KR20230130694A - Compositions, films, optical filters, solid-state imaging devices, image displays, infrared sensors, camera modules, compounds, and infrared absorbers - Google Patents

Abstract

A composition capable of forming a film with low fluorescence quantum yield and excellent spectral characteristics is provided. The composition contains a pigment represented by formula (1) and a curable compound. In formula (1), X ^a and X ^b each independently represent =NR ^X1 or a specific group, R ^X1 represents a substituent, Ya and Yb each independently represent a hydrogen atom or a substituent, and R1 and ^R2 each independently represent an aliphatic hydrocarbon group which may have a substituent.

Description

Compositions, membranes, optical filters, solid-state imaging devices, image display devices, infrared sensors, camera modules, compounds, and infrared absorbers

The present invention relates to a composition containing a pyrrolopyrrole compound. Additionally, the present invention relates to a membrane, an optical filter, a solid-state imaging device, an image display device, an infrared sensor, and a camera module using the above-described composition. Additionally, the present invention relates to pyrrolopyrrole compounds and infrared absorbers.

Video cameras, digital still cameras, mobile phones equipped with camera functions, etc. use solid-state imaging devices for color images, such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor). These solid-state imaging devices use silicon photodiodes that are sensitive to infrared rays in their light-receiving parts. For this reason, there are cases where an infrared cut-off filter is provided and visual sensitivity correction is performed.

Infrared cut filters are manufactured using a composition containing an infrared absorbing dye. As infrared absorbing dyes, pyrrolopyrrole compounds and the like are known.

On the other hand, Patent Document 1 describes using a compound represented by the following formula (I) in a solar cell module or the like.

[Formula 1]

Patent Document 1: International Publication No. 2016/158819 Patent Document 2: Japanese Patent Publication No. 2014-240371

Recently, additional improvements in spectral characteristics have been required for films obtained using compositions containing infrared absorbing dyes. For example, excellent visual transparency is required.

Additionally, when using a film obtained using a composition containing an infrared absorbing dye in a solid-state imaging device or the like, it is preferable that the fluorescence quantum yield of the film is low. If the fluorescence quantum yield of the film is high, fluorescence emission from the film is likely to become noise.

On the other hand, Patent Document 2 is an invention aimed at increasing the fluorescence quantum yield. In addition, as a result of the present inventor's examination of the compound described in Patent Document 2, it was found that there is room for further improvement in visible transparency.

Therefore, an object of the present invention is to provide a composition capable of forming a film having a low fluorescence quantum yield and excellent spectral characteristics. Additionally, an object of the present invention is to provide a film, an optical filter, a solid-state imaging device, an image display device, an infrared sensor, and a camera module using the composition. Additionally, an object of the present invention is to provide a compound and an infrared absorber.

The present invention provides the following.

<1> A composition containing a pigment represented by formula (1) and a curable compound;

[Formula 2]

In formula ( ¹ ), X ^a and X ^b each independently represent a group represented by ⁼ NR

Y ^a and Y ^b each independently represent a hydrogen atom or a substituent,

R ¹ and R ² each independently represent an aliphatic hydrocarbon group which may have a substituent;

[Formula 3]

In formulas (X-1) to (X-5), * represents a connection part,

R ^a11 ~R ^a29 each independently represent a hydrogen atom or a substituent,

X ^c and X ^d each independently represent S, O or NR ^X2 , R ^X2 represents a hydrogen atom or a substituent,

A ¹ represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a condensed ring thereof which may have a substituent.

<2> The composition according to <1>, wherein X ^a and X ^b in the formula (1) are each independently a group represented by any one of formulas (X-1-1) to (X-1-3);

[Formula 4]

In formulas (X-1-1) to (X-1-3), * represents a connection part,

R ^a51 to R ^a63 each independently represent a hydrogen atom or a substituent,

Among R ^a51 to R ^a54 in formula (X-1-1), two adjacent groups may be combined to form a ring,

Among R ^a55 to R ^a58 in formula (X-1-2), two adjacent groups may be combined to form a ring,

Among R ^a60 to R ^a63 in formula (X-1-3), two adjacent groups may be bonded to form a ring.

<3> Y ^a and Y ^b in the above formula (1) each independently represent -BR ^Y1 R ^Y2 ,

R ^Y1 and R ^Y2 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group,

The composition according to <1> or <2>, wherein R ^Y1 and R ^Y2 may be bonded to each other to form a ring.

<4> The composition according to any one of <1> to <3>, wherein at least one of R ¹ and R ² in the formula (1) is an alkyl group having 9 or less carbon atoms which may have a substituent.

<5> The composition according to any one of <1> to <3>, wherein at least one of R ¹ and R ² in the formula (1) is a group represented by formula (R-1);

[Formula 5]

In formula (R-1), * represents a connecting portion, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a substituent, Ar ¹⁰¹ represents an aryl group or heteroaryl group, and n represents an integer of 1 or more.

<6> The composition according to any one of <1> to <5>, wherein the pigment represented by the formula (1) has a maximum absorption wavelength of 650 nm or more.

<7> A film obtained using the composition according to any one of <1> to <6>.

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

<9> A solid-state imaging device comprising the film according to <7>.

<10> An image display device comprising the film according to <7>.

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

<12> A camera module including the membrane according to <7>.

<13> Compound represented by formula (1);

[Formula 6]

In formula ( ¹ ), X ^a and X ^b each independently represent a group represented by ⁼ NR

Y ^a and Y ^b each independently represent a hydrogen atom or a substituent,

R ¹ and R ² each independently represent an aliphatic hydrocarbon group which may have a substituent;

[Formula 7]

In formulas (X-1) to (X-5), * represents a connection part,

R ^a11 ~R ^a29 each independently represent a hydrogen atom or a substituent,

X ^c and X ^d each independently represent S, O or NR ^X2 , R ^X2 represents a hydrogen atom or a substituent,

A ¹ represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a condensed ring thereof which may have a substituent.

<14> An infrared absorber containing the compound described in <13>.

According to the present invention, it is possible to provide a composition capable of forming a film having a low fluorescence quantum yield and excellent spectral characteristics. Additionally, according to the present invention, a film, an optical filter, a solid-state imaging device, an image display device, an infrared sensor, a camera module, a compound, and an infrared absorber can be provided.

1 is a schematic diagram showing one embodiment of an infrared sensor.

Below, the contents of the present invention will be described in detail.

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

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

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

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

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

In this specification, Me in the formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In this specification, infrared rays refer to light (electromagnetic waves) with a wavelength of 700 to 2500 nm.

In this specification, total solid content refers to the total mass of components excluding the solvent from all components of the composition.

In this specification, pigment means a compound that is difficult to dissolve in a solvent.

In this specification, the term "process" includes not only an independent process, but also a process that cannot be clearly distinguished from other processes if the intended effect of the process is achieved.

<Composition>

The composition of the present invention is characterized by containing a pigment represented by formula (1) and a curable compound.

The dye represented by formula (1) has a low fluorescence quantum yield and is excellent in visible transparency. Although the detailed reason is unknown, it is presumed that when R ¹ and R ² are aliphatic hydrocarbon groups, the transition of the pigment in the visible region can be reduced, and as a result, visible transparency can be improved. In addition, it is presumed that since ^{X a} and X ^b are groups represented by =NR For this reason, by using the composition of the present invention, it is possible to form a film with low fluorescence quantum yield and excellent spectral characteristics.

The composition of the present invention can be used as a composition for optical filters. Types of optical filters include infrared cutoff filters and infrared transmission filters. Since the pigment represented by formula (1) is excellent in visible transparency, an infrared cut filter with excellent visible transparency can be formed by using the composition of the present invention. Additionally, in an infrared transmission filter, the dye represented by formula (1) has a role in limiting the transmitted light (infrared rays) to a longer wavelength side. Since the dye represented by formula (1) has excellent visible transparency, it is easy to control the spectrum in the visible region to be shielded and the spectrum in the infrared region to be transmitted to an appropriate range.

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

<<Pigment (specific pigment) expressed in equation (1)>>

The composition of the present invention contains a pigment represented by formula (1) (hereinafter also referred to as a specific pigment).

[Formula 8]

In formula ( ¹ ), X ^a and X ^b each independently represent a group represented by ⁼ NR

Y ^a and Y ^b each independently represent a hydrogen atom or a substituent,

R ¹ and R ² each independently represent an aliphatic hydrocarbon group which may have a substituent;

[Formula 9]

In formulas (X-1) to (X-5), * represents a connection part,

R ^a11 ~R ^a29 each independently represent a hydrogen atom or a substituent,

X ^c and X ^d each independently represent S, O or NR ^X2 , R ^X2 represents a hydrogen atom or a substituent,

A ¹ represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a condensed ring thereof which may have a substituent.

In formula (1), X ^a and X ^b each independently represent a group represented by =NR ^X1 or any of formulas (X-1) to (X-5).

The substituent represented by ^R

The number of carbon atoms in the aryl group is preferably 6 to 40, more preferably 6 to 30, and still more preferably 6 to 20. The aryl group may be a monocyclic ring, but is preferably a condensed ring.

Although the heteroaryl group may be a single ring, it is preferable that it is a condensed ring. The number of heteroatoms constituting the heteroaryl ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl ring is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The number of carbon atoms constituting the heteroaryl ring is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12. The heteroaryl ring is preferably a 5-membered ring or a 6-membered ring.

The aryl group and heteroaryl group may have a substituent or may be unsubstituted. The substituent includes a group represented by the substituent T described later and a group represented by the formula (R-100) described later, and includes a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an acyl group, an alkoxycarbonyl group, an acyloxy group, It is preferably an aryl group, an aryloxy group, a hydroxy group, a carboxyl group, a carboxylic acid amide group, a sulfonamide group, an imide group, a sulfo group or a group represented by the formula (R-100), a halogen atom, an alkyl group, an alkoxy group, It is more preferable that it is an acyl group, an aryl group, an aryloxy group, a hydroxy group, a carboxyl group, a sulfonamide group, an imide group, or a sulfo group.

Substituents represented by R ^a11 to R ^a29 in formulas (X-1) to (X-5) include groups represented by the substituent T described later and groups represented by the formula (R-100) described later, and include a halogen atom, Alkyl group, alkoxy group, alkylthio group, acyl group, alkoxycarbonyl group, acyloxy group, aryl group, aryloxy group, hydroxy group, carboxyl group, carboxylic acid amide group, sulfonamide group, imide group, sulfo group or formula ( It is preferable that it is a group represented by R-100), and it is more preferable that it is a halogen atom, an alkyl group, an alkoxy group, an acyl group, an aryl group, an aryloxy group, a hydroxy group, a carboxyl group, a sulfonamide group, an imide group, or a sulfo group. do.

In formulas (X-1) to (X-5), X ^c and X ^d each independently represent S, O or NR ^X2 , and R ^X2 represents a hydrogen atom or a substituent. The substituent represented by ^R The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3. The alkyl group may be straight-chain, branched, or cyclic, but is preferably straight-chain or branched, and more preferably is straight-chain. ^R

A ¹ in the formula (X-1) represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a condensed ring thereof that may have a substituent. Examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring. Examples of the aromatic heterocycle include imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, isothiazole ring, and isoxazole ring. Examples of the condensed ring include benzimidazole ring, benzopyrazole ring, benzoxazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, quinazoline ring, quinoxaline ring, etc. The substituent includes a group represented by the substituent T described later and a group represented by the formula (R-100) described later, and includes a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an acyl group, an alkoxycarbonyl group, and an acyloxy group. , an aryl group, an aryloxy group, a hydroxy group, a carboxyl group, a carboxylic acid amide group, a sulfonamide group, an imide group, a sulfo group, or a group represented by the formula (R-100), and is preferably a halogen atom, an alkyl group, or an alkoxy group. , an acyl group, an aryl group, an aryloxy group, a hydroxy group, a carboxyl group, a sulfonamide group, an imide group, or a sulfo group.

The group represented by the formula (X-1) is preferably a group represented by any one of the formulas (X-1-1) to (X-1-3).

[Formula 10]

In formulas (X-1-1) to (X-1-3), * represents a connection part,

R ^a51 to R ^a63 each independently represent a hydrogen atom or a substituent,

Among R ^a51 to R ^a54 in formula (X-1-1), two adjacent groups may be combined to form a ring,

Among R ^a55 to R ^a58 in formula (X-1-2), two adjacent groups may be combined to form a ring,

Among R ^a60 to R ^a63 in formula (X-1-3), two adjacent groups may be bonded to form a ring.

Substituents represented by R ^a51 to R ^a63 in formulas (X-1-1) to (X-1-3) include groups represented by substituent T described later and groups represented by formula (R-100) described later.

The substituents represented by R ^a51 to R ^a58 , R ^a60 to R ^a63 are halogen atom, alkyl group, alkoxy group, alkylthio group, acyl group, alkoxycarbonyl group, acyloxy group, aryl group, aryloxy group, and hydroxy group. , a carboxyl group, a carboxylic acid amide group, a sulfonamide group, an imide group, a sulfo group, or a group represented by the formula (R-100), preferably a halogen atom, an alkyl group, an alkoxy group, an acyl group, an aryl group, an aryloxy group, More preferably, it is a hydroxy group, carboxyl group, sulfonamide group, imide group or sulfo group.

The substituent represented by R ^a59 is preferably an alkyl group, an alkoxy group, an acyl group, an aryl group, or an aryloxy group, and more preferably an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3. The alkyl group may be straight-chain, branched, or cyclic, but is preferably straight-chain or branched, and more preferably is straight-chain.

R ^a59 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

Two adjacent groups among R ^a51 to R ^a54 in formula (X-1-1) may combine to form a ring, and two adjacent groups among R ^a55 to R ^a58 in formula (X-1-2) The groups may combine with each other to form a ring, and two adjacent groups of R ^a60 to R ^a63 in the formula (X-1-3) may combine with each other to form a ring. The ring formed by combining these groups is preferably a 5-membered ring or a 6-membered ring. Specific examples of the rings formed include benzene ring, pyrrole ring, furan ring, thiophene ring, oxazole ring, thiazole ring, imidazole ring, pyridine ring, pyrimidine ring, pyran ring, isothiazole ring, isoxazole ring, and pyran ring. Polyazine rings, pyrazine rings, cyclohexane rings, cyclopentane rings, or combinations thereof can be mentioned.

For the reason of excellent light resistance, it is preferable that ^{X a} and X ^b in formula (1) are each independently =NR For the reason that excellent visible transparency can be obtained, it is more preferable to use = ^NR It is more preferable that it is a group represented by any one of -1) to (X-1-3).

R ¹ and R ² in formula (1) each independently represent an aliphatic hydrocarbon group that may have a substituent. The aliphatic hydrocarbon group represented by R ¹ and R ² may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group represented by R ¹ and R ² may be linear, branched, or cyclic. Additionally, the cyclic aliphatic hydrocarbon group may be any of a monocyclic aliphatic hydrocarbon group, a condensed ring aliphatic hydrocarbon group, and a cross-linked aliphatic hydrocarbon group, but is preferably a monocyclic aliphatic hydrocarbon group. The aliphatic hydrocarbon group represented by R ¹ and R ² may have a substituent. Substituents include a group represented by the substituent T described later and a group represented by the formula (R-100) described later, including a halogen atom, an alkoxy group, an alkylthio group, a ureido group, an acyl group, an alkoxycarbonyl group, an acyloxy group, It is preferably a sulfamoyl group, an aryl group, an aryloxy group, a hydroxy group, a carboxyl group, a carboxylic acid amide group, a sulfonamide group, an imide group, a sulfo group, or a group represented by the formula (R-100). R ¹ in formula (1) has the same contribution as R ² , but is preferably a different group (that is, asymmetric).

Specific examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.

The number of carbon atoms of the alkyl group is preferably 1 to 30. The lower limit is preferably 3 or more. When the specific dye is a pigment, the upper limit of the number of carbon atoms of the alkyl group is preferably 15 or less, more preferably 10 or less, and even more preferably 7 or less. When the specific dye is a dye, the upper limit of the number of carbon atoms in the alkyl group is preferably 25 or less, and more preferably 19 or less. The alkyl group may be linear, branched, or cyclic.

The number of carbon atoms of the alkenyl group is preferably 2 to 30. The lower limit is preferably 3 or more. When the specific dye is a pigment, the upper limit of the carbon number of the alkenyl group is preferably 15 or less, more preferably 10 or less, and still more preferably 7 or less. When the specific dye is a dye, the upper limit of the carbon number of the alkenyl group is preferably 25 or less, and more preferably 19 or less. The alkene group may be linear, branched, or cyclic.

The number of carbon atoms of the alkyne group is preferably 2 to 30. The lower limit is preferably 3 or more. When the specific dye is a pigment, the upper limit of the number of carbon atoms of the alkynyl group is preferably 15 or less, more preferably 10 or less, and still more preferably 7 or less. When the specific dye is a dye, the upper limit of the number of carbon atoms in the alkynyl group is preferably 25 or less, and more preferably 19 or less. The alkaline diary may be linear, branched, or cyclic.

The alkyl group, alkenyl group, and alkynyl group may have a substituent or may be unsubstituted. Substituents include a group represented by the substituent T described later and a group represented by the formula (R-100) described later, including a halogen atom, an alkoxy group, an alkylthio group, a ureido group, an acyl group, an alkoxycarbonyl group, an acyloxy group, It is preferably a sulfamoyl group, an aryl group, an aryloxy group, a hydroxy group, a carboxyl group, a carboxylic acid amide group, a sulfonamide group, an imide group, a sulfo group, or a group represented by the formula (R-100).

