WO2023219010A1

WO2023219010A1 - Resin composition, film, optical filter, solid-state imaging element, image display device, infrared sensor, camera module, and compound

Info

Publication number: WO2023219010A1
Application number: PCT/JP2023/016844
Authority: WO
Inventors: 一成八木; 直幸花木
Original assignee: 富士フイルム株式会社
Priority date: 2022-05-13
Filing date: 2023-04-28
Publication date: 2023-11-16
Also published as: TW202346385A

Abstract

This resin composition contains a resin and at least one infrared-absorbing dye A selected from a dye A1 represented by formula (1) and die multimers A2 including two or more dye structures derived from the dye A1 per molecule. The present invention also pertains to a film, an optical filter, a solid-state imaging element, an image display device, an infrared sensor, a camera module, and a compound.

Description

Resin compositions, films, optical filters, solid-state imaging devices, image display devices, infrared sensors, camera modules and compounds

The present invention relates to a resin composition containing an infrared absorbing dye. The present invention also relates to a film, an optical filter, a solid-state image sensor, an image display device, an infrared sensor, and a camera module using the resin composition. The invention also relates to compounds.

Video cameras, digital still cameras, mobile phones with camera functions, and the like use CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors), which are solid-state imaging devices for color images. These solid-state image sensors use silicon photodiodes sensitive to infrared rays in their light receiving portions. For this reason, an infrared cut filter may be provided to correct visibility. Infrared cut filters are manufactured using resin compositions containing infrared absorbing dyes and resins.

Patent Document 1 describes that an infrared cut filter or the like is manufactured using a resin composition containing an infrared absorbing dye containing an iminium compound and a resin.

Japanese Patent Application Publication No. 2007-233368

In recent years, there has been a demand for further improvements in the heat resistance and light resistance of films obtained using resin compositions containing infrared absorbing dyes and resins.

Therefore, an object of the present invention is to provide a resin composition that can form a film with excellent heat resistance and light resistance. Another object of the present invention is to provide a film, an optical filter, a solid-state image sensor, an image display device, an infrared sensor, a camera module, and a compound.

The present invention provides the following.
<1> At least one infrared absorbing dye A selected from a dye A1 represented by formula (1) and a dye multimer A2 containing two or more dye structures derived from the dye A1 in one molecule,
A resin composition comprising a resin;
In formula (1), L ¹⁰¹ is -P(=O)(R ^L101 )-, -P(=S)(R ^L102 )-, -Si(R ^L103 )(R ^L104 )-, -B(R ^L105 )-, -S(=O) ₂ - or -S(=O)-, R ^L101 to R ^L105 represent a hydrogen atom or a substituent, and R ^L103 and R ^L104 combine to form a ring. It is okay to do
X ¹⁰¹ to X ¹⁰³ each independently represent a nitrogen atom or -CR ^X101 -, R ^X101 represents a hydrogen atom or a substituent,
L ¹⁰² and L ¹⁰³ each independently represent a sulfur atom or -X ¹⁰⁴ =X ¹⁰⁵ -, X ¹⁰⁴ and X ¹⁰⁵ each independently represent a nitrogen atom or -CR ^X102 -, and ^R , represents a hydrogen atom or a substituent,
Ar ¹⁰¹ and Ar ¹⁰² each independently represent -(CR ^Ar101 = CR ^Ar102 ) _n101 -, an arylene group, a heterocyclic group, or a group combining two or more of these groups, and R ^Ar101 and R ^Ar102 each represent independently represents a hydrogen atom or a substituent, n101 represents an integer of 1 to 3,
Y ¹⁰¹ and Y ¹⁰² each independently represent -OR ^Y101 , -NR ^Y102 ^RY103 or -SR Y104, and R ^Y101 to ^R ^Y104 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl represents a group, an aryl group or a heteroaryl group, and R ^Y102 and R ^Y103 may be bonded via a single bond or a divalent linking group to form a ring,
Ar ¹⁰¹ and X ¹⁰¹ may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar ¹⁰¹ and Y ¹⁰¹ may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar ¹⁰² and X ¹⁰² may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar ¹⁰² and Y ¹⁰² may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Z ¹ represents a counter ion,
p1 represents an integer from 0 to 5,
q1 represents an integer from 1 to 5.
<2> X ¹⁰³ in the above formula (1) is -CR ^X101 -, R ^X101 is a hydrogen atom or a substituent,
The resin composition according to <1>, wherein L ¹⁰² and L ¹⁰³ are each a sulfur atom.
<3> X ¹⁰³ in the above formula (1) is -CR ^X101 -, R ^X101 is a hydrogen atom or a substituent,
L ¹⁰² and L ¹⁰³ are each a sulfur atom,
The resin composition according to <1>, wherein L ¹⁰¹ is -P(=O)(R ^L101 )-, and R ^L101 is a hydrogen atom or a substituent.
<4> X ¹⁰³ in the above formula (1) is -CR ^X101 -, R ^X101 is a hydrogen atom or a substituent,
L ¹⁰² and L ¹⁰³ are each a sulfur atom,
L ¹⁰¹ is -P(=O)(R ^L101 )-, R ^L101 is a hydrogen atom or a substituent,
Y ¹⁰¹ and Y ¹⁰² are each independently -NR ^Y102 R ^Y103 , and R ^Y102 and R ^Y103 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. The resin composition according to <1>, wherein R ^Y102 and R ^Y103 may be bonded via a single bond or a divalent linking group to form a ring.
<5> X ¹⁰³ in the above formula (1) is -CR ^X101 -, R ^X101 is a hydrogen atom or a substituent,
L ¹⁰² and L ¹⁰³ are each a sulfur atom,
L ¹⁰¹ is -Si(R ^L103 )(R ^L104 )- or -S(=O)-, and R ^L103 and R ^L104 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, is an aryl group or a heteroaryl group,
Y ¹⁰¹ and Y ¹⁰² are each independently -NR ^Y102 R ^Y103 , and R ^Y102 and R ^Y103 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. The resin composition according to <1>, wherein R ^Y102 and R ^Y103 may be bonded via a single bond or a divalent linking group to form a ring.
<6> The resin composition according to any one of <1> to <5>, further comprising an infrared absorber other than the infrared absorbing dye A.
<7> The resin composition according to <6>, wherein the maximum absorption wavelength of the infrared absorbing agent other than the infrared absorbing dye A is on the shorter wavelength side than the maximum absorption wavelength of the infrared absorbing dye A.
<8> The resin composition according to any one of <1> to <7>, wherein the maximum absorption wavelength of the infrared absorbing dye A is in a wavelength range of 700 to 1800 nm.
<9> The resin composition according to any one of <1> to <8>, further comprising a polymerizable compound and a photopolymerization initiator.
<10> A film obtained using the resin composition according to any one of <1> to <9>.
<11> An optical filter comprising the film according to <10>.
<12> A solid-state imaging device comprising the film according to <10>.
<13> An image display device including the film according to <10>.
<14> An infrared sensor comprising the film according to <10>.
<15> A camera module including the film according to <10>.
<16> Compound represented by formula (4);
In the formula, Ar ⁴⁰¹ represents an aryl group or a heteroaryl group,
R ⁴⁰¹ to R ⁴⁰⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group,
R ⁴⁰⁵ and R ⁴⁰⁶ each independently represent an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group or a cyano group,
R ⁴⁰⁷ and R ⁴⁰⁸ each independently represent an alkyl group or an aryl group,
n401 and n402 each independently represent an integer from 0 to 4,
q4 represents 1 or 2,
Z ⁴ represents a q4-valent counteranion.
<17> Compound represented by formula (5);
In the formula, Ar ⁵⁰¹ represents an aryl group or a heteroaryl group,
R ⁵⁰¹ to R ⁵⁰⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group,
R ⁵⁰⁵ and R ⁵⁰⁶ each independently represent an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group or a cyano group,
n ⁵⁰¹ and n ⁵⁰² each independently represent an integer from 0 to 4,
q5 represents 1 or 2,
Z ⁵ represents a q5-valent counteranion.

According to the present invention, it is possible to provide a resin composition that can form a film with excellent heat resistance and light resistance. Further, the present invention can provide a film, an optical filter, a solid-state imaging device, an image display device, an infrared sensor, a camera module, and a compound.

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

The content of the present invention will be explained in detail below.
In this specification, "~" is used to include the numerical values described before and after it as a lower limit and an upper limit.
In the description of a group (atomic group) in this specification, the description that does not indicate substituted or unsubstituted includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the term "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth)acrylate" represents acrylate and/or methacrylate, "(meth)acrylic" represents both acrylic and/or methacrylic, and "(meth)acrylate" represents acrylic and/or methacrylate. ) "Acryloyl" refers to acryloyl and/or methacryloyl.
In this specification, the weight average molecular weight and number average molecular weight are defined as polystyrene equivalent values measured by gel permeation chromatography (GPC).
In this specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, infrared rays refer to light (electromagnetic waves) with a wavelength of 700 to 2500 nm.
In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent.
In this specification, the term "process" is used not only to refer to an independent process, but also to include any process that achieves the intended effect even if it cannot be clearly distinguished from other processes. .

<Resin composition>
The resin composition of the present invention includes at least one infrared absorbing dye A selected from a dye A1 represented by formula (1) and a dye multimer A2 containing two or more dye structures derived from the dye A1 in one molecule;
It is characterized by containing a resin.

By using the resin composition of the present invention, a film with excellent heat resistance and light resistance can be formed. It is presumed that the infrared absorbing dye A is likely to form associations in the resin during film formation. By associating infrared absorbing dye A in the resin, the frequency of contact with chemical species that induce decomposition such as oxygen and water is reduced, and the decomposition of infrared absorbing dye A is suppressed, resulting in excellent heat resistance and light resistance. It is presumed that a film could be formed.

Furthermore, by using the above-mentioned infrared absorbing dye A, it is possible to form a film with a steep slope of transmittance on the longer wavelength side than the maximum absorption wavelength and excellent contrast between transmittance and light-shielding properties. A film having such spectral characteristics is preferably used as an optical filter such as an infrared cut filter or an infrared transmission filter. Therefore, the resin composition of the present invention can be used as a resin composition for optical filters. Types of optical filters include infrared cut filters and infrared transmission filters.

Each component used in the resin composition of the present invention will be explained below.

<<Specific infrared absorbing dye>>
The resin composition of the present invention comprises at least one infrared absorbing dye A2 selected from a dye A1 represented by formula (1) and a dye multimer A2 containing two or more dye structures derived from the above-mentioned dye A1 in one molecule. including. Hereinafter, the above-mentioned infrared absorbing dye will also be referred to as a specific infrared absorbing dye.

