content of the yellow colorant as the other color material shall be 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and it is more preferably 20 to 150 parts by mass. It is also possible that the yellow colorant as another coloring material is not contained.

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. Further, it is preferable to contain 100 to 1000 parts by mass of the blue colorant, and more preferably 200 to 800 parts by mass. When the yellow colorant as another color material is further contained, the content of the yellow colorant as the other color material shall be 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and it is more preferably 20 to 150 parts by mass. It is also possible that the yellow colorant as another coloring material is not contained.

In the combination of (C4) above, 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 more preferably 200 to 800 parts by mass. Further, it is preferable to contain 50 to 500 parts by mass of the purple colorant, and more preferably 75 to 400 parts by mass. When the yellow colorant as another color material is further contained, the content of the yellow colorant as the other color material shall be 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and it is more preferably 20 to 150 parts by mass. It is also possible that the yellow colorant as another coloring material is not contained.

In the combination of (C5) above, the purple colorant is preferably contained in an amount of 50 to 500 parts by mass, more preferably 75 to 400 parts by mass, based on 100 parts by mass of the metal azo pigment A. Further, the black colorant is preferably contained in an amount of 50 to 1000 parts by mass, more preferably 100 to 800 parts by mass. When the yellow colorant as another color material is further contained, the content of the yellow colorant as the other color material shall be 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and it is more preferably 20 to 150 parts by mass. It is also possible that the yellow colorant as another coloring material is not contained.

In the combination of (C6) above, 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 more preferably 200 to 800 parts by mass. Further, the black colorant is preferably contained in an amount of 50 to 1000 parts by mass, more preferably 100 to 800 parts by mass. When the yellow colorant as another color material is further contained, the content of the yellow colorant as the other color material shall be 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and it is more preferably 20 to 150 parts by mass. It is also possible that the yellow colorant as another coloring material is not contained.

In the composition of the present invention, the content of the other coloring material is preferably 10 to 80% by mass based on 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, and more preferably 60% by mass or less. The content of the other coloring material is preferably 50 to 1000 parts by mass with respect to 100 parts by mass of the metal azo pigment 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. The total content of the metal azo pigment A and the other coloring material is preferably 10 to 70% by mass based on the total solid content of the composition of the present invention. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more. When the composition of the present invention contains two or more other coloring materials, the total amount thereof is preferably in the above range.

<< Near-infrared absorbing pigment >>
The composition of the present invention can contain a near-infrared absorbing dye. In the infrared transmission filter, the near-infrared absorbing dye has a role of limiting the transmitted light (infrared ray) to the longer wavelength side. When the composition of the present invention contains a near-infrared absorbing dye, the composition having the spectral characteristics of (3) described above can be easily obtained. In particular, when the metal azo pigment A and another coloring material are contained in the combination of the above (C2) to (C6), the composition having the above-mentioned spectral characteristics of (3) is further contained by containing the near-infrared absorbing dye. Is easy to obtain. Further, when the composition of the present invention contains a near-infrared absorbing dye, it is possible to more effectively suppress the occurrence of foreign matter defects in a high temperature and high humidity environment.

In the present invention, examples of the near-infrared absorbing dye include compounds having an absorption maximum in the near-infrared region (preferably a wavelength of 700 to 1100 nm, more preferably a wavelength of 700 to 1000 nm, still more preferably a wavelength of 800 to 900 nm). Be done. 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 an aromatic ring of a monocyclic ring or a condensed 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 30 or more. The above is particularly preferable. The upper limit is, for example, preferably 80 or less, and more preferably 50 or less. Further, the π-conjugated plane of the near-infrared absorbing dye preferably contains two or more aromatic rings of a monocyclic ring or a fused ring, more preferably three or more aromatic rings described above, and the aromatic rings described above. It is more preferable to contain 4 or more rings, and it is particularly preferable to contain 5 or more of the above-mentioned 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 rings include a benzene ring, a naphthalene ring, an inden ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentasen ring, a quaterylene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, and a chrysene ring. Triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzoxazole ring, imidazoline ring, pyrazine Examples thereof include a ring, a quinoxaline ring, a pyrimidine ring, a quinazoline ring, a pyridazine ring, a triazine ring, a pyrrole ring, an indole ring, an isoindol ring, a carbazole ring, and a fused ring having these rings.

Near-infrared absorbing dyes include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonor compounds, diimonium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, and azomethine. At least one selected from compounds, anthraquinone compounds, indigo compounds and dibenzofuranone compounds is preferred, and at least one selected from pyrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds and indigo compounds is more preferred. Preferably, at least one selected from a pyrolopyrrole compound, a cyanine compound and a squarylium compound is more preferable, and a pyrolopyrrole compound is particularly preferable. Examples of the diimonium compound include the compounds described in JP-A-2008-528706, the contents of which are incorporated in the present specification. Examples of the phthalocyanine compound include the compound described in paragraph No. 0093 of JP2012-77153, the oxytitanium phthalocyanine described in JP2006-343631, and paragraph numbers 0013 to 0029 of JP2013-195480. , And vanadium phthalocyanines described in Japanese Patent No. 6081771, the contents of which are incorporated herein by reference. Examples of the naphthalocyanine compound include the compound described in paragraph No. 0093 of JP2012-77153A, the contents of which are incorporated in the present specification. The indigo compound is preferably an indigo boron complex compound. Examples of the indigo compound include the compounds described in Japanese Patent No. 564201, the contents of which are incorporated in the present specification. The near-infrared absorbing dye is a compound described in JP-A-2016-146619, a compound described in JP-A-2016-79331, a compound described in JP-A-2017-82029, and JP-A-2015. The compound described in JP-A-40176 and the compound described in Japanese Patent No. 5539676 can also be used. Further, as the near-infrared absorbing dye, a compound having the following structure can also be used.

式中、Ｒ^１ａおよびＲ^１ｂは、各々独立にアルキル基、アリール基またはヘテロアリール基を表し、Ｒ^２およびＲ^３は、各々独立に水素原子または置換基を表し、Ｒ^２およびＲ^３は、互いに結合して環を形成してもよく、Ｒ^４は、各々独立に、水素原子、アルキル基、アリール基、ヘテロアリール基、−ＢＲ^４ＡＲ^４Ｂ、または金属原子を表し、Ｒ^４は、Ｒ^１ａ、Ｒ^１ｂおよびＲ^３から選ばれる少なくとも一つと共有結合もしくは配位結合していてもよく、Ｒ^４ＡおよびＲ^４Ｂは、各々独立に置換基を表す。式（ＰＰ）の詳細については、特開２００９−２６３６１４号公報の段落番号００１７〜００４７、特開２０１１−６８７３１号公報の段落番号００１１〜００３６、国際公開ＷＯ２０１５／１６６８７３号公報の段落番号００１０〜００２４の記載を参酌でき、これらの内容は本明細書に組み込まれる。The pyrrolopyrrole compound is preferably a compound represented by the formula (PP).

In the formula, R ^1a and R ^1b 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 are. They may be bonded to each other to form a ring, where R ⁴ independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B , or a metal atom, where R ⁴ is R. ^It may be covalently or coordinated with at least one selected from ^1a , R ^1b and R ³ , where R ^4A and R ^4B each independently represent a substituent. For details of the formula (PP), paragraph numbers 0017 to 0047 of JP2009-263614, paragraphs 0011 to 0036 of JP2011-68831, and paragraphs 0010 to 0024 of International Publication WO2015 / 166873. The description of the above can be taken into consideration, and these contents are incorporated in the present specification.

In the formula (PP), R ^1a and R ^1b are each independently preferably an aryl group or a heteroaryl group, and more preferably an aryl group. Further, the alkyl group, aryl group and heteroaryl group represented by R ^1a and R ^1b may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described in paragraphs 0020 to 0022 of JP-A-2009-263614 and the above-mentioned substituent T. 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 acyloxy group as a substituent.

In formula (PP), R ² and R ³ each independently represent a hydrogen atom or substituent. Examples of the substituent include the above-mentioned Substituent T. At least one of R ² and R ³ is preferably an electron attracting group. Substituents with a positive Hammett substituent constant σ value (sigma value) act as electron-attracting groups. Here, the substituent constants obtained by Hammett's law include σp value and σm value. These values can be found in many common books. In the present invention, a substituent having a Hammett substituent constant σ value of 0.2 or more can be exemplified as an electron-attracting group. 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-attracting group include a cyano group (-CN: σp value = 0.66), a carboxyl group (-COOH: σp value = 0.45), and an alkoxycarbonyl group (for example, -COOME: σp value). = 0.45), aryloxycarbonyl group (eg, -COOPh: σp value = 0.44), carbamoyl group (eg, -CONH ₂ : σp value = 0.36), alkylcarbonyl group (eg, -COMe:: .sigma.p value = 0.50), an arylcarbonyl group (e.g., -COPh: σp value = 0.43), an alkylsulfonyl group (e.g., _-SO 2 Me: σp value = 0.72), an arylsulfonyl group (e.g., −SO ₂ Ph: σp value = 0.68) and the like, and a cyano group is preferable. Here, Me represents a methyl group and Ph represents a phenyl group. Regarding the substituent constant σ value of Hammett, for example, paragraphs 0017 to 0018 of JP2011-68831A can be referred to, and the contents thereof are incorporated in the present specification.

In formula (PP), R ² preferably represents an electron-attracting 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. The heteroaryl group is preferably a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 8, and more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. The heteroaryl group preferably has one or more nitrogen atoms. Two R ² together in the formula (PP) may be the same or may be different. Also, two R ³ together in the formula (PP) may be the same or may be different.

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 , preferably a hydrogen atom, an alkyl group, an aryl group or -BR. more preferably a group represented by ^4A R ^4B, and more preferably a group represented by ^-BR 4A ^{R 4B.} 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 preferable. Especially preferable. These groups may further have substituents. Two R ⁴ together in the formula (PP) may be the same or may be different. R ^4A and R ^4B may be coupled 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. Examples of the pyrrolopyrrole compound include the compounds described in paragraphs 0016 to 0058 of JP2009-263614, the compounds described in paragraphs 0037 to 0052 of JP2011-68831, and WO2015 / 166873. Examples include the compounds described in paragraphs 0010 to 0033 of the publication, the contents of which are incorporated herein by reference.

式（ＳＱ）中、Ａ^１およびＡ^２は、それぞれ独立に、アリール基、ヘテロアリール基または式（Ａ−１）で表される基を表す；

式（Ａ−１）中、Ｚ^１は、含窒素複素環を形成する非金属原子団を表し、Ｒ^２は、アルキル基、アルケニル基またはアラルキル基を表し、ｄは、０または１を表し、波線は連結手を表す。式（ＳＱ）の詳細については、特開２０１１−２０８１０１号公報の段落番号００２０〜００４９、特許第６０６５１６９号公報の段落番号００４３〜００６２、国際公開ＷＯ２０１６／１８１９８７号公報の段落番号００２４〜００４０の記載を参酌でき、これらの内容は本明細書に組み込まれる。As the squarylium compound, a compound represented by the following formula (SQ) is preferable.

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

In formula (A-1), Z ¹ represents a non-metal atomic group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, and d represents 0 or 1. The wavy line represents the connecting hand. For details of the formula (SQ), paragraph numbers 0020 to 0049 of JP2011-208101A, paragraphs 0043 to 0062 of Japanese Patent No. 6065169, and paragraphs 0024 to 0040 of International Publication WO2016 / 181987. These contents are incorporated herein by reference.

In the formula (SQ), the cation is delocalized and exists as follows.

Examples of the squarylium compound include compounds having the following structures. Further, the compounds described in paragraphs 0044 to 0049 of JP2011-208101A, the compounds described in paragraphs 0060 to 0061 of Patent No. 6065169, and paragraph numbers 0040 of International Publication WO2016 / 181987. Compounds, compounds described in International Publication WO2013 / 133099, compounds described in International Publication WO2014 / 088063, compounds described in JP2014-126642, compounds described in JP2016-146619, Compounds described in JP-A-2015-176046, compounds described in JP-A-2017-25311, compounds described in International Publication WO2016 / 154782, compounds described in Patent No. 5884953, Patent No. 60366689. Examples thereof include the compounds described in Japanese Patent Application Laid-Open No. 581604, the compounds described in JP-A-2017-068120, and the contents thereof are incorporated in the present specification.