[Formula 11]

In formula (R-100), L ^R1 represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, -O-, -S-, -NR ^L1 -, -CO-, -COO-, -OCO-, -SO ₂ - represents an n+1 valent linking group consisting of or a combination thereof, R ^L1 represents a hydrogen atom, an alkyl group or an aryl group, X ^R1 represents an acid group or a basic group, and n represents an integer of 1 or more. When n is 1, L ^R1 may be a single bond.

The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 2 to 20, more preferably 2 to 10, and especially preferably 2 to 5. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include groups represented by the substituent T, which will be described later.

The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. The aromatic hydrocarbon group may have a substituent. Examples of the substituent include groups represented by the substituent T, which will be described later.

The heterocyclic group is preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 4. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The heteroatom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and more preferably 3 to 12. Specific examples of heterocyclic groups include piperazine ring, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, and thiazine ring. Azine group, indole group, isoindole group, benzimidazole group, purine group, quinoline group, isoquinoline group, quinolsaline group, cinnoline group, carbazole group and the following formulas (L-1) to (L-7) You can mention the group that appears as .

[Formula 12]

* in the formula represents a connection part. R represents a hydrogen atom or a substituent. Examples of the substituent include groups represented by the substituent T described later.

The aliphatic hydrocarbon group, aromatic hydrocarbon group, and heterocyclic group may have a substituent. Examples of the substituent include the substituent T described later, and it is preferably a halogen atom, and more preferably a fluorine atom.

The number of carbon atoms of the alkyl group represented by R ^L1 is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 8. The alkyl group may be straight-chain, branched, or cyclic, and is preferably straight-chain or branched, and more preferably straight-chain. The alkyl group represented by R ^L1 may further have a substituent. Examples of the substituent include groups represented by the substituent T, which will be described later.

The number of carbon atoms of the aryl group represented by R ^L1 is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. The aryl group represented by R ^L1 may further have a substituent. Examples of the substituent include groups represented by the substituent T, which will be described later.

Examples of the ^acid group represented by The atoms or atomic groups constituting the salt include alkali metal ions (Li ⁺ , Na ⁺ , K ^{+ ,} etc.), alkaline earth metal ions (Ca ²⁺ , Mg ^{2+ ,} etc.), ammonium ions, imidazolium ions, and pyridinium ions. , phosphonium ion, etc. As the carboxylic acid amide group, the group represented by -NHCOR ^XR1 is preferable. As the sulfonamide group, a group represented by -NHSO ₂ R ^XR2 is preferable. As the imide acid group, a group represented by -SO ₂ NHSO ₂ R ^XR3 , -CONHSO ₂ R ^XR4 , -CONHCOR ^XR5 or -SO ₂ NHCOR ^XR6 is preferable, and -CONHSO ₂ R ^XR4 or -SO ₂ NHSO ₂ R ^XR3 is preferable. desirable. R ^XR1 to R ^XR6 each independently represent an alkyl group or an aryl group. The alkyl group and aryl group represented by R ^XR1 to R ^XR6 may have a substituent. The substituent is preferably a halogen atom, and more preferably a fluorine atom.

Examples of the basic ^group represented by Examples of the atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylic acid ions, sulfonic acid ions, and phenoxide ions.

Examples of the amino group include groups represented by -NRx ^R1 Rx ^R2 and cyclic amino groups. In the group represented by -NRx ^R1 Rx ^R2 , Rx ^R1 and Rx ^R2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and are preferably an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but linear or branched is preferable, and straight chain is more preferable. The alkyl group may have a substituent. Examples of the substituent include groups represented by the substituent T described later. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. The aryl group may have a substituent. Examples of the substituent include groups represented by the substituent T described later. Additionally, Rx ^R1 and Rx ^R2 may be combined to form a ring. Examples of the cyclic amino group include pyrrolidine group, piperidine group, piperazine group, and morpholine group. These groups may further have substituents. Examples of the substituent include groups represented by the substituent T described later. Specific examples of the substituent include an alkyl group and an aryl group.

n in the formula (R-100) represents an integer of 1 or more, and is preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.

As a preferable aspect of Formula (1), at least one of R ¹ and R ² of Formula (1) is an alkyl group having 9 or less carbon atoms which may have a substituent. When the dye is a pigment, the number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 5, more preferably 1 to 4, and especially preferably 1 to 3. According to this aspect, the effect of improving the dispersibility of the pigment and the generation of foreign substances in the pigment dispersion liquid can be suppressed. When the pigment is a dye, the carbon number of the alkyl group is preferably 4 to 9, more preferably 5 to 9, more preferably 6 to 9, and especially preferably 7 to 9. Additionally, in the case of dyes, it is preferable that the alkyl group having 9 or less carbon atoms is branched. According to this aspect, the effect of being able to suppress the generation of foreign substances in the dye solution and the effect of being able to suppress defects in the film formed using the dye solution are obtained. In addition, substituents that an alkyl group having 9 or less carbon atoms may have include a halogen atom, an alkoxy group, an alkylthio group, a ureido group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a sulfamoyl group, a hydroxy group, a carboxyl group, A carboxylic acid amide group, a sulfonamide group, an imide group, a sulfo group, or a group represented by the above-mentioned formula (R-100) can be mentioned, and a halogen atom is preferable. The alkyl group having 9 or less carbon atoms is preferably an unsubstituted alkyl group or an alkyl group (fluoroalkyl group) having a halogen atom as a substituent.

As a preferable aspect of formula (1), at least one of R ¹ and R ² of formula (1) is a group represented by formula (R-1). According to this aspect, associations are easily formed during film formation, and the heat resistance and light resistance of the resulting film can be further improved. In this embodiment, when R ¹ and R ² in formula (1) are each a group represented by formula (R-1), the above-described effect appears more significantly.

[Formula 13]

In formula (R-1), * represents a connecting portion, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a substituent, Ar ¹⁰¹ represents an aryl group or heteroaryl group, and n represents an integer of 1 or more.

Substituents represented by R ¹⁰¹ and R ¹⁰² include alkyl groups, aryl groups, and heteroaryl groups, and are preferably alkyl groups. R ¹⁰¹ and R ¹⁰² are preferably each independently a hydrogen atom.

Ar ¹⁰¹ represents an aryl group or heteroaryl group, and is preferably an aryl group.

n in formula (1) represents an integer of 1 or more, is preferably an integer of 1 to 4, more preferably is an integer of 1 to 3, and is still more preferably 1 or 2.

The number of carbon atoms of the alkyl groups represented by R ¹⁰¹ and R ¹⁰² is preferably 1 to 30, more preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 5, and more preferably 1 to 3. Particularly desirable. The alkyl group may be straight-chain, branched, or cyclic, but is preferably straight-chain or branched, and more preferably is straight-chain. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include groups represented by the substituent T, which will be described later.

The number of carbon atoms of the aryl group represented by R ¹⁰¹ , R ¹⁰² and Ar ¹⁰¹ is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include groups represented by the substituent T, which will be described later.

The number of carbon atoms constituting the heteroaryl group represented by R ¹⁰¹ , R ¹⁰² and Ar ¹⁰¹ is preferably 1 to 30, and more preferably 1 to 12. Examples of heteroatoms constituting the heteroaryl group include nitrogen atom, oxygen atom, and sulfur atom. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 or 2. The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocycle or a condensed ring with a condensation number of 2 to 8, and more preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 4. The heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include groups represented by the substituent T, which will be described later.

As a preferred aspect of Formula (1), R ¹ in Formula (1) is a group with a different structure from R ² . In this aspect, R ¹ and R ² are each independently an alkyl group which may have a substituent, and it is preferable that R ¹ is a group with a different structure from R ² .

Y ^a and Y ^b in formula (1) each independently represent a hydrogen atom or a substituent, and are preferably a substituent. Substituents represented by Y ^a and Y ^b in formula (1) include an alkyl group, an aryl group, a heteroaryl group, and -BR ^Y1 R ^Y2 , and -BR ^Y1 R ^Y2 is preferable.

The number of carbon atoms of the alkyl groups represented by Y ¹ and Y ² is preferably 1 to 30, more preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 5, and still more preferably 1 to 3. Particularly desirable. The alkyl group may be straight-chain, branched, or cyclic, but is preferably straight-chain or branched, and more preferably is straight-chain. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include groups represented by the substituent T, which will be described later.

The number of carbon atoms of the aryl group represented by Y ¹ and Y ² is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include groups represented by the substituent T, which will be described later.

The number of carbon atoms constituting the heteroaryl group represented by Y ¹ and Y ² is preferably 1 to 30, and more preferably 1 to 12. Examples of heteroatoms constituting the heteroaryl group include nitrogen atom, oxygen atom, and sulfur atom. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 or 2. The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocycle or a condensed ring with a condensation number of 2 to 8, and more preferably a monocyclic ring or a condensed ring with a condensation number of 2 to 4. The heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include groups represented by the substituent T, which will be described later.

-R ^Y1 and R ^Y2 in the group represented by BR ^Y1 R ^Y2 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group. It is preferably a halogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a halogen atom, an alkyl group, or an aryl group, and even more preferably an aryl group.

The halogen atom represented by R ^Y1 and R ^Y2 includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

The number of carbon atoms of the alkyl group and alkoxy group represented by R ^Y1 and R ^Y2 is preferably 1 to 40, more preferably 1 to 30, and still more preferably 1 to 20. The alkyl group and the alkoxy group may be straight chain, branched, or cyclic, but are preferably straight chain or branched. The alkyl group and the alkoxy group may have a substituent or may be unsubstituted. Examples of the substituent include an aryl group, heteroaryl group, and halogen atom.

The number of carbon atoms of the alkenyl group represented by R ^Y1 and R ^Y2 is preferably 2 to 40, more preferably 2 to 30, and still more preferably 2 to 20. The alkenyl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, and a halogen atom.

The number of carbon atoms of the aryl group and aryloxy group represented by R ^Y1 and R ^Y2 is preferably 6 to 20, and more preferably 6 to 12. The aryl group and the aryloxy group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom.

The heteroaryl group and heteroaryloxy group represented by R ^Y1 and R ^Y2 may be monocyclic or may be a condensed ring. The number of heteroatoms constituting the heteroaryl ring of the heteroaryl group and heteroaryloxy group is preferably 1 to 3. The hetero atom constituting the heteroaryl ring is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The number of carbon atoms constituting the heteroaryl ring is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12. The heteroaryl ring is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group and heteroaryloxy group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom.

R ^Y1 and R ^Y2 of the group represented by -BR ^Y1 R ^Y2 may be bonded to each other to form a ring. Examples of the formed ring include structures shown in (B-1) to (B-5) below. In the following, Rb represents a substituent, Rb ¹ to Rb ⁴ each independently represent a hydrogen atom or a substituent, b1 to b3 each independently represent an integer of 0 to 4, and b4 is an integer of 0 to 6. Represents an integer, and * indicates a connection part. Substituents represented by Rb and Rb ¹ to Rb ⁴ include groups represented by the substituent T described later, and a halogen atom, an alkyl group, and an alkoxy group are preferable.

[Formula 14]

(substituent T)

As the substituent T, the following groups can be mentioned. Halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (preferably an alkyl group with 1 to 30 carbon atoms), alkenyl group (preferably an alkenyl group with 2 to 30 carbon atoms) , an alkyneyl group (preferably an alkynyl group with 2 to 30 carbon atoms), an aryl group (preferably an aryl group with 6 to 30 carbon atoms), a heteroaryl group (preferably a heteroaryl group with 1 to 30 carbon atoms), Amino group (preferably an amino group with 0 to 30 carbon atoms), alkoxy group (preferably an alkoxy group with 1 to 30 carbon atoms), aryloxy group (preferably an aryloxy group with 6 to 30 carbon atoms), heteroaryloxy group ( Preferably a heteroaryloxy group with 1 to 30 carbon atoms), an acyl group (preferably an acyl group with 2 to 30 carbon atoms), an alkoxycarbonyl group (preferably an alkoxycarbonyl group with 2 to 30 carbon atoms), an aryloxycarbonyl group. (preferably an aryloxycarbonyl group with 7 to 30 carbon atoms), heteroaryloxycarbonyl group (preferably a heteroaryloxycarbonyl group with 2 to 30 carbon atoms), acyloxy group (preferably an acyloxy group with 2 to 30 carbon atoms) group), acylamino group (preferably acylamino group with 2 to 30 carbon atoms), aminocarbonylamino group (preferably aminocarbonylamino group with 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably with 2 to 30 carbon atoms) alkoxycarbonylamino group), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group with 7 to 30 carbon atoms), sulfamoyl group (preferably a sulfamoyl group with 0 to 30 carbon atoms), sulfamoylamino group (preferably a sulfamoyl group with 0 to 30 carbon atoms) is a sulfamoylamino group with 0 to 30 carbon atoms), carbamoyl group (preferably a carbamoyl group with 1 to 30 carbon atoms), an alkylthio group (preferably an alkylthio group with 1 to 30 carbon atoms), and an arylthio group (preferably a carbamoyl group with 1 to 30 carbon atoms). Examples include an arylthio group with 6 to 30 carbon atoms), a heteroarylthio group (preferably a heteroarylthio group with 1 to 30 carbon atoms), an alkyl sulfone group (preferably an alkyl sulfone group with 1 to 30 carbon atoms), and an alkyl group. Ponylamino group (preferably alkylsulfonylamino group with 1 to 30 carbon atoms), arylsulfonyl group (preferably arylsulfonyl group with 6 to 30 carbon atoms), arylsulfonylamino group (preferably arylsulfonyl group with 6 to 30 carbon atoms) amino group), heteroaryl sulfonyl group (preferably a heteroaryl sulfonyl group with 1 to 30 carbon atoms), heteroaryl sulfonylamino group (preferably a heteroaryl sulfonylamino group with 1 to 30 carbon atoms), alkylsulfinyl group (preferably a heteroaryl sulfonyl group with 1 to 30 carbon atoms) alkylsulfinyl group with 1 to 30 carbon atoms), arylsulfinyl group (preferably an arylsulfinyl group with 6 to 30 carbon atoms), heteroaryl sulfinyl group (preferably a heteroaryl sulfinyl group with 1 to 30 carbon atoms), ureido group (preferably a heteroaryl sulfinyl group with 1 to 30 carbon atoms) (e.g., ureido group having 1 to 30 carbon atoms), hydroxy group, nitro group, carboxyl group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imide group, phosphino group, mercapto group, cyano group, Alkyl sulfino group, aryl sulfino group, arylazo group, heteroarylazo group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, hydrazino group, imino group. If these groups are groups that can be further substituted, they may further have substituents. Examples of the substituent include the groups described in the substituent T described above.

The maximum absorption wavelength of a specific dye is preferably in the range of 650 nm or more, more preferably in the range of 650 to 1,500 nm, more preferably in the range of 660 to 1,200 nm, and more preferably in the range of 660 to 1,000 nm. It is particularly preferable that it exists in the range of

In addition, for a specific dye, when the absorbance value at the wavelength (λmax) showing the highest absorbance value in the wavelength range of 400 nm to 1200 nm is set to 1, the average absorbance value in the wavelength range of 420 to 550 nm is It is preferable that it is less than 0.010, and it is more preferable that it is less than 0.005.

The absorbance and maximum absorption wavelength of a specific dye can be obtained by dissolving the specific dye in a solvent, preparing a dye solution, and measuring the absorbance of the dye solution. Solvents used to prepare the dye solution include chloroform, dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF). Additionally, when a specific pigment is a compound that dissolves in chloroform, chloroform is used as a solvent. If a specific pigment is a compound that is not soluble in chloroform but soluble in dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF) is used as the solvent.

In addition, the average absorbance value in the wavelength range of 420 to 550 nm is calculated by taking the absorbance value at λmax as 1 and calculating the weighted average of the normalized values of each absorbance in the wavelength range of 420 to 550 nm. do.

The specific dye may be a pigment or a dye. For example, R ¹ and R ² in formula (1) are the same group, at least one (preferably both) of R ¹ and R ² is a cyclic aliphatic hydrocarbon group, or at least one of R ¹ and R ² is a cyclic aliphatic hydrocarbon group. By making (preferably both) a straight-chain aliphatic hydrocarbon group, or by making at least one (preferably both) of R ¹ and R ² an aliphatic hydrocarbon group with 6 or less carbon atoms, the crystallinity of the pigment, etc. It can reduce the solubility, and such specific dyes can be preferably used as pigments. In addition, R ¹ and R ² in formula (1) may be different groups, or at least one of R ¹ and R ² (preferably both) may be a branched aliphatic hydrocarbon group, or at least one of R ¹ and R ² (preferably both) may be a branched aliphatic hydrocarbon group. By making both (both sides) into an aliphatic hydrocarbon group having 7 or more carbon atoms, the crystallinity of the dye can be lowered and the solubility in the solvent can be improved, and such specific dyes can be preferably used as dyes.

Additionally, the specific dye may be a dye derivative. Dye derivatives are used, for example, as dispersion aids. A dispersion aid is a material for improving the dispersibility of the pigment in the composition. When the composition further contains a resin such as a dispersant, the dispersibility of the pigment can be further improved by forming a network between the pigment, the dispersion aid, and the resin. Compounds ^{having a} structure in which ^{at least} one of X ^{a ,} You can. Additionally, compounds with this structure can also be used as pigments or dyes. The dye derivative is described in detail later.