The specific infrared absorbing dye may be a dye or a pigment.
When the specific infrared absorbing dye is a pigment, the specific infrared absorbing dye preferably has a solubility of 0.1 g/100 g or less at 25° C. in both propylene glycol monomethyl ether acetate and water. Further, when the specific infrared absorbing dye is a pigment, the average particle size of the pigment is preferably 20 to 300 nm, more preferably 25 to 250 nm, and even more preferably 30 to 200 nm. The term "average particle size" as used herein means the average particle size of secondary particles which are aggregates of primary pigment particles. In addition, the particle size distribution of the secondary particles of the pigment (hereinafter also simply referred to as "particle size distribution") is such that the secondary particles having an average particle size of ±100 nm account for 70% by mass or more of the total, preferably 80% by mass or more. It is preferable that it is at least % by mass. Note that the particle size distribution of the secondary particles can be measured using scattering intensity distribution.

-Dye A1-
First, the dye A1 represented by formula (1) will be explained.

L ¹⁰¹ in formula (1) is -P(=O)(R ^L101 )-, -P(=S)(R ^L102 )-, -Si(R ^L103 )(R ^L104 )-, -B(R ^L105 )-, -S(=O) ₂ - or -S(=O)-, and R ^L101 to R ^L105 each independently represent a hydrogen atom or a substituent.
Examples of the substituents represented by R ^L101 to R ^L105 include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, and alkenyloxy groups, and it is an alkyl group or an aryl group. is preferable, and an aryl group is more preferable. These groups may further have a substituent. Examples of the substituent include the groups listed for the substituent T described below and the anion-containing groups described below.
The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The alkyl group may be straight, branched or cyclic.
The alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The alkenyl group may be either straight or branched.
The number of carbon atoms in the alkynyl group is preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 4. The alkynyl group may be either straight or branched.
The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12. Further, the aryl group is preferably a monocyclic aryl group.
The heteroaryl group preferably has a 5-membered ring or a 6-membered ring. The hetero atoms constituting the ring of the heteroaryl group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3.
The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The alkoxy group may be either straight or branched.
The number of carbon atoms in the aryloxy group is preferably 6 to 20, more preferably 6 to 12.
The alkenyloxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The alkenyloxy group may be either straight or branched.

L ¹⁰¹ in formula (1) is preferably -P(=O)(R ^L101 )- because the maximum absorption wavelength can be made longer and the light resistance can be further improved.

It is also preferable that L ¹⁰¹ in formula (1) is -Si(R ^L103 )(R ^L104 )- or -S(=O)-.

In formula (1), X ¹⁰¹ to X ¹⁰³ each independently represent a nitrogen atom or -CR ^X101 -, and R ^X101 represents a hydrogen atom or a substituent. Examples of the substituent represented by ^R , an alkenyloxy group or an amino group. These groups may further have a substituent. Examples of the substituent include the groups listed for the substituent T described later, a group containing an anion described below, and an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and the like.
The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The alkyl group may be straight, branched or cyclic.
The alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The alkenyl group may be either straight or branched.
The number of carbon atoms in the alkynyl group is preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 4. The alkynyl group may be either straight or branched.
The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12. Further, the aryl group is preferably a monocyclic aryl group.
The heteroaryl group preferably has a 5-membered ring or a 6-membered ring. The hetero atoms constituting the ring of the heteroaryl group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3.
The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The alkoxy group may be either straight or branched.
The number of carbon atoms in the aryloxy group is preferably 6 to 20, more preferably 6 to 12.
The alkenyloxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The alkenyloxy group may be either straight or branched.

^R More preferably, it is a monocyclic aryl group having a substituent, even more preferably a monocyclic aryl group having a substituent at the ortho position. Examples of the above-mentioned substituents include the groups listed in substituent T described below, groups containing anions described below, ethylenically unsaturated bond-containing groups, and alkyl groups, sulfo groups, carboxy groups, salts of carboxy groups, Preferably, it is a salt of a sulfo group, a group containing an anion described below, or a group containing an ethylenically unsaturated bond.

It is preferable that X ¹⁰¹ and X ¹⁰² in formula (1) are each independently -CR ^X101 -. Furthermore, R ^X101 is preferably a hydrogen atom.

X ¹⁰³ in formula (1) is preferably -CR ^X101 -. In addition, ^R A monocyclic aryl group having a substituent at the ortho position is even more preferable, and a monocyclic aryl group having a substituent at the ortho position is particularly preferable.

In formula (1), L ¹⁰² and L ¹⁰³ each independently represent a sulfur atom or -X ¹⁰⁴ =X ¹⁰⁵ -, and X ¹⁰⁴ and X ¹⁰⁵ each independently represent a nitrogen atom or -CR ^X102 -. and R ^X102 represents a hydrogen atom or a substituent. Examples of the substituent represented by R ^X102 include the groups described above as the substituent represented by R ^X101 , and the preferred ranges are also the same.
L ¹⁰² is preferably a sulfur atom because the maximum absorption wavelength can be present on the longer wavelength side.
L ¹⁰³ is preferably a sulfur atom because the maximum absorption wavelength can be present on the longer wavelength side.
It is particularly preferable that L ¹⁰² and L ¹⁰³ are each a sulfur atom

Ar ¹⁰¹ and Ar ¹⁰² in formula (1) each independently represent -(CR ^Ar101 = CR ^Ar102 ) _n101 -, an arylene group, a heterocyclic group, or a group combining two or more of these groups, and R ^Ar101 and R ^Ar102 each independently represents a hydrogen atom or a substituent, and n101 represents an integer of 1 to 3.

Examples of the substituent represented by R ^Ar101 and R ^Ar102 include the groups described above as the substituent represented by R ^X101 , and the preferred ranges are also the same.

n101 represents an integer from 1 to 3, preferably 1 or 2, and more preferably 1.

The number of carbon atoms in the arylene group represented by Ar ¹⁰¹ and Ar ¹⁰² in formula (1) is preferably 6 to 20, more preferably 6 to 12. Furthermore, the arylene group is preferably a monocyclic arylene group.
The heterocyclic group represented by Ar ¹⁰¹ and Ar ¹⁰² in formula (1) is preferably a 5-membered ring or a 6-membered ring. The hetero atoms constituting the ring of the heterocyclic group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3.

Ar ¹⁰¹ and Ar ¹⁰² in formula (1) are preferably each independently -(CR ^Ar101 =CR ^Ar102 ) _n101 -, an arylene group, or a group combining these.
A preferred embodiment includes an embodiment in which Ar ¹⁰¹ and Ar ¹⁰² are each independently an arylene group.
Another preferred embodiment includes an embodiment in which Ar ¹⁰¹ and Ar ¹⁰² are each independently a group combining -(CR ^Ar101 =CR ^Ar102 ) _n101 - and an arylene group. The group combining the above -(CR ^Ar101 = CR ^Ar102 ) _n101 - and an arylene group is preferably ^*1 -(CR ^Ar101 = CR ^Ar102 ) _n101 -arylene group - ^*2 . Further, ^*2 is preferably a bond with Y ¹⁰¹ or Y ¹⁰² in formula (1).

Y ¹⁰¹ and Y ¹⁰² in formula (1) each independently represent -OR ^Y101 , -NR ^Y102 ^RY103 or -SR Y104, and R ^Y101 to ^{R Y104} ^each independently represent a hydrogen atom or an alkyl group. , represents an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and R ^Y102 and R ^Y103 may be bonded via a single bond or a divalent linking group to form a ring.

R ^Y101 to R ^Y104 are each independently preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, more preferably an alkyl group or an aryl group, and preferably an aryl group. More preferred.

The number of carbon atoms in the alkyl group represented by R ^Y101 to R ^Y104 is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The alkyl group may be straight, branched or cyclic. The alkyl group may further have a substituent. Examples of the substituent include the groups listed for the substituent T described later, a group containing an anion described below, and an ethylenically unsaturated bond-containing group.
The alkenyl group represented by R ^Y101 to R ^Y104 preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. The alkenyl group may be either straight or branched. The alkenyl group may further have a substituent. Examples of the substituent include the groups listed for the substituent T described later, a group containing an anion described below, and an ethylenically unsaturated bond-containing group.
The number of carbon atoms in the alkynyl group represented by R ^Y101 to R ^Y104 is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4. The alkynyl group may be either straight or branched. The alkynyl group may further have a substituent. Examples of the substituent include the groups listed for the substituent T described later, a group containing an anion described below, and an ethylenically unsaturated bond-containing group.
The number of carbon atoms in the aryl group represented by R ^Y101 to R ^Y104 is preferably 6 to 20, more preferably 6 to 12. Further, the aryl group is preferably a monocyclic aryl group. The aryl group may further have a substituent. Examples of the substituent include the groups listed for the substituent T described later, a group containing an anion described below, and an ethylenically unsaturated bond-containing group.
The heteroaryl group represented by R ^Y101 to R ^Y104 is preferably a 5-membered ring or a 6-membered ring. The hetero atoms constituting the ring of the heteroaryl group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroaryl group may further have a substituent. Examples of the substituent include the groups listed for the substituent T described later, a group containing an anion described below, and an ethylenically unsaturated bond-containing group.

-NR ^Y102 R ^Y102 and R ^Y103 in R ^Y103 may be bonded via a single bond or a divalent linking group to form a ring. Examples of the divalent linking group include -CR ^Y111 R ^Y112 -, -O-, -S-, and a combination of two or more of these. R ^Y111 and R ^Y112 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heteroaryl group. These groups may further have a substituent. Examples of the substituent include the groups listed for the substituent T described later, a group containing an anion described below, and an ethylenically unsaturated bond-containing group.

It is preferable that Y ¹⁰¹ and Y ¹⁰² in formula (1) are each independently -NR ^Y102 R ^Y103 .

In formula (1), Ar ¹⁰¹ and X ¹⁰¹ may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar ¹⁰¹ and Y ¹⁰¹ may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar ¹⁰² and X ¹⁰² may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar ¹⁰² and Y ¹⁰² may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring.

Examples of the above-mentioned divalent linking group include -CR ^Y121 R ^Y122 -, -O-, -S-, and a group combining two or more of these. R ^Y121 and R ^Y122 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heteroaryl group. These groups may further have a substituent. Examples of the substituent include the groups listed for the substituent T described later, a group containing an anion described below, and an ethylenically unsaturated bond-containing group.

Z ¹ in formula (1) represents a counter ion. Counter ions include counter anions and counter cations.