式中、Ｚ^１およびＺ^２は、それぞれ独立に、縮環してもよい５員または６員の含窒素複素環を形成する非金属原子団であり、
Ｒ^１０１およびＲ^１０２は、それぞれ独立に、アルキル基、アルケニル基、アルキニル基、アラルキル基またはアリール基を表し、
Ｌ^１は、奇数個のメチン基を有するメチン鎖を表し、
ａおよびｂは、それぞれ独立に、０または１であり、
ａが０の場合は、炭素原子と窒素原子とが二重結合で結合し、ｂが０の場合は、炭素原子と窒素原子とが単結合で結合し、
式中のＣｙで表される部位がカチオン部である場合、Ｘ^１はアニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位がアニオン部である場合、Ｘ^１はカチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位の電荷が分子内で中和されている場合、ｃは０である。The cyanine compound is preferably a compound represented by the formula (C).
Equation (C)

In the formula, Z ¹ and Z ² are non-metal atomic groups that independently form a 5- or 6-membered nitrogen-containing heterocycle that may be fused, respectively.
R ¹⁰¹ and R ¹⁰² independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, respectively.
L ¹ represents a methine chain having an odd number of methine groups.
a and b are independently 0 or 1, respectively.
When a is 0, the carbon atom and the nitrogen atom are bonded by a double bond, and when b is 0, the carbon atom and the nitrogen atom are bonded by a single bond.
When the part represented by Cy in the formula is a cation part, X ¹ represents an anion, c represents the number required to balance the charges, and the part represented by Cy in the formula is an anion part. When, X ¹ represents a cation, c represents the number required to balance the charge, and c is neutralized in the molecule at the site represented by Cy in the equation. It is 0.

Examples of the cyanine compound include the compounds described in paragraphs 0044 to 0045 of JP2009-108267A, the compounds described in paragraphs 0026 to 0030 of JP2002-194040, and the compounds described in JP2015-172004. , The compound described in JP-A-2015-172102, the compound described in JP-A-2008-88426, the compound described in JP-A-2017-031394, and the like, and the contents thereof are described in the present specification. Is incorporated into.

In the present invention, a commercially available product can also be used as the near-infrared absorbing dye. For example, SDO-C33 (manufactured by Arimoto Chemical Co., Ltd.), E-Excolor IR-14, E-Excolor IR-10A, E-Excolor TX-EX-801B, E-Excolor TX-EX-805K (Co., Ltd.) (Made by Nippon Catalyst), ShigenoxNIA-8041, ShigenoxNIA-8042, ShigenoxNIA-814, ShigenoxNIA-820, ShigenoxNIA-839 (manufactured by Hakko Chemicals), EpolyteV-63, EpoliteV-63, EpoliteV-63, EpoliteV-63, Epolite38 Examples include NK-3027 (manufactured by Hayashihara Co., Ltd.), YKR-3070 (manufactured by Mitsui Chemicals Co., Ltd.), FDN-307 (manufactured by Yamada Chemical Co., Ltd.), etc. ..

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 based on the total solid content of the composition of the present invention. The upper limit is preferably 20% by mass or less, and more preferably 10% by mass or less. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The content of the near-infrared absorbing dye is preferably 5 to 50 parts by mass with respect to 100 parts by mass in total of the metal azo pigment A and the other coloring material. The upper limit is preferably 45% by mass or less, more preferably 40% by mass or less. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more. The total content of the metal azo pigment A, the other coloring material, and the near-infrared absorbing dye is preferably 10 to 70% by mass in the total solid content of the composition of the present invention. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more. The composition of the present invention may contain only one kind of near-infrared absorbing dye, or may contain two or more kinds. When two or more kinds of near-infrared absorbing dyes are contained, the total amount thereof is preferably in the above range.

<< Curable compound >>
The composition of the present invention contains at least one compound selected from a compound having an ethylenically unsaturated bond group and a compound having a cyclic ether group. Hereinafter, both are also collectively referred to as a curable compound. Examples of the ethylenically unsaturated bond group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group.

(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. Further, a polymer having an ethylenically unsaturated bond group is also referred to as 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 even more preferably 1500 or less. The lower limit is preferably 100 or more, more preferably 150 or more, and even 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 to 15 ethylenically unsaturated bond groups, and the ethylenically unsaturated bond group. It is more preferable that the compound contains 3 to 6 compounds. The polymerizable monomer is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities. Specific examples of the polymerizable monomer are described in paragraphs 0905 to 0108 of JP2009-288705A, paragraph 0227 of JP2013-29760A, and paragraphs 0254 to 0257 of JP2008-292970. Compounds are mentioned and these contents are incorporated herein.

The C = C equivalent of the polymerizable monomer (molecular weight [g / mol] of the polymerizable monomer / number of ethylenically unsaturated bond groups contained in the polymerizable monomer) is preferably 50 to 1000. 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 preferably 200 or less, further 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 pigment active surface, and the aggregation of the metal azo pigment A can be suppressed more remarkably.

As polymerizable monomers, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku Co., Ltd.) , Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; NK ester A-DPH-12E manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues. (For example, SR454, SR499 commercially available from Sartmer), NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), KAYARAD RP-1040, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.), etc. Can be mentioned. Further, as the polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy-modified tri (meth) acrylate, trimethylolpropane ethyleneoxy-modified tri (meth) acrylate, and isocyanurate ethyleneoxy-modified tri (meth) acrylate. , Pentaerythritol Tri (meth) acrylate and other trifunctional (meth) acrylate compounds are also preferred. Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305. , M-303, M-452, M-450 (manufactured by Toa Synthetic 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 Industry Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) , TMPEOTA (manufactured by Daicel Ornex Co., Ltd.) and the like.

It is also preferable to use a polymerizable monomer having an acid group as the polymerizable monomer. By using a polymerizable monomer having an acid group, the composition layer in the unexposed portion can be easily removed during development, and the generation of development residue can be effectively suppressed. Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferable. Examples of commercially available products of the polymerizable monomer having an acid group include Aronix M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.). 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. When the acid value of the polymerizable monomer is 0.1 mgKOH / g or more, the solubility in a developing solution is good, and more excellent developability can be obtained. When the acid value of the polymerizable monomer is 40 mgKOH / g or less, it is advantageous in production and handling.

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

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

It is also preferable to use a compound having a caprolactone structure as the polymerizable monomer. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, but for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, dimethylolpropane, pentaerythritol, dipentaerythritol, etc. Ε-Caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as tripentaerythritol, glycerin, diglycerol, trimethylolmelamine with (meth) acrylic acid and ε-caprolactone. Can be done. The compound having a caprolactone structure is preferably a compound represented by the following formula (Z-1).

In formula (Z-1), all 6 Rs are groups represented by formula (Z-2), or 1 to 5 of the 6 Rs are represented by formula (Z-2). The residue is a group represented by the formula (Z-3), an acid group or a hydroxy group.

式（Ｚ−２）中、Ｒ^１は水素原子又はメチル基を示し、ｍは１又は２の数を示し、「＊」は結合手であることを示す。

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

式（Ｚ−３）中、Ｒ^１は水素原子又はメチル基を示し、「＊」は結合手であることを示す。

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

Examples of the polymerizable monomer include compounds represented by the formula (Z-4) or (Z-5).

In formulas (Z-4) and (Z-5), E is independently − ((CH ₂ ) _y CH ₂ O) − or − ((CH ₂ ) _y CH (CH ₃ ) O) −. , Y 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, each of m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. In formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, each of n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

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

A compound having an alkyleneoxy group can also be used as the polymerizable monomer. The polymerizable monomer having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and having 4 to 20 ethyleneoxy groups. More preferably, it is a 3-6 functional (meth) acrylate compound. Commercially available products of the polymerizable monomer having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartmer, and a trifunctional (meth) having three isobutyleneoxy groups. Examples thereof include KAYARAD TPA-330, which is an acrylate.

Examples of the polymerizable monomer include urethane acrylates described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, Japanese Patent Application Laid-Open No. 2-16765, and Japanese Patent Application Laid-Open No. 58. A urethane compound having an ethylene oxide-based skeleton described in JP-A-49860, JP-A-56-17654, JP-A-62-39417, and JP-A-62-39418, JP-A-63-277653. , JP-A-63-260909 and JP-A-1-105238 are also mentioned, and compounds having an amino structure or a sulfide structure in the molecule are also mentioned, and it is also preferable to use these compounds. Commercially available products include UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T- Examples include 600 and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).
Further, as the polymerizable monomer, it is also preferable to use 8UH-1006, 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
Further, as the polymerizable monomer, the compounds described in Japanese Patent Application Laid-Open No. 2017-48637, Japanese Patent No. 6057891, and Japanese Patent No. 6031807 can also be used.

The weight average molecular weight of the polymerizable polymer is preferably 3000 or more, more preferably 5000 or more, further preferably 7000 or more, and particularly preferably 10000 or more. 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 (molecular weight of the polymerizable polymer / number of ethylenically unsaturated bond groups contained in the polymerizable polymer) is preferably 100 to 5000. 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. When the C = C equivalent of the polymerizable polymer 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 remarkably.

式（Ａ−１−１）において、Ｘ^１は繰り返し単位の主鎖を表し、Ｌ^１は単結合または２価の連結基を表し、Ｙ^１はエチレン性不飽和結合基を表す。The polymerizable polymer preferably contains a repeating unit having an ethylenically unsaturated bond group in the side chain, and more preferably contains a repeating unit represented by the following formula (A-1-1). Further, the polymerizable polymer preferably contains 10 mol% or more of the repeating units having an ethylenically unsaturated bond group in all the repeating units of the polymerizable polymer, more preferably 10 to 80 mol%. It is more preferably contained in an amount of 70 mol%.

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 binding group.

In the 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 linking group formed from a known polymerizable monomer. For example, poly (meth) acrylic linking groups, polyalkyleneimine-based linking groups, polyester-based linking groups, polyurethane-based linking groups, polyurea-based linking groups, polyamide-based linking groups, polyether-based linking groups, polystyrene-based linking groups, etc. From the viewpoint of availability of raw materials and production suitability, poly (meth) acrylic-based linking groups and polyalkyleneimine-based linking groups are preferable, and poly (meth) acrylic-based linking groups are 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) and an alkyleneoxy group (preferably an alkylene group having 1 to 12 carbon atoms). Oxy group), oxyalkylene carbonyl group (preferably oxyalkylene carbonyl group having 1 to 12 carbon atoms), arylene group (preferably arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO _2- , -CO-, -O-, -COO-, OCO-, -S- and groups consisting of a combination of two or more of these.

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

The polymerizable polymer preferably further contains a repeating unit having a graft chain. When the polymerizable polymer contains a repeating unit having a graft chain, it is possible to more effectively suppress aggregation of the metal azo pigment A or the like due to steric hindrance due to the graft chain. The polymerizable polymer preferably contains 1.0 to 60 mol%, more preferably 1.5 to 50 mol%, of the repeating units having a graft chain in all the repeating units of the polymerizable polymer. A polymerizable polymer containing a repeating unit having a graft chain is preferably used as a dispersant.

In the present invention, the graft chain means a polymer chain that branches and extends from the main chain of a repeating unit. The length of the graft chain is not particularly limited, but the longer the graft chain, the higher the steric repulsion effect, and the dispersibility of the metal azo pigment A or the like can be improved. As the graft chain, the number of atoms excluding hydrogen atoms is preferably 40 to 10,000, the number of atoms excluding hydrogen atoms is more preferably 50 to 2000, and the number of atoms excluding hydrogen atoms is 60 to. It is more preferably 500.

The graft chain contained in the polymerizable polymer preferably contains at least one structure selected from a polyester structure, a polyether structure, a poly (meth) acrylic structure, a polyurethane structure, a polyurea structure and a polyamide structure, and preferably contains a polyester structure and a polyether structure. It is more preferable to include at least one structure selected from the structure and the poly (meth) acrylic structure, and further preferably to include a polyester structure. Examples of the polyester structure include structures represented by the following formulas (G-1), formulas (G-4) or formulas (G-5). Further, as the polyether structure, a structure represented by the following formula (G-2) can be mentioned. Moreover, as a poly (meth) acrylic structure, the structure represented by the following formula (G-3) can be mentioned.