Additionally, in this specification, equation (1) also includes the resonance structure. That is, compounds having the resonance structure of formula (1) are also included in the specific dye in the present invention.

Specific examples of specific dyes include compounds (PPB-A-1 to PPB-A-45, PPB-B-1 to PPB-B-13, PPB-B-15, PPB-B-) having the structures described in the examples below. 16, PPB-C-1 to PPB-C-3).

The content of the specific pigment is preferably 0.5% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more based on the total solid content of the composition. Moreover, the upper limit of the content of the specific pigment is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less. The composition may contain only one type of specific pigment or may contain two or more types. When two or more types are included, it is preferable that their total amount falls within the above range. The composition of the present invention may contain a decomposition product of a specific pigment.

<<hardenable compound>>

The composition of the present invention contains a curable compound. Examples of the curable compound include polymerizable compounds and resins. The resin may be a non-polymerizable resin (a resin that does not have a polymerizable group) or a polymerizable resin (a resin that has a polymerizable group). Examples of the polymerizable group include an ethylenically unsaturated bond-containing group, a cyclic ether group, a methylol group, and an alkoxymethyl group. Examples of ethylenically unsaturated bond-containing groups include vinyl group, vinylphenyl group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamide group, etc., ( Meth)allyl group, (meth)acryloyl group, and (meth)acryloyloxy group are preferable, and (meth)acryloyloxy group is more preferable. Examples of the cyclic ether group include an epoxy group and an oxetane group, with an epoxy group being preferred.

As a curable compound, it is preferable to use one containing at least a resin. In addition, when using the composition of the present invention as a composition for photolithography, it is preferable to use a resin and a polymerizable monomer (monomer type polymerizable compound) as the curable compound, and the resin and a polymerizable compound having an ethylenically unsaturated bond-containing group are preferably used as the curable compound. It is more preferable to use a polymerizable monomer (monomer type polymerizable compound).

(polymerizable compound)

Examples of the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group, compounds having a cyclic ether group, compounds having a methylol group, and compounds having an alkoxymethyl group. Compounds having an ethylenically unsaturated bond-containing group can be preferably used as radically polymerizable compounds. Moreover, a compound having a cyclic ether group can be preferably used as a cationically polymerizable compound.

Examples of the resin-type polymerizable compound include a resin containing a repeating unit having a polymerizable group.

The molecular weight of the monomer type polymerizable compound (polymerizable monomer) is preferably less than 2000, and more preferably 1500 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, and more preferably 200 or more. The weight average molecular weight (Mw) of the resin-type polymerizable compound is preferably 2,000 to 2,000,000. The upper limit of the weight average molecular weight is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit of the weight average molecular weight is preferably 3000 or more, and more preferably 5000 or more.

The compound having an ethylenically unsaturated bond-containing group as a polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, and more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples include paragraphs 0095 to 0108 of Japanese Patent Application Publication No. 2009-288705, paragraphs 0227 of Japanese Patent Application Publication 2013-029760, paragraphs 0254 to 0257 of Japanese Patent Application Publication 2008-292970, and paragraphs 0254 to 0257 of Japanese Patent Application Publication No. 2013-253224. Paragraph numbers 0034 to 0038, paragraph number 0477 of Japanese Patent Application Publication No. 2012-208494, Japanese Patent Application Publication No. 2017-048367, Japanese Patent Application Publication No. 6057891, Japanese Patent Application Publication No. 6031807, and Japanese Patent Application Publication No. 2017-194662 The compounds described can be mentioned, the contents of which are incorporated herein by reference.

Examples of compounds having an ethylenically unsaturated bond-containing group include dipentaerythritol tri(meth)acrylate (as a commercial product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (as a commercial product) KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate Rate (commercially available products include KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and the (meth)acryloyl group of these compounds is ethylene glycol and /Or compounds having a structure bonded through a propylene glycol residue (for example, SR454, SR499, commercially available from Sartomer), etc. In addition, as compounds having an ethylenically unsaturated bond-containing group, diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available as M-460; Toagosei Co., Ltd.), pentaerythritol tetraacrylate (Shin Nakamura Chemical Industry Co., Ltd.) Co., Ltd., NK Ester A-TMMT), 1,6-hexanediol diacrylate (Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (Nippon Kayaku Co., Ltd.), Aronics TO-2349 (manufactured by Toa Kosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shinnakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate You can also use POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.).

In addition, compounds having an ethylenically unsaturated bond-containing group include trimethylolpropane tri(meth)acrylate, trimethylolpropanepropylene oxide-modified tri(meth)acrylate, and trimethylolpropaneethylene oxide-modified tri(meth)acrylate. ) It is also preferable to use trifunctional (meth)acrylate compounds such as acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. 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 Kosei 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 Shinnakamura Kagaku Kogyo Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) ), etc.

The compound having an ethylenically unsaturated bond-containing group may further have an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group. Commercially available products of such compounds include Aronix M-305, M-510, M-520, and Aronix TO-2349 (manufactured by Toa Kosei Co., Ltd.).

As a compound having an ethylenically unsaturated bond-containing group, a compound having a caprolactone structure can also be used. For compounds having a caprolactone structure, the description in paragraphs 0042 to 0045 of Japanese Patent Application Laid-Open No. 2013-253224 can be referred to, and this content is incorporated herein by reference. Examples of compounds having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, and DPCA-120, which are commercially available as a series from Nippon Kayaku Co., Ltd.

As a compound having an ethylenically unsaturated bond-containing group, a compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used. Such a compound is preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group and/or a propyleneoxy group, and more preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group, and the ethyleneoxy group is It is more preferable that it is a 3- to 6-functional (meth)acrylate compound having 20 units. Commercially available products include, for example, SR-494, a tetrafunctional (meth)acrylate with four ethyleneoxy groups, manufactured by Sartomer, and KAYARAD TPA-330, a trifunctional (meth)acrylate with three isobutyleneoxy groups. I can hear it.

As a compound having an ethylenically unsaturated bond-containing group, a polymerizable compound having a fluorene skeleton can also be used. Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).

As a compound having an ethylenically unsaturated bond-containing group, it is also preferable to use a compound that does not substantially contain environmentally regulated substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

Examples of compounds having an ethylenically unsaturated bond-containing group include UA-7200 (manufactured by Shinnakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (above, manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate It is also preferable to use POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.) or the like.

Examples of the compound having a cyclic ether group include a compound having an epoxy group, a compound having an oxetanyl group, etc., and a compound having an epoxy group is preferable. Examples of compounds having an epoxy group include compounds having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups may be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably two or more. Compounds having an epoxy group include compounds described in paragraphs 0034 to 0036 of JP2013-011869, paragraphs 0147 to 0156 of JP2014-043556, and paragraphs 0085 to 0092 of JP2014-089408. , compounds described in Japanese Patent Application Laid-Open No. 2017-179172 can also be used, the contents of which are incorporated herein by reference.

The compound having a cyclic ether group may be a low molecular compound (for example, a molecular weight of less than 1000) or a macromolecule (for example, a molecular weight of 1000 or more; in the case of a polymer, a weight average molecular weight of 1000 or more). It's okay. The weight average molecular weight of the cyclic ether group is preferably 200 to 100,000, and more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

Compounds having a cyclic ether group include compounds described in paragraphs 0034 to 0036 of JP2013-011869, compounds described in paragraphs 0147 to 0156 of JP2014-043556, and compounds described in JP2014-089408. The compounds described in paragraph numbers 0085 to 0092 and the compounds described in Japanese Patent Application Publication No. 2017-179172 can also be used.

Commercially available compounds having a cyclic ether group include Denacol EX-212L, EX-212, EX-214L, EX-214, EX-216L, EX-216, EX-321L, EX-321, EX-850L, EX- 850 (above, manufactured by Nagase Chemtex Co., Ltd.), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA Co., Ltd.), NC-2000, NC-3000, NC- 7300, Daicel Co., Ltd.), Cyclomer P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, ACA Z320 (above, Daicel Co., Ltd.), jER1031S, jER157S65, jER152, jER154, jER157S70 (above, Mitsubishi) Chemical Co., Ltd.), Aaron Oxetane OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei Co., Ltd.), Adeka Glycyrol ED-505 (made by ADEKA Co., Ltd., epoxy group) monomers contained), Maproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (Nichiyu Co., Ltd. ) agent, epoxy group-containing polymer), OXT-101, OXT-121, OXT-212, OXT-221 (above, Toagosei Co., Ltd. product, oxetanyl group-containing monomer), OXE-10, OXE-30 (above, Osaka Yuki Chemical Co., Ltd. product, oxetane group-containing monomer), etc. are mentioned.

Compounds having a methylol group (hereinafter also referred to as methylol compounds) include compounds in which the methylol group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring.

Additionally, compounds having an alkoxymethyl group (hereinafter also referred to as an alkoxymethyl compound) include compounds in which the alkoxymethyl group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Compounds in which an alkoxymethyl group or methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, and alkoxylamine. Methylated urea, methylolated urea, etc. are preferred. Additionally, the compounds described in paragraphs 0134 to 0147 of Japanese Patent Application Laid-Open No. 2004-295116 and paragraphs 0095 to 0126 of Japanese Patent Application Publication No. 2014-089408 can also be used.

(profit)

The composition of the present invention can use a resin as a curable compound. It is preferable to use a curable compound containing at least a resin. Resins are blended, for example, for dispersing pigments or the like in a composition or for use as a binder. In addition, the resin mainly used to disperse pigments etc. in the composition is also called a dispersant. However, this use of the resin is only an example, and the resin may be used for purposes other than these uses. In addition, resins having a polymerizable group also correspond to polymerizable compounds.

The weight average molecular weight of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4000 or more, and more preferably 5000 or more.

Resins include (meth)acrylic resin, epoxy resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene. Etherphosphine oxide resin, polyimide resin, polyamide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, vinyl acetate resin, polyvinyl alcohol resin, polyvinyl acetal resin, poly oil. Lethane resin, polyurea resin, etc. can be mentioned. One type of these resins may be used individually, or two or more types may be mixed and used. As the cyclic olefin resin, norbornene resin is preferable from the viewpoint of improving heat resistance. Examples of commercially available norbornene resins include the ARTON series (eg, ARTON F4520) manufactured by JSR Corporation. In addition, as the resin, the resin described in the examples of International Publication No. 2016/088645, the resin described in Japanese Patent Application Publication No. 2017-057265, the resin described in Japanese Patent Application Publication No. 2017-032685, and the resin described in Japanese Patent Application Publication No. 2017-075248. Resin described in Japanese Patent Application Publication No. 2017-066240, resin described in Japanese Patent Application Publication No. 2017-167513, resin described in Japanese Patent Application Publication No. 2017-173787, paragraph of Japanese Patent Application Publication No. 2017-206689 Resin described in numbers 0041 to 0060, resin described in paragraph numbers 0022 to 0071 of Japanese Patent Application Publication No. 2018-010856, block polyisocyanate resin described in Japanese Patent Application Publication No. 2016-222891, Japanese Patent Application Publication 2020-122052 A resin described in Japanese Patent Application Publication No. 2020-111656, a resin described in Japanese Patent Application Publication No. 2020-139021, a structural unit having a ring structure in the main chain and a side chain described in Japanese Patent Application Publication No. 2017-138503. A resin containing a structural unit having a biphenyl group can also be used. Moreover, as the resin, a resin having a fluorene skeleton can also be preferably used. Regarding the resin having a fluorene skeleton, the description of US Patent Application Publication No. 2017/0102610 can be referred to, and this content is incorporated herein by reference.

As the resin, it is preferable to use a resin having an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group. The number of these acid groups may be one, or two or more types may be used. A resin having an acid group can also be used as a dispersant. The acid value of the resin having an acid group is preferably 30 to 500 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 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.

As the resin, it is also preferable to include a resin containing a repeating unit derived from a compound represented by the formula (ED1) and/or a compound represented by the formula (ED2) (hereinafter, these compounds may be referred to as "ether dimers"). do.

[Formula 15]

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[Formula 16]

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

For specific examples of ether dimers, reference may be made to paragraph number 0317 of Japanese Patent Application Laid-Open No. 2013-029760, the content of which is incorporated herein by reference.

As the resin, it is also preferable to use a resin having a polymerizable group. The polymerizable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, and is more preferably an ethylenically unsaturated bond-containing group.

As the resin, it is also preferable to use a resin containing a repeating unit derived from a compound represented by formula (X).

[Formula 17]

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represent an alkylene group, and n represents an integer of 0 to 15. The carbon number of the alkylene group represented by R ²¹ and R ²² is preferably 1 to 10, more preferably 1 to 5, more preferably 1 to 3, and especially preferably 2 or 3. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and still more preferably an integer of 0 to 3.

Examples of the compound represented by formula (X) include ethylene oxide or propylene oxide modified (meth)acrylate of paracumylphenol. Commercially available products include Aronics M-110 (manufactured by Toa Kosei Co., Ltd.).

It is preferable that the resin contains 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) refers to a resin in which the amount of acidic groups is greater than the amount of basic groups. As an acidic dispersant (acidic resin), a resin in which the amount of acidic groups is 70 mol% or more when the total amount of acidic groups and basic groups is set to 100 mol% is preferable. The acid group contained in the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. In addition, basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups. As a basic dispersant (basic resin), a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is set to 100 mol% is preferable. The basic group that the basic dispersant has is preferably an amino group.

The resin used as a dispersant is also preferably a graft resin. For details of the graft resin, reference may be made to the description in paragraph numbers 0025 to 0094 of Japanese Patent Application Laid-Open No. 2012-255128, the contents of which are incorporated herein by reference.

The resin used as a dispersant is also preferably a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. As a polyimine-based dispersant, a resin having a main chain with a partial structure having a functional group of pKa 14 or less, a side chain with 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain is preferable. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom that exhibits basicity. Regarding the polyimine-based dispersant, reference may be made to the description in paragraph numbers 0102 to 0166 of Japanese Patent Application Laid-Open No. 2012-255128, and this content is incorporated herein by reference.

The resin used as a dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core portion. Examples of such resins include dendrimers (including star-shaped polymers). In addition, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Laid-Open No. 2013-043962.

The resin used as a dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in the side chain. The content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and still more preferably 20 to 70 mol% of the total repeating units of the resin. .

Additionally, as a dispersant, resins described in Japanese Patent Application Publication No. 2018-087939, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent Application Publication No. 6432077, and International Publication No. 2016. /Polyethyleneimine having a polyester side chain described in No. 104803, a block copolymer described in International Publication No. 2019/125940, a block polymer having an acrylamide structural unit described in Japanese Patent Application Publication No. 2020-066687, Japanese Patent Application Publication No. 2020-066687. A block polymer having an acrylamide structural unit described in 2020-066688, etc. can also be used.

Dispersants are also available as commercial products, and specific examples thereof include the DISPERBYK series manufactured by Big Chemistry, the SOLSPERSE series manufactured by Nippon Lubrizol, the Efka series manufactured by BASF, and the Azisper series manufactured by Ajinomoto Fine Techno Co., Ltd. I can hear it. Additionally, the product described in paragraph number 0129 of Japanese Patent Application Laid-Open No. 2012-137564 and the product described in paragraph number 0235 of Japanese Patent Application Laid-Open No. 2017-194662 can also be used as a dispersant.

The content of the curable compound is preferably 1 to 95% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, more preferably 7% by mass or more, and especially preferably 10% by mass or more. The upper limit is preferably 94 mass% or less, more preferably 90 mass% or less, more preferably 85 mass% or less, and especially preferably 80 mass% or less.

When the composition of the present invention contains a polymerizable compound as a curable compound, the content of the polymerizable compound is preferably 1 to 85% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. The upper limit is preferably 80 mass% or less, and more preferably 70 mass% or less.

When the composition of the present invention contains a polymerizable monomer as a curable compound, the content of the polymerizable monomer is preferably 1 to 50% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 20% by mass or less.

When the composition of the present invention contains a compound having an ethylenically unsaturated bond-containing group as a curable compound, the content of the compound having an ethylenically unsaturated bond-containing group is preferably 1 to 70% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. The upper limit is preferably 65 mass% or less, and more preferably 60 mass% or less.

When the composition of the present invention contains a resin as a curable compound, the content of the resin is preferably 1 to 85% by mass based on the total solid content of the composition. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, more preferably 7% by mass or more, and especially preferably 10% by mass or more. The upper limit is preferably 80 mass% or less, more preferably 75 mass% or less, more preferably 70 mass% or less, and especially preferably 40 mass% or less.

When the composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant is preferably 0.1 to 40% by mass based on the total solid content of the composition. The upper limit is preferably 25% by mass or less, and more preferably 20% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. Moreover, the content of the resin as a dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the specific dye described above. The upper limit is preferably 80 parts by mass or less, and more preferably 75 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, and more preferably 5 parts by mass or more.

The composition of the present invention may contain only one type of curable compound or may contain two or more types of curable compounds. When two or more types of curable compounds are included, it is preferable that their total amount falls within the above range.