The counter cation may be an inorganic cation or an organic cation.
Examples of inorganic cations include monovalent metal cations such as Na (sodium) cation, Li (lithium) cation, and K (potassium) cation; Mg (magnesium) cation, Ca (calcium) cation, and Sr (strontium). ) cation, Ba (barium) cation, Ti (titanium) cation, Zr (zirconium) cation, Cr (chromium) cation, Mn (manganese) cation, Fe (iron) cation, Co (cobalt) cation, Ni (nickel) cation , Cu (copper) cation, Zn (zinc) cation, Cd (cadmium) cation, Al (aluminum) cation, In (indium) cation, Sn (tin) cation, Pb (lead) cation, Bi (bismuth) cation, etc.2 Examples include metal cations with higher valences.
Examples of organic cations include ammonium cations (tetraalkylammonium cations, trialkylammonium cations, etc.), imidazolium cations, pyridinium cations (pyridinium cations, N-methylpyridinium cations, N-ethylpyridinium cations, etc.), phosphonium cations, etc. .
The counter cation is preferably an inorganic cation, and more preferably a Na cation, Li cation, K cation, Mg cation, or Ba cation, because it can further improve light resistance and heat resistance.

The counter anion may be an organic anion or an inorganic anion. Counter anions include the anion represented by formula (AN1), the anion represented by formula (AN2), the anion represented by formula (AN3), the anion represented by formula (AN4), and the anion represented by formula (AN5). Anions represented: fluorine anion, chlorine anion, bromine anion, iodine anion, cyanide ion, perchlorate anion, carboxylate anion, sulfonate anion, phosphate anion, heteropolyacid (phosphotungstic acid, phosphomolybdic acid, phosphorus anion) Gustomolybdic acid, silicotungstic acid, silicomolybdic acid, silicotungstomolybdic acid, etc.) anion, isopolyacid (tungstic acid, molybdic acid, etc.) anion, and the like.

In formula (AN1), R ^AN1 and R ^AN2 each independently represent a halogen atom or an alkyl group, and R ^AN1 and R ^AN2 may be combined to form a ring;
In formula (AN2), R ^AN3 to R ^AN5 each independently represent a halogen atom or an alkyl group, and R ^AN3 and R ^AN4 , R ^AN4 and R ^AN5 , or R ^AN3 and R ^AN5 are bonded together. May form a ring;
In formula (AN3), R ^AN6 to R ^AN9 each independently represent a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a cyano group;
In formula (AN4), ^RAN10 represents a halogenated hydrocarbon group which may be connected by a linking group having a nitrogen atom or an oxygen atom;
In formula (AN5), R ^AN11 to R ^AN16 each independently represent a halogen atom or a halogenated hydrocarbon group.

The halogen atoms represented by R ^AN1 and R ^AN2 in formula (AN1), the halogen atoms represented by R ^AN3 to R ^AN5 in formula (AN2), and the halogen atoms represented by R ^AN6 to R ^AN9 in formula (AN3) include fluorine. Atom, chlorine atom, bromine atom, and iodine atom are mentioned, and fluorine atom is preferable.

The number of carbon atoms in the alkyl group represented by R ^AN1 and R ^AN2 in formula (AN1), the alkyl group represented by R ^AN3 to R ^AN5 in formula (AN2), and the alkyl group represented by R ^AN6 to R ^AN9 in formula (AN3) is , 1 to 10 are preferred, 1 to 6 are more preferred, and 1 to 3 are still more preferred. The alkyl group may be linear, branched, or cyclic, preferably linear or branched, and more preferably linear. The alkyl group may have a substituent or may be unsubstituted. The alkyl group is preferably an alkyl group having a halogen atom as a substituent, and more preferably an alkyl group having a fluorine atom as a substituent (fluoroalkyl group). Further, the fluoroalkyl group is preferably a perfluoroalkyl group.

The number of carbon atoms in the aryl group represented by R ^AN6 to R ^AN9 in formula (AN3) is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6. The aryl group may have a substituent or may be unsubstituted. Examples of substituents include halogen atoms and alkyl groups. The halogen atom is preferably a fluorine atom. The alkyl group is preferably a fluoroalkyl group.

The number of carbon atoms in the alkoxy group represented by R ^AN6 to R ^AN9 in formula (AN3) is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The alkoxy group may be linear, branched, or cyclic, preferably linear or branched, and more preferably linear. The alkoxy group may have a substituent or may be unsubstituted. Examples of substituents include halogen atoms and alkyl groups. The halogen atom is preferably a fluorine atom. The alkyl group is preferably a fluoroalkyl group.

The number of carbon atoms in the aryloxy group represented by R ^AN6 to R ^AN9 in formula (AN3) is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6. The aryloxy group may have a substituent or may be unsubstituted. Examples of substituents include halogen atoms and alkyl groups. The halogen atom is preferably a fluorine atom. The alkyl group is preferably a fluoroalkyl group.

R ^AN1 and R ^AN2 in formula (AN1) may be combined to form a ring. ^RAN3 and ^RAN4 , ^RAN4 and ^RAN5 , or ^RAN3 and ^RAN5 in formula (AN2) may be bonded to form a ring.

^RAN10 in formula (AN4) represents a halogenated hydrocarbon group which may be connected by a linking group having a nitrogen atom or an oxygen atom. The halogenated hydrocarbon group refers to a monovalent hydrocarbon group substituted with a halogen atom, and is preferably a monovalent hydrocarbon group substituted with a fluorine atom. Examples of the hydrocarbon group include an alkyl group and an aryl group. The monovalent hydrocarbon group substituted with a halogen atom may further have a substituent. Examples of the linking group having a nitrogen atom or an oxygen atom include -O-, -CO-, -COO-, -CO-NH-, and the like.

R ^AN11 to R ^AN16 in formula (AN5) each independently represent a halogen atom or a halogenated hydrocarbon group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated hydrocarbon group is preferably an alkyl group having a halogen atom as a substituent, and more preferably an alkyl group having a fluorine atom as a substituent.

Specific examples of heteropolyacid anions and isopolyate anions include tungstate anions ([W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , [WO ₄ ] ^2-, etc.), molybdate anions ([Mo ₂ O ₇ ] ^2- , [Mo ₆ O ₁₉ ] ^2- , [Mo ₈ O ₂₆ ] ^4-, etc.), phosphotungstate anions ([PW ₄ O ₂₀ ] ^4- , [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₈ O ₆₂ ] ^6-, etc.), phosphomolybdate anion ([P ₂ Mo ₁₈ O ₆₂ ] ^6-) , [PMo ₁₂ O ₄₀ ] ^3- ), phosphotungsten molybdate anion ([PW _12-x Mo _x O ₄₀ ] ^3- (x is an integer from 1 to 11), [P ₂ W _18-y Mo _y O ₆₂ ] ^6- (y is an integer from 1 to 17), etc.), silicotungstate anions ([SiW ₉ O ₃₄ ] ^10- , [SiW ₁₀ O ₃₆ ] ^8- , [SiW ₁₁ O ₃₉ ] ^8- , [SiW ₁₂ O ₄₀ ] ^4- , etc.), silicomolybdate anions ([SiMo ₁₂ O ₄₀ ] ^4-, etc.), silicomolybdate anions ([SiW _12-x Mo _x O ₄₀ ] ^4- (x is 1 to 11), (integer), etc.), and tungsten-based isopolya acid anions.

The counter anion may be a divalent or higher anion. Examples of divalent or higher anions include anions having two or more monovalent anions in one molecule, such as imide anions, methide anions, borate anions, and sulfonate anions.

In formula (1), p1 represents an integer from 0 to 5, and q1 represents an integer from 1 to 5. p1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2. q1 is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.

When the charges in [ ] in formula (1) are biased toward positive charges, p1 is an integer of 1 or more, and the counter ion represented by Z ¹ is preferably a counter anion. Further, the product of the valence of the positive charge in [ ] in formula (1) and q1 is preferably the same value as the product of the valence of the charge of the counter anion represented by Z ¹ and p1.
When the charges in [ ] in formula (1) are biased toward negative charges, p1 is an integer of 1 or more, and the counter ion represented by Z ¹ is preferably a counter cation. Furthermore, the product of the negative charge valence in [ ] in formula (1) and q1 is preferably the same value as the product of the charge valence of the counter cation represented by Z ¹ and p1.
When the charge in brackets [ ] in formula (1) is electrically neutral, Z ¹ is preferably absent, that is, p1 is 0 and q1 is 1.

It is also preferable that the dye A1 is a dye represented by formula (2).

In formula (2), L ²⁰¹ is -P(=O)(R ^L101 )-, -P(=S)(R ^L102 )-, -Si(R ^L103 )(R ^L104 )-, -B(R ^L105 )-, -S(=O) ₂ - or -S(=O)-, R ^L101 to R ^L105 each independently represent a hydrogen atom or a substituent, and R ^L103 and R ^L104 are bonded. may form a ring,
R ^X111 and R ^X112 each independently represent a hydrogen atom or a substituent,
X ²⁰³ represents a nitrogen atom or -CR ^X101 -, R ^X101 represents a hydrogen atom or a substituent,
L ²⁰² to L ²⁰⁵ each independently represent a sulfur atom or -X ¹⁰⁴ =X ¹⁰⁵ -, X ¹⁰⁴ and X ¹⁰⁵ each independently represent a nitrogen atom or -CR ^X102 -, and ^R , represents a hydrogen atom or a substituent,
Ar ²⁰¹ and Ar ²⁰² each independently represent -(CR ^Ar201 = CR ^Ar202 ) _n201 -, an arylene group, a heterocyclic group, or a group combining two or more of these groups, and R ^Ar201 and R ^Ar202 each represent independently represents a hydrogen atom or a substituent, n201 represents an integer of 1 to 3,
Y ²⁰¹ and Y ²⁰² each independently represent -OR ^Y101 , -NR ^Y102 ^RY103 or -SR Y104, and R ^Y101 to ^R ^Y104 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl represents a group, an aryl group or a heteroaryl group, and R ^Y102 and R ^Y103 may be bonded via a single bond or a divalent linking group to form a ring,
Ar ²⁰¹ and X ²⁰¹ may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar ²⁰¹ and Y ²⁰¹ may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar ²⁰² and X ²⁰² may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar ²⁰² and Y ²⁰² may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Z ² represents a counterion,
p2 represents an integer from 0 to 5,
q2 represents an integer from 1 to 5.

L ²⁰¹ , L ²⁰² , L ²⁰³ , X ²⁰³ , Y 201 , Y ²⁰² , Z ² , q2, p2 in formula (2) are the same as L ¹⁰¹ , L ¹⁰² , L ¹⁰³ , X ¹⁰³ , Y ¹⁰¹ in formula (1 ⁾ , Y ¹⁰² , Z ¹ , q1, and p1, and the preferred ranges are also the same.

The substituents represented by R ^X111 and R ^X112 in formula (2) include the groups described as the substituent represented by R ^X101 in formula (1), and the preferred ranges are also the same. R ^X111 and R ^X112 in formula (2) are preferably hydrogen atoms.