In the above formula, ^RG1 and ^RG2 each represent an alkylene group. It is not particularly restricted but includes alkylene groups represented by R ^G1 and R ^G2, preferably a linear or branched alkylene group having 1 to 20 carbon atoms, 2 to 16 carbon atoms linear or branched alkylene A group is more preferable, and a linear or branched alkylene group having 3 to 12 carbon atoms is further preferable.
In the above formula, ^RG3 represents a hydrogen atom or a methyl group.
In the above formula, Q ^G1 represents -O- or -NH-, and LG ¹ 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 alkyleneoxy group having 1 to 12 carbon atoms), and an oxyalkylenecarbonyl group (preferably 1 to 12 carbon atoms). ~ 12 oxyalkylene carbonyl group), arylene group (preferably arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO _2- , -CO-, -O-, -COO-, OCO Examples thereof include groups consisting of −, −S− and a combination of two or more of these.
In the above formula, ^RG4 represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like.

The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like. Among them, a group having a steric repulsion effect is preferable, and an alkyl group having 5 to 24 carbon atoms or an alkoxy group is preferable, from the viewpoint of improving the dispersibility of the coloring material or the like. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and are preferably linear or branched.

In the present invention, the graft chain has a structure represented by the following formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a) or formula (G-5a). It is preferable to have.

In the above ^formula, and ^{R G1} and ^{R G2} each independently 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 -valent linking group, R ^G4 represents a hydrogen atom or a substituent, W ¹⁰⁰ represents a hydrogen atom or a substituent. Each of n1 to n5 independently represents an integer of 2 or more. For ^{R G1 ~R G4, Q G1,} L G1 , Formula (G1) ~ (G-5 ) has the same meaning as ^{R G1 ~R G4, Q G1,} L G1 described in, the preferred range is also the same is there.

In formulas (G-1a) to (G-5a), W ¹⁰⁰ is preferably a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like. Among them, 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, from the viewpoint of improving the dispersibility of the coloring material or the like. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and are preferably linear or branched.

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

Examples of the repeating unit having a graft chain include a repeating unit represented by the following formula (A-1-2).

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 structure described by X ¹ in the formula (A-1-1) can be mentioned, and the preferable range is also the same. The divalent linking group represented by L ² in the formula (A-1-2) includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an arylene group (preferably an arylene group having 6 to 20 carbon atoms). , -NH-, -SO-, -SO _2- , -CO-, -O-, -COO-, OCO-, -S- and groups consisting of a combination of two or more of these. Examples of the graft chain represented by W ¹ in the formula (A-1-2) include the above-mentioned graft chain.

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 1000 or more, more preferably 1000 to 10000, and 1000 to 7500. Is more preferable. In the present invention, the weight average molecular weight of the repeating unit having a graft chain is a value calculated from the weight average molecular weight of the raw material monomer used for the polymerization of the repeating unit. For example, repeating units with graft chains can be formed by polymerizing macromonomers. Here, the macromonomer means a polymer compound in which a polymerizable group is introduced at the polymer terminal. When a repeating unit having a graft chain is formed using a macromonomer, the weight average molecular weight of the macromonomer corresponds to the weight average molecular weight of the repeating unit having a graft chain.

The polymerizable polymer also preferably contains a repeating unit having an acid group. By further including the repeating unit having an acid group in the polymerizable polymer, the dispersibility of the metal azo pigment A or the like can be further improved. Furthermore, the developability can be improved. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group.

Examples of the repeating unit having an acid group include a repeating unit represented by the following formula (A-1-3).

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 structure described by X ¹ in the formula (A-1-1) can be mentioned, and the preferable range is also the same.
The divalent linking group represented by L ³ in the formula (A-1-3) includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an alkyleneoxy group (preferably an alkyleneoxy having 1 to 12 carbon atoms). Group), oxyalkylene carbonyl group (preferably an oxyalkylene carbonyl group having 1 to 12 carbon atoms), arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO _2- , Examples thereof include -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these. The alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may be linear, branched, or cyclic, and are preferably linear or branched. Further, the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and the like.
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. When the acid value of the polymerizable polymer is in the above range, particularly excellent dispersibility can be easily obtained. Furthermore, excellent developability can be easily obtained.

Further, as another repeating unit, the polymerizable polymer may be referred to as a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer". Can include repeating units derived from monomeric components containing).

式（ＥＤ２）中、Ｒは、水素原子または炭素数１〜３０の有機基を表す。式（ＥＤ２）の具体例としては、特開２０１０−１６８５３９号公報の記載を参酌できる。In the formula (ED1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description of JP-A-2010-168539 can be referred to.

As a specific example of the ether dimer, for example, paragraph number 0317 of JP2013-29760A can be referred to, and the content thereof is incorporated in the present specification. The ether dimer may be only one type or two or more types.

Specific examples of the polymerizable polymer include the following.

(Compound having a cyclic ether group)
Examples of the compound having a cyclic ether group used in the present invention include a compound having two or more cyclic ether groups in one molecule. 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 further preferably 5 or less. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, and an epoxy group is preferable. That is, the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter, also referred to as an epoxy compound).

The epoxy equivalent of the epoxy compound (= molecular weight of the compound having an epoxy group / 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 high molecular weight compound (macromolecular) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 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 3000 or less, more preferably 2000 or less, still more preferably 1500 or less.

Epoxy compounds are the compounds described in paragraphs 0034 to 0036 of JP2013-011869, paragraphs 0147 to 0156 of JP2014-043556, and paragraphs 0083-0092 of JP2014-089408. Can also be used. These contents are incorporated in the present specification. Commercially available epoxy compounds include, for example, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (all manufactured by Mitsubishi Chemical Corporation), as bisphenol A type epoxy resins. EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (all manufactured by DIC Co., Ltd.), etc. Examples of the bisphenol F type epoxy resin include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (all manufactured by Mitsubishi Chemical Corporation), and the like. EPICLON830, EPICLON835 (above, manufactured by DIC Co., Ltd.), LCE-21, RE-602S (above, manufactured by Nippon Kayaku Co., Ltd.), etc. Examples of the phenol novolac type epoxy resin are jER152, jER154, jER157S70, jER157S65. (These are manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Co., Ltd.), etc. As the cresol novolac type epoxy resin, EPICLON N-660 , EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (all manufactured by DIC Co., Ltd.), EOCN-1020 (Nippon Kayaku Co., Ltd.) As the aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (all manufactured by ADEKA Co., Ltd.), celoxide 2021P, celoxide 2081, celoxide 2083, celoxide 2085, etc. EHPE3150, EPOLEAD PB 3600, PB 4700 (manufactured by Daicel Co., Ltd.), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (manufactured by Nagase ChemteX Corporation) And so on. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, 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 (all manufactured by Nichiyu Co., Ltd., epoxy group-containing polymer) and the like can be mentioned.

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 based on the total solid content of the composition. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. 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, based on 100 parts by mass of the above-mentioned metal azo pigment A. It is more preferably 50 parts by mass or more. The upper limit is preferably 750 parts by mass or less, more preferably 700 parts by mass or less, further preferably 650 parts by mass or less, and particularly preferably 600 parts by mass or less. When the ratio of the metal azo pigment A and the compound having an ethylenically unsaturated bond group is in the above range, the effect of the present invention can be obtained more remarkably. 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 5 to 500 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is preferable to have. 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, and 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 based on the total solid content of the composition. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 45% by mass or less, and more preferably 40% by 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 50 parts by mass with respect to 100 parts by mass of the above-mentioned metal azo pigment A. The above is more preferable. The upper limit is preferably 750 parts by mass or less, more preferably 700 parts by mass or less, further preferably 650 parts by mass or less, and particularly preferably 600 parts by mass or less. When the ratio of the metal azo pigment A and the compound having a cyclic ether group is in the above range, the effect of the present invention can be obtained more remarkably.

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 based on the total solid content of the composition. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. 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 with respect to 100 parts by mass of the above-mentioned metal azo pigment A. It is more preferably parts by mass or more, and even more preferably 50 parts by mass or more. The upper limit is preferably 750 parts by mass or less, more preferably 700 parts by mass or less, further preferably 650 parts by mass or less, and particularly preferably 600 parts by mass or less. When the content is in the above range, the effect of the present invention can be obtained more remarkably. When the composition of the present invention contains a compound having an ethylenically unsaturated bond group and a compound having a cyclic ether group, the cyclic ether group is added to 100 parts by mass of the compound having an ethylenically unsaturated bond group. It is preferable to contain 1 to 50 parts by mass of the compound having the compound. The upper limit is preferably 40 parts by mass or less, and 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 further preferably 10 parts by mass or more.

<< Other resins >>
The composition of the present invention can further contain a resin other than the curable compound described above (hereinafter, also referred to as another resin). Other resins are blended, for example, for the purpose of dispersing particles such as pigments in the composition and for the purpose of binders. A resin mainly used for dispersing particles such as pigments is also referred to as a dispersant. However, such an application of the resin is an example, and the resin can be used for a purpose other than such an application.

The weight average molecular weight (Mw) of the other resin is preferably 2000 to 2000000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3000 or more, and more preferably 5000 or more.

Other resins include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, and polyamide. Examples thereof include imide resin, polyolefin resin, cyclic olefin resin, polyester resin and styrene resin. One of these resins may be used alone, or two or more of these resins may be mixed and used. The resins include the resin described in Examples of International Publication WO2016 / 088645, the resin described in JP-A-2017-57265, the resin described in JP-A-2017-32685, and JP-A-2017. The resin described in Japanese Patent Application Laid-Open No. -075248 and the resin described in JP-A-2017-066240 can also be used. Further, a resin having a fluorene skeleton can also be used. Examples of the resin having a fluorene skeleton include resins having the following structures. In the following structural formula, A is the residue of the carboxylic acid dianhydride selected from pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride and diphenyl ether tetracarboxylic dianhydride. It is a group, and M is a phenyl group or a benzyl group. For resins having a fluorene skeleton, the description of US Patent Application Publication No. 2017/0102610 can be taken into consideration, the contents of which are incorporated in the present specification.

Other resins may have acid groups. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferable. These acid groups may be only one type or two or more types. The resin having an acid group can also be used as an alkali-soluble resin.

As the resin having an acid group, a polymer having a carboxyl group in the side chain is preferable. Specific examples include alkali-soluble methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolak resins. Examples thereof include a phenol resin, an acidic cellulose derivative having a carboxyl group in the side chain, and a resin in which an acid anhydride is added to a polymer having a hydroxy group. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like. 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, and pentyl (meth) acrylate. Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, trill (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate and the like. Be done. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, polymethylmethacrylate macromonomer and the like. As the other monomer, a maleimide monomer such as N-phenylmaleimide or N-cyclohexylmaleimide can also be used. The other monomer copolymerizable with these (meth) acrylic acids may be only one kind or two or more kinds.

Resins having an acid group are benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth). A multi-element copolymer composed of acrylate / (meth) acrylic acid / other monomer can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethylmethacrylate macromonomer / benzylmethacrylate / methacrylate copolymer, 2-hydroxyethylmethacrylate / polystyrene macromonomer / methylmethacrylate / methacrylate copolymer, 2-hydroxyethylmethacrylate / polystyrene Macromonomers / benzyl methacrylate / methacrylic acid copolymers and the like can also be preferably used.

The resin having an acid group is also preferably a polymer containing a repeating unit derived from the above-mentioned monomer component containing an ether dimer.

式（Ｘ）において、Ｒ_１は、水素原子またはメチル基を表し、Ｒ_２は炭素数２〜１０のアルキレン基を表し、Ｒ_３は、水素原子またはベンゼン環を含んでもよい炭素数１〜２０のアルキル基を表す。ｎは１〜１５の整数を表す。The resin having an acid group may contain a repeating unit derived from the compound represented by the following formula (X).

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 a benzene ring having 1 to 20 carbon atoms. Represents the alkyl group of. n represents an integer of 1 to 15.