<<Other infrared absorbers>>

The composition of the present invention may contain an infrared absorber (another infrared absorber) other than the specific pigment described above. By containing another infrared absorber, it is possible to form a film capable of shielding infrared rays over a wider range of wavelengths. Other infrared absorbers may be dyes or pigments (particles). Other infrared absorbers include pyrrolopyrrole compounds, cyanine compounds, squaryllium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, and iminium. compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, azomethane compounds, anthraquinone compounds, dibenzofuranone compounds, dithiorene metal complexes, metal oxides, metal borides, etc. As pyrrolopyrrole compounds, compounds described in paragraph numbers 0016 to 0058 of Japanese Patent Application Laid-Open No. 2009-263614, compounds described in paragraph numbers 0037 to 0052 of Japanese Patent Application Laid-Open No. 2011-068731, and paragraph numbers of International Publication No. 2015/166873. The compounds described in 0010 to 0033, etc. can be mentioned. Examples of squarylium compounds include compounds described in paragraphs 0044 to 0049 of Japanese Patent Application Publication No. 2011-208101, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 6065169, and paragraphs 0040 of International Publication No. 2016/181987. Compounds described, compounds described in Japanese Patent Application Laid-Open No. 2015-176046, compounds described in paragraph number 0072 of International Publication No. 2016/190162, compounds described in paragraphs 0196 to 0228 of Japanese Patent Application Laid-Open No. 2016-074649, Japanese Patent Application Laid-Open The compound described in paragraph number 0124 of Publication No. 2017-067963, the compound described in International Publication No. 2017/135359, the compound described in Japanese Patent Application Publication No. 2017-114956, the compound described in Japanese Patent Publication No. 6197940, the compound described in International Publication No. 2016 /Compounds described in No. 120166, etc. can be mentioned. Examples of cyanine compounds include compounds described in paragraphs 0044 to 0045 of JP2009-108267, compounds described in paragraphs 0026 to 0030 of JP2002-194040, and compounds described in JP2015-172004. , a compound described in Japanese Patent Application Laid-Open No. 2015-172102, a compound described in Japanese Patent Application Laid-Open No. 2008-088426, a compound described in paragraph number 0090 of International Publication No. 2016/190162, a compound described in Japanese Patent Application Laid-Open No. 2017-031394. Compounds, etc. can be mentioned. As a croconium compound, the compound described in Unexamined-Japanese-Patent No. 2017-082029 is mentioned. Examples of iminium compounds include compounds described in Japanese Patent Application Laid-Open No. 2008-528706, compounds described in Japanese Patent Application Laid-Open No. 2012-012399, compounds described in Japanese Patent Application Laid-Open No. 2007-092060, and International Publication No. 2018. The compounds described in paragraph numbers 0048 to 0063 of /043564 can be mentioned. Examples of the phthalocyanine compound include compounds described in paragraph number 0093 of Japanese Patent Application Laid-Open No. 2012-077153, oxytitanium phthalocyanine described in Japanese Patent Application Laid-Open No. 2006-343631, and paragraph number 0013 of Japanese Patent Application Laid-Open No. 2013-195480. -0029, the vanadium phthalocyanine compound described in Japanese Patent Publication No. 6081771, and the compound described in International Publication No. 2020/071470. Examples of naphthalocyanine compounds include compounds described in paragraph number 0093 of Japanese Patent Application Laid-Open No. 2012-077153. Examples of the dithiorene metal complex include compounds described in Japanese Patent Publication No. 5733804. Examples of metal oxides include indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, and tungsten oxide. For details of tungsten oxide, reference may be made to paragraph number 0080 of Japanese Patent Application Laid-Open No. 2016-006476, the content of which is incorporated herein by reference. Examples of metal boride include lanthanum boride. Commercially available products of lanthanum boride include LaB ₆ -F (manufactured by Nippon Shinginzoku Co., Ltd.). Moreover, as a metal boride, the compound described in International Publication No. 2017/119394 can also be used. Commercially available products of indium tin oxide include F-ITO (manufactured by DOWA Hitech Co., Ltd.).

In addition, as an infrared absorber, a squarylium compound described in Japanese Patent Application Publication No. 2017-197437, a squarylium compound described in Japanese Patent Application Publication No. 2017-025311, and a squarylium compound described in International Publication No. 2016/154782. , the squarylium compound described in Japanese Patent Publication No. 5884953, the squarylium compound described in Japanese Patent Publication No. 6036689, the squarylium compound described in Japanese Patent Publication No. 5810604, paragraph number of International Publication No. 2017/213047. Squarylium compounds described in paragraphs 0090 to 0107, pyrrole ring-containing compounds described in paragraph numbers 0019 to 0075 of Japanese Patent Application Laid-Open No. 2018-054760, pyrrole ring-containing compounds described in paragraph numbers 0078 to 0082 of Japanese Patent Application Laid-Open No. 2018-040955, Pyrrole ring-containing compounds described in paragraphs No. 0043 to 0069 of Japanese Patent Application Laid-Open No. 2018-002773, squarylium compounds having an aromatic ring on amide α described in paragraphs Nos. 0024 to 0086 of Japanese Patent Application Laid-Open No. 2018-041047, Japanese Patent Laid-open An amide-linked squarylium compound described in Publication No. 2017-179131, a compound having a pyrrolebis-type squarylium skeleton or croconium skeleton described in Japanese Patent Application Laid-Open No. 2017-141215, and a die described in Japanese Patent Application Publication No. 2017-082029. Hydrocarbazole bis-type squarylium compounds, asymmetric compounds described in paragraph numbers 0027 to 0114 of Japanese Patent Application Laid-Open No. 2017-068120, pyrrole ring-containing compounds (carbazole type) described in Japanese Patent Application Laid-Open No. 2017-067963, A phthalocyanine compound described in Japanese Patent Publication No. 6251530, etc. can also be used.

The content of the other infrared absorber is preferably 1 to 100 parts by mass, more preferably 3 to 60 parts by mass, and even more preferably 5 to 40 parts by mass, per 100 parts by mass of the specific dye described above. Moreover, the total content of the above-mentioned specific pigment and other infrared absorbers is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more of the total solid content of the composition. The upper limit of the total content is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less.

<<Pigment derivative>>

As described above, the composition of the present invention may contain a dye derivative itself (hereinafter also referred to as a “derivative”), but may further contain a dye derivative in addition to the specific dye described above. Color derivatives are used as dispersion aids. Examples of the dye derivative include compounds having a structure in which an acid group or a basic group is bonded to the dye skeleton.

As the pigment skeleton constituting the dye derivative, squarylium pigment skeleton, pyrrolopyrrole pigment skeleton, diketopyrrolopyrrole pigment skeleton, quinacridone pigment skeleton, anthraquinone pigment skeleton, dianthraquinone pigment skeleton, and benzisoindole pigment. Skeleton, thiazine indigo pigment skeleton, azo pigment skeleton, quinophthalone pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, dioxazine pigment skeleton, perylene pigment skeleton, perrinone pigment skeleton, benzimida Examples include sol-on pigment skeleton, benzothiazole pigment skeleton, benzimidazole pigment skeleton, and benzoxazole pigment skeleton, squarylium pigment skeleton, pyrrolopyrrole pigment skeleton, diketopyrrolopyrrole pigment skeleton, and phthalocyanine. The pigment skeleton, quinacridone pigment skeleton, and benzimidazolone pigment skeleton are preferred, and the squarylium pigment skeleton and pyrrolopyrrole pigment skeleton are more preferred.

Examples of the acid group include carboxyl group, sulfo group, phosphoric acid group, boronic acid group, carboxylic acid amide group, sulfonamide group, imide acid group, and salts thereof. The atoms or atomic groups constituting the salt include alkali metal ions (Li ⁺ , Na ⁺ , K ^{+ ,} etc.), alkaline earth metal ions (Ca ²⁺ , Mg ^{2+ ,} etc.), ammonium ions, imidazolium ions, and pyridinium ions. , phosphonium ion, etc. As the carboxylic acid amide group, the group represented by -NHCOR ^A1 is preferable. As the sulfonamide group, a group represented by -NHSO ₂ R ^A2 is preferable. As the imidic acid group, a group represented by -SO ₂ NHSO ₂ R ^A3 , -CONHSO ₂ R ^A4 , -CONHCOR ^A5 or -SO ₂ NHCOR ^A6 is preferable, and -SO ₂ NHSO ₂ R ^A3 is more preferable. R ^A1 to R ^A6 each independently represent an alkyl group or an aryl group. The alkyl group and aryl group represented by R ^A1 to R ^A6 may have a substituent. The substituent is preferably a halogen atom, and more preferably a fluorine atom.

Examples of basic groups include amino groups, pyridinyl groups and their salts, salts of ammonium groups, and phthalimide methyl groups. Examples of the atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylic acid ions, sulfonic acid ions, and phenoxide ions. Specific examples and preferred examples of each group are the same as the basic group represented by X ^R1 in the formula (R-100) described above.

In a preferred embodiment of the composition of the present invention, in addition to ^the above-mentioned specific dye ⁽ however ^, it is not a dye derivative ⁾ , as ^a dye derivative, X ^a , An embodiment in which at least one of these contains a dye having a group represented by the formula (R-100) as a substituent can also be mentioned. In such an aspect, it is more preferable that the dye derivative is a dye in which at least one of R ¹ and R ² of formula (1) has a group represented by the formula (R-100) as a substituent. Moreover, it is also preferable that the dye derivative is a compound in which at least one of R ¹ and R ² of formula (1) has a group represented by formulas (A-1) to (B-2) described later.

Specific examples of the dye derivative include the compounds described in the Examples described later. Additionally, Japanese Patent Application Laid-Open No. 56-118462, Japanese Patent Application Publication No. 63-264674, Japanese Patent Application Publication No. 01-217077, Japanese Patent Application Publication No. 03-009961, and Japanese Patent Application Publication No. 03-026767. 03-153780, Japanese Unexamined Patent Publication No. 03-045662, Japanese Unexamined Patent Publication No. 04-285669, Japanese Unexamined Patent Publication No. 06-145546, Japanese Unexamined Patent Publication No. 06-212088. No., Japanese Patent Publication No. 06-240158, Japanese Patent Publication No. 10-030063, Japanese Patent Publication No. 10-195326, paragraph numbers 0086-0098 of International Publication No. 2011/024896, International Publication No. Compounds described in paragraph numbers 0063 to 0094 of 2012/102399 can also be cited, the contents of which are incorporated herein by reference.

The content of the dye derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the specific dye described above. 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 40 parts by mass or less, and more preferably 30 parts by mass or less. Only one type of pigment derivative may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.

<<Solvent>>

The composition of the present invention preferably contains a solvent. Examples of solvents include water and organic solvents, and it is preferable that they are organic solvents. Examples of organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For these details, reference may be made to paragraph number 0223 of International Publication No. 2015/166779, the contents of which are incorporated herein by reference. Additionally, ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene glycol dimethyl. Ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone , 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether. Teracetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone , gamma-butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol. Colmethyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropyl alcohol etc. can be mentioned. However, in some cases, it is desirable to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents for environmental reasons (for example, 50 ppm by mass relative to the total amount of organic solvents). (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less).

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

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

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

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

It is preferable that the solvent content in the composition is 10 to 97 mass%. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and especially preferably 70% by mass or more. The upper limit is preferably 96 mass% or less, and more preferably 95 mass% or less. The composition may contain only one type of solvent or may contain two or more types of solvent. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Photopolymerization initiator>>

When the composition of the present invention contains a polymerizable compound, it is preferable that the composition of the present invention further contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light from the ultraviolet region to the visible region are preferred. It is preferable that the photopolymerization initiator is a radical photopolymerization initiator.

As a photopolymerization initiator, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, Thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. can be mentioned. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, and a metallocene. compounds, oxime compounds, hexaarylbiimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarins. It is preferable that it is a compound, and it is more preferable that it is a compound selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and it is still more preferable that it is an oxime compound. Additionally, as photopolymerization initiators, compounds described in paragraphs 0065 to 0111 of Japanese Patent Application Laid-Open No. 2014-130173, compounds described in Japanese Patent Application Publication No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, no. 3, the peroxide-based photopolymerization initiator described in 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, the photopolymerization initiator described in Japanese Patent Application Publication No. 2019-043864, Photopolymerization initiator described in Japanese Patent Laid-open No. 2019-044030, peroxide-based initiator described in Japanese Patent Laid-Open No. 2019-167313, aminoacetophenone-based initiator having an oxazolidine group described in Japanese Patent Laid-Open No. 2020-055992, Japanese Patent Laid-open Examples include the oxime-based photopolymerization initiator described in Patent Publication No. 2013-190459, the polymer described in Japanese Patent Application Laid-Open No. 2020-172619, and the contents of these are incorporated herein by reference.

Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'- Biimidazole, etc. can be mentioned.

Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (manufactured by BASF). You can. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (manufactured by BASF). there is. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (above, manufactured by BASF), etc.

Examples of oxime compounds include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, compounds described in Japanese Patent Application Laid-Open No. 2006-342166, and J. C. S. Perkin II (1979, pp. 1653). -1660), a compound described in J. C. S. Perkin II (1979, pp. 156-162), a compound described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), Japanese Patent Application Publication 2000- Compounds described in Japanese Patent No. 066385, compounds described in Japanese Patent Application Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Japanese Patent Application Publication No. 6065596, and International Publication No. 2015/152153. Compounds described, compounds described in International Publication No. 2017/051680, compounds described in Japanese Patent Application Publication No. 2017-198865, compounds described in paragraph numbers 0025 to 0038 of International Publication No. 2017/164127, International Publication No. 2013/ The compounds described in No. 167515, etc. can be mentioned. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentan-3-one. , 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), and Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., photopolymerization initiator 2 described in Japanese Patent Application Publication No. 2012-014052). Additionally, as the oxime compound, it is also preferable to use a compound that does not have coloring properties or a compound that has high transparency and is difficult to discolor. Commercially available products include Adeka Ackles NCI-730, NCI-831, and NCI-930 (above, manufactured by ADEKA Co., Ltd.).

As a photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include compounds described in Japanese Patent Application Publication No. 2014-137466, compounds described in Japanese Patent Application Publication No. 6636081, and compounds described in Korean Patent Application Publication No. 10-2016-0109444. .

As a photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring becomes a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

As a photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of oxime compounds having a fluorine atom include compounds described in JP2010-262028, compounds 24, 36 to 40 described in JP2014-500852, and compounds described in JP2013-164471. (C-3), etc. may be mentioned.

As a photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably used as a dimer. Specific examples of oxime compounds having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466, and JP2014-137466. Examples include the compounds described in paragraph numbers 0007 to 0025 of No. 4223071, and Adeka Archles NCI-831 (manufactured by ADEKA Co., Ltd.).

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

As a photopolymerization initiator, an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019/088055.

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

[Formula 18]

[Formula 19]

[Formula 20]

As for the oxime compound, a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm is preferable, and a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm is more preferable. In addition, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high from the viewpoint of sensitivity, more preferably 1000 to 300000, more preferably 2000 to 300000, and 5000 to 200000. This is particularly desirable. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure the concentration at a concentration of 0.01 g/L using a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent.

As a photopolymerization initiator, you may use a difunctional or trifunctional or more radical photopolymerization initiator. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity is obtained. In addition, when a compound with an asymmetric structure is used, crystallinity decreases, solubility in solvents etc. improves, precipitation becomes difficult over time, and the stability of the composition over time can be improved. Specific examples of di- or tri-functional or higher radical photopolymerization initiators include paragraphs of Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. No. 0407-0412, dimer of the oxime compound described in paragraph number 0039-0055 of International Publication No. 2017/033680, compound (E) and compound (G) described in Japanese Patent Publication No. 2013-522445, Cmpd 1 to 7 described in International Publication No. 2016/034963, oxime ester-based initiator described in paragraph number 0007 of Japanese Patent Publication No. 2017-523465, and paragraph numbers 0020 to 0033 of Japanese Patent Publication No. 2017-167399. The photoinitiator described in , the photopolymerization initiator (A) described in paragraph numbers 0017 to 0026 of Japanese Patent Application Laid-Open No. 2017-151342, the oxime ester-based initiator described in Japanese Patent Application Publication No. 6469669, etc. can be mentioned.

The content of the photopolymerization initiator is preferably 0.1 to 40% by mass, more preferably 0.5 to 35% by mass, and still more preferably 1 to 30% by mass of the total solid content of the composition. The composition may contain only one type of photopolymerization initiator or may contain two or more types of photopolymerization initiators. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Hardener>>

When the composition of the present invention contains a compound having a cyclic ether group, it is preferable to further contain a curing agent. Examples of the curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, polyhydric carboxylic acids, and thiol compounds. Specific examples of the curing agent include succinic acid, trimellitic acid, pyromellitic acid, N,N-dimethyl-4-aminopyridine, and pentaerythritol tetrakis(3-mercaptopropionate). The curing agent may be a compound described in paragraph numbers 0072 to 0078 of Japanese Patent Application Laid-Open No. 2016-075720, or a compound described in Japanese Patent Application Laid-Open No. 2017-036379. The content of the curing agent is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and still more preferably 0.1 to 6.0 parts by mass, per 100 parts by mass of the compound having a cyclic ether group.

<<Colorful colorant>>

The composition of the present invention may contain a chromatic colorant. In the present invention, a chromatic colorant means a colorant other than a white colorant and a black colorant. The chromatic colorant is preferably a colorant that has absorption in a wavelength range of 400 nm or more and less than 650 nm.