L ²⁰⁴ and L ²⁰⁵ in formula (2) each independently represent a sulfur atom or -X ¹⁰⁴ =X ¹⁰⁵ -, and are preferably sulfur atoms. The above X ¹⁰⁴ and X ¹⁰⁵ have the same meanings as X ¹⁰⁴ and X ¹⁰⁵ described in formula (1), and the preferred ranges are also the same.

Ar ²⁰¹ and Ar ²⁰² in formula (2) each independently represent -(CR ^Ar201 = CR ^Ar202 ) _n201 -, an arylene group, a heterocyclic group, or a group combining two or more of these groups, and R ^Ar201 and R ^Ar202 each independently represents a hydrogen atom or a substituent, and n201 represents an integer of 1 to 3. R ^Ar201 , R ^Ar202 and n201 have the same meanings as R ^Ar101 , R ^Ar102 and n101 explained in formula (1), and their preferred ranges are also the same.

Ar ²⁰¹ and Ar ²⁰² in formula (2) are preferably each independently -(CR ^Ar201 =CR ^Ar202 ) _n201 -, an arylene group, or a group combining these.
A preferred embodiment includes an embodiment in which Ar ²⁰¹ and Ar ²⁰² are each independently an arylene group.
Another preferred embodiment includes an embodiment in which Ar ²⁰¹ and Ar ²⁰² are each independently a group combining -(CR ^Ar201 =CR ^Ar202 ) _n201 - and an arylene group. The group combining the above -(CR ^Ar201 = CR ^Ar202 ) _n201 - and an arylene group is preferably ^*1 -(CR ^Ar201 = CR ^Ar202 ) _n201 -arylene group - ^*2 . Further, ^*2 is preferably a bond with Y ²⁰¹ or Y ²⁰² in formula (2).

In formula (2), Ar ²⁰¹ and X ²⁰¹ may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar ²⁰¹ and Y ²⁰¹ may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar ²⁰² and X ²⁰² may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar ²⁰² and Y ²⁰² may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring.

It is also preferable that the dye A1 is a dye (compound) represented by formula (4). The dye (compound) represented by formula (4) is also a compound of the present invention.
In the formula, Ar ⁴⁰¹ represents an aryl group or a heteroaryl group,
R ⁴⁰¹ to R ⁴⁰⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group,
R ⁴⁰⁵ and R ⁴⁰⁶ each independently represent an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group or a cyano group,
R ⁴⁰⁷ and R ⁴⁰⁸ each independently represent an alkyl group or an aryl group,
n401 and n402 each independently represent an integer from 0 to 4,
q4 represents 1 or 2,
Z ⁴ represents a q4-valent counteranion.

The number of carbon atoms in the aryl group represented by Ar ⁴⁰¹ is preferably 6 to 20, more preferably 6 to 12. Further, the aryl group is preferably a monocyclic aryl group.
The heteroaryl group represented by Ar ⁴⁰¹ is preferably a 5-membered ring or a 6-membered ring. The hetero atoms constituting the ring of the heteroaryl group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3.
The above aryl group and heteroaryl group may further have a substituent. Examples of the substituent include the groups listed for the substituent T described later, a group containing an anion described below, and an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and the like.
Ar ⁴⁰¹ is preferably an aryl group, more preferably a monocyclic aryl group, even more preferably a monocyclic aryl group having a substituent, and even more preferably a monocyclic aryl group having a substituent at the ortho position. Particularly preferred is an aryl group. Examples of the above-mentioned substituents include the groups listed in substituent T described below, groups containing anions described below, ethylenically unsaturated bond-containing groups, and alkyl groups, sulfo groups, carboxy groups, salts of carboxy groups, A salt of a sulfo group, a group containing an anion as described below, or a group containing an ethylenically unsaturated bond is preferable.

R ⁴⁰¹ to R ⁴⁰⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and preferably an alkyl group or an aryl group.
The number of carbon atoms in the alkyl group represented by R ⁴⁰¹ to R ⁴⁰⁴ is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The alkyl group may be straight, branched or cyclic. The alkyl group may further have a substituent. Examples of the substituent include the groups listed for the substituent T described later, a group containing an anion described below, and an ethylenically unsaturated bond-containing group.
The number of carbon atoms in the aryl group represented by R ⁴⁰¹ to R ⁴⁰⁴ is preferably 6 to 20, more preferably 6 to 12. Further, the aryl group is preferably a monocyclic aryl group. The aryl group may further have a substituent. Examples of the substituent include the groups listed for the substituent T described later, a group containing an anion described below, and an ethylenically unsaturated bond-containing group.
The heteroaryl group represented by R ⁴⁰¹ to R ⁴⁰⁴ is preferably a 5-membered ring or a 6-membered ring. The hetero atoms constituting the ring of the heteroaryl group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroaryl group may further have a substituent. Examples of the substituent include the groups listed for the substituent T described later, a group containing an anion described below, and an ethylenically unsaturated bond-containing group.

R ⁴⁰⁵ and R ⁴⁰⁶ each independently represent an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group, or a cyano group.

n401 and n402 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

Examples of the q4-valent counter anion represented by Z ⁴ include the above-mentioned counter anions.

It is also preferable that the dye A1 is a dye (compound) represented by formula (5). The dye (compound) represented by formula (5) is also a compound of the present invention.
In the formula, Ar ⁵⁰¹ represents an aryl group or a heteroaryl group,
R ⁵⁰¹ to R ⁵⁰⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group,
R ⁵⁰⁵ and R ⁵⁰⁶ each independently represent an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group or a cyano group,
n ⁵⁰¹ and n ⁵⁰² each independently represent an integer from 0 to 4,
q5 represents 1 or 2,
Z ⁵ represents a q5-valent counteranion.

Ar ⁵⁰¹ , R ⁵⁰¹ to R ⁵⁰⁶ , n ⁵⁰¹ , n ⁵⁰² , q5 and Z ⁵ in formula (5) are the same ^as Ar ⁴⁰¹ , R ⁴⁰¹ to R 406 , n ⁴⁰¹ , n ⁴⁰² , q4 and Z ⁴ in formula (4) It has the same meaning as , and the preferred range is also the same.

-Dye multimer A2-
The specific infrared absorbing dye may be a dye multimer A2 (hereinafter also simply referred to as a dye multimer) containing two or more dye structures derived from the above dye A1 in one molecule.

Examples of the dye multimer include a dye multimer having a repeating unit represented by formula (A) (hereinafter also referred to as dye multimer (A)), a dye multimer having a repeating unit represented by formula (C) ( (hereinafter also referred to as dye multimer (C)), the dye multimer represented by formula (D) (hereinafter also referred to as dye multimer (D)), and dye multimer (A) or dye multimer ( D) is preferred.

(Dye multimer (A))
The dye multimer (A) contains a repeating unit represented by formula (A). The proportion of the repeating unit represented by formula (A) is preferably 10% by mass or more of all repeating units constituting the dye multimer (A), more preferably 20% by mass or more, even more preferably 30% by mass or more, Particularly preferred is 50% by mass or more. The upper limit can be 100% by mass or less, or 95% by mass or less.
In formula (A), A ¹ represents a trivalent linking group,
L ¹ represents a single bond or a divalent linking group,
DyeI represents a dye structure derived from the above dye A1.

The trivalent linking group represented by ^A1 in formula (A) includes a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, and a polyamide linking group. Examples include a linking group, a polyether linking group, a polystyrene linking group, a bisphenol linking group, a novolak linking group, and a poly(meth)acrylic linking group is preferred.

L ¹ in formula (A) represents a single bond or a divalent linking group. Divalent linking groups include alkylene groups, arylene groups, heterocyclic groups, -CH=CH-, -O-, -S-, -CO-, -COO-, -NR-, -CONR-, -OCO -, -SO-, -SO ₂ -, and a linking group formed by linking two or more of these. R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

The alkylene group preferably has 1 to 30 carbon atoms. The upper limit is more preferably 25 or less, and even more preferably 20 or less. The lower limit is more preferably 2 or more, and even more preferably 3 or more. The alkylene group may be linear, branched, or cyclic. The alkylene group may have a substituent or may be unsubstituted.
The number of carbon atoms in the arylene group is preferably 6 to 20, more preferably 6 to 12. The arylene group may have a substituent or may be unsubstituted.
The heterocyclic group preferably has a 5-membered ring or a 6-membered ring. The hetero atoms constituting the ring of the heterocyclic group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The heterocyclic group may have a substituent or may be unsubstituted.

L ¹ is preferably an alkylene group, an arylene group, -NH-, -CO-, -O-, -COO-, -OCO-, -S-, or a linking group combining two or more of these; More preferably, the connecting group is a combination of at least one selected from arylene groups and arylene groups and one or more selected from -O-, -COO-, -OCO-, and -S-. The divalent linking group represented by L ¹ is also preferably a group containing -S- or -O-.

In L ¹ , the number of atoms constituting the chain connecting DyeI and A ¹ is preferably 2 or more, more preferably 3 or more. The upper limit can be, for example, 30 or less, or 25 or less.

The dye structure derived from dye A1 represented by DyeI in formula (A) is preferably a residue obtained by removing one hydrogen atom from the dye (dye A1) represented by formula (1) described above.
Furthermore, any of the sites X ¹⁰¹ to X ¹⁰³ , L ¹⁰¹ to L ¹⁰³ , Ar ¹⁰¹ , Ar ¹⁰² , Y ¹⁰¹ , and Y ¹⁰² in formula (1) includes a connecting portion with L ¹ in formula (A). More preferably, X ¹⁰³ in formula (1) includes a linkage with L ¹ in formula (A).

The dye multimer (A) may contain other repeating units in addition to the repeating unit represented by formula (A). Examples of other repeating units include repeating units having a polymerizable group and repeating units having an acid group. Examples of the polymerizable group include ethylenically unsaturated bond-containing groups such as a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. Examples of the acid group include a carboxy group, a sulfo group, and a phosphoric acid group.

The proportion of repeating units having a polymerizable group is preferably 50% by mass or less of all repeating units constituting the dye multimer (A). The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less.

The proportion of repeating units having acid groups is preferably 50% by mass or less of all repeating units constituting the dye multimer (A). The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less.

The dye multimer (A) is produced by (1) a method of synthesizing dye A1 having a polymerizable group by addition polymerization, (2) a method of synthesizing a dye A1 having a polymerizable group, and (2) a polymer having a highly reactive functional group such as an isocyanate group, an acid anhydride group, or an epoxy group. It can be synthesized by a method such as a method of reacting a highly reactive functional group with a dye A1 having a reactive functional group (hydroxy group, primary or secondary amino group, carboxy group, etc.). Known addition polymerizations (radical polymerization, anionic polymerization, cationic polymerization) can be applied to the addition polymerization, but among these, synthesis by radical polymerization is particularly preferable because the reaction conditions can be moderated and the dye skeleton is not decomposed. Known reaction conditions can be applied to radical polymerization. From the viewpoint of heat resistance, the dye multimer (A) is preferably a radical polymer obtained by radical polymerization using dye A1 having an ethylenically unsaturated bond.