Regarding the resin having an acid group, the description in paragraph Nos. 0558 to 0571 of JP2012-208494A (paragraph number 0685-0700 of the corresponding US Patent Application Publication No. 2012/0235099), JP2012-198408 The description of paragraphs 0076 to 0999 of the publication can be taken into consideration, and these contents are incorporated in the present specification. Further, as the resin having an acid group, a commercially available product can also be used.

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, and more preferably 120 mgKOH / g or less.

Examples of the resin having an acid group include a resin having the following structure.

The composition of the present invention may also contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more, and substantially acid, when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. A resin consisting only of groups is more preferable. The acid group of the acidic dispersant (acidic resin) is preferably 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. Further, the basic dispersant (basic resin) represents 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%. The basic group contained in the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably contains a repeating unit having an acid group. Since the resin used as the dispersant contains a repeating unit having an acid group, it is possible to further reduce the residue generated on the base of the pixel when forming a pattern by the photolithography method.

The resin used as the dispersant is preferably a resin containing a repeating unit having a graft chain in the side chain (hereinafter, also referred to as a graft resin). According to this aspect, the dispersibility of the metal azo pigment A or the like can be further improved. Here, the graft chain means a polymer chain that branches and extends from the main chain of a repeating unit. The length of the graft chain is not particularly limited, but the longer the graft chain, the higher the steric repulsion effect, and the dispersibility of pigments and the like can be improved. In the graft chain, the number of atoms excluding hydrogen atoms is preferably 40 to 10,000, the number of atoms excluding hydrogen atoms is more preferably 50 to 2000, and the number of atoms excluding hydrogen atoms is 60 to. It is more preferably 500.

The graft chain preferably contains at least one structure selected from a polyester chain, a polyether chain, a poly (meth) acrylic chain, a polyurethane chain, a polyurea chain and a polyamide chain, and preferably contains a polyester chain, a polyether chain and a poly (meth) chain. ) It is more preferable to include at least one structure selected from acrylic chains, and it is further preferable to include polyester chains.

The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like. Among them, a group having a steric repulsion effect is preferable, and an alkyl group having 5 to 24 carbon atoms or an alkoxy group is preferable, from the viewpoint of improving the dispersibility of the metal azo pigment A or the like. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and are preferably linear or branched.

Examples of the graft resin include resins having the following structures. Further, the details of the graft resin can be referred to in paragraphs 0025 to 0094 of JP2012-255128A, and the contents thereof are incorporated in the present specification.

The resin used as the dispersant is also preferably an oligoimine-based resin containing a nitrogen atom in at least one of the main chain and the side chain. The oligoimine-based resin has a structural unit having a partial structure X having a functional group of pKa14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and at least a main chain and a side chain. A resin having a basic nitrogen atom on one side is preferable. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. Regarding the oligoimine-based resin, the description in paragraphs 0102 to 0166 of JP2012-255128A can be referred to, and the above contents are incorporated in the present specification. Specific examples of the oligoimine-based resin include the following. Further, the resin described in paragraph numbers 0168 to 0174 of JP2012-255128A can be used.

Dispersants are also available as commercial products, and specific examples thereof include the Disperbyk series manufactured by BYK Chemie (for example, Disperbyk-111) and the Solsparse series manufactured by Japan Lubrizol K.K. (for example,). Solsparse 76500, etc.) and the like. Further, the pigment dispersant described in paragraphs 0041 to 0130 of JP2014-130338A can also be used. Further, the above-mentioned resin having an acid group, a polymerizable polymer, or the like can also be used as a dispersant. The resin described as the dispersant can also be used for purposes other than the dispersant. For example, it can also be used as a binder.

When the composition of the present invention contains other resins, the content of the other resins is preferably 1 to 50% by mass based on the total solid content of the composition of the present invention. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. When two or more other resins are contained, the total amount thereof is preferably in the above range.
In addition, the composition of the present invention may be substantially free of other resins. 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% by mass or less, and is 0. It is more preferably 0.05% by mass or less, and particularly preferably not contained.
The total content of the above-mentioned curable compound and the other resin is preferably 5 to 50% by mass based on the total solid content of the composition of the present 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% by mass or less, and more preferably 40% by mass or less. When two or more other resins are contained, the total amount thereof is preferably in the above range.

<< Solvent >>
The composition of the present invention can contain 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.

Examples of the organic solvent include the following organic solvents. Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyloxyoxyacetate. (For example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionate Esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate) (Ethyl, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate)) , 2-Methyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylpropionate methyl and 2-alkyloxy-2- Ethyl methyl propionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate , 2-oxobutanoate methyl, 2-oxobutanoate ethyl and the like. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol. Examples thereof include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like. As the aromatic hydrocarbons, for example, toluene, xylene and the like are preferably mentioned. Further, 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are also preferable from the viewpoint of improving solubility. As the organic solvent, one type may be used alone, or two or more types may be used in combination.

In the present invention, it is preferable to use a solvent having a low metal content as the solvent. The metal content in the solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, a solvent having a metal content of mass ppt (parts per tension) may be used, and such a high-purity solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015) Day). Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.

The organic solvent used in the present invention preferably has a peroxide content of 0.8 mmol / L or less, and more preferably substantially no peroxide.

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

Further, it is preferable that the composition of the present invention does not substantially contain an environmentally regulated substance from the viewpoint of environmental regulation. In the present invention, substantially free of the environmentally regulated substance means that the content of the environmentally regulated substance in the composition is 50 mass ppm or less, and preferably 30 mass ppm or less. It is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Examples of the environmentally regulated substance include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are REACH (Registration Evolution Analysis and Restriction of Chemicals) regulations, PRTR (Pollutant Release and Transfer Register) law, VOC (Volatile Organic Compounds), VOCs (Volatile Organic Compounds), VOCs (Volatile Organic Compounds), VOCs (Volatile Organic Compounds) The method is strictly regulated. These compounds may be used as a solvent in producing each component used in the composition of the present invention, and may be mixed in the composition as a residual solvent. From the viewpoint of human safety and consideration for the environment, it is preferable to reduce these substances as much as possible. Examples of the method for reducing the environmentally regulated substance include a method of heating or depressurizing the inside of the system to raise the boiling point of the environmentally regulated substance to the boiling point or higher, and distilling off the environmentally regulated substance from the system to reduce the amount of the environmentally regulated substance. Further, when distilling off a small amount of an environmentally regulated substance, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to improve efficiency. When a compound having radical polymerization property is contained, a polymerization inhibitor or the like is added and distilled under reduced pressure in order to prevent the radical polymerization reaction from proceeding and cross-linking between molecules during distillation under reduced pressure. You may. These distillation methods are either at the stage of the raw material, at the stage of the product obtained by reacting the raw materials (for example, a resin solution after polymerization or a polyfunctional monomer solution), or at the stage of a composition prepared by mixing these compounds. It is also possible in stages.

<< Photopolymerization Initiator >>
The composition of the present invention may 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 may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, and the like. Examples thereof include thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds and α-aminoketone compounds. From the viewpoint of exposure sensitivity, the photopolymerization initiator includes trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, and triarylimidazole. Dimer, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxaziazole compounds and 3-aryl substituted coumarin compounds are preferred, oxime compounds, α-hydroxyketone compounds, α- A compound selected from an aminoketone compound and an acylphosphine compound is more preferable, and an oxime compound is further preferable. Excellent curability can be obtained by using an oxime compound as a photopolymerization initiator. Furthermore, even when the composition is stored for a long period of time in a low temperature environment, a film having more suppressed defects can be produced. It is presumed that the reason why such an effect is obtained is as follows. The metal azo pigment A contained in the composition of the present invention contains two or more kinds of metal ions, and depending on the type of metal ion, a metal azo compound (metal complex) composed of the above-mentioned anion and metal ion is arranged. The seat is different. For example, in the case of Cu ²⁺ , a metal complex having a planar conformation is formed, and in the case of Zn ²⁺ , a metal complex having a regular octahedral conformation is formed. Therefore, it is presumed that the above-mentioned metal azo pigment A exists in an unstable state in which it is difficult to associate in the composition containing a solvent or the like, and the metal azo pigment A tends to aggregate easily during storage of the composition. It is presumed to be in. Further, in particular, when the content of nickel ion (Ni ²⁺ ) in the metal azo pigment A is small, or when the metal azo pigment A does not contain nickel ion, it is presumed to be energetically unstable, and the composition. It is presumed that the metal azo pigment A tends to agglomerate more easily during storage. However, it is presumed that the oxime compound coordinates with the metal azo pigment A and acts as a chelating agent by blending the oxime compound, and as a result, the metal azo pigment A can be stabilized, and the metal azo pigment A can be stabilized. It is presumed that the aggregation of azo compounds can be suppressed more effectively. Therefore, it is presumed that a film having more suppressed defects can be produced even when the composition is stored for a long period of time in a low temperature environment.

Examples of commercially available α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all manufactured by BASF). Examples of commercially available α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (all manufactured by BASF). Examples of commercially available acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (all manufactured by BASF).

Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, and the compounds described in JP-A-2006-342166. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photosystemer Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-66385, the compound described in JP-A-2000-66385. Compounds described in JP-A-2000-80068, compounds described in JP-A-2004-534977, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-197666, Patent No. Examples thereof include the compounds described in WO 6065596, the compounds described in WO2015 / 152153, and the compounds described in WO2017 / 051680. Specific examples of the oxime compound include, for example, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxyiminopentane-3-3. On, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxy Examples thereof include carbonyloxyimino-1-phenylpropane-1-one. Commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF), TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-P. 305 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd. (CANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD)), ADEKA ARCLUS NCI-930, ADEKA PTOMER N-1919 (Photopolymerization Initiator 2 of JP2012-14052A). ) (Manufactured by ADEKA CORPORATION) and the like.

Further, as an oxime compound other than the above, a compound described in JP-A-2009-5199004 in which an oxime is linked to the N-position of the carbazole ring, and a compound described in US Pat. No. 7,626,957 in which a heterosubstituted group is introduced at a benzophenone moiety. , The compounds described in JP-A-2010-15025 and US Patent Publication No. 2009-292039, the keto-oxime compounds described in International Publication WO2009 / 131189, the triazine skeleton and the oxime skeleton, in which a nitro group was introduced into the dye site. Examples thereof include the compound described in Japanese Patent Application Laid-Open No. 7556910 contained in the same molecule, and the compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source. ..

In the present invention, an oxime compound having a fluorene ring can also be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466.

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

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

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

In the present invention, an oxime compound having a nitro group can be used as the photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466, and Patents 4223071. Examples thereof include the compounds described in paragraphs 0007 to 0025 of the publication, ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation).

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

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

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

In the present invention, a bifunctional or trifunctional or higher functional photopolymerization initiator may 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. Further, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the composition with time can be improved. Specific examples of the bifunctional or trifunctional or higher functional photopolymerization initiator include paragraphs of JP-A-2010-527339, JP-A-2011-524436, WO2015 / 004565, and JP-A-2016-532675. Nos. 0417 to 0412, dimers of oxime compounds described in paragraphs 0039 to 0055 of WO2017 / 033680, compounds (E) and compounds (G) described in JP2013-522445. ), Cmpd1-7 described in International Publication WO2016 / 034963, oxime ester photoinitiator described in paragraph number 0007 of Japanese Patent Application Laid-Open No. 2017-523465, paragraph of JP-A-2017-167399. Examples thereof include the photoinitiator described in Nos. 0020 to 0033 and the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342.

When the composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 30% by mass based on the total solid content of the composition. The lower limit is, for example, more preferably 0.5% by mass or more, further preferably 1% by mass or more. The upper limit is, for example, more preferably 20% by mass or less, further preferably 10% by mass or less.
The content of the photopolymerization initiator is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the above-mentioned metal azo pigment 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 more, and more preferably 80 parts by mass or less.
When an oxime compound is used as the photopolymerization initiator, the content of the oxime compound is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the above-mentioned metal azo pigment 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 more, and more preferably 80 parts by mass or less. According to this aspect, the above-mentioned effects of the present invention tend to be obtained more remarkably.
The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators. When two or more kinds of photopolymerization initiators are contained, the total amount thereof is preferably in the above 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. When the polyfunctional thiol is used together with the above-mentioned photopolymerization initiator, it acts as a chain transfer agent in the radical polymerization process after light irradiation and generates chile radicals that are less susceptible to polymerization inhibition by oxygen, thus increasing the sensitivity of the composition. be able to. In particular, a polyfunctional aliphatic thiol in which the SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.