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

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

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

Color Index (C.I.) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35 :1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94 , 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 13 7 , 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, 215, 228, 231, 232 (methane type), 233 (quinoline type), 234 (aminoketone type) ), 235 (amino ketone series), 236 (amino ketone series), etc. (above, yellow pigment),

C. I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 etc. (above, orange pigment),

C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4 , 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3 , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 18 4 , 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291 , 294 (xanthene type, Organo Ultramarine, Bluish Red), 295 (monoazo type), 296 (diazo type), 297 (aminoketone type), etc. (above, red pigment),

C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine series), 65 (phthalocyanine series), 66 (phthalocyanine series), etc. (above, green pigment),

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane type), 61 (xanthene type), etc. (above, purple pigment),

C. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazoline) ), 88 (metaphosphorus series), etc. (above, blue pigment).

Additionally, as a green pigment, a halogenated zinc phthalocyanine pigment can be used, with an average number of halogen atoms per molecule of 10 to 14, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms. there is. Specific examples include compounds described in International Publication No. 2015/118720. In addition, as a green pigment, a compound described in Chinese Patent Application No. 106909027, a phthalocyanine compound having a phosphoric acid ester described in International Publication No. 2012/102395 as a ligand, and a phthalocyanine compound described in Japanese Patent Application Publication No. 2019-008014. Other compounds, phthalocyanine compounds described in Japanese Patent Application Laid-Open No. 2018-180023, compounds described in Japanese Patent Application Laid-Open No. 2019-038958, core-shell type pigments described in Japanese Patent Application Laid-Open No. 2020-076995, etc. can also be used.

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

Additionally, as the yellow pigment, the compounds described in Japanese Patent Application Laid-Open No. 2017-201003, the compounds described in Japanese Patent Application Laid-Open No. 2017-197719, and the compounds described in paragraph numbers 0011 to 0062 and 0137 to 0276 of Japanese Patent Application Laid-Open No. 2017-171912. , compounds described in paragraph numbers 0010 to 0062 and 0138 to 0295 of Japanese Patent Application Laid-Open No. 2017-171913, compounds described in paragraphs numbers 0011 to 0062 and 0139 to 0190 of Japanese Patent Application Laid-Open No. 2017-171914, Japanese Patent Application Laid-Open No. 2017-171915 Compounds described in paragraph numbers 0010 to 0065 and 0142 to 0222, quinophthalone compounds described in paragraphs 0011 to 0034 of Japanese Patent Application Laid-Open No. 2013-054339, and quinophthalone compounds described in paragraphs 0013 to 0058 of Japanese Patent Application Laid-Open No. 2014-026228. Nophthalone compound, isoindoline compound described in Japanese Patent Application Publication No. 2018-062644, quinophthalone compound described in Japanese Patent Application Publication No. 2018-203798, quinophthalone compound described in Japanese Patent Application Publication No. 2018-062578, Japan The quinophthalone compound described in Patent Publication No. 6432076, the quinophthalone compound described in Japanese Patent Application Publication No. 2018-155881, the quinophthalone compound described in Japanese Patent Application Publication No. 2018-111757, and the Japanese Patent Application Publication No. 2018-040835. The quinophthalone compound described in, the quinophthalone compound described in JP2017-197640, the quinophthalone compound described in JP2016-145282, the quinophthalone described in JP2014-085565A. Compound, quinophthalone compound described in Japanese Patent Application Publication No. 2014-021139, quinophthalone compound described in Japanese Patent Application Publication No. 2013-209614, quinophthalone compound described in Japanese Patent Application Publication No. 2013-209435, Japanese Patent Application Laid-Open The quinophthalone compound described in JP2013-181015, the quinophthalone compound described in JP2013-061622, the quinophthalone compound described in JP2013-032486, and the JP2012-226110. The quinophthalone compound described in, the quinophthalone compound described in JP2008-074987, the quinophthalone compound described in JP2008-081565, the quinophthalone described in JP2008-074986. Compound, quinophthalone compound described in Japanese Patent Application Publication No. 2008-074985, quinophthalone compound described in Japanese Patent Application Publication No. 2008-050420, quinophthalone compound described in Japanese Patent Application Publication No. 2008-031281, Japanese Patent Publication Quinophthalone compound described in Publication No. 48-032765, Quinophthalone compound described in Japanese Patent Application Publication No. 2019-008014, Quinophthalone compound described in Japanese Patent Application Publication No. 6607427, Korean Patent Application Publication No. 10-2014- The compound described in Japanese Patent Application Publication No. 0034963, the compound described in Japanese Patent Application Publication No. 2017-095706, the compound described in Taiwan Patent Application Publication No. 201920495, the compound described in Japanese Patent Application Publication No. 6607427, the compound described in Japanese Patent Application Publication No. 2020-033525 Compounds, compounds described in Japanese Patent Application Laid-Open No. 2020-033524, compounds described in Japanese Patent Application Laid-Open No. 2020-033523, compounds described in Japanese Patent Application Laid-Open No. 2020-033522, compounds described in Japanese Patent Application Laid-Open No. 2020-033521, The compounds described in International Publication No. 2020/045200, the compounds described in International Publication No. 2020/045199, and the compounds described in International Publication No. 2020/045197 can also be used. In addition, multimerization of these compounds is also preferably used from the viewpoint of improving color value.

As a red pigment, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in Japanese Patent Application Laid-Open No. 2017-201384, and a diketopyrrolopyrrole compound described in paragraph numbers 0016 to 0022 of Japanese Patent Application Publication No. 6248838. , diketopyrrolopyrrole compounds described in International Publication No. 2012/102399, diketopyrrolopyrrole compounds described in International Publication No. 2012/117965, naphtholazo compounds described in Japanese Patent Application Publication No. 2012-229344, Japan. Red pigment described in Patent Publication No. 6516119, red pigment described in Japanese Patent Publication No. 6525101, brominated diketopyrrolopyrrole compound described in paragraph number 0229 of Japanese Patent Application Publication No. 2020-090632, Korean Patent Publication No. 10- An anthraquinone compound described in 2019-0140741, an anthraquinone compound described in Korean Patent Application Publication No. 10-2019-0140744, a perylene compound described in Japanese Patent Application Publication No. 2020-079396, etc. can also be used. Additionally, as a red pigment, a compound having a structure in which an aromatic ring group in which a group bonded to an oxygen atom, a sulfur atom, or a nitrogen atom is introduced to an aromatic ring bonded to a diketopyrrolopyrrole skeleton can also be used.

For the diffraction angle that various pigments preferably have, the descriptions in Japanese Patent Publication No. 6561862, Japanese Patent Publication No. 6413872, Japanese Patent Publication No. 6281345, and Japanese Patent Application Publication No. 2020-026503 can be referred to, and the contents of these is used herein. In addition, as a pyrrolopyrrole pigment, it is also preferable to use one with a crystallite size of 140 Å or less in the plane direction corresponding to the maximum peak in the do. Additionally, the physical properties of the pyrrolopyrrole pigment are preferably set as described in paragraph numbers 0028 to 0073 of Japanese Patent Application Publication No. 2020-097744.

Dyes can also be used as chromatic colorants. There are no particular restrictions on the dye, and known dyes can be used. For example, pyrazolazo dyes, anilinoazo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazoleazo dyes, and pyridonezo dyes. Dyes, cyanine-based dyes, phenothiazine-based dyes, pyrrolopyrazolazomethane-based dyes, xanthene-based dyes, phthalocyanine-based dyes, benzopyran-based dyes, indigo-based dyes, pyromethene-based dyes, etc. there is.

A dye multimer can also be used as a chromatic colorant. The dye multimer is preferably a dye that is dissolved in a solvent and used. Additionally, the dye multimer may form particles. When the dye multimer is a particle, it is usually used in a state dispersed in a solvent. Particle-state dye multimers can be obtained, for example, by emulsion polymerization, and specific examples include the compounds and production methods described in Japanese Patent Application Laid-Open No. 2015-214682. A dye multimer has two or more dye structures per molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures in one molecule may be the same dye structure or may be different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and more preferably 20,000 or less. The dye multimer is described in Japanese Patent Application Laid-Open No. 2011-213925, Japanese Patent Application Publication No. 2013-041097, Japanese Patent Application Publication No. 2015-028144, Japanese Patent Application Publication No. 2015-030742, International Publication No. 2016/031442, etc. The compounds described can also be used.

In addition, the chromatic colorants include thiazole compounds described in Japanese Patent Application Laid-Open No. 2012-158649, azo compounds described in Japanese Patent Application Laid-Open No. 2011-184493, azo compounds described in Japanese Patent Application Laid-Open No. 2011-145540, and Korean Patent Application Laid-Open No. 2011-145540. Triarylmethane dye polymer described in No. 10-2020-0028160, xanthene compound described in Japanese Patent Application Publication No. 2020-117638, phthalocyanine compound described in International Publication No. 2020/174991, Japanese Patent Application Publication 2020 The isoindoline compounds described in -160279 or their salts can be used.

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

<<Color material that transmits infrared rays and blocks visible light>>

The composition of the present invention may contain a colorant that transmits infrared rays and blocks visible light (hereinafter also referred to as a colorant that blocks visible light). A composition containing a colorant that blocks visible light is preferably used as a composition for forming an infrared transmission filter.

The colorant that blocks visible light is preferably a colorant that absorbs light in the violet to red wavelength range. Additionally, the colorant that blocks visible light is preferably a colorant that blocks light in the wavelength range of 450 to 650 nm. Additionally, the colorant that blocks visible light is preferably a colorant that transmits light with a wavelength of 900 to 1500 nm. It is preferable that the colorant that blocks visible light satisfies at least one of the requirements of (A) and (B) below.

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

(B): Contains an organic black colorant.

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

When black is formed by a combination of two or more chromatic colorants, examples of the combination of chromatic colorants include the following aspects (1) to (8).

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

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

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

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

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

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

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

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

When the composition of the present invention contains a colorant that blocks visible light, the content of the colorant that blocks visible light is preferably 1 to 50% by mass based on the total solid content of the composition. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass or more, and especially preferably 30% by mass or more.

<<Surfactant>>

The composition of the present invention preferably contains a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant. Regarding the surfactant, the surfactant described in paragraph numbers 0238 to 0245 of International Publication No. 2015/166779 can be mentioned, the contents of which are incorporated herein by reference.

As fluorine-based surfactants, surfactants described in paragraphs No. 0060 to 0064 of Japanese Patent Application Publication No. 2014-041318 (paragraphs No. 0060 to 0064 of corresponding International Publication No. 2014/017669), etc., paragraph numbers of Japanese Patent Application Publication No. 2011-132503. The surfactants described in 0117 to 0132 and the surfactants described in Japanese Patent Application Publication No. 2020-008634 are included, the contents of which are incorporated herein by reference. Commercially available fluorine-based surfactants include, for example, Megapak F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F -437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F -561, F-563, F-565, F-568, F-575, F-780, EXP, MFS-330, R-01, R-40, R-40-LM, R-41, R-41 -LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (above, Sumitomo 3M) Co., Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, (manufactured by AGC Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA), Aftergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS, F TX-218( The above, manufactured by NEOS Co., Ltd.), etc. can be mentioned.

Additionally, as a fluorine-based surfactant, an acrylic compound that has a molecular structure having a functional group containing a fluorine atom and in which the portion of the functional group containing a fluorine atom is cut when heat is applied and the fluorine atom volatilizes can also be suitably used. Examples of such fluorine-based surfactants include the Megapaak DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shinbun (February 23, 2016)), for example, Megapaak DS. -21.

Additionally, as the fluorine-based surfactant, it is also preferable to use a polymer 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. Such fluorine-based surfactants include the fluorine-based surfactants described in Japanese Patent Application Laid-Open No. 2016-216602, the content of which is incorporated herein by reference.

As a fluorine-based surfactant, a block polymer can also be used. As a fluorine-based surfactant, it has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth) ) Fluorine-containing polymer compounds containing repeating units derived from acrylate compounds can also be preferably used. Additionally, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of Japanese Patent Application Laid-Open No. 2010-032698 and the following compounds are also exemplified as fluorine-containing surfactants used in the present invention.

[Formula 21]

The weight average molecular weight of the above compound is preferably 3000 to 50000, for example, 14000. Among the above compounds, % representing the ratio of repeating units is mole %.

Additionally, as the fluorine-based surfactant, a fluorinated polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Laid-Open No. 2010-164965, Megapak RS-101, RS-102, RS-718K, and RS-72- manufactured by DIC Corporation. K, etc. can be mentioned. Additionally, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Laid-Open No. 2015-117327 can also be used.

In addition, it is also preferable from the viewpoint of environmental regulations to use the surfactant described in International Publication No. 2020/084854 as a replacement for the surfactant having a perfluoroalkyl group with 6 or more carbon atoms.

Additionally, it is also preferable to use a fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant.

[Formula 22]

In the formula (fi-1), m represents 1 or ² , n represents an integer of 1 to 4, a represents 1 or 2, and It represents a quaternary ammonium ion, a tertiary ammonium ion, a quaternary ammonium ion, or NH ₄ ⁺ .

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), and polyoxyethylene lauryl. ether, polyoxyethylene stearyl ether, 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 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (Nippon Lu) Brizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Junyaku Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto Yushi Co., Ltd. ), Olfin E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.), etc.

Examples of cationic surfactants include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridium salts, and imidazolium salts. Specific examples include dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, and stearamidemethylpyridium chloride.

Cationic surfactants include dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyl diphenyl ether disulfonate, sodium alkylnaphthalenesulfonate, sodium dialkyl sulfosuccinate, sodium stearate, Potassium oleate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium dialkyl sulfosuccinate, sodium oleate, t- Octylphenoxyethoxypolyethoxyethyl sulfate sodium salt, etc. can be mentioned.

Silicone-based surfactants include, for example, SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (above, manufactured by Shin-Etsu Chemical) Examples include BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, and BYK-UV3510 (manufactured by Big Chemistry Co., Ltd.).

Additionally, a compound having the following structure can also be used as the silicone-based surfactant.

[Formula 23]

The content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and still more preferably 0.001 to 0.2% by mass, based on the total solid content of the composition. The composition may contain only one type of surfactant or may contain two or more types of surfactant. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Polymerization inhibitor>>

The composition of the present invention may contain a polymerization inhibitor. As polymerization inhibitors, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6) -tert-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, primary cerium salt, etc.). , p-methoxyphenol is preferred. The content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the composition. The composition may contain only one type of polymerization inhibitor or may contain two or more types of polymerization inhibitor. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Silane coupling agent>>

The compositions of the present invention may contain a silane coupling agent. In this specification, a silane coupling agent means a silane compound having a hydrolyzable group and a functional group other than that. In addition, a hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can generate a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, with an alkoxy group being preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, functional groups other than hydrolyzable groups include, for example, vinyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group, isocyanate group, phenyl group, etc. Examples include, (meth)acryloyl group and epoxy group are preferred. Silane coupling agents include compounds described in paragraphs 0018 to 0036 of Japanese Patent Application Laid-Open No. 2009-288703, and compounds described in paragraphs 0056 to 0066 of Japanese Patent Application Laid-Open No. 2009-242604, the details of which are included in this specification. It is used. The content of the silane coupling agent is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass, based on the total solid content of the composition. The composition may contain only one type of silane coupling agent, or may contain two or more types. When two or more types are included, it is preferable that their total amount falls within the above range.

<<UV absorbent>>

The composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and merocytes. Other pigments, etc. may be mentioned. Specific examples of such compounds include paragraphs 0038 to 0052 of Japanese Patent Application Laid-Open No. 2009-217221, paragraphs 0052 to 0072 of Japanese Patent Application Laid-Open No. 2012-208374, and paragraphs 0317 to 0334 of Japanese Patent Application Laid-Open No. 2013-068814. The compounds described in paragraph numbers 0061 to 0080 of Unexamined Patent Publication No. 2016-162946 can be cited, the contents of which are incorporated herein by reference. Commercially available ultraviolet absorbers include the Tinuvin series and Uvinul series manufactured by BASF. Additionally, examples of benzotriazole compounds include the MYUA series manufactured by Yushi Miyoshi (Kagaku High School Nippo, February 1, 2016). In addition, as the ultraviolet absorber, the compounds described in paragraphs 0049 to 0059 of Japanese Patent Publication No. 6268967 and paragraphs 0059 to 0076 of International Publication No. 2016/181987 can also be used. The content of the ultraviolet absorber is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, based on the total solid content of the composition. The composition may contain only one type of ultraviolet absorber or may contain two or more types of ultraviolet absorbers. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Antioxidant>>

The composition of the present invention may contain an antioxidant. Examples of antioxidants include phenol compounds, phosphorous acid ester compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferred phenol compounds include hindered phenol compounds. Compounds having a substituent at the site (orthosite) adjacent to the phenolic hydroxy group are preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Also, the antioxidant is preferably a compound having a phenol group and a phosphorous acid ester group in the same molecule. Additionally, phosphorus-based antioxidants can also be suitably used as antioxidants. As a phosphorus-based antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-6- yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl) Oxy]ethyl]amine, ethylbisphosphorous acid (2,4-di-tert-butyl-6-methylphenyl), etc. Commercially available antioxidants include, for example, Adeka Stab AO-20, Adeka Stab AO-30, Adeka Stab AO-40, Adeka Stab AO-50, Adeka Stab AO-50F, Adeka Stab AO-60, Adeka Stab AO-60G, Adeka Stab AO-80, Adeka Stab AO-330 (above, manufactured by ADEKA Co., Ltd.), etc. In addition, as antioxidants, compounds described in paragraphs 0023 to 0048 of Japanese Patent Publication No. 6268967, compounds described in International Publication No. 2017/006600, and compounds described in International Publication No. 2017/164024 can also be used. The content of the antioxidant is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass, based on the total solid content of the composition. The composition may contain only one type of antioxidant or may contain two or more types of antioxidant. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Other ingredients>>

The composition of the present invention may, if necessary, contain sensitizers, curing accelerators, fillers, thermal curing accelerators, plasticizers, and other auxiliaries (e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, peeling accelerators, fragrances, and surface tension agents). regulator, chain transfer agent, etc.) may be contained. By appropriately containing these components, properties such as membrane physical properties can be adjusted. These components are, for example, described in Japanese Patent Application Publication No. 2012-003225, paragraph number 0183 onward (paragraph number 0237 of corresponding U.S. Patent Application Publication No. 2013/0034812), and paragraph numbers of Japanese Patent Application Publication No. 2008-250074. Reference may be made to descriptions such as 0101 to 0104, 0107 to 0109, etc., and these contents are incorporated herein by reference. Additionally, the composition of the present invention may contain a latent antioxidant if necessary. Potential antioxidants are compounds in which the portion that functions as an antioxidant is protected by a protecting group, and when heated at 100 to 250°C or heated at 80 to 200°C in the presence of an acid/base catalyst, the protecting group is removed and functions as an antioxidant. Compounds may be mentioned. Potential antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Application Publication No. 2017-008219. Commercially available latent antioxidants include Adeka Ackles GPA-5001 (manufactured by ADEKA Co., Ltd.).