(Dye multimer (C))
The dye multimer (C) contains a repeating unit represented by formula (C). The proportion of the repeating unit represented by formula (C) is preferably 10% by mass or more of all the repeating units constituting the dye multimer (C), more preferably 20% by mass or more, even more preferably 30% by mass or more, Particularly preferred is 50% by mass or more. The upper limit can be 100% by mass or less, or 95% by mass or less.
In formula (C), L ³ represents a single bond or a divalent linking group,
DyeIII represents the dye structure derived from the above dye A1,
m represents 0 or 1.

L ³ in formula (C) represents a single bond or a divalent linking group. Divalent linking groups include alkylene groups, arylene groups, heterocyclic groups, -CH=CH-, -O-, -S-, -CO-, -COO-, -NR-, -CONR-, -OCO -, -SO-, -SO ₂ -, and a linking group formed by linking two or more of these. Each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

The number of carbon atoms in the alkyl group and alkylene group is preferably 1 to 30. The upper limit is more preferably 25 or less, and even more preferably 20 or less. The lower limit is more preferably 2 or more, and even more preferably 3 or more. The alkyl group and alkylene group may be linear, branched, or cyclic.
The number of carbon atoms in the aryl group and arylene group is preferably 6 to 20, more preferably 6 to 12.
The heterocyclic group preferably has a 5-membered ring or a 6-membered ring. The hetero atoms constituting the ring of the heterocyclic group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3.
The alkylene group, arylene group, heterocyclic group, alkyl group and aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the groups listed below for substituent T, a polymerizable group, and an acid group.

L ³ in formula (C) is an alkylene group, an arylene group, -NH-, -CO-, -O-, -COO-, -OCO-, -S-, -SO ₂ -, or a combination of two or more of these. A linking group is preferred.

The dye structure derived from dye A1 represented by DyeIII of formula (C) is preferably a residue obtained by removing two hydrogen atoms from the dye (dye A1) represented by formula (1) described above.
Furthermore, any of the sites X ¹⁰¹ to X ¹⁰³ , L ¹⁰¹ to L ¹⁰³ , Ar ¹⁰¹ , Ar ¹⁰² , Y ¹⁰¹ , and Y ¹⁰² in formula (1) includes a connecting portion with L ¹ in formula (A). It is preferable.

m in formula (C) represents 0 or 1, and 1 is preferable.

In addition to the repeating unit represented by the general formula (C), the dye multimer (C) may contain other repeating units described for the dye multimer (A).

(Dye multimer (D))
The dye multimer (D) is a compound represented by formula (D).
In formula (D), L ⁴ represents a (n+k)-valent linking group,
n represents an integer from 2 to 20,
k represents an integer from 0 to 20,
DyeIV represents the dye structure derived from the above dye A1,
P ⁴ represents a substituent,
Each of the n DyeIVs may be different,
When k is 2 or more, the plurality of ^P4s may be different from each other,
n+k represents an integer from 2 to 20.

In formula (D), n is preferably 2 to 14, more preferably 2 to 8, particularly preferably 2 to 7, and even more preferably 2 to 6.
In formula (D), k is preferably 0 to 13. The lower limit can be 1 or more, or 2 or more. The upper limit is preferably 10 or less, more preferably 8 or less, even more preferably 7 or less, and even more preferably 6 or less.

The (n+k)-valent linking group represented by L ⁴ in formula (D) includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 Mention may be made of groups consisting of from 3 to 200 hydrogen atoms and from 0 to 20 sulfur atoms. The (n+k)-valent linking group is preferably the following structural unit or a group formed by combining two or more of the following structural units (which may form a ring structure). * in the formula below represents a bond.

The (n+k)-valent linking group represented by L ⁴ is preferably a linking group derived from a polyfunctional thiol, a linking group derived from a polyfunctional alcohol, or a linking group derived from an acid anhydride, More preferably, it is a linking group derived from a polyfunctional thiol.

The (n+k)-valent linking group represented by L ⁴ is preferably a group represented by any one of formulas (Za-1) to (Za-5).
In formula (Za-1), La ² represents a divalent group, Ta ² represents a single bond or a divalent linking group, and the two Ta ^2s present may be the same or different from each other. .
In formula (Za-2), La ³ represents a trivalent group, Ta ³ represents a single bond or a divalent linking group, and the three Ta ^3s present may be the same or different from each other. .
In formula (Za-3), La ⁴ represents a tetravalent group, Ta ⁴ represents a single bond or a divalent linking group, and the four Ta ^4s present may be the same or different from each other. .
In formula (Za-4), La ⁵ represents a pentavalent group, Ta ⁵ represents a single bond or a divalent linking group, and the five Ta ^5s present may be the same or different from each other. .
In formula (Za-5), La ⁶ represents a hexavalent group, Ta ⁶ represents a single bond or a divalent linking group, and the six Ta ^6s present may be the same or different from each other. .
In the above formula, * represents a bond.

The divalent linking groups represented by La ² , Ta ² to Ta ⁶ include alkylene groups, arylene groups, heterocyclic groups, -CH=CH-, -O-, -S-, -CO-, -COO-, Examples include -NR-, -CONR-, -OCO-, -SO-, -SO ₂ -, and a linking group formed by linking two or more of these. Each R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Examples of the trivalent group represented by La ³ include a group obtained by removing one hydrogen atom from the above divalent linking group. Examples of the tetravalent group represented by La ⁴ include a group obtained by removing two hydrogen atoms from the above divalent linking group. Examples of the pentavalent group represented by La ⁵ include a group obtained by removing three hydrogen atoms from the above divalent linking group. Examples of the hexavalent group represented by La ⁶ include a group obtained by removing four hydrogen atoms from the above divalent linking group. The trivalent to hexavalent groups represented by La ³ to La ⁶ may have the above-mentioned substituents.

Specific examples of (n+k)-valent linking groups include the linking groups described in paragraph numbers 0071 to 0072 of JP-A No. 2008-222950, and the linking groups described in paragraph number 0176 of JP-A No. 2013-029760. , and the linking groups described in paragraph numbers 0022 to 0024 of International Publication No. 2016/031442.

The dye structure derived from dye A1 represented by Dye IV of formula (D) is preferably a residue obtained by removing one hydrogen atom from the dye (dye A1) represented by formula (1) described above.
Furthermore, any of the sites X ¹⁰¹ to X ¹⁰³ , L ¹⁰¹ to L ¹⁰³ , Ar ¹⁰¹ , Ar ¹⁰² , Y ¹⁰¹ , and Y ¹⁰² in formula (1) includes a connecting portion with L ¹ in formula (A). More preferably, X ¹⁰³ in formula (1) includes a linkage with L ¹ in formula (A).

Examples of the substituent represented by P ⁴ in formula (D) include the groups listed below for substituent T, acid groups, and polymerizable groups. Further, the substituent represented by P ⁴ may be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having repeating units is preferably a monovalent polymer chain having repeating units derived from a vinyl compound. When k is 2 or more, the k ^P4s may be the same or different.

When P ⁴ is a monovalent polymer chain having repeating units and k is 1, P ⁴ contains 2 to 20 repeating units (preferably 2 to 15 repeating units, more preferably 2 to 15 repeating units) derived from a vinyl compound. It is preferable to use a monovalent polymer chain having 1 to 10 polymer chains. In addition, when P ⁴ is a monovalent polymer chain having repeating units and k is 2 or more, the average number of vinyl compound-derived repeating units in k P ⁴ is 2 to 20 ( The number is preferably 2 to 15, more preferably 2 to 10.
When P ⁴ is a monovalent polymer chain having repeating units, the number of repeating units and the average value of the number of repeating units can be determined by nuclear magnetic resonance (NMR).

When P ⁴ is a monovalent polymer chain having a repeating unit, examples of the repeating unit constituting P ⁴ include other repeating units explained in explaining the embodiment of the dye multimer (A) mentioned above. . It is preferable that the other repeating unit has one or more types selected from the above-mentioned repeating unit having an acid group and repeating unit having a polymerizable group.
When P ⁴ contains a repeating unit containing an acid group, the proportion of the repeating unit containing an acid group is preferably 10 to 80 mol%, and 10 to 65 mol%, based on the total repeating units of P ⁴ . is more preferable.
When P ⁴ contains a repeating unit having a polymerizable group, the proportion of the repeating unit having a polymerizable group is preferably 10 to 80 mol%, and 10 to 65 mol%, based on the total repeating units of P ⁴ . % is more preferable.

-Substituent T-
Examples of the substituent T include the following groups. Halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an aryl group having 6 to 30 carbon atoms), an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an amino group having 0 to 30 carbon atoms), 1 to 30 alkoxy groups), aryloxy groups (preferably aryloxy groups having 6 to 30 carbon atoms), heteroaryloxy groups, acyl groups (preferably acyl groups having 2 to 30 carbon atoms), alkoxycarbonyl groups (preferably is an alkoxycarbonyl group having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), a heteroaryloxycarbonyl group, an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms) ), acylamino group (preferably acylamino group having 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably alkoxycarbonylamino group having 2 to 30 carbon atoms), aryloxycarbonylamino group (preferably 7 to 30 carbon atoms) aryloxycarbonylamino group), sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms) ), arylthio group (preferably arylthio group having 6 to 30 carbon atoms), heteroarylthio group (preferably having 1 to 30 carbon atoms), alkylsulfonyl group (preferably having 1 to 30 carbon atoms), arylsulfonyl group (preferably carbon number 6-30), heteroarylsulfonyl group (preferably carbon number 1-30), alkylsulfinyl group (preferably carbon number 1-30), arylsulfinyl group (preferably carbon number 6-30), heteroarylsulfinyl group group (preferably 1 to 30 carbon atoms), ureido group (preferably 1 to 30 carbon atoms), hydroxy group, carboxy group, salt of carboxy group, sulfo group, salt of sulfo group, phosphoric acid group, phosphoric acid group salt, carboxylic acid amide group, sulfonic acid amide group, imide acid group, mercapto group, cyano group, alkylsulfino group, arylsulfino group, hydrazino group, imino group, heteroaryl group (preferably having 1 to 30 carbon atoms) . In the salts of carboxy groups, salts of sulfo groups, and salts of phosphoric acid groups, atoms or atomic groups constituting the salts include alkali metal ions (Li ⁺ , Na ⁺ , K ^{+ ,} etc.), alkaline earth metal ions ( Ca ²⁺ , Mg ²⁺ , etc.), ammonium ions (tetraalkylammonium ions, trialkylammonium ions, etc.), imidazolium ions, pyridinium ions (pyridinium ions, N-methylpyridinium ions, N-ethylpyridinium ions, etc.), phosphonium ions, etc. can be mentioned. These groups may further have a substituent when the group is a substitutable group. Examples of the substituent include the groups described above for the substituent T.