Examples of the polyfunctional thiol include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropio. Nate, trimethylolpropanetristhioglycolate, trimethylolpropanetristhiopropionate, trimethylolethanetris (3-mercaptobutyrate), trimethylolpropanetris (3-mercaptobutylate), trimethylolpropanetris (3- Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropion Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s -Triazine and the like. In addition, compounds having the following structures can also be mentioned.

The content of the polyfunctional thiol is preferably 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, still more preferably 0.1 to 10% by mass, based on the total solid content of the composition of the present invention. .. The composition of the present invention may contain only one type of polyfunctional thiol, or may contain two or more types of polyfunctional thiols. When two or more kinds of polyfunctional thiols are contained, the total amount thereof is preferably in the above range.

式（ｓｙｎ１）中、Ｐは色素構造を表し、Ｌは単結合または連結基を表し、Ｘは酸基、塩基性基またはフタルイミド基を表し、ｍは１以上の整数を表し、ｎは１以上の整数を表し、ｍが２以上の場合は複数のＬおよびＸは互いに異なっていてもよく、ｎが２以上の場合は複数のＸは互いに異なってもよい。<< 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 are suppressed with respect to temperature changes. Examples of the pigment derivative 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).

In the formula (syn1), P represents a dye 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 1 or more. When m is 2 or more, the plurality of Ls and Xs may be different from each other, and when n is 2 or more, the plurality of Xs may be different from each other.

The pigment structure represented by P in the formula (syn1) includes a pyrolopyrrolop pigment structure, a diketopyrrolopyrrole pigment structure, a quinoline pigment structure, a quinacridone pigment structure, an isoindolin pigment structure, an isoindolinone pigment structure, an anthraquinone pigment structure, and a dianthraquinone. Pigment structure, benzoisoindole pigment structure, thiazine indigo pigment structure, azo pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, dioxazine pigment structure, perylene pigment structure, perinone pigment structure, benzoimidazolone pigment structure, At least one selected from benzothiazole pigment structure, benzoimidazole pigment structure and benzoxazole pigment structure is preferable, and at least one selected from pyrolopyrrolop pigment structure, diketopyrrolopyrrole pigment structure, quinacridone pigment structure and benzoimidazolone pigment structure. Is more preferable, and the pyrolopyrrolop dye structure is particularly preferable.

The linking group represented by L in the formula (syn1) includes a hydrocarbon group, a heterocyclic group, -NR-, -SO _2- , -S-, -O-, -CO-, -COO-, -OCO-, Alternatively, a group consisting of a combination of these can be mentioned. 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. Further, it may be a group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are combined. The hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a condensed ring. The number of condensed rings is preferably 2 to 8, and more preferably 2 to 4. Examples of the hetero atom constituting the ring of the heterocyclic group include a nitrogen atom, a sulfur atom and an oxygen atom, and a nitrogen atom is preferable.

In the formula (syn1), X represents an acid group, a basic group or a phthalimide group. Examples of the acid group represented by X include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, and an imic acid group. As the carboxylic acid amide group, a group represented by -NHCOR ^X1 is preferable. The sulfonic acid amide _group, preferably a group represented by _-NHSO ^{2 R X2.} 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. Represented by R ^X1 to R ^X6, the hydrocarbon group and heterocyclic group may have a substituent. Examples of the substituent include the above-mentioned Substituent T, which is preferably a halogen atom and more preferably a fluorine atom. Examples of the basic group represented by X include an amino group. The amino 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. Examples of the substituent include the above-mentioned Substituent T. The phthalimide group represented by X may be unsubstituted or may have a substituent. Examples of the substituent include the above-mentioned Substituent T.

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

Examples of the pigment derivative include compounds having the following structures. In the following structural formula, Me represents a methyl group and Ph represents a phenyl group. Examples of the pigment derivative include JP-A-56-118462, JP-A-63-264674, JP-A-1-2170777, JP-A-3-9961 and JP-A-3-26767. Kaihei 3-153780, JP-A-3-455662, JP-A-4-285669, JP-A-6-145546, JP-A-6-21288, JP-A-6-241588, JP-A-10. -0063, JP-A-10-195326, paragraph numbers 0083 to 0998 of International Publication WO2011 / 024896, paragraphs 0063 to 0094 of International Publication WO2012 / 102399, paragraphs of International Publication WO2017 / 0328252 The description is given in No. 882, Japanese Patent No. 5299151.

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, based on 100 parts by mass of the pigment contained in the composition. The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the metal azo pigment A. The composition of the present invention may contain only one type of pigment derivative, or may contain two or more types of pigment derivatives. When two or more kinds of pigment derivatives are contained, the total amount thereof is preferably in the above range.

<< Surfactant >>
The composition of the present invention can contain a surfactant. Regarding surfactants, the description in paragraphs 0238 to 0245 of International Publication WO2015 / 166779 can be referred to, and the contents thereof are incorporated in the present specification. Examples of the surfactant include a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a silicone-based surfactant, and the like, and a fluorine-based surfactant is preferable. By containing a fluorine-based surfactant in the composition of the present invention, liquid properties (particularly, fluidity) can be improved, and liquid saving can be further improved. It is also possible to form a film having a small thickness unevenness.

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. Fluorine-based surfactants having a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving.

Examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of JP2014-413318 (paragraphs 0060 to 0064 of the corresponding international publication WO2014 / 17669), JP-A-2011-132503. Examples thereof include the surfactants described in paragraphs 0117 to 0132 of the publication. Commercially available products of fluorine-based surfactants include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, and MFS. -330 (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, Examples thereof include SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA) and the like. ..

The fluorine-based surfactant is an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes. Acrylic compounds can be used. Examples of such a fluorine-based surfactant include Megafuck DS series (for example, Megafuck 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-A-2016-216602 can be referred to, and the content thereof is incorporated in the present specification.

上記の化合物の重量平均分子量は、好ましくは３，０００〜５０，０００であり、例えば、１４，０００である。上記の化合物中、繰り返し単位の割合を示す％はモル％である。As the fluorine-based surfactant, a block polymer can be used. Examples of the block polymer include compounds described in JP-A-2011-89090. Further, the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (preferably 5 or more). Fluorine-containing copolymers containing a repeating unit derived from a meta) acrylate compound can be used. The following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compounds is preferably 3,000 to 50,000, for example 14,000. Among the above compounds,% indicating the ratio of the repeating unit is mol%.

Further, as the fluorine-based surfactant, a fluorine-containing copolymer containing a repeating unit having an ethylenically unsaturated group in the side chain can be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965, Megafvck RS-101, RS-102, RS-718K manufactured by DIC Corporation. RS-72-K and the like can be mentioned. Further, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP2015-117327A can also be used.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF) , Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsparse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.) Industrial Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orphine E1010, Surfinol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) And so on.

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

<< UV absorber >>
The composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indol compound, a triazine compound and the like can be used. For details thereof, refer to paragraph numbers 0052 to 0072 of JP2012-208374A, paragraph numbers 0317 to 0334 of JP2013-68814, and paragraph numbers 0061 to 0080 of JP2016-162946. It can be taken into consideration and these contents are incorporated in the present specification. Specific examples of the ultraviolet absorber include compounds having the following structures. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Examples of the benzotriazole compound include the MYUA series made by Miyoshi Oil & Fat Co., Ltd. (The Chemical Daily, February 1, 2016).

When the composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total solid content of the composition. , 0.1 to 3% by mass is particularly preferable. The composition of the present invention may contain only one kind of ultraviolet absorber, or may contain two or more kinds of ultraviolet absorbers. When two or more kinds of ultraviolet absorbers are contained, it is preferable that the total amount thereof is within the above range.

<< Silane Coupling Agent >>
The composition of the present invention can contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group and the like. Meta) Acryloyl and epoxy groups are preferred. Examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP2009-288703A and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A. Incorporated into the specification.

The content of the silane coupling agent is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly 0.1 to 5% by mass, based on the total solid content of the composition of the present invention. preferable. The composition of the present invention may contain only one type of silane coupling agent, or may contain two or more types of silane coupling agent. When two or more kinds of silane coupling agents are contained, the total amount thereof is preferably in the above range.

<< Polymerization inhibitor >>
The composition of the present invention preferably contains a polymerization inhibitor. Since the composition of the present invention contains a polymerization inhibitor, it is possible to produce a film in which defects are further suppressed even when the composition is stored for a long period of time in a low temperature environment. The detailed reason for obtaining such an effect is unknown, but it is presumed to be due to the following. That is, since the metal azo pigment A contained in the composition of the present invention contains two or more kinds of metal ions, the metal azo compounds composed of the above-mentioned anions and metal ions are metal to each other during storage of the composition. It is presumed that exchange will occur and precipitates will be generated, but it is presumed that the inclusion of a polymerization inhibitor reduces the degree of activation of the metal azo compounds and makes it difficult for metal azo compounds to exchange with each other. , It is presumed that the above-mentioned effect was obtained.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, quaternary-4'-thiobis (3-methyl-6-t-butylphenol), and the like. 2,2'-Methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, first cerium salt, etc.), etc. 2,2,6,6-tetramethylpiperidine 1- Oxyl and the like can be mentioned.
When the composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.0001 to 1% by mass in the composition. The lower limit is preferably 0.0005% by mass or more, and more preferably 0.001% by mass or more. The upper limit is preferably 0.5% by mass or less, more preferably 0.1% by mass or less. The composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types of polymerization inhibitors. When two or more kinds of polymerization inhibitors are contained, the total amount thereof is preferably in the above range.

<< Other additives >>
Various additives such as fillers, adhesion promoters, antioxidants, latent antioxidants, thermal polymerization initiators and the like can be added to the composition of the present invention, if necessary. Regarding these additives, the description in paragraph No. 0183 of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraph number of JP-A-2008-250074. The descriptions of 0101 to 0104, 0107 to 0109, etc. can be taken into consideration, and these contents are incorporated in the present specification. Further, as the antioxidant, for example, a phenol compound and a phosphorus compound (for example, paragraph No. 004 of JP2011-90147A)
The compound described in 2), a thioether compound and the like can be used. Commercially available products include, for example, the ADEKA stub series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-" manufactured by ADEKA Corporation. 330, etc.). The latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. As a result, a compound in which the protecting group is eliminated and functions as an antioxidant can be mentioned. Examples of the latent antioxidant include compounds described in International Publications WO2014 / 021023, International Publications WO2017 / 030005, and JP-A-2017-008219. Examples of commercially available products include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like. Examples of the thermal polymerization initiator include pinacol compounds, organic peroxides, azo compounds and the like, and pinacol compounds are 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-tetra (4-methoxyphenyl) ethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, 1,2-bis (triethylsiloxy) -1,1,2,2-tetraphenyl Etan, 1,2-bis (t-butyldimethylsiloxy) -1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1- Examples thereof include hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane and 1-hydroxy-2-t-butyldimethylsiloxy-1,1,2,2-tetraphenylethane. Further, regarding the pinacol compound, the description of Japanese Patent Publication No. 2014-521772, Japanese Patent Publication No. 2014-523939, and Japanese Patent Publication No. 2014-521772 can be referred to, and the contents thereof are incorporated in the present specification.

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

The viscosity (23 ° C.) of the composition of the present invention is preferably 1 to 100 mPa · s, for example, when a film is formed by coating. The lower limit is more preferably 2 mPa · s or more, and further preferably 3 mPa · s or more. The upper limit is more preferably 50 mPa · s or less, further preferably 30 mPa · s or less, and particularly preferably 15 mPa · s or less.