<Receiving container>

There is no particular limitation as a container for containing the composition of the present invention, and a known container can be used. In addition, as a storage container, for the purpose of suppressing the incorporation of impurities into the raw materials or composition, it is also possible to use a multi-layer bottle whose inner wall is made of 6 types of 6-layer resin or a bottle with a 7-layer structure of 6 types of resin. desirable. Examples of such containers include those described in Japanese Patent Application Publication No. 2015-123351. Additionally, the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, increasing the stability of the composition over time, and suppressing deterioration of components.

<Method for preparing composition>

The composition of the present invention can be prepared by mixing the above-mentioned components. When preparing a composition, all components may be simultaneously dissolved or dispersed in a solvent to prepare the composition. If necessary, two or more solutions or dispersions with each component appropriately mixed may be prepared in advance and used (at the time of application). These may be mixed to prepare a composition.

When preparing the composition, a process for dispersing the pigment may be included. In the process of dispersing the pigment, mechanical forces used to disperse the pigment include compression, compression, impact, shear, and cavitation. Specific examples of 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, and ultrasonic dispersion. In addition, when grinding pigments in a sand mill (bead mill), it is preferable to use beads with a small diameter or to process under conditions that increase grinding efficiency by increasing the filling rate of the beads. In addition, it is preferable to remove coarse particles by filtration, centrifugation, etc. after the grinding treatment. In addition, the process and disperser for dispersing pigments are described in "Dispersion Technology Collection, Johokiko Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid/liquid dispersion system) and the actual use of industrial applications." The process and disperser described in paragraph number 0022 of “Comprehensive Data Collection,” published by Keiei Kaihatsu Center Press, October 10, 1978, Japanese Patent Publication No. 2015-157893 can be suitably used. Additionally, in the process of dispersing the pigment, the pigment may be refined in a salt milling process. For materials, equipment, processing conditions, etc. used in the salt milling process, the descriptions in, for example, Japanese Patent Application Laid-Open No. 2015-194521 and Japanese Patent Application Publication No. 2012-046629 can be referred to.

When preparing a composition, it is preferable to filter the composition through a filter for purposes such as removing foreign matter or reducing defects. The filter can be used without particular limitation as long as it is a filter that has been conventionally used for filtration purposes. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (e.g. nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) ( Filters using materials such as high-density, ultra-high molecular weight polyolefin resin can be mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore diameter of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and still more preferably 0.05 to 0.5 μm. If the hole diameter of the filter is within the above range, fine foreign substances can be removed more reliably. For the hole diameter value of the filter, you can refer to the filter manufacturer's nominal value. As filters, various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nippon Microlis Co., Ltd.), and Kits Micro Filter Co., Ltd. can be used.

Moreover, it is also preferable to use a fibrous filter medium as a filter. Examples of fibrous filter media include polypropylene fiber, nylon fiber, and glass fiber. Commercially available products include the SBP type series (SBP008, etc.), the TPR type series (TPR002, TPR005, etc.), and the SHPX type series (SHPX003, etc.) manufactured by Loki Techno.

When using a filter, different filters (for example, a first filter and a second filter, etc.) may be combined. In that case, filtration using each filter may be performed only once, or may be performed twice or more. Additionally, filters with different pore diameters may be combined within the above-mentioned range. Additionally, filtration using the first filter may be performed only on the dispersion liquid, and filtration may be performed using the second filter after mixing the other components.

<Act>

Next, the membrane of the present invention will be described. The film of the present invention is obtained from the composition of the present invention described above. The film of the present invention can be suitably used as an optical filter. The use of the optical filter is not particularly limited, but examples include an infrared cut-off filter and an infrared-transmitting filter. Examples of the infrared cut filter include an infrared cut filter on the light-receiving side of the solid-state imaging device (e.g., for an infrared cut-off filter for a wafer level lens, etc.), and an infrared cutting filter on the back side (light-receiving side) of the solid-state imaging device. an infrared cut-off filter on the opposite side), an infrared cut-off filter for an environmental light sensor (for example, an illuminance sensor that detects the illuminance or color tone of the environment in which the information terminal device is placed and adjusts the color tone of the display, or a color tone sensor) A sensor for color correction that adjusts), etc. In particular, it can be suitably used as an infrared cut-off filter on the light-receiving side of a solid-state imaging device. Examples of the infrared transmission filter include filters that block visible light and can selectively transmit infrared rays of a specific wavelength or higher.

The film of the present invention may have a pattern or may be a film without a pattern (flat film). Additionally, the membrane of the present invention may be used by laminating it on a support, or the membrane of the present invention may be used by peeling it from the support. Examples of the support include semiconductor substrates such as silicon substrates and transparent substrates.

A charge-coupled device (CCD), complementary metal oxide semiconductor (CMOS), transparent conductive film, etc. may be formed on the semiconductor substrate used as the support. Additionally, a black matrix that isolates each pixel may be formed on the semiconductor substrate. Additionally, an undercoating layer may be provided on the semiconductor substrate, if necessary, to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

The transparent substrate used as the support is not particularly limited as long as it is made of a material that can transmit at least visible light. Examples include base materials made of materials such as glass and resin. Resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymer, and acrylic resins such as norbornene resin, polyacrylate, and polymethyl methacrylate. , urethane resin, vinyl chloride resin, fluorine resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin, etc. Examples of glass include soda lime glass, borosilicate glass, alkali-free glass, quartz glass, and copper-containing glass. Examples of glass containing copper include phosphate glass containing copper and fluorophosphate glass containing copper. Glass containing copper may be a commercially available product. Commercially available glass containing copper includes NF-50 (manufactured by AGC Techno Glass Co., Ltd.).

The thickness of the film of the present invention can be adjusted appropriately depending on the purpose. The thickness of the film is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the thickness of the film is preferably 0.1 μm or more, and more preferably 0.2 μm or more.

When using the film of the present invention as an infrared cut-off filter, the film of the present invention preferably has a maximum absorption wavelength in the range of 650 to 1500 nm (preferably 660 to 1200 nm, more preferably 660 to 1000 nm). . Moreover, the average transmittance of light with a wavelength of 420 to 550 nm is preferably 50% or more, more preferably 70% or more, more preferably 80% or more, and especially preferably 85% or more. Additionally, the transmittance in all wavelength ranges of 420 to 550 nm is preferably 50% or more, more preferably 70% or more, and even more preferably 80% or more. In addition, the film of the present invention preferably has a transmittance of 15% or less at at least one point in the range of wavelength 650 to 1500 nm (preferably wavelength 660 to 1200 nm, more preferably wavelength 660 to 1000 nm), and preferably 10% or less. It is more preferable, and 5% or less is more preferable. In addition, when the absorbance at the maximum absorption wavelength of the film of the present invention is set to 1, the average absorbance in the wavelength range of 420 to 550 nm is preferably less than 0.030, and more preferably less than 0.025.

Additionally, the light-shielding ability of light around a wavelength of 400 nm can be evaluated by the transmittance (ultraviolet ray shielding property) at a wavelength of 390 nm, and it is preferable that the ultraviolet ray shielding property is 5% or less.

When using the membrane of the present invention as an infrared transmission filter, the membrane of the present invention preferably has, for example, any one of the following spectral characteristics (i1) to (i3).

(i1): The maximum value of the transmittance in the wavelength range of 400 to 850 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance value in the wavelength range of 1000 to 1500 nm A filter of 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in the wavelength range of 400 to 850 nm and transmit light with a wavelength exceeding 950 nm.

(i2): The maximum transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range is 1100 to 1500 nm. A filter of 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in the wavelength range of 400 to 950 nm and transmit light with a wavelength exceeding 1050 nm.

(i3): The maximum value of the transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1200 to 1500 nm A filter of 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in the wavelength range of 400 to 1050 nm and transmit light exceeding 1150 nm in wavelength.

Additionally, the light-shielding ability of light around a wavelength of 400 nm can be evaluated by the transmittance (ultraviolet ray shielding property) at a wavelength of 390 nm, and it is preferable that the ultraviolet ray shielding property is 5% or less.

The film of the present invention can also be used in combination with a color filter containing a chromatic colorant. A color filter can be manufactured using a coloring composition containing a chromatic colorant. When the film of the present invention is used as an infrared cut-off filter and the film of the present invention and a color filter are used in combination, it is preferable that the color filter is disposed on the optical path of the film of the present invention. For example, it is preferable to laminate the film of the present invention and a color filter to use it as a laminate. In the laminate, the film of the present invention and the color filter may be adjacent to each other in the thickness direction, or may not be adjacent to each other. When the film of the present invention and the color filter are not adjacent to each other in the thickness direction, the film of the present invention may be formed on a support different from the support on which the color filter is formed, and between the film of the present invention and the color filter, Other members constituting the solid-state imaging device (for example, microlens, planarization layer, etc.) may be interposed.

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

<Method for manufacturing membrane>

The film of the present invention can be manufactured through a process of applying the composition of the present invention.

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

The composition layer formed by applying the composition may be dried (prebaked). When performing prebaking, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, and can also be 80°C or higher. The prebake time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and still more preferably 80 to 220 seconds. Drying can be performed using a hot plate, oven, etc.

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

(When forming patterns using photolithography)

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

In the exposure process, the composition layer is exposed in a pattern. For example, the composition layer can be exposed in a pattern by exposing it through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, etc. Thereby, the exposed portion can be cured.

Radiation (light) that can be used during exposure includes g-rays, i-rays, etc. Additionally, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can be used. Light with a wavelength of 300 nm or less includes KrF lines (wavelength 248 nm) and ArF lines (wavelength 193 nm), with KrF lines (wavelength 248 nm) being preferable. In addition, light sources with long wavelengths of 300 nm or more can be used.

Moreover, during exposure, the light may be exposed by continuously irradiating the light, or the light may be exposed by irradiating in pulses (pulse exposure). In addition, pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and rest in cycles of a short period of time (for example, millisecond level or less).

The irradiation amount (exposure amount) is preferably, for example, 0.03 to 2.5 J/cm ² and more preferably 0.05 to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be appropriately selected. In addition to performing under the atmosphere, for example, under a low-oxygen atmosphere with an oxygen concentration of 19 volume% or less (e.g., 15 volume%, 5 volume%, or substantially oxygen-free atmosphere) ), or may be exposed under a high-oxygen atmosphere in which the oxygen concentration exceeds 21 volume% (for example, 22 volume%, 30 volume%, or 50 volume%). In addition, the exposure illuminance can be set appropriately, and can usually be selected from the range of 1000 W/m ² to 100,000 W/m ² (e.g., 5000 W/m ² , 15,000 W/m ² , or 35,000 W/m ² ). . The oxygen concentration and exposure illuminance may be combined with appropriate conditions, for example, the oxygen concentration is 10 volume% and the illuminance is 10,000 W/m ² , the oxygen concentration is 35 volume % and the illuminance is 20,000 W/m ² , etc.

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

Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used. As an alkaline developer, an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable. Examples of alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. Side, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole , organic alkaline compounds such as piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. Inorganic alkaline compounds can be mentioned. The alkaline agent is preferably a compound with a large molecular weight from environmental and safety aspects. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. Additionally, the developer may further contain a surfactant. As the surfactant, nonionic surfactants are preferred. From the viewpoint of convenience of transportation and storage, etc., the developer may be prepared as a concentrated solution and then diluted to the concentration required for use. The dilution ratio is not particularly limited, but can be set in the range of 1.5 to 100 times, for example. Additionally, it is also desirable to wash (rinse) with pure water after development. Additionally, rinsing is preferably performed by supplying a rinse solution to the developed composition layer while rotating the support on which the developed composition layer is formed. Additionally, it is also preferable to move the nozzle that discharges the rinse liquid from the center of the support to the peripheral edge of the support. At this time, when moving the nozzle from the center of the support body to the peripheral edge, the nozzle may be moved while gradually reducing its moving speed. By performing rinsing in this way, in-plane unevenness of the rinsing can be suppressed. Additionally, the same effect can be obtained by gradually lowering the rotational speed of the support while moving the nozzle from the center of the support to the peripheral edge.

After development and drying, it is preferable to perform additional exposure treatment or heat treatment (post-bake). Additional exposure treatment or post-bake is a curing treatment after development to ensure complete curing. For example, the heating temperature in post-baking is preferably 100 to 240°C, and more preferably 200 to 240°C. Post-baking can be performed continuously or in a batch manner by using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater so that the developed film can be subjected to the above-mentioned conditions. When performing additional exposure processing, the light used for exposure is preferably light with a wavelength of 400 nm or less. Additionally, additional exposure treatment may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

(When forming a pattern using dry etching)

Pattern formation using a dry etching method involves curing a composition layer formed by applying the composition on a support to form a cured layer, then forming a patterned photoresist layer on this cured layer, and then, This can be done by using the patterned photoresist layer as a mask and dry etching the cured layer using an etching gas. In forming the photoresist layer, it is preferable to perform a prebake process. Regarding pattern formation using a dry etching method, reference may be made to the description in paragraph numbers 0010 to 0067 of Japanese Patent Application Laid-Open No. 2013-064993, the contents of which are incorporated herein by reference.

<Optical filter>

The optical filter of the present invention has the film of the present invention described above. Types of optical filters include infrared cutoff filters and infrared transmission filters.

The optical filter of the present invention may further include a copper-containing layer, a dielectric multilayer film, an ultraviolet absorbing layer, etc., in addition to the film of the present invention described above. Examples of the ultraviolet absorbing layer include the absorbing layers described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/099060. Examples of the dielectric multilayer film include those described in paragraphs 0255 to 0259 of Japanese Patent Application Laid-Open No. 2014-041318. As the layer containing copper, a glass substrate made of glass containing copper (copper-containing glass substrate) or a layer containing a copper complex (copper complex-containing layer) can also be used. Examples of the copper-containing glass substrate include phosphate glass containing copper, fluorophosphate glass containing copper, and the like. Commercially available copper-containing glasses include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (above, manufactured by Schott Corporation), and CD5000 (manufactured by HOYA Co., Ltd.).

<Solid-state imaging device>

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

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

<Image display device>

The image display device of the present invention includes the film of the present invention. Examples of image display devices include liquid crystal display devices and organic electroluminescence (organic EL) display devices. For definitions and details of image display devices, see, for example, "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)" and "Display Device (Written by Ibuki Sumiaki, Sankyo Tosho Co., Ltd.) Hei. (published in the first year of Sei)", etc. Additionally, liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd., 1994)." There is no particular limitation on the liquid crystal display device to which the present invention can be applied, and for example, it can be applied to various types of liquid crystal display devices described in the "Next Generation Liquid Crystal Display Technology" above. The image display device may have a white organic EL element. As a white organic EL element, it is preferable to have a tandem structure. Regarding the tandem structure of organic EL elements, Japanese Patent Publication No. 2003-045676, supervised by Akiyoshi Mikami, "The forefront of organic EL technology development - high brightness, high precision, long life, know-how collection -", Kijutsu Joho Kyokai, 326 It is listed on page 328, 2008, etc. The spectrum of white light emitted by an organic EL device preferably has strong maximum emission peaks in the blue region (430 to 485 nm), green region (530 to 580 nm), and yellow region (580 to 620 nm). In addition to these emission peaks, it is more preferable to further have a maximum emission peak in the red region (650 to 700 nm).

<Infrared sensor>

The infrared sensor of the present invention includes the film of the present invention described above. The configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. Hereinafter, one embodiment of the infrared sensor of the present invention will be described using the drawings.

In FIG. 1, symbol 110 denotes a solid-state imaging device. An infrared cutoff filter 111 and an infrared ray transmission filter 114 are disposed on the imaging area of the solid-state imaging device 110. Additionally, a color filter 112 is disposed on the infrared cut-off filter 111. A micro lens 115 is disposed on the incident light hν side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed to cover the micro lens 115.