-Group containing anion-
Examples of the anion-containing group include a group represented by formula (P-1) and a group represented by formula (P-2).

Lp ¹ in formula (P-1) represents a single bond or a divalent linking group. The divalent linking group represented by Lp ¹ is an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, -NR ^Lp1 -, -O-, -S-, -CO-, -SO ₂ - Or a group consisting of a combination thereof, etc. can be mentioned. At least some of the hydrogen atoms in the alkylene group are preferably substituted with fluorine atoms, and more preferably a perfluoroalkylene group. Specific examples of such alkylene groups include difluoromethylene groups, tetrafluoroethylene groups, hexafluoropropylene groups, and the like. It is preferable that at least some of the hydrogen atoms of the arylene group are substituted with fluorine atoms. Specific examples of such an arylene group include a tetrafluorophenylene group, a hexafluoro-1-naphthylene group, a hexafluoro-2-naphthylene group, and the like.
Lp ¹ in formula (P-1) is a single bond, a group consisting of a combination of -NR ^Lp1 -, -SO ₂ and an alkylene group containing a fluorine atom, or a combination of -O- and an arylene group containing a fluorine atom. or a group consisting of a combination of -NR ^Lp1 -, -SO ₂ and an alkylene group containing a fluorine atom.
Xp ¹ in formula (P-1) represents -SO ₃ ^- , -COO ^- , -PO ₄ H ^- or an anion containing a boron atom, and is preferably -SO ₃ ^- or -COO ^- .

Lp ² in formula (P-2) represents a single bond or a divalent linking group, and is preferably a single bond. Examples of the divalent linking group represented by Lp ² include an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, -O-, -S-, or a group consisting of a combination thereof.
Lp ³ in formula (P-2) represents -SO ₂ - or -CO-, and preferably -SO ₂ -.
G in formula (P-2) represents a carbon atom or a nitrogen atom, and is preferably a nitrogen atom.
n in formula (P-2) represents 2 when G is a carbon atom, and represents 1 when G is a nitrogen atom.
Rp ¹ in formula (P-2) represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom. When n is 2, the two Rp ¹ 's may be the same or different. The number of carbon atoms in the alkyl group containing a fluorine atom represented by Rp ¹ is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The number of carbon atoms in the fluorine atom-containing aryl group represented by Rp ¹ is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10. The alkyl group containing a fluorine atom and the aryl group containing a fluorine atom may further have a substituent. Examples of the substituent include the groups listed above for the substituent T.

From the viewpoint of preventing one-electron reduction or decomposition of the dye A1 by a nucleophile, it is preferable that the LUMO (Lowest Unoccupied Molecular Orbital) level of the dye A1 is high. The LUMO level of the dye A1 is preferably −6.5 eV or higher, more preferably −6.0 eV or higher, and still more preferably −5.5 eV or higher. The LUMO level of the dye A1 is determined by, for example, optimizing the structure of the cation moiety of the dye A1 using the quantum chemical calculation program Gaussian09 under conditions of functional B3LYP/basis set 6-31g(d)/vacuum. It can be determined by performing calculations.

-About specific examples-
Specific examples of specific infrared absorbing dyes include compounds having the structures shown below. Resonance structures of these compounds are also mentioned as specific examples of specific compounds. In the structural formula shown below, Bu represents a butyl group and Ph represents a phenyl group.

The compound represented by formula (4) can be synthesized using a known method according to the following synthesis scheme, for example. The types and amounts of the solvent, catalyst, and reagent used, as well as synthesis conditions such as reaction time and reaction temperature, can be adjusted as appropriate.

Compound 4A is reacted with a brominating agent such as N-bromosuccinimide (NBS) to provide compound 4B. Thereafter, bispinacolborane is reacted in the presence of a palladium catalyst to obtain 4C in which bromine is replaced with boron.
The bromine moiety of Compound 4D synthesized by a known method is lithiated with alkyllithium, and then reacted with a dichlorosilicon compound to obtain Compound 4E. Compound 4E is reacted with an alkyllithium and then reacted with 1,2-dibromo-1,1,2,2,-tetrachloroethane to obtain compound 4F.
Compound 4C and Compound 4F are reacted in the presence of a palladium catalyst (Suzuki-Miyaura reaction conditions) to obtain Compound 4G. Compound 4G is reacted under acidic conditions to deprotect the acetal moiety, and compound 4H is synthesized.
Compound 4I is obtained by reacting Compound 4H with a Grignard reagent. Thereafter, a reaction is performed under acidic conditions to obtain compound 4J.
By reacting Compound 4J with a salt compound having the desired anion, a compound represented by formula (4) in which the chloride anion is replaced with the desired anion can be obtained.

The compound represented by formula (5) can be synthesized in the same manner except for using thionyl chloride instead of the dichlorosilicon compound in the compound 4E synthesis step in the synthesis of the compound represented by formula (4). A compound represented by formula (5) can be synthesized using the formula (5).

The maximum absorption wavelength of the specific infrared absorbing dye is preferably in a wavelength range of 700 to 1800 nm, more preferably in a wavelength range of 1000 to 1800 nm, and even more preferably in a wavelength range of 1030 to 1750 nm. , it is even more preferable that the wavelength be in the range of 1050 to 1700 nm, and still more preferably be in the wavelength range of 1070 to 1650 nm.

The ratio of the absorbance A _max at the maximum absorption wavelength of the specific infrared absorbing dye to the absorbance A _{max +200} at the maximum absorption wavelength + 200 nm, A _{max + 200} /A _max , is preferably 4.5 or more, and preferably 10 or more. is more preferable, and even more preferably 30 or more. The upper limit is preferably 90 or less, for example. According to this aspect, it is possible to form an optical filter with excellent contrast between infrared transmittance and light blocking performance.

The content of the specific infrared absorbing dye is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more based on the total solid content of the resin composition. The upper limit of the content of the specific infrared absorbing dye is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. The resin composition may contain only one type of specific infrared absorbing dye, 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.

<<Other infrared absorbers>>
The resin composition of the present invention can contain an infrared absorber (another infrared absorber) other than the above-mentioned specific infrared absorbing dye. Furthermore, by containing other infrared absorbers, it is possible to form a film that can block infrared rays in a wider wavelength range. Other infrared absorbers may be dyes or pigments.

The maximum absorption wavelength of the other infrared absorbent is preferably within a wavelength range of 700 to 1800 nm, more preferably within a wavelength range of 1000 to 1800 nm, and even more preferably within a wavelength range of 1030 to 1750 nm. Preferably, the wavelength range is from 1050 to 1700 nm, even more preferably from 1070 to 1650 nm.

Further, the maximum absorption wavelength of the other infrared absorbing agent is preferably on the shorter wavelength side than the maximum absorption wavelength of the above-mentioned specific infrared absorbing dye.
In addition, the difference between the maximum absorption wavelength of other infrared absorbers and the maximum absorption wavelength of the above-mentioned specific infrared absorbing dye is 50 to 1000 nm because it is possible to form a film that can block infrared rays in a wider wavelength range. It is preferable that there be. The upper limit is preferably 800 nm or less, more preferably 500 nm or less. The lower limit is preferably 100 nm or more, more preferably 150 nm or more.

Other infrared absorbers include pyrrolopyrrole compounds, polymethine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, and pyrromethene compounds. , azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, and the like.
As other infrared absorbers, polymethine compounds, squarylium compounds, and oxonol compounds are preferably used. These compounds generally tend to have low heat resistance and light resistance, but by using them together with the above-mentioned specific infrared-absorbing dyes, they can be adsorbed to the aggregates of the above-mentioned specific infrared-absorbing dyes during film formation. It is presumed that the specific infrared absorbing dye forms an association with the specific infrared absorbing dye, and it is possible to form a film with excellent light resistance and heat resistance, so that the effects of the present invention are more significantly exhibited.

Examples of pyrrolopyrrole compounds include compounds described in paragraph numbers 0016 to 0058 of JP2009-263614A, compounds described in paragraphs 0037 to 0052 of JP2011-068731A, and compounds described in WO2015/166873A. Examples include compounds described in paragraph numbers 0010 to 0033. Examples of squarylium compounds include compounds described in paragraph numbers 0044 to 0049 of JP-A No. 2011-208101, compounds described in paragraph numbers 0060 to 0061 of Japanese Patent No. 6065169, and paragraph number 0040 of International Publication No. 2016/181987. Compounds described in JP 2015-176046, Compounds described in paragraph number 0072 of WO 2016/190162, Compounds described in paragraph numbers 0196 to 0228 of JP 2016-074649 , the compound described in paragraph number 0124 of JP 2017-067963, the compound described in WO 2017/135359, the compound described in JP 2017-114956, the compound described in JP 6197940, Examples include compounds described in International Publication No. 2016/120166. Examples of polymethine compounds include compounds described in paragraph numbers 0044 to 0045 of JP2009-108267A, compounds described in paragraphs 0026 to 0030 of JP2002-194040A, and compounds described in JP2015-172004A. Compounds described in JP 2015-172102, compounds described in JP 2008-088426, compounds described in paragraph number 0090 of WO 2016/190162, JP 2017-031394 Examples include the compounds described in . Examples of the croconium compound include compounds described in JP-A No. 2017-082029. Examples of iminium compounds include compounds described in Japanese Patent Publication No. 2008-528706, compounds described in Japanese Patent Application Publication No. 2012-012399, compounds described in Japanese Patent Application Publication No. 2007-092060, and International Publication No. 2018/043564. Examples include the compounds described in paragraph numbers 0048 to 0063 of . Examples of phthalocyanine compounds include compounds described in paragraph number 0093 of JP-A No. 2012-077153, oxytitanium phthalocyanine described in JP-A 2006-343631, and paragraphs 0013 to 0029 of JP-A 2013-195480. , the vanadium phthalocyanine compound described in Patent No. 6081771, and the compound described in International Publication No. 2020/071470. Examples of naphthalocyanine compounds include compounds described in paragraph number 0093 of JP-A No. 2012-077153. Examples of the dithiolene metal complex include compounds described in Japanese Patent No. 5733804. Examples of the metal oxide 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 on tungsten oxide, paragraph number 0080 of JP-A-2016-006476 can be referred to, the contents of which are incorporated herein. Examples of metal borides include lanthanum boride. Commercially available lanthanum boride products include LaB ₆ -F (manufactured by Nippon Shinkinzoku Co., Ltd.). Moreover, as a metal boride, the compound described in International Publication No. 2017/119394 can also be used. Commercially available indium tin oxide products include F-ITO (manufactured by DOWA Hitech Co., Ltd.).