The container for the composition of the present invention is not particularly limited, and a known container can be used. In addition, as a storage container, for the purpose of suppressing impurities from being mixed into raw materials and compositions, a multi-layer bottle having a container inner wall composed of 6 types and 6 layers of resin and a bottle having 6 types of resin having a 7-layer structure are used. It is also preferable to use it. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

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

<Method of preparing composition>
The composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the composition, all the components may be dissolved or dispersed in a solvent at the same time to prepare the composition, or if necessary, two or more solutions or dispersions in which each component is appropriately mixed may be prepared in advance. They may be prepared and mixed at the time of use (at the time of application) to prepare a composition.

In addition, the composition is preferably prepared by including a process of dispersing the pigment. In the process of dispersing the pigment, the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of means for carrying out these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like. Be done. Further, in the pulverization of the pigment in the sand mill (bead mill), it is preferable to use beads having a small diameter and to process the pigment under the condition that the pulverization efficiency is increased by increasing the filling rate of the beads. Further, it is preferable to remove coarse particles by filtration, centrifugation or the like after the pulverization treatment. Regarding the process and disperser for dispersing pigments, "Dispersion Technology Taizen, published by Information Organization Co., Ltd., July 15, 2005", "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial Practical application The process and disperser described in Paragraph No. 0022 of JP-A-2015-157893, "Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be used. Further, in the process of dispersing the pigment, the pigment may be miniaturized in the salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling step, for example, the descriptions of JP-A-2015-194521 and JP-A-2012-046629 can be referred to.

In preparing the composition, it is preferable to filter the composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultrahigh molecular weight). A filter using a material such as (including the polyolefin resin of) is mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

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. If the pore size of the filter is within the above range, fine foreign matter can be removed more reliably. For the pore size value of the filter, the nominal value of the filter manufacturer can be referred to. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc. can be used.

It is also preferable to use a fibrous filter medium as the filter. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Examples of 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, different filters (eg, first filter and second filter, etc.) may be combined. At that time, the filtration with each filter may be performed only once or twice or more. Further, filters having different pore diameters may be combined within the above-mentioned range. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration with the second filter may be performed.

<Membrane>
Next, the film of the present invention will be described. The film of the present invention is obtained from the above-mentioned composition of the present invention. The film of the present invention can be preferably used as an infrared transmission filter.

In the film of the present invention, the maximum value of the light transmittance 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 wavelength is 1000 to 1000 to. It is preferable that the minimum value in the range of 1300 nm satisfies the spectral characteristics of 70% or more (preferably 75% or more, more preferably 80% or more).

It is more preferable that the film of the present invention satisfies any of the following spectral characteristics (111) to (113).
(111): The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 600 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and is in the film thickness direction. An embodiment in which the minimum value of the light transmittance in the wavelength range of 800 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 600 nm can be shielded to form a film capable of transmitting light having a wavelength of more than 650 nm.
(112): The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 720 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and is in the film thickness direction. An embodiment in which the minimum value of the light transmittance in the wavelength range of 900 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 750 nm can be shielded to form a film capable of transmitting light having a wavelength exceeding 800 nm.
(113): The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and is in the film thickness direction. An embodiment in which the minimum value of the light transmittance in the wavelength range of 1000 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 830 nm can be shielded to form a film capable of transmitting light having a wavelength exceeding 900 nm.

The film thickness of the film of the present invention can be appropriately adjusted according to the intended purpose. 10.0 μm or less is preferable, 5.0 μm or less is more preferable, 3.0 μm or less is further preferable, 2.5 μm or less is further preferable, 2.0 μm or less is further preferable, and 1.5 μm or less is particularly preferable. The lower limit of the film thickness is preferably 0.4 μm or more, more preferably 0.5 μm or more, further preferably 0.6 μm or more, further preferably 0.7 μm or more, even more preferably 0.8 μm or more, and 0. 9.9 μm or more is particularly preferable.

<Membrane manufacturing method>
Next, the method for producing the film of the present invention will be described. The film of the present invention can be produced through a step of applying the composition of the present invention.

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

As a method for applying the composition, a known method can be used. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a rotary coating method (spin coating method); a casting coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395). (Methods described in the publication); Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Various printing methods; transfer method using a mold or the like; nano-imprint method and the like. The application by inkjet is not particularly limited, and is, for example, the method shown in "Expandable and usable inkjet-Infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (particularly pages 115 to 133). ), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. .. Further, the application by the spin coating method is preferably performed at a rotation speed of 1000 to 2000 rpm. Regarding the coating by the spin coating method, as described in JP-A-10-142603, JP-A-11-302413, and JP-A-2000-157922, the rotation speed is increased during coating. Is also good. In addition, the spin coating process described in "State-of-the-art color filter process technology and chemicals", January 31, 2006, CMC Publishing, can also be preferably used. Further, as a method for applying the composition, the methods described in International Publication WO2017 / 0307174 and International Publication WO2017 / 018419 are mentioned, and these contents are incorporated in the present specification.

The composition layer (coating film) formed by applying the composition may be dried (prebaked). When the film is produced by a low temperature process, prebaking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 110 ° C. or lower. The lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher. The prebaking time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.

It is also preferable that the method for producing a film further includes a step of forming a pattern. Examples of the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method, and a pattern forming method using a photolithography method is preferable. When the film of the present invention is used as a flat film, it is not necessary to perform the step of forming the pattern. Hereinafter, the process of forming the pattern will be described in detail.

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

<< Exposure process >>
In the exposure step, the composition layer is exposed in a pattern. For example, a pattern exposure can be performed by exposing the composition layer through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. As a result, the exposed portion can be cured. Examples of radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF line (wavelength 193 nm), and KrF line (wavelength 248 nm) is preferable. Irradiation dose (exposure dose), for example, preferably 0.03~2.5J / cm ^2, more preferably 0.05~1.0J / cm ^2, and most preferably 0.08~0.5J / cm ² .. The oxygen concentration at the time of exposure can be appropriately selected. For example, it may be exposed in the atmosphere, or may be exposed in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially anoxic), and the oxygen concentration is high. Exposure may be carried out in a high oxygen atmosphere exceeding 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume). Further, the exposure illuminance can be appropriately set and is preferably selected from the range of 1000 to 100,000 W / m ² . Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / ^{m 2} at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / ^{m 2.}

<< Development process >>
Next, the composition layer in the unexposed portion of the composition layer after exposure is developed and removed to form a pattern. Development and removal of the composition layer in the unexposed portion can be performed using a developing solution. As a result, the composition layer of the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion remains on the support. The temperature of the developing solution is preferably, for example, 20 to 30 ° C. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.

The developing solution is preferably an alkaline aqueous solution obtained by diluting an alkaline agent with pure water. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, organics such as 1,8-diazabicyclo [5.4.0] -7-undecene. Examples thereof include alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. As the alkaline agent, a compound having a large molecular weight is preferable in terms of environment and safety. 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. Examples of the surfactant include the above-mentioned surfactants, and nonionic surfactants are preferable. The developer may be once produced as a concentrated solution and diluted to a concentration required for use from the viewpoint of convenience of transfer and storage. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. When an alkaline aqueous solution is used as a developing solution, it is preferable to wash (rinse) with pure water after development. Further, it is preferable that the rinsing is performed by supplying the rinsing liquid to the developed composition layer while rotating the support on which the developed composition layer is formed. It is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral edge of the support. At this time, when moving the nozzle from the central portion of the support to the peripheral portion, the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the center to the peripheral edge of the support.

It is also possible to perform heat treatment (post-baking) after development and drying. Post-baking is a post-development heat treatment to complete the curing of the film. When post-baking is performed, the post-baking temperature is preferably 100 to 240 ° C., for example. From the viewpoint of film curing, 200 to 230 ° C. is more preferable. Post-baking should be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the above conditions are met. Can be done.

(When forming a pattern by dry etching method)
In the pattern formation by the dry etching method, the composition layer formed by applying the composition of the present invention on a support is cured to form a cured product layer, and then a resist patterned on the cured product layer. A layer can be formed, and then the cured product layer can be dry-etched with an etching gas using the patterned resist layer as a mask. Regarding the pattern formation by the dry etching method, the description in paragraphs 0010 to 0067 of JP2013-064993A can be referred to, and this content is incorporated in the present specification.

<Infrared transmission filter>
Next, the infrared transmission filter of the present invention will be described. The infrared transmission filter of the present invention has the above-mentioned film of the present invention.

The infrared transmission filter of the present invention can also be used in combination with a color filter containing a chromatic colorant. The color filter can be produced by using a coloring composition containing a chromatic colorant. Examples of the chromatic colorant include the chromatic colorant described in the composition of the present invention. 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. For these details, the materials described in the compositions of the present invention can be mentioned and they can be used.

Further, the infrared transmission filter of the present invention is also preferably an embodiment having pixels of the film of the present invention and pixels selected from red, green, blue, magenta, yellow, cyan, black and colorless.

<Solid image sensor>
The solid-state image sensor of the present invention includes the film of the present invention described above. The configuration of the solid-state image sensor is not particularly limited as long as it has the film of the present invention and functions as a solid-state image sensor. For example, the following configuration can be mentioned.

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

<Optical sensor>
The optical sensor of the present invention includes the above-mentioned film of the present invention. The configuration of the optical sensor is not particularly limited as long as it 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 image sensor. The imaging region provided on the solid-state image sensor 110 includes a near-infrared cut filter 111 and an infrared transmission filter 114. Further, a 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 flattening layer 116 is formed so as to cover the microlens 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 on which pixels that transmit and absorb light of a specific wavelength in the visible region are formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used. For example, the description in paragraphs 0214 to 0263 of JP2014-043556 can be referred to, and this content is incorporated in the present specification. The characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used.

In the infrared sensor shown in FIG. 1, a near-infrared cut filter (another near-infrared cut filter) different from the near-infrared cut filter 111 may be further arranged on the flattening layer 116. Other near-infrared cut filters include those having a copper-containing layer and / or a dielectric multilayer film. These details include those described above. Further, as another near-infrared cut filter, a dual bandpass filter may be used.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. Unless otherwise specified, "parts" are based on mass.

<Measurement of weight average molecular weight>
The weight average molecular weight of the resin was measured by gel permeation chromatography (GPC) according to the following conditions.
Column type: Column in which TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 are linked Developing solvent: tetrahydrofuran Column temperature: 40 ° C.
Flow rate (sample injection amount): 1.0 μL (sample concentration 0.1% by mass)
Device name: HLC-8220GPC manufactured by Tosoh Corporation
Detector: RI (refractive index) detector Calibration curve base resin: Polystyrene resin

<Manufacturing of metal azo pigments>
(Manufacture of Metal Azo Pigment 1)
46.2 g of diazobarbituric 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 about 5, and then the mixture was stirred for 90 minutes to produce an azobarbituric acid precursor.
Then, 1500 g of distilled water at 82 ° C. was added to the azobarbituric acid precursor produced according to the above method. Then, 10 g of 30% hydrochloric acid was added dropwise. Then 79.4 g of melamine was added. A mixture of 0.282 mol of about 25% zinc chloride solution and 0.0015 mol of about 30% copper (II) chloride solution was then added dropwise. Then, the solution to which these were added was held at a temperature of 82 ° C. for 3 hours, and then KOH was added to adjust the pH to about 5.5. Then, the temperature of this solution was raised to 90 ° C., and 100 g of distilled water was added to dilute the solution while maintaining the temperature of 90 ° C. Then, 21 g of 30% hydrochloric acid was added dropwise to this solution, and then heat treatment was performed at a temperature of 90 ° C. for 12 hours. Next, an aqueous potassium hydroxide solution was added to the heat-treated solution to adjust the pH to about 5. The pigment was then isolated from this solution on a suction filter, washed, dried in a vacuum drying cabinet at 80 ° C. and then ground in a standard laboratory mill for about 2 minutes to produce the metal azo pigment 1.