The infrared cut-off filter 111 can be formed using the composition of the present invention. The color filter 112 is a color filter formed with pixels that transmit and absorb light of a specific wavelength in the visible region. There is no particular limitation, and a conventionally known color filter for forming pixels can be used. For example, a color filter with red (R), green (G), and blue (B) pixels is used. For example, the description of paragraph numbers 0214 to 0263 of Japanese Patent Application Laid-Open No. 2014-043556 can be referred to, and this content is incorporated herein by reference. The characteristics of the infrared transmission filter 114 are selected depending on the emission wavelength of the infrared LED used. The infrared transmission filter 114 can be formed using the composition of the present invention.

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

<Camera module>

The camera module of the present invention includes a solid-state imaging device and the film of the present invention described above. The camera module preferably further includes a lens and a circuit that processes images obtained from a solid-state imaging device. The solid-state imaging device used in the camera module may be the solid-state imaging device according to the above-described present disclosure, or may be a known solid-state imaging device. Additionally, known lenses can be used as the lens used in the camera module and the circuit that processes the image captured from the solid-state imaging device. As an example of a camera module, reference may be made to the camera modules described in Japanese Patent Application Laid-Open No. 2016-006476 and Japanese Patent Application Publication No. 2014-197190, the contents of which are incorporated herein by reference.

<Compound>

The compound of the present invention is a compound represented by formula (1).

[Formula 24]

In formula (1) ^, X ^a and X ^b each independently represent a group represented by ⁼ NR

Y ^a and Y ^b each independently represent a hydrogen atom or a substituent,

R ¹ and R ² each independently represent an aliphatic hydrocarbon group which may have a substituent.

X ^a , ^{X b ,} Y ^a , Y ^b , R ¹ and R ² in formula (1) are respectively , Y ^a , Y ^b , R ¹ and R ² have the same meaning.

The maximum absorption wavelength of the compound of the present invention is preferably in the wavelength range of 650 nm or more, more preferably in the range of 650 to 1,500 nm, more preferably in the range of 660 to 1,200 nm, and has a wavelength of 660 nm. It is particularly preferred to be in the range of -1000 nm.

In addition, the compound of the present invention has an average absorbance in the wavelength range of 420 to 550 nm when the absorbance value at the wavelength (λmax) showing the highest absorbance in the wavelength range of 400 nm to 1200 nm is set to 1. It is preferable that the value of is less than 0.010, and it is more preferable that it is less than 0.005.

The compound of the present invention can be suitably used as an infrared absorber. Additionally, the compound of the present invention can also be used as a dispersion aid.

<Infrared absorber>

The infrared absorber of the present invention contains a compound represented by formula (1). The infrared absorber may contain only one type of the compound represented by formula (1), or may contain two or more types. Additionally, the infrared absorber of the present invention may contain a decomposition product of the compound represented by formula (1).

Example

The present invention will be described in more detail below with reference to examples. Materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the spirit of the present invention. In addition, in the structural formula, Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, and Ac represents an acetyl group.

<Synthesis of pigment (specific pigment) expressed in formula (1)>

<<Synthesis example of pigment PPB-A-13>>

The pigment PPB-A-13 was synthesized according to the following scheme.

[Formula 25]

(Synthesis of Intermediate 1)

Under a nitrogen atmosphere, 75.0 g of diethyl acetylsuccinate, 267.4 g of ammonium acetate, and 375 mL of acetic acid were added to a three-necked flask, and the mixture was heated and stirred under reflux for 3 hours. This reaction solution was cooled to 25°C, 300 mL of ethyl acetate, 300 mL of hexane, and 600 mL of distilled water were added, and then stirred for 30 minutes while maintaining the internal temperature of the reaction solution at 20 to 25°C. The aqueous layer was subjected to liquid separation three times with 600 mL of a mixture of ethyl acetate and hexane = 1:1, and then the organic layers were combined and concentrated under reduced pressure at 70°C. 300 mL of distilled water was added to the resulting residue and stirred for 20 minutes. This reaction liquid was filtered, washed with 300 mL of distilled water, and the obtained solid was blown-dried at 50°C for 12 hours to obtain 18.9 g of Intermediate 1 (yield 32.2%).

¹ H-NMR (CDCl ₃ ): δ=1.30(t, J=7.1Hz, 3H), 2.36-2.37(m, 3H), 3.29-3.31(m,2H), 4.20(q, J=7.1Hz, 2H), 8.06(s, 1H)

(Synthesis of Intermediate 2)

Under a nitrogen atmosphere, 71.77 g of sodium pentoxide and 600 mL of t-amyl alcohol were added to a three-necked flask at room temperature, and 400 mL of t-amyl alcohol was distilled off under heating and reflux. To the obtained reaction liquid, 158 mg of sodium bis(2-ethylhexyl)sulfosuccinate was added while maintaining the internal temperature of the reaction liquid at 105 to 115°C, and then 33.54 g of butyronitrile was added. Next, a solution in which 15.0 g of Intermediate 1 was suspended in 50 mL of t-amyl alcohol was added dropwise to the obtained reaction solution over 10 minutes while maintaining the internal temperature of the reaction solution at 105 to 115°C, and the mixture was heated to reflux and stirred for an additional hour. did. The obtained reaction liquid was cooled to 40°C, and while maintaining the internal temperature of the reaction liquid in the range of 40°C to 70°C, 105 mL of methanol and 71.88 g of acetic acid were sequentially added dropwise, the reaction liquid was cooled to 25°C, and the reaction liquid was cooled to 25°C. While maintaining the internal temperature in the range of 20°C to 30°C, 210 mL of ethyl acetate, 210 mL of saturated saline solution, and 105 mL of distilled water were sequentially added. Next, this reaction solution was stirred at 25°C for 5 minutes, filtered, and washed with 105 mL of distilled water to obtain a crude solid. The obtained solid was added to a three-neck flask, 53 mL of distilled water was added, stirred for 30 minutes, filtered, washed with 53 mL of distilled water, and the obtained solid was blown-dried at 50°C for 12 hours to obtain 3.40 g of Intermediate 2. (Yield 20.0%) was obtained.

¹ H-NMR (dimethyl sulfoxide (DMSO)): δ=0.90(t, J=7.4Hz, 3H), 1.70(sext, J=7.4Hz, 2H), 2.15(s, 3H), 2.45( t, J=7.4Hz, 2H), 10.1-10.2(m, 2H)

(Synthesis of Intermediate 3)

Under a nitrogen atmosphere, 237.46 g of malononitrile, 201 mL of acetic acid, and 1,977 mL of methanol were added to a three-neck flask, and while maintaining the liquid temperature in the flask below 40°C, 450 g of o-aminothiophenol was washed with 150 mL of methanol. It was dropped as it came out. The obtained reaction solution was stirred at 30°C for 2 hours, then stirred at 10°C or lower for 30 minutes, filtered, washed with 300 mL of cold methanol, and the obtained crystals were blown-dried at 40°C for 12 hours to obtain Intermediate 3 as 510.55. g (81.5% yield) was obtained.

¹ H-NMR (CDCl ₃ ): δ=4.24(s, 2H), 7.44(m, 1H), 7.53(m, 1H), 7.89(m, 1H), 8.04(m, 1H)

(Synthesis of Intermediate 4)

Under a nitrogen atmosphere, 3.0 g of Intermediate 2, 13.05 g of Intermediate 3, and 63 mL of toluene were added to a three-necked flask, and 3 mL of toluene was distilled off under heating and reflux. The obtained reaction liquid was cooled to 95°C, 7.18 g of phosphorus oxychloride was added while maintaining the internal temperature of the reaction liquid within the range of 90 to 95°C, and the mixture was stirred under heating and reflux for 1 hour. The obtained reaction liquid was cooled to 10°C or lower, and 90 mL of hexane was added dropwise while maintaining the internal temperature of the reaction liquid at 0°C to 10°C, and then stirred for 30 minutes while maintaining the internal temperature of the reaction liquid at 0°C to 10°C. Next, this reaction liquid was filtered and washed with 15 mL of hexane to obtain a solid. The obtained solid was added to a three-neck flask, 75 mL of saturated aqueous sodium bicarbonate was added, and the mixture was stirred for 5 minutes, then filtered and washed with 15 mL of saturated aqueous sodium bicarbonate to obtain a solid. Next, the obtained solid was added to a three-neck flask, 60 mL of a mixture of methanol: distilled water = 4:1 was added, stirred for 5 minutes, filtered, and washed with 60 mL of a mixture of methanol: distilled water = 4: 1, and the solid got it Additionally, the obtained solid was added to a three-neck flask, 60 mL of a mixture of methanol: distilled water = 9:1 was added, stirred for 5 minutes, filtered, and then washed with 60 mL of a mixture of methanol: distilled water = 9: 1. The obtained solid was blown-dried at 50°C for 12 hours to obtain 0.08 g of Intermediate 4 (yield 1.0%).

(Synthesis of pigment PPB-A-13)

Under a nitrogen atmosphere, 0.08 g of Intermediate 4, 0.29 g of 2-aminoethyl diphenylborate, and 2 mL of toluene were added to a three-necked flask, and 0.36 g of titanium tetrachloride was added to the toluene while maintaining the temperature in the range of 90 to 100°C. It was added while washing with 2mL. This reaction liquid was stirred under heating and reflux for 2 hours, then cooled to 20°C, and 2 mL of methanol was added while maintaining the internal temperature of the reaction liquid at 20°C to 30°C. The obtained crystals are filtered and washed with 1 mL of methanol, 2 mL of methanol is added to the obtained crude body, heated and stirred under reflux for 30 minutes, cooled to 20°C, filtered and washed with 1 mL of methanol, and then the obtained crystals are washed with 1 mL of methanol. By blow drying at 50°C for 12 hours, 0.06 g (46.2% yield) of the pigment PPB-A-13 was obtained. As a result of mass analysis by MALDI TOF-MASS (time-of-flight mass spectrometry), the obtained crystal was identified as the pigment PPB-A-13 with the following structure.

MALDI TOF-MASS: Calc. for [M+H] ⁺ : 833.3 found: 833.4

[Formula 26]

<<Synthesis example of pigment PPB-A-45>>

The pigment PPB-A-45 was synthesized according to the following scheme.

[Formula 27]

(Synthesis of Intermediate 6)

Intermediate 5 was synthesized using the same method as Intermediate 2. Under a nitrogen atmosphere, 0.75 g of Intermediate 5 and 7.5 g of benzonitrile were added to a three-necked flask, and 2.16 g of phenyl dichlorophosphate was added at 35°C. This reaction solution was stirred at 35°C for 30 minutes, then heated to 50°C and stirred for 1 hour, then heated to 70°C and stirred for an additional hour to prepare reaction solution A.

Subsequently, 2.85 g of Intermediate 3 and 14.3 g of toluene were added under a nitrogen atmosphere, and 3 mL of toluene was distilled off under heating and reflux. The obtained reaction solution was cooled to 95°C, reaction solution A was added dropwise over 30 minutes while maintaining the internal temperature of the reaction solution in the range of 90 to 95°C, and 2.16 g of phenyl dichlorophosphate was added, followed by stirring at 90 to 95°C. Stirred for 15 minutes. The obtained reaction liquid was cooled to 10°C or lower, and 44.2 g of hexane was added dropwise while maintaining the internal temperature of the reaction liquid at 0°C to 10°C, and then stirred for 30 minutes while maintaining the internal temperature of the reaction liquid at 0°C to 10°C. . Next, this reaction liquid was filtered and washed with 10 g of hexane to obtain a solid. The obtained solid was added to a three-necked flask, 19 mL of saturated sodium bicarbonate water was added, and the mixture was stirred for 5 minutes, then 38 mL of methanol was further added, stirred for 5 minutes, and then filtered to obtain a solid. Additionally, the obtained solid was added to a three-neck flask, 20 mL of a mixture of methanol: distilled water = 9:1 was added, stirred for 5 minutes, filtered, and then washed with 30 mL of a mixture of methanol: distilled water = 9: 1. The obtained solid was blown-dried at 50°C for 12 hours to obtain 0.9 g of Intermediate 6.

(Synthesis of pigment PPB-A-45)

Under a nitrogen atmosphere, 0.8 g of Intermediate 6, 2.7 g of 2-aminoethyl diphenylborate, and 16 mL of toluene were added to a three-necked flask, and 3.42 g of titanium tetrachloride was added to the toluene while maintaining the temperature in the range of 90 to 100°C. It was added while washing with 2mL. This reaction solution was stirred under heating and reflux for 2 hours, then cooled to 20°C, and 208 mL of methanol was added dropwise while maintaining the internal temperature at 20°C to 30°C. After stirring this reaction solution for 30 minutes, the obtained crystals were filtered and washed with 44 mL of methanol. The obtained crude was purified by silica gel column chromatography (chloroform), and the obtained crystals were blown-dried at 50°C for 12 hours to obtain 0.09 g of the pigment PPB-A-45.

¹ H-NMR(CDCl ₃ ) δ7.74(2H, d, J=8.2Hz), 7.73(2H, d, J=8.2Hz), 7.69-7.51(6H, m), 7.42-7.07(18H, m) ), 3.48(1H. m), 2.93(2H, m), 1.54(2H, m), 0.82(3H, d, J=7.4Hz), 0.78(3H, d, J=7.4Hz), 0.60(3H) , t, J=7.4Hz)

[Formula 28]

<Evaluation of visible transparency>

A dye solution was prepared by dissolving the dyes listed in the table below in the solvent listed in the table below. The absorbance of the obtained dye solution to light with a wavelength of 400 to 1200 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High Technologies Co., Ltd.). In the wavelength range of 400 nm to 1200 nm, the wavelength (λmax) at which the absorbance is highest is measured, and when the absorbance value at λmax is set to 1, the average absorbance value in the wavelength range of 420 to 550 nm is By calculation, visible transparency was evaluated based on the following standards. It can be said that the smaller the average absorbance, the higher the visible transparency.

A: Average absorbance of wavelength 420~550nm is less than 0.005

B: Average absorbance of wavelength 420~550nm is 0.005 or more and less than 0.010

C: Average absorbance at wavelength 420~550nm is 0.010 or more

[Table 1]

[Table 2]

Pigment PPB-A-1 to PPB-A-45 and pigment PPB-C-1 to pigment PPB-3 were superior in visual transparency to pigment PPB-D-1 and pigment PPB-D-2.

The details of each pigment are as follows.

PPB-A-1 to PPB-A-45: Compounds with the following structure (pigments (specific pigments) represented by formula (1))

PPB-C-1 to PPB-C-3: Compounds with the following structure (pigments (specific pigments) represented by formula (1))

PPB-D-1, PPB-D-2, PPB-E-1: Compounds with the following structures (comparative dyes)

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

<Preparation of dispersion>

1.902 parts by mass of the dye (pigment) shown in the table below, 0.36 parts by mass of the derivative shown in the table below, 9 parts by mass of the dispersant shown in the table below, 18.74 parts by mass of the solvent shown in the table below, and zirconia with a diameter of 0.3 mm. 40 parts by mass of beads were mixed, dispersion treatment was performed for 5 hours using a paint shaker, and the beads were separated by filtration to prepare a dispersion liquid.

[Table 3]

(pigment)

PPB-A-1 to PPB-A-45: Compounds with the above-mentioned structure (pigments (specific pigments) represented by formula (1))

PPB-D-1, PPB-D-2: Compounds with the above-mentioned structure (comparative dyes)

(derivative)

PPB-B-1 to PPB-B-16: Compounds with the following structures (PPB-B-1 to PPB-B-13, PPB-B-15, PPB-B-16 are pigments represented by formula (1) ( (specific pigment), and PPB-B-14 is a different compound from the pigment (specific pigment) expressed in formula (1).)

[Formula 39]

[Formula 40]

[Formula 41]

(Dispersant)

D-1: Resin with the following structure (the numbers given in the main chain are molar ratios, and the numbers given in the side chains indicate the number of repeating units. Weight average molecular weight 38900, acid value 99.1 mgKOH/g) is added to propylene glycol monomethyl. A mixed solution of teracetate:propylene glycol monomethyl ether = 9:1 (mass ratio), with solid content concentration adjusted to 20% by mass.

D-2: A resin with the following structure (the numbers given in the main chain are molar ratios, and the numbers given in the side chain indicate the number of repeating units. Weight average molecular weight 21000, acid value 36.0 mgKOH/g, amine value 47.0 mgKOH/g) is mixed with propylene. A mixed solution of glycol monomethyl ether acetate:propylene glycol monomethyl ether = 9:1 (mass ratio), with solids concentration adjusted to 20% by mass.

[Formula 42]

(solvent)

S-1: Propylene glycol monomethyl ether acetate

S-2: propylene glycol monomethyl ether

<Preparation of dye solution>

A dye solution was prepared by mixing 8.02 parts by mass of the pigment (dye) shown in the table below and 91.98 parts by mass of the solvent shown in the table below.

[Table 4]

(pigment)

PPB-C-1 to PPB-C-3: Compounds with the above-mentioned structure (pigments (specific pigments) represented by formula (1))

PPB-E-1: Compound with the above-mentioned structure (comparative dye)

(solvent)

S-3: Cyclopentanone

S-4: Cyclohexanone

S-5: Anisole

<Preparation of composition>

Each material was mixed in the proportions of formulas 1 to 6 shown below, and filtered through a nylon filter with a pore diameter of 0.45 μm (manufactured by Nippon Poll Co., Ltd.) to prepare each composition.