Other infrared absorbers include squarylium compounds described in JP2017-197437A, squarylium compounds described in JP2017-025311A, squarylium compounds described in International Publication No. 2016/154782, and Japanese Patent No. 5884953. Squarylium compounds described in Japanese Patent No. 6036689, squarylium compounds described in Japanese Patent No. 5810604, squarylium compounds described in paragraphs 0090 to 0107 of International Publication No. 2017/213047, Pyrrole ring-containing compounds described in paragraph numbers 0019 to 0075 of JP-A No. 2018-054760, pyrrole ring-containing compounds described in paragraph numbers 0078 to 0082 of JP-A No. 2018-040955, paragraphs of JP-A No. 2018-002773 Pyrrole ring-containing compounds described in Nos. 0043 to 0069, squarylium compounds having an aromatic ring at the amide α-position described in paragraph numbers 0024 to 0086 of JP 2018-041047, and amides described in JP 2017-179131. Linked squarylium compounds, compounds having a pyrrole bis-type squarylium skeleton or croconium skeleton described in JP 2017-141215, dihydrocarbazole bis-type squarylium compounds described in JP 2017-082029, JP 2017-068120 Asymmetric compounds described in paragraph numbers 0027 to 0114 of the publication, pyrrole ring-containing compounds (carbazole type) described in JP 2017-067963, phthalocyanine compounds described in Patent No. 6251530, etc. are used. You can also do that.

As another infrared absorber, tungsten oxide represented by the following formula described in paragraph number 0025 of European Patent No. 3,628,645 can also be used.
M ¹ _a M ² _b W _c O _d (P(O) _n R _m ) _e
M ¹ and M ² represent ammonium cations or metal cations, a is 0.01 to 0.5, b is 0 to 0.5, c is 1, and d is 2.5 to 3. , e is 0.01 to 0.75, n is 1, 2 or 3, m is 1, 2 or 3, and R represents a hydrocarbon group which may have a substituent. represent.

The content of the other infrared absorbing agent is preferably 5 to 500 parts by mass based on 100 parts by mass of the above-mentioned specific infrared absorbing dye. The upper limit is preferably 200 parts by mass or less, more preferably 100 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 15 parts by mass or more.
The total content of the above-mentioned specific infrared absorbing dye and other infrared absorbing agent is preferably 2% by mass or more, more preferably 5% by mass or more, and 10% by mass or more based on the total solid content of the resin composition. More preferably, it is at least % by mass. The upper limit of the total content is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

<<Resin>>
The resin composition of the present invention contains a resin. The resin is blended, for example, for dispersing pigments and the like in a resin composition or for use as a binder. Note that a resin used mainly for dispersing pigments and the like in a resin composition is also referred to as a dispersant. However, this use of the resin is just one example, and the resin can also be used for purposes other than this use.

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, more preferably 500,000 or less. The lower limit is preferably 4000 or more, more preferably 5000 or more.

Examples of resins include (meth)acrylic resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, Examples include polyamide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, vinyl acetate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyurethane resin, and polyurea resin. One type of these resins may be used alone, or two or more types may be used in combination. As the cyclic olefin resin, norbornene resin is preferable from the viewpoint of improving heat resistance. Commercially available norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (eg, ARTON F4520). In addition, the resins include the resin described in the examples of International Publication No. 2016/088645, the resin described in JP 2017-057265, the resin described in JP 2017-032685, and the resin described in JP 2017-032685. The resin described in JP 2017-075248, the resin described in JP 2017-066240, the resin described in JP 2017-167513, the resin described in JP 2017-173787, Resins described in paragraph numbers 0041 to 0060 of JP 2017-206689, resins described in paragraph numbers 0022 to 0071 of JP 2018-010856, and blocks described in JP 2016-222891. Polyisocyanate resin, resin described in JP 2020-122052, resin described in JP 2020-111656, resin described in JP 2020-139021, JP 2017-138503 It is also possible to use a resin containing a constitutional unit having a ring structure in the main chain and a constitutional unit having a biphenyl group in the side chain as described in . Further, as the resin, a resin having a fluorene skeleton can also be preferably used. Regarding the resin having a fluorene skeleton, the description in US Patent Application Publication No. 2017/0102610 can be referred to, the contents of which are incorporated herein. In addition, examples of the resin include resins described in paragraphs 0199 to 0233 of JP2020-186373A, alkali-soluble resins described in JP2020-186325A, and Korean Patent Publication No. 10-2020-0078339. The resin represented by Formula 1, the resin described in JP-A No. 2021-134350, can also be used.

It is preferable to use a resin having acid groups as the resin. Examples of the acid group include a carboxy 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. A resin having an acid group can also be used as a dispersant. The acid value of the resin having acid groups is preferably 30 to 500 mgKOH/g. The lower limit is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more. The upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, even more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.

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

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.
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 JP-A No. 2010-168539 can be referred to.

For specific examples of ether dimers, paragraph number 0317 of JP-A-2013-029760 can be referred to, the contents of which are incorporated herein.

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 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).
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 alkylene group represented by R ²¹ and R ²² preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly 2 or 3 carbon atoms. preferable. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, even 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 Aronix M-110 (manufactured by Toagosei Co., Ltd.).

The resin composition of the present invention preferably contains a resin as a dispersant. Examples of the dispersant include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %. The acid group that the acidic dispersant (acidic resin) has is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. Moreover, the basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%. The basic group that the basic dispersant has is preferably an amino group.

It is also preferable that the resin used as a dispersant is a graft resin. For details of the graft resin, the descriptions in paragraphs 0025 to 0094 of JP-A No. 2012-255128 can be referred to, the contents of which are incorporated herein.

It is also preferable that the resin used as a dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain. Preferably, the resin has The basic nitrogen atom is not particularly limited as long as it exhibits basicity. Regarding the polyimine dispersant, the descriptions in paragraph numbers 0022 to 0097 of JP 2009-203462A and paragraph numbers 0102 to 0166 of JP 2012-255128 can be referred to, and the contents of these are incorporated herein. .

It is also preferable that the resin used as the dispersant has 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). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A 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 its side chain. The content of the repeating unit having an ethylenically unsaturated bond-containing group in its side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and more preferably 20 to 70 mol% of the total repeating units of the resin. More preferably, it is mol%.

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

Dispersants are also available as commercial products, and specific examples include the DISPERBYK series manufactured by BYK Chemie, the SOLSPERSE series manufactured by Japan Lubrizol, the Efka series manufactured by BASF, and Ajinomoto Fine Techno Co., Ltd. Examples include the Ajisper series manufactured by Manufacturer. Further, the product described in paragraph number 0129 of JP 2012-137564A and the product described in paragraph number 0235 of JP 2017-194662A can also be used as a dispersant.

The content of the resin in the total solid content of the resin composition is preferably 1 to 95% by mass. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 85% by mass or less.
Further, when the resin composition of the present invention further contains a polymerizable compound described below, the content of the resin in the total solid content of the resin composition is preferably 1 to 75% by mass. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less. The lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 10% by mass or more.

When the resin composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant in the total solid content of the resin composition is preferably 0.1 to 40% by mass. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. Further, the content of the resin as a dispersant is preferably 1 to 200 parts by weight per 100 parts by weight of the pigment. The upper limit is preferably 150 parts by mass or less, more preferably 125 parts by mass or less, and even more preferably 100 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more.

The resin composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more types of resin are included, the total amount thereof is preferably within the above range.

<<Solvent>>
It is preferable that the resin composition of the present invention contains a solvent. Examples of the solvent include water and organic solvents, with organic solvents being preferred. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For these details, paragraph number 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein. Ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group 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, 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 acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxy Butanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as Examples include diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol. However, it may be better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, 50 mass ppm (parts) based on the total amount of organic solvents). per million), 10 mass ppm or less, and 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 at a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by Toyo Gosei Co., Ltd. (Kagaku Kogyo Nippo, November 13, 2015).

Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The 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 included, or multiple types may be included.

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 the organic solvent contains substantially no peroxide.

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

<<Pigment derivative>>
The resin composition of the present invention can further contain a pigment derivative. Pigment derivatives are used as dispersion aids. Examples of pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.

The pigment skeletons constituting the pigment derivatives include squarylium pigment skeleton, pyrrolopyrrole pigment skeleton, diketopyrrolopyrrole pigment skeleton, quinacridone pigment skeleton, anthraquinone pigment skeleton, dianthraquinone pigment skeleton, benzisoindole pigment skeleton, and thiazine indigo pigment skeleton. , azo dye skeleton, quinophthalone dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, dioxazine dye skeleton, perylene dye skeleton, perinone dye skeleton, benzimidazolone dye skeleton, benzothiazole dye skeleton, benzimidazole dye skeleton and benzoxazole dye skeleton can be mentioned.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imide acid group, and salts thereof. 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, pyridinium ions, Examples include phosphonium ions. As the carboxylic acid amide group, a group represented by -NHCOR ^A1 is preferable. As the sulfonic acid amide group, a group represented by -NHSO ₂ R ^A2 is preferable. The imide acid group is preferably a group represented by -SO ₂ NHSO ₂ R ^A3 , -CONHSO ₂ R ^A4 , -CONHCOR ^A5 or -SO ₂ NHCOR ^A6 , and -SO ₂ NHSO ₂ R ^A3 is more preferred. 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, more preferably a fluorine atom.

Examples of the basic group include an amino group, a pyridinyl group and its salts, an ammonium group salt, and a phthalimidomethyl group. Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

Specific examples of pigment derivatives include compounds described in Examples below. Also, JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, JP-A-03-009961, JP-A-03-026767, and JP-A-03-153780. Publication, JP 03-045662, JP 04-285669, JP 06-145546, JP 06-212088, JP 06-240158, JP 10-030063, Compounds described in JP-A-10-195326, paragraph numbers 0086 to 0098 of International Publication No. 2011/024896, and paragraph numbers 0063 to 0094 of International Publication No. 2012/102399 are also included, and the contents of these are incorporated herein by reference. be incorporated into.

The content of the pigment derivative is preferably 1 to 50 parts by weight based on 100 parts by weight of the pigment. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, 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.

<<Polymerizable compound>>
The resin composition of the present invention can further contain a polymerizable compound. Examples of the polymerizable compound include a compound having an ethylenically unsaturated bond-containing group, a compound having a cyclic ether group, a compound having a methylol group, a compound having an alkoxymethyl group, and the like. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and the like. Examples of the cyclic ether group include an epoxy group and an oxetanyl group.
It is also preferable that the polymerizable compound is a radically polymerizable compound. Examples of the radically polymerizable compound include compounds having an ethylenically unsaturated bond-containing group.