(Manufacture of Metal Azo Pigment 2)
154.1 g of diazobarbituric 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 about 5, and then the mixture was stirred for 90 minutes to produce an azobarbituric acid precursor.
Then, 5000 g of distilled water at 82 ° C. was added to the azobarbituric acid precursor produced according to the above method. Then 252.2 g of melamine was added. Then a mixture of 0.68 mol of about 30% nickel (II) chloride solution, 0.02 mol of about 30% copper (II) chloride solution, and 0.200 mol of about 20% lanthanum chloride (III) solution. It was added by dropping. Then, the solution to which these were added was held at 82 ° C. for 3 hours, and then KOH was added to adjust the pH to about 5.5. Then, the temperature of this solution was raised to 90 ° C., and 1000 g of distilled water was added to dilute the solution while maintaining the temperature of 90 ° C. Then, 113 g of 30% hydrochloric acid was added dropwise to this solution, and then heat treatment was performed at a temperature of 90 ° C. for 12 hours. Next, an aqueous potassium hydroxide solution was added to the heat-treated solution to adjust the pH to about 5. The pigment was then isolated from this solution on a suction filter, washed, dried in a vacuum drying cabinet at 80 ° C. and then ground in a standard laboratory mill for about 2 minutes to produce the metal azo pigment 2.

(Manufacture of Metal Azo Pigment 3)
154.1 g of diazobarbituric 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 about 5, and then the mixture was stirred for 90 minutes to produce an azobarbituric acid precursor.
Then, 5000 g of distilled water at 82 ° C. was added to the azobarbituric acid precursor produced according to the above method. Then 252.2 g of melamine was added. Then a mixture of 0.70 mol of about 30% nickel (II) chloride solution, 0.05 mol of about 30% zinc chloride (II) solution, and 0.167 mol of about 20% lanthanum chloride (III) solution. It was added by dropping. Then, the solution to which these were added was held at 82 ° C. for 3 hours, and then KOH was added to adjust the pH to about 5.5. Then, the temperature of this solution was raised to 90 ° C., and 1000 g of distilled water was added to dilute the solution while maintaining the temperature of 90 ° C. Then, 113 g of 30% hydrochloric acid was added dropwise to this solution, and then heat treatment was performed at a temperature of 90 ° C. for 12 hours. Next, an aqueous potassium hydroxide solution was added to the heat-treated solution to adjust the pH to about 5. The pigment was then isolated from this solution on a suction filter, washed, dried in a vacuum drying cabinet at 80 ° C. and then ground in a standard laboratory mill for about 2 minutes to produce the metal azo pigment 3.

(Manufacture of Metal Azo Pigment 4)
46.2 g of diazobarbituric 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 about 5, and then the mixture was stirred for 90 minutes to produce an azobarbituric acid precursor.
Then, 5000 g of distilled water at 82 ° C. was added to the azobarbituric acid precursor produced according to the above method. Then 252.2 g of melamine was added. A mixture of 0.285 mol of about 25% nickel chloride solution and 0.010 mol of about 10% gadolinium chloride (III) solution was then added dropwise. Then, the solution to which these were added was held at 82 ° C. for 3 hours, and then KOH was added to adjust the pH to about 5.5. Then, the temperature of this solution was raised to 90 ° C., and 1000 g of distilled water was added to dilute the solution while maintaining the temperature of 90 ° C. Then, 113 g of 30% hydrochloric acid was added dropwise to this solution, and then heat treatment was performed at a temperature of 90 ° C. for 12 hours. Next, an aqueous potassium hydroxide solution was added to the heat-treated solution to adjust the pH to about 5. The pigment was then isolated from this solution on a suction filter, washed, dried in a vacuum drying cabinet at 80 ° C. and then ground in a standard laboratory mill for about 2 minutes to produce the metal azo pigment 4.

<How to remove environmentally regulated substances>
(Production Example 1) Production of polymerizable monomer D5 50 g of polyfunctional acrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) containing 238 mass ppm of toluene as a residual solvent in a flask, and propylene glycol monomethyl acetate (PGMEA). 50 g and 80 mg of 2,2,6,6-tetramethylpiperidin 1-oxyl (TEMPO) were added, the external temperature was set to 90 ° C., and the pressure inside the flask was gradually reduced from normal pressure. The pressure was adjusted to 68 mmHg, and distillation was carried out under reduced pressure over 4 hours. Then, the weight in the system was adjusted with PGMEA so as to be 100 g, and a polyfunctional acrylate solution 1 (polymerizable monomer D5) was obtained. When the amount of residual solvent (toluene) contained in the polyfunctional acrylate solution 1 was measured by gas chromatography, it was confirmed that the amount was reduced to 11 mass ppm. In addition, a peak derived from a polyfunctional acrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) was detected by ¹ H-NMR (nuclear magnetic resonance), and it was confirmed that a cross-linking reaction due to radical polymerization did not occur.

(Production Example 2) Production of Dispersant C5 50 g of an acrylate compound (Aronix M-5300, manufactured by Toa Synthetic Co., Ltd.) containing 835 mass ppm of toluene as a residual solvent in a flask, 50 g of PGMEA, and 40 mg of TEMPO. The external temperature was set to 90 ° C., and the pressure inside the flask was gradually reduced from normal pressure to 66 mmHg, and distillation was carried out under reduced pressure over 4 hours. Then, the weight in the system was adjusted with PGMEA so as to be 100 g, and the monomer solution 1 was obtained. When the amount of residual solvent (toluene) contained in the monomer solution 1 was measured by gas chromatography, it was confirmed that the amount was reduced to 9 mass ppm. In addition, a peak derived from an acrylate compound (Aronix M-5300, manufactured by Toagosei Co., Ltd.) was detected by ¹ H-NMR, and it was confirmed that a cross-linking reaction due to radical polymerization did not occur.

1044.2 g of ε-caprolactone, 184.3 g of δ-valerolactone and 71.6 g of 2-ethyl-1-hexanol were introduced into a three-necked flask to obtain a mixture. Next, the mixture was stirred while blowing nitrogen. Next, 0.61 g of monobutyltin oxide was added to the mixture and the resulting mixture was heated to 90 ° C. After 6 hours, ¹ H-NMR was used to confirm that the signal derived from 2-ethyl-1-hexanol in the mixture had disappeared, and then the mixture was heated to 110 ° C. After continuing the polymerization reaction at 110 ° C. for 12 hours under nitrogen and confirming the disappearance of the signals derived from ε-caprolactone and δ-valerolactone by ¹ H-NMR, the obtained compound had a molecular weight by the GPC method. Measurements were made. After confirming that the molecular weight of the compound reached the desired value, 0.35 g of 2,6-di-t-butyl-4-methylphenol was added to the mixture containing the above compound. After that, 87.0 g of 2-methacryloyloxyethyl isocyanate was added dropwise to the obtained mixture over 30 minutes. Six hours after the completion of the dropping, after confirming that the signal derived from 2-methacryloyloxyethyl isocyanate (MOI) had disappeared by ¹ H-NMR, 1387.0 g of PGMEA was added to the mixture, and the concentration was 50 mass by mass. 2770 g of a% macromonomer A-1 solution was obtained. The structure of macromonomer A-1 (shown in formula (A-1)) was confirmed by ^{1 1} H-NMR. The weight average molecular weight of the obtained macromonomer A-1 was 6,000.

To a three-necked flask, 120 g of the macromonomer A-1 solution, 280 g of the monomer solution 1 and 266.7 g of PGMEA were added to obtain a mixture. The mixture was stirred while blowing nitrogen. The mixture was then warmed to 75 ° C. while flowing nitrogen into the flask. 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 to carry out the polymerization reaction. Started. After heating the mixture at 75 ° C. for 2 hours, an additional 0.83 g of V-601 was added to the mixture. After 2 hours, an additional 0.83 g of V-601 was added to the mixture. After a further reaction for 2 hours, the mixture was heated to 90 ° C. and stirred for 3 hours. The polymerization reaction was completed by the above operation.
After completion of the reaction, 6.0 g of dimethyldodecylamine and 2.46 g of TEMPO were added under air, and then 15.7 g of glycidyl methacrylate was added. After continuing the reaction at 90 ° C. for 24 hours under air, the completion of the reaction was confirmed by acid value measurement. After cooling to 60 ° C., 15.6 g of 2-isocyanatoethylacryllate (AOI) was further added to the obtained mixture, and the mixture was reacted at 60 ° C. for 6 hours. ¹ The disappearance of AOI was confirmed by ¹ H-NMR measurement. An appropriate amount of PGMEA was added to the obtained mixture to obtain a 20% by mass solution of the dispersant C-5. The weight average molecular weight of the obtained resin C-5 was 25,000, the acid value was 80 mgKOH / mg, and the C = C value was 0.9 mmol / g. Moreover, when the amount of toluene contained in the resin C-5 was measured, it was confirmed that it was 5 mass ppm or less.

[Test Example 1]
<Manufacturing of pigment dispersion>
After mixing the raw materials shown in Table 1 below, 230 parts by mass of zirconia beads having a diameter of 0.3 mm are added, and dispersion treatment is performed for 5 hours using a paint shaker. The beads are separated by filtration to prepare a pigment dispersion liquid. Manufactured. The numbers listed in the table below are parts by mass.

<Preparation of composition>
The raw materials shown in Tables 2 to 5 below were mixed to prepare the compositions of Examples 1 to 25 and Comparative Examples 1 to 3. The numbers listed in the table below are parts by mass.

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

(Color material)
Metal azo pigments 1 to 4: The above-mentioned metal azo pigments 1 to 4
PR254: C.I. I. Pigment Red 254
PY139: C.I. I. Pigment Yellow 139
PV23: C.I. I. Pigment Violet 23
PB15: 6: C.I. I. Pigment Blue 15: 6
PB16: C.I. I. Pigment Blue 16
IB: Irgaphor Black (manufactured by BASF)
PBk32: C.I. I. Pigment Black 32

(Near infrared absorbing pigment)
K1, K2, K5, K6, K7, K8, K10: Compounds with the following structure. In the following formula, Me represents a methyl group and Ph represents a phenyl group.
K9: FDN-003 (manufactured by Yamada Chemical Co., Ltd.)

(Pigment derivative)
B1, K3, K4: Compounds with the following structure. In the following structural formula, Ph represents a phenyl group and Me represents a methyl group.

(Dispersant)
C1: Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Mw = 20,000)
C2: Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Mw = 24,000)
C3: Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Mw = 20,000)
C4: BYK2000 (solid content concentration 40% by mass, manufactured by Big Chemie Japan Co., Ltd.)
C5: Dispersant C5 (solid content concentration 20% by mass) produced in Production Example 2 described above.

(resin)
P1: Resin having the following structure (Mw = 11000, the numerical value added to the main chain is the molar ratio. Me is a methyl group)
P2: Resin having the following structure. (Mw = 4400, acid value = 95 mgKOH / g, in the following structural formula, M is a phenyl group and A is a biphenyltetracarboxylic dianhydride residue.)
P3: Cyclomer ACA250 (solid content concentration 45% by mass, manufactured by Daicel Corporation)
P4: Resin having the following structure (Mw = 30,000, the numerical value added to the main chain is the molar ratio)

Ｄ４：下記構造の化合物

Ｄ５：上記製造例１で製造した重合性モノマーＤ５（固形分濃度５０質量％）
Ｄ６：アロニックスＭ−５２０（東亞合成（株）製）(Polymerizable monomer)
D1: Compound with the following structure (a + b + c = 3)
D2: Compound with the following structure (a + b + c = 4)
D3: Mixture of compounds having the following structure (compound of a + b + c = 5: compound of a + b + c = 6 = 3: 1 (molar ratio))

D4: Compound with the following structure

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 having the following structure (Et is an ethyl group in the following structural formula)

Ｉ６：アデカアークルズＮＣＩ−８３１（（株）ＡＤＥＫＡ製、オキシム化合物）
Ｉ７：ＩＲＧＡＣＵＲＥ−３７９（ＢＡＳＦ社製、α−アミノケトン化合物）
Ｉ８：特表２０１７−５２３４６５号公報の段落番号０００７に記載された化合物ＮＯ．１２
Ｉ９：特開２０１７−１５１３４２号公報の段落番号００２５に記載された式（２）の化合物
Ｉ１０：特開２０１７−１６７３９９号公報の段落番号００３１に記載された化合物６
（紫外線吸収剤）
Ｌ１：下記構造の化合物

(Photopolymerization initiator)
I1 to I5: Compounds with the following structure (oxime compounds)

I6: ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation, oxime compound)
I7: IRGACURE-379 (manufactured by BASF, α-aminoketone compound)
I8: Compound No. 0007 described in paragraph No. 0007 of JP-A-2017-523465. 12
I9: Compound of formula (2) described in paragraph number 0025 of JP-A-2017-151342 I10: Compound 6 described in paragraph number 0031 of JP-A-2017-167399.
(UV absorber)
L1: Compound with the following structure

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

(Surfactant)
F1: The following mixture (Mw = 14000). In the formula below,% indicating the ratio of the repeating unit is mol%.