<Prescription 1>

Dispersions listed in the table below... 15.873 parts by mass

Resins listed in the table below... 2.943 parts by mass

Polymerizable compounds listed in the table below... 0.45 parts by mass

Photopolymerization initiator listed in the table below... 0.45 parts by mass

Polymerization inhibitor (p-methoxyphenol)… 0.001 parts by mass

Surfactants listed in the table below... 0.0075 parts by mass

Solvents listed in the table below: 10.276 parts by mass

<Prescription 2>

Dispersions listed in the table below... 15.873 parts by mass

Resins listed in the table below... 2.943 parts by mass

Epoxy compounds listed in the table below... 0.9 parts by mass

Hardener listed in the table below (if indicated in the table)...0.045 parts by mass

Polymerization inhibitor (p-methoxyphenol)… 0.001 parts by mass

Surfactants listed in the table below... 0.0075 parts by mass

Solvents listed in the table below… 10.276 parts by mass

<Prescription 3>

Color solutions listed in the table below… 14.921 parts by mass

Resins listed in the table below... 3.895 parts by mass

Polymerizable compounds listed in the table below... 0.45 parts by mass

Photopolymerization initiator listed in the table below... 0.45 parts by mass

Polymerization inhibitor (p-methoxyphenol)… 0.001 parts by mass

Surfactants listed in the table below... 0.00075 parts by mass

Solvents listed in the table below… 10.276 parts by mass

<Prescription 4>

Color solutions listed in the table below… 14.921 parts by mass

Resins listed in the table below... 3.895 parts by mass

Epoxy compounds listed in the table below... 0.9 parts by mass

Hardeners listed in the table below (if indicated in the table)... 0.045 parts by mass

Polymerization inhibitor (p-methoxyphenol)… 0.001 parts by mass

Surfactants listed in the table below... 0.0075 parts by mass

Solvents listed in the table below… 10.276 parts by mass

<Prescription 5>

Dispersions listed in the table below... 8.333 parts by mass

A propylene glycol monomethyl ether acetate solution with a solid content concentration of 45% by mass of a resin of the following structure (weight average molecular weight 24600, the value given to the main chain indicates the mass ratio of the repeating unit)... 4.886 parts by mass

[Formula 43]

Ultraviolet absorbers listed in the table below… 2.7 parts by mass

Polymerization inhibitor (p-methoxyphenol)… 0.001 parts by mass

Surfactants listed in the table below... 0.011 parts by mass

Solvents listed in the table below… 6.305 parts by mass

<Prescription 6>

Color solutions listed in the table below… 7.833 parts by mass

A propylene glycol monomethyl ether acetate solution with a solid content concentration of 45% by mass of a resin of the following structure (weight average molecular weight 24600, the value given to the main chain indicates the mass ratio of the repeating unit)... 5.386 parts by mass

[Formula 44]

Ultraviolet absorbers listed in the table below… 2.7 parts by mass

Polymerization inhibitor (p-methoxyphenol)… 0.001 parts by mass

Surfactants listed in the table below... 0.011 parts by mass

Solvents listed in the table below… 6.030 parts by mass

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

Among the materials listed in the table above, details of materials other than dispersions and dye solutions are as follows.

(profit)

E-1: Copolymer resin of benzyl methacrylate, methacrylic acid, and 2-hydroxyethyl methacrylate (weight average molecular weight 14000, acid value 77 mgKOH/g, alkali-soluble resin)

E-2: ARTON F4520 (manufactured by JSR Co., Ltd., cyclic polyolefin resin)

E-3: Resin with the following structure (weight average molecular weight 40000, acid value 100 mgKOH/g, the value added to the main chain indicates the mass ratio of the repeating unit. Alkali-soluble resin)

[Formula 45]

(polymerizable compound)

M-1: Aronics M-305 (manufactured by Toa Gosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate. The content of pentaerythritol triacrylate is 55% by mass to 63% by mass. .)

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

M-3: Aronix M-510 (manufactured by Toagosei Co., Ltd., polybasic acid-modified acrylic oligomer)

(Photopolymerization initiator)

C-1: Irgacure OXE01 (manufactured by BASF, oxime ester initiator)

C-2: Irgacure OXE02 (manufactured by BASF, oxime ester initiator)

C-3: Omnirad 907 (manufactured by IGM Resins B.V., α-aminoalkylphenone initiator)

(Epoxy compound)

F-1: Glycidyl methacrylate skeleton random polymer (Nichiyu Co., Ltd., Maproof G-0150M, weight average molecular weight 10000)

F-2: EPICLON N-695 (DIC Co., Ltd., novolac type epoxy resin)

F-3: JER1031S (Mitsubishi Chemical Co., Ltd., multifunctional epoxy resin)

F-4: EHPE3150 (manufactured by Daicel Co., Ltd., 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol)

(hardener)

G-1: trimellitic acid

G-2: Pyromellitic anhydride

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

G-4: Pentaerythritol tetrakis (3-mercaptopropionate)

(Surfactants)

H-1: Megapak RS-72-K (manufactured by DIC Co., Ltd., fluorine-based surfactant)

H-2: Compound with the following structure (weight average molecular weight 14000, % value indicating the ratio of repeating units is mole %)

[Formula 46]

H-3: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., carbinol-modified polydimethylsiloxane at both ends, hydroxyl value 62 mgKOH/g)

(UV absorbent)

U-1: Uvinul3050 (manufactured by BASF, compound with the following structure)

[Formula 47]

U-2: Tinuvin477 (manufactured by BASF, hydroxyphenyltriazine-based ultraviolet absorber)

U-3: Tinuvin326 (manufactured by BASF, compound with the following structure)

[Formula 48]

(solvent)

S-1: Propylene glycol monomethyl ether acetate

S-2: propylene glycol monomethyl ether

S-3: Cyclopentanone

S-4: Cyclohexanone

<Manufacture of membrane>

(Production Example 1) Method for producing a membrane using the compositions of Examples 1 to 51 and Comparative Examples 1 to 3

Each composition was applied on a glass substrate by spin coating, and then heated at 100°C for 2 minutes using a hot plate to obtain a composition layer. The obtained composition layer was exposed to an exposure dose of 500 mJ/cm ² using an i-line stepper. Next, the composition layer after exposure was cured by heating at 220°C for 5 minutes using a hot plate to obtain a film with a thickness of 1.5 μm.

(Production Example 2) Method for producing a membrane using the composition of Examples 401 to 451 and Comparative Examples 401 to 403

Each composition prepared above was applied on a glass substrate by spin coating, then heated (pre-baked) at 100°C for 10 minutes using a hot plate, and then cured by heating at 200°C for 8 minutes. , a membrane with a thickness of 1.5 μm was obtained.

(Production Example 3) Method for producing a membrane using the composition of Examples 701 to 751

Each composition prepared above was applied on a glass substrate by spin coating, then heated (pre-baked) at 100°C for 10 minutes using a hot plate, and then cured by heating at 200°C for 8 minutes. , a membrane with a thickness of 8.0 μm was obtained.

<Evaluation of fluorescence quantum yield>

The fluorescence quantum yield of the obtained film was measured using an absolute PL quantum yield measuring device C9920-03G (manufactured by Hamamatsu Photonics Co., Ltd.), and the fluorescence quantum yield was evaluated based on the following criteria.

A: Fluorescence quantum yield is less than 0.01

B: Fluorescence quantum yield is 0.01 or more

<Evaluation of visible transparency>

The absorbance of the obtained film to light with a wavelength of 400 nm to 1200 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High Technologies). In the wavelength range of 400 nm to 1200 nm, the wavelength (λmax) at which the absorbance is highest is measured, and when the absorbance value at λmax is set to 1, the average absorbance value in the wavelength range of 420 to 550 nm is By calculation, visible transparency was evaluated based on the following standards.

A: Average absorbance of wavelength 420~550nm is less than 0.025

B: Average absorbance of wavelength 420~550nm is 0.025 or more and less than 0.050

C: Average absorbance at wavelength 420~550nm is 0.050 or more

<Evaluation of visible transparency after heating>

The obtained membrane was placed in a thermostat at 150°C and subjected to heat treatment for 1000 hours. For the film after heat treatment, the absorbance of light with a wavelength of 400 to 1200 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High Technologies Co., Ltd.). In the range of 400 nm to 1200 nm, the wavelength (λmax) with the highest absorbance is measured, and the absorbance value at λmax is set to 1. The average absorbance is the value in the range of 420 to 550 nm. was calculated, and the visible transparency after heating was evaluated based on the following standards.

A: Average absorbance of wavelength 420~550nm is less than 0.025

B: Average absorbance of wavelength 420~550nm is 0.025 or more and less than 0.050

C: Average absorbance at wavelength 420~550nm is 0.050 or more

<Evaluation of change in transmittance after heating>

For the obtained film, the light transmittance with a wavelength of 400 to 1200 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High Technologies Co., Ltd.). Next, the membrane was placed in a thermostat at 150°C and subjected to heat treatment for 1000 hours. For the film after heat treatment, the transmittance of light with a wavelength of 400 to 1200 nm is similarly measured, and the transmittance change (ΔT) at each wavelength in the range of 400 to 1200 nm before and after heat treatment is measured to determine the transmittance change. The maximum value (ΔTmax) was obtained, and the maximum value (ΔTmax) of the change in transmittance was evaluated based on the following criteria.

Transmittance change (ΔT) = | Transmittance of the membrane before heat treatment (%) - Transmittance of the membrane after heat treatment (%) |

Here, ΔTmax refers to the largest value in the transmittance change ΔT at each wavelength of 400 to 1200 nm calculated above.

A: Transmittance change ΔTmax of wavelength 400~1200nm is less than 4%

B: Transmittance change ΔTmax of wavelength 400~1200nm is 4% or more and less than 10%

C: Transmittance change ΔTmax of wavelength 400~1200nm is more than 10%

[Table 11]

[Table 12]

[Table 13]

[Table 14]

[Table 15]

[Table 16]

As shown in the table above, the composition of the example was able to form a film with a low fluorescence quantum yield and excellent visible transparency. In addition, the film obtained using the composition of the example had excellent visible transparency even after heating, and the change in transmittance before and after heating was small.

In addition, the films obtained using the compositions of Examples 701 to 751 all had a transmittance of 5% at a wavelength of 390 nm and were also excellent in ultraviolet ray shielding properties.

Additionally, Examples 1 to 19, 21, 25, 26, 27, 29 to 51, 401 to 419, 421, 425, 426, 427, 429 to 451, 701 to 719, 721, 725, 726, 727, 729 to Light fastness was also excellent for 751.

In the above examples, among PPB-B-1 to PPB-B-13, PPB-B-15, and PPB-16 used as derivatives, a compound having a group represented by the following formula (A-1) (PPB-B -1, PPB-B-4, PPB-B-15), a compound having a structure in which the group represented by the following formula (A-1) is replaced with a group represented by the following formula (B-1), or a mixture of both Even when used, the same effect as in each example was obtained. In addition, among PPB-B-1 to PPB-B-13, PPB-B-15, and PPB-16 used as derivatives in the above examples, a compound having a group represented by the following formula (A-2) (PPB -B-3, PPB-B-6, PPB-B-11) are compounds having a structure in which the group represented by the following formula (A-2) is replaced with a group represented by the following formula (B-2), or both. Even when a mixture was used, the same effect as in each example was obtained.

[Formula 49]

In the above formula, M represents Li, Na, K, Rb, Cs or a structure represented by formula (C) or formula (D).

[Formula 50]

In formula (C), R _z ¹ to R _z ⁴ each independently represent a hydrogen atom, a branched or straight-chain alkyl group which may have a substituent, or an aryl group which may have a substituent. However, R _z ¹ to R _z ⁴ may be connected to each other to form a ring.

In formula (D), R _z ⁵ to R _z ⁹ each independently represent a substituent, and R _z ⁵ and R _z ⁶ , R _z ⁶ and R z ⁷ , _{R z 7} ^and R _z ⁸ , R _z ⁸ and R _z ⁹ may be connected to each other to form a ring.

By using the membrane of the example in an optical filter, solid-state imaging device, image display device, infrared sensor, or camera module, an optical filter, solid-state imaging device, image display device, infrared sensor, or camera module with excellent performance can be obtained.

<Preparation of composition IR>

Each material was mixed in the ratio shown below and filtered through a nylon filter with a pore diameter of 0.45 μm (manufactured by Nippon Poll Co., Ltd.) to prepare composition IR.

Infrared absorber (FDR-3, manufactured by Yamada Kagaku Kogyo Co., Ltd.)... 0.045 parts by mass

A propylene glycol monomethyl ether acetate solution with a solid content concentration of 45% by mass of a resin of the following structure (weight average molecular weight 24600, the value given to the main chain indicates the mass ratio of the repeating unit)... 6.9 parts by mass

[Formula 51]

Ultraviolet absorber (Uvinul3050, manufactured by BASF)… 1.35 parts by mass

Polymerization inhibitor (p-methoxyphenol)… 0.001 parts by mass

Propylene glycol monomethyl ether acetate… 6.705 parts by mass

<Manufacture of laminated membrane>

(Examples 1001 to 1051)

The composition IR prepared above was applied on a glass substrate by spin coating so that the post-baked film thickness was 7.0 μm, then heated (pre-baked) at 100°C for 10 minutes using a hot plate, and then heated at 200° C. Curing was performed by heating at ℃ for 8 minutes to obtain a film with a thickness of 7.0 μm. On the obtained film, the composition of Examples 401 to 451 as a composition for the second layer was applied by spin coating on a glass substrate so that the film thickness of the second layer after post-baking was 1.0 μm, and then applied at 100 μm using a hot plate. It was heated (prebaked) at ℃ for 10 minutes, and then cured by heating at 200℃ for 8 minutes to form a second layer film with a thickness of 1.0 μm, thereby obtaining a laminated film with a thickness of 8.0 μm.

The laminated films of Examples 1001 to 1051 were observed using an optical microscope at a bright field of 200x to see if there was any precipitation of foreign matter in the film, and no precipitation of foreign matter was observed in any of them. In addition, the laminated films of Examples 1001 to 1051 all had a light transmittance of less than 5% at a wavelength of 390 nm and were excellent in ultraviolet ray shielding properties.

By using the laminated film of the example in an optical filter, a solid-state imaging device, an image display device, an infrared sensor, or a camera module, an optical filter, a solid-state imaging device, an image display device, an infrared sensor, or a camera module with excellent performance can be obtained.

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

Claims (14)

A composition containing a pigment represented by formula (1) and a curable compound;
[Formula 1]

In formula ( ¹ ), X ^a and X ^b each independently represent a group represented by ⁼ NR
Y ^a and Y ^b each independently represent a hydrogen atom or a substituent,
R ¹ and R ² each independently represent an aliphatic hydrocarbon group which may have a substituent;
[Formula 2]

In formulas (X-1) to (X-5), * represents a connection part,
R ^a11 ~R ^a29 each independently represent a hydrogen atom or a substituent,
X ^c and X ^d each independently represent S, O or NR ^X2 , R ^X2 represents a hydrogen atom or a substituent,
A ¹ represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a condensed ring thereof which may have a substituent. In claim 1,
A composition in which X ^a and X ^b in the formula (1) are each independently a group represented by any one of formulas (X-1-1) to (X-1-3);
[Formula 3]

In formulas (X-1-1) to (X-1-3), * represents a connection part,
R ^a51 to R ^a63 each independently represent a hydrogen atom or a substituent,
Among R ^a51 to R ^a54 in formula (X-1-1), two adjacent groups may be combined to form a ring,
Among R ^a55 to R ^a58 in formula (X-1-2), two adjacent groups may be combined to form a ring,
Among R ^a60 to R ^a63 in formula (X-1-3), two adjacent groups may be bonded to form a ring. In claim 1 or claim 2,
Y ^a and Y ^b in the formula (1) each independently represent -BR ^Y1 R ^Y2 ,
R ^Y1 and R ^Y2 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group,
A composition in which R ^Y1 and R ^Y2 may be bonded to each other to form a ring. The method according to any one of claims 1 to 3,
A composition in which at least one of R ¹ and R ² in the formula (1) is an alkyl group having 9 or less carbon atoms which may have a substituent. The method according to any one of claims 1 to 3,
A composition in which at least one of R ¹ and R ² in the formula (1) is a group represented by the formula (R-1);
[Formula 4]

In formula (R-1), * represents a connecting portion, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a substituent, Ar ¹⁰¹ represents an aryl group or heteroaryl group, and n represents an integer of 1 or more. The method according to any one of claims 1 to 5,
A composition in which the pigment represented by the formula (1) has a maximum absorption wavelength of 650 nm or more. A membrane obtained by using the composition according to any one of claims 1 to 6. An optical filter comprising the membrane according to claim 7. A solid-state imaging device comprising the film according to claim 7. An image display device comprising the film according to claim 7. An infrared sensor comprising the membrane according to claim 7. A camera module comprising the membrane according to claim 7. Compounds represented by formula (1);
[Formula 5]

In formula ( ¹ ), X ^a and X ^b each independently represent a group represented by ⁼ NR
Y ^a and Y ^b each independently represent a hydrogen atom or a substituent,
R ¹ and R ² each independently represent an aliphatic hydrocarbon group which may have a substituent;
[Formula 6]

In formulas (X-1) to (X-5), * represents a connection part,
R ^a11 ~R ^a29 each independently represent a hydrogen atom or a substituent,
X ^c and X ^d each independently represent S, O or NR ^X2 , R ^X2 represents a hydrogen atom or a substituent,
A ¹ represents an aromatic hydrocarbon ring, an aromatic heterocycle, or a condensed ring thereof which may have a substituent. An infrared absorber comprising the compound according to claim 13.