(Epoxy compound)
N1: EHPE3150 (manufactured by Daicel Corporation)
(Polymerization inhibitor)
G1: p-methoxyphenol (solvent)
J1: Propylene glycol monomethyl ether acetate (PGMEA)
J2: Cyclohexanone J3: 3-methoxy-N, N-dimethylpropanamide J4: 3-Butoxy-N, N-dimethylpropanamide

<Evaluation of spectral characteristics>
Each composition was applied onto a glass substrate using a spin coater so that the film thickness after post-baking would be the film thickness shown in the table below, and prebaked for 120 seconds using a hot plate at 100 ° C. Next, the entire surface of the prebaked 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.
Using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Co., Ltd.), the absorbance and transmittance of the obtained film at a wavelength of 400 to 1300 nm were measured, and the maximum transmittance in the wavelength range of 400 to 600 nm was measured. Value (transparency T1), minimum value of transmittance in the wavelength range of 1000 to 1300 nm (transparency T2), minimum value of absorbance in the wavelength range of 400 to 600 nm (absorbance A), absorbance in the wavelength range of 1000 to 1300 nm The maximum value (absorbance B), the ratio of the minimum value of absorbance in the wavelength range of 400 to 600 nm and the maximum value of absorbance in the wavelength range of 1000 to 1300 nm (absorbance A / absorbance B) was measured.

<Film thickness uniformity>
Each composition was applied on an 8-inch (20.32 cm) silicon wafer by a spin coating method. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. The film thickness of the obtained film was measured using an optical film thickness meter (Fimetrics Co., Ltd., F50), and the difference between the thinnest part and the thickest part (hereinafter referred to as the film thickness difference). ) Was calculated. It can be said that the smaller the film thickness difference, the better the film thickness uniformity.
5: The film thickness difference is 0.02 μm or less.
4: The film thickness difference is greater than 0.02 μm and 0.03 μm or less 3: The film thickness difference is greater than 0.03 μm and 0.04 μm or less 2: The film thickness difference is greater than 0.04 μm and 0.05 μm or less Yes 1: The film thickness difference is larger than 0.05 μm

<Moisture resistance>
Each composition was applied onto a glass substrate using a spin coater so that the film thickness after post-baking would be the film thickness shown in the table below, and prebaked for 120 seconds using a hot plate at 100 ° C. Next, the entire surface of the prebaked 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% to perform a high temperature and high humidity test. With respect to the film after the high temperature and high humidity test, a 1 cm square portion was observed with an optical microscope, and the number of crystalline defects having a size of 0.5 μm or more was counted to evaluate the moisture resistance.
5: Number of defects is 0 4: Number of defects is 1 to 4 3: Number of defects is 5 to 9 2: Number of defects is 10 to 15 1: Number of defects is 16 or more

As shown in the above table, the examples were excellent in film thickness uniformity and moisture resistance. In addition, the composition of the example was excellent in light blocking property in the wavelength range of 400 to 600 nm, and could be preferably used as an infrared transmission filter.
In addition, the compositions of Examples 1 to 4 were able to block light in the wavelength range of 400 to 600 nm to form a film capable of transmitting light having a wavelength of more than 650 nm.
In addition, the compositions of Examples 5 to 13 were able to block light in the wavelength range of 400 to 720 nm to form a film capable of transmitting light having a wavelength of more than 800 nm.
In addition, the compositions of Examples 14 to 25 were able to block light in the wavelength range of 400 to 830 nm to form a film capable of transmitting light having a wavelength of more than 900 nm.

In each example, even when benzopinacol is further contained in the total solid content of the composition in an amount of 1% by mass, 2% by mass, 3% by mass, 4% by mass or 5% by mass, the same as in each example. The effect of is obtained.

[Test Example 2]
The compositions of Examples 1 to 25 were applied onto a silicon wafer using a spin coater so that the film thicknesses after post-baking were the film thicknesses shown in Table 6, respectively, and used on a hot plate at 100 ° C. for 120 seconds. Pre-baked. Next, the entire surface of the prebaked 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 forming an absorption layer was applied to the surface of the obtained membrane using a spin coater, and prebaked for 120 seconds using a hot plate at 100 ° C. Next, the entire surface of the prebaked 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. A laminate was formed. This laminate was able to block and transmit light in the same wavelength range as in Test Example 1. Furthermore, it was also excellent in light resistance.

(Composition for forming an absorption layer)
C. I. 12 parts by mass of 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 having a diameter of 0.3 mm, and dispersed for 5 hours using a paint shaker. Then, the beads were separated by filtration to produce a Yellow pigment dispersion.
35 parts by mass of the obtained Yellow pigment dispersion, 12 parts by mass of the resin P1, 4 parts by mass of the polymerizable monomer D5, 1.8 parts by mass of the photopolymerization initiator I1, and 47.2 parts by mass of PGMEA. The parts were mixed to produce a composition for forming an absorption layer.

[Test Example 3]
The IR composition was applied onto a silicon wafer by a spin coating method so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus (FPA-3000i5 +, manufactured by Canon Inc.), exposure was performed at an exposure amount of 1000 mJ / cm ² through a mask having a 2 μm square Bayer pattern.
Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. Next, a 2 μm square Bayer pattern (near infrared cut filter) was formed by heating at 200 ° C. for 5 minutes using a hot plate.
Next, the Red composition was applied onto the Bayer pattern of the near-infrared cut filter by a spin coating method so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus (FPA-3000i5 +, manufactured by Canon Inc.), exposure was performed at an exposure amount of 1000 mJ / cm ² through a mask having a 2 μm square pattern. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. The Red composition was then patterned on the Bayer pattern of the near-infrared cut filter by heating at 200 ° C. for 5 minutes using a hot plate. Similarly, the Green composition and the Blue composition were sequentially patterned to form red, green and blue coloring patterns.
Next, the compositions of Examples 14 to 25 were applied onto the patterned film by a spin coating method so that the film thickness after film formation was 2.0 μm. Then, it was heated at 100 ° C. for 2 minutes using a hot plate. Next, using an i-line stepper exposure apparatus (FPA-3000i5 +, manufactured by Canon Inc.), exposure was performed at an exposure amount of 1000 mJ / cm ² through a mask having a 2 μm square pattern. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. Next, by heating at 200 ° C. for 5 minutes using a hot plate, a film (infrared ray transmitting filter) of the compositions of Examples 14 to 25 was formed in the missing portion of the Bayer pattern of the near infrared ray cut filter. This was incorporated into a solid-state image sensor according to a known method.
The obtained solid-state image sensor was irradiated with light from an infrared light emitting diode (infrared LED) light source in a low illuminance environment (0.001 Lux), and an image was captured to evaluate the image performance. I was able to clearly recognize the subject on the image. In addition, the angle of incidence dependence was good. Further, the infrared transmission filter can obtain the same effect even if the film thickness described is achieved by the multi-layer coating. For example, in the case of Example 14, the composition is applied by a spin coating method to form a coating film, then the coating film is heated at 100 ° C. for 120 seconds, then exposed and developed, and then at 200 ° C. 5 The film thickness may be adjusted to 2.0 μm by repeating a series of operations for minute heating a plurality of times.

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, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a Red composition.
Red pigment dispersion: 51.7 parts by mass Resin 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 Kagaku Co., Ltd.) ・ ・ ・ 0.3 parts by mass PGMEA ・ ・ ・ 46.6 parts by mass

(Green composition)
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a Green composition.
Green pigment dispersion ・ ・ ・ 73.7 parts by mass Resin 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 UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ・ ・ ・ 0.5 parts by mass PGMEA ・ ・ ・ 23.5 parts by mass

(Blue composition)
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a Blue composition.
Blue pigment dispersion 44.9 parts by mass Resin 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 UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ・ ・ ・ 0.3 parts by mass PGMEA ・ ・ ・ 49.8 parts by mass

(IR composition)
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare an IR composition.
IR pigment dispersion ・ ・ ・ 85 parts by mass Polymerizable monomer D6 ・ ・ ・ 1.8 parts by mass Resin P1 ・ ・ ・ 1.1 parts by mass Photopolymerization initiator I1 ・ ・ ・ 0.9 parts by mass Surface active agent F1 ・・ ・ 0.2 parts by mass Polymerization inhibitor (p-methoxyphenol) ・ ・ ・ 0.001 parts by mass PGMEA ・ ・ ・ 11.0 parts by mass

The pigment dispersions used in the Red composition, Green composition, Blue composition and IR composition are as follows.

-Red pigment dispersion C. I. 9.6 parts by mass of Pigment Red 254 and C.I. I. A mixed solution consisting of 4.3 parts by mass of Pigment Yellow 139, 6.8 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0. 3 mm diameter) was mixed and dispersed for 3 hours. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion.

-Green pigment dispersion C. I. 6.4 parts by mass of Pigment Green 36 and C.I. I. A mixed solution consisting of 5.3 parts by mass of Pigment Yellow 150, 5.2 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0. 3 mm diameter) was mixed and dispersed for 3 hours. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion.

-Blue pigment dispersion C. I. Pigment Blue 15: 6 with 9.7 parts by mass and C.I. I. A mixed solution consisting of 2.4 parts by mass of Pigment Violet 23, 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie) and 82.4 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0. 3 mm diameter) was mixed and dispersed for 3 hours. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion.

-IR pigment dispersion liquid A mixed liquid consisting of 6.25 parts by mass of the near infrared absorbing dye K2, 1.25 parts by mass of the pigment derivative K4, 6 parts by mass of the dispersant C3, and 86.5 parts by mass of PGMEA. Was mixed and dispersed in a bead mill (zirconia beads 0.3 mm in diameter) for 3 hours. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain an IR pigment dispersion.

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

Claims (14)

A metal azo pigment containing at least one anion selected from an azo compound represented by the following formula (I) and an azo compound having a telecommunication structure thereof, two or more metal ions, and a melamine compound.
Color materials other than the metal azo pigments, which have an absorption maximum in the wavelength range of 400 to 700 nm, and
A composition comprising a compound having an ethylenically unsaturated bond group and at least one compound selected from a compound having a cyclic ether group.
A composition having an A / B of 4.5 or more, which is the ratio of the minimum absorbance A in the wavelength range of 400 to 600 nm to the maximum absorbance B in the wavelength range of 1000 to 1300 nm.

In the equation, R ¹ and R ² are independently OH or NR ⁵ R ⁶ , respectively.
R ³ and R ⁴ are independently = O or = NR ⁷ , respectively.
R ^{5 to} R ⁷ are independently hydrogen atoms or alkyl groups. The composition according to claim 1, wherein the metal azo pigment contains the anion, a metal ion containing at least Zn ²⁺ and Cu ²⁺ , and the melamine compound. The composition according to claim 2, wherein a total of 95 to 100 mol% of Zn ²⁺ and Cu ²⁺ are contained based on 1 mol of all metal ions in the metal azo pigment. The composition according to claim 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 to 1:15. The composition according to any one of claims 1 to 4, 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 independently hydrogen atoms or alkyl groups. The composition according to any one of claims 1 to 5, wherein the coloring material 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. The composition according to any one of claims 1 to 6, further comprising a near-infrared absorbing dye. The composition according to claim 7, wherein the near-infrared absorbing dye has an absorption maximum in the wavelength range of 800 to 900 nm. The composition according to claim 7 or 8, wherein the near-infrared absorbing dye is at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, and a croconium compound. The composition according to any one of claims 1 to 9, which is for an infrared transmission filter. A film obtained by using the composition according to any one of claims 1 to 10. The infrared transmission filter having the film according to claim 11. The solid-state imaging device having the film according to claim 11. The optical sensor having the film according to claim 11.

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