The polymerizable compound may be in any chemical form such as a monomer, prepolymer, or oligomer, but monomers are preferred.

The molecular weight of the monomer-type polymerizable compound (polymerizable monomer) is preferably less than 2,000, more preferably 1,500 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 200 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, more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples include paragraph numbers 0095 to 0108 of JP 2009-288705, paragraph 0227 of JP 2013-029760, paragraph 0254 to 0257 of JP 2008-292970, and JP 2013-253224. Described in paragraph numbers 0034 to 0038 of the publication, paragraph number 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, JP 6031807, JP 2017-194662. , the contents of which are incorporated herein.

Examples of compounds having an ethylenically unsaturated bond-containing group include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available) Examples of commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available products are KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol hexa (meth) ) acrylate (commercially available products are 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 and/or compounds having a structure in which they are bonded via a propylene glycol residue (eg, SR454, SR499, commercially available from Sartomer). Further, as compounds having an ethylenically unsaturated bond-containing group, diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available product is M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (Shin Nakamura Chemical Co., Ltd.) (manufactured by Nippon Kayaku Co., Ltd., NK ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Nippon Kayaku Co., Ltd.) Toagosei Co., Ltd.), NK Oligo UA-7200 (Shin Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (Kyoeisha Chemical Co., Ltd.) ) etc. can also be used.

Examples of compounds having an ethylenically unsaturated bond-containing group include trimethylolpropane tri(meth)acrylate, trimethylolpropanepropylene oxide-modified tri(meth)acrylate, trimethylolpropaneethylene oxide-modified tri(meth)acrylate, and isocyanuric acid ethylene oxide-modified tri(meth)acrylate. It is also preferable to use trifunctional (meth)acrylate compounds such as (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, M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Examples include.

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

As the compound having an ethylenically unsaturated bond-containing group, a compound having a caprolactone structure can also be used. Regarding the compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP-A No. 2013-253224 can be referred to, the contents of which are incorporated herein. 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 the 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 preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group. More preferably, it is a 3- to 6-functional (meth)acrylate compound having 4 to 20 ethyleneoxy groups. Commercially available products include, for example, SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer, and trifunctional (meth)acrylate having three isobutyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. Examples include KAYARAD TPA-330.

As the 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 the compound having an ethylenically unsaturated bond-containing group, it is also preferable to use a compound substantially free of environmentally regulated substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT, KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.), and 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 epoxy groups include compounds having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably 2 or more.

The compound having a cyclic ether group may be a low molecular compound (for example, molecular weight less than 1000) or a macromolecule (for example, molecular weight 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more). The weight average molecular weight of the cyclic ether group is preferably 200 to 100,000, 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.

Examples of compounds having a cyclic ether group include compounds described in paragraph numbers 0034 to 0036 of JP-A No. 2013-011869, compounds described in paragraph numbers 0147 to 0156 of JP-A-2014-043556, and JP-A No. 2014. Compounds described in paragraph numbers 0085 to 0092 of JP-A-089408 and compounds described in JP-A-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 (manufactured by Nagase ChemteX Corporation), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC -7300, ) Daicel), Cyclomer P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, ACA Z320 (manufactured by Daicel Corporation), jER1031S, jER157S65, jER152, jER154, jER157S70 (all manufactured by Mitsubishi Chemical Corporation) ), Aronoxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.), ADEKA Glycilol ED-505 (manufactured by ADEKA Co., Ltd., epoxy group-containing monomer), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G -01758 (manufactured by NOF Corporation, epoxy group-containing polymer), OXT-101, OXT-121, OXT-212, OXT-221 (all of the above, manufactured by Toagosei Co., Ltd., oxetanyl group-containing monomer), OXE-10 , OXE-30 (monomer containing an oxetanyl group, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.

Examples of compounds having a methylol group (hereinafter also referred to as methylol compounds) include compounds in which a methylol group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Examples of compounds having an alkoxymethyl group (hereinafter also referred to as alkoxymethyl compounds) include compounds in which an alkoxymethyl group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Compounds in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxymethylated Preferred are urea and methylolated urea. Further, compounds described in paragraphs 0134 to 0147 of JP-A No. 2004-295116 and paragraphs 0095 to 0126 of JP-A No. 2014-089408 can also be used.

The content of the polymerizable compound in the total solid content of the resin composition is preferably 0.1 to 50% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. The resin composition of the present invention may contain only one kind of polymerizable compound, or may contain two or more kinds of polymerizable compounds. When two or more types of polymerizable compounds are included, it is preferable that the total amount thereof falls within the above range.

<<Photopolymerization initiator>>
When the resin composition of the present invention contains a polymerizable compound, it is preferable that the resin 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 in the ultraviolet to visible range are preferred. When a radically polymerizable compound is used as the polymerizable compound, the photopolymerization initiator is preferably a radical photopolymerization initiator.

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with 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, and the like. From the viewpoint of exposure sensitivity, photopolymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and hexaarylbylene compounds. Preferred are imidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds, oxime compounds, α-hydroxyketones The compound is more preferably a compound selected from a compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound. In addition, as photopolymerization initiators, compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3,2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, JP 2019-043864 The photopolymerization initiator described in JP-A No. 2019-044030, the peroxide-based initiator described in JP-A No. 2019-167313, the photopolymerization initiator described in JP-A No. 2020-055992 The aminoacetophenone initiator having an oxazolidine group as described, the oxime photopolymerization initiator described in JP 2013-190459, the polymer described in JP 2020-172619, the WO 2020/152120 Examples include the compound represented by Formula 1, the compound described in JP-A-2021-181406, and the contents thereof are incorporated herein.

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, and Irgacure 1. 173, Irgacure 2959, Irgacure 127 (all BASF (manufactured by a company). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, and Irgacure. 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF) (manufactured by). Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (manufactured by BASF), and the like.

Examples of oxime compounds include the compounds described in JP-A No. 2001-233842, the compounds described in JP-A No. 2000-080068, the compounds described in JP-A No. 2006-342166, and the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660); C. S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000 - Compounds described in Publication No. 066385, Compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2006-342166, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, International Publication No. 2015 /152153, the compound described in International Publication No. 2017/051680, the compound described in JP 2017-198865, the compound described in paragraph numbers 0025 to 0038 of International Publication No. 2017/164127, Compounds described in paragraph numbers 0029 to 0044 of International Publication No. 2013/167515, International Publication No. 2017/169819, JP 2019-168654, and general formula (1) of JP 2021-173858 Examples include compounds represented by the general formula (1) and compounds described in paragraphs 0117 to 0120 of JP-A-2021-170089. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-327 (TRONL). manufactured by Y Company), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., photopolymerization initiator 2) described in JP-A-2012-014052 can be mentioned. Further, as the oxime compound, it is also preferable to use a compound without coloring property or a compound with high transparency and resistance to discoloration. Commercially available products include ADEKA Arkles NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Co., Ltd.).

As the 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 JP-A No. 2014-137466, compounds described in Japanese Patent No. 6636081, compounds described in Korean Patent Publication No. 10-2016-0109444, and Examples include fluorenylaminoketone photoinitiators described in Table 2020-507664 and oxime ester compounds described in International Publication No. 2021/023144.

As the photopolymerization initiator, it is also possible to use an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring. 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 JP-A No. 2010-262028, compounds 24, 36 to 40 described in Japanese Patent Application Publication No. 2014-500852, and compounds described in JP-A No. 2013-164471. Examples include compound (C-3).

As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is in the form of a dimer. Specific examples of oxime compounds having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP 2013-114249, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466, Examples include compounds described in paragraph numbers 0007 to 0025 of Japanese Patent No. 4223071, and Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

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, it is also possible to use an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton. 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 thereto.

The oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm. In addition, from the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably from 1000 to 300,000, even more preferably from 2000 to 300,000, and even more preferably from 5000 to 200,000. It is particularly preferable that there be. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photopolymerization initiator, a difunctional, trifunctional or more functional photoradical polymerization initiator may be used. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity decreases and the solubility in solvents improves, making it difficult to precipitate over time, thereby improving the stability of the resin composition over time. . Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include those listed in Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Application Publication No. 2016-532675. Dimers of oxime compounds described in paragraph numbers 0407 to 0412, paragraph numbers 0039 to 0055 of International Publication No. 2017/033680, compound (E) and compound ( G), Cmpd 1 to 7 described in International Publication No. 2016/034963, oxime ester initiator described in paragraph number 0007 of Japanese Patent Application Publication No. 2017-523465, paragraph of Japanese Patent Application Publication No. 2017-167399 Photoinitiators described in paragraph numbers 0020 to 0033, photoinitiators (A) described in paragraph numbers 0017 to 0026 of JP2017-151342A, oxime described in Japanese Patent No. 6469669 Examples include ester-based initiators.

The content of the photopolymerization initiator is preferably 0.1 to 40% by weight, more preferably 0.5 to 35% by weight, and even more preferably 1 to 30% by weight based on the total solid content of the resin composition. The resin 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.

<<Curing agent>>
When the resin composition of the present invention contains a compound having a cyclic ether group, it is preferable that it further contains 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, pentaerythritol tetrakis (3-mercaptopropionate), and the like. As the curing agent, compounds described in paragraph numbers 0072 to 0078 of JP-A No. 2016-075720 and compounds described in JP-A No. 2017-036379 can also be used. The content of the curing agent is preferably 0.01 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and 0.1 to 6.0 parts by weight per 100 parts by weight of the compound having a cyclic ether group. is even more preferable.

<<Chromatic colorant>>
The resin composition of the present invention can 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 having absorption in a wavelength range of 400 nm or more and less than 650 nm.

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. A pigment and a dye may be used together. Further, the pigment may be either an inorganic pigment or an organic pigment. Further, as the pigment, an inorganic pigment or an organic-inorganic pigment partially substituted with an organic chromophore can also be used. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be facilitated.

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

The crystallite size determined from the half-width of the peak derived from any crystal plane in the X-ray diffraction spectrum when the CuKα ray of the pigment is used as the X-ray source is preferably 0.1 nm to 100 nm, and preferably 0.1 nm to 100 nm. The thickness is more preferably 5 nm to 50 nm, even more preferably 1 nm to 30 nm, and particularly preferably 5 nm to 25 nm.

The specific surface area of the pigment is preferably 1 to 300 m ² /g. The lower limit is preferably 10 m ² /g or more, more preferably 30 m ² /g or more. The upper limit is preferably 250 m ² /g or less, more preferably 200 m ² /g or less. The value of the specific surface area is determined according to DIN 66131: determination of the specific surface area of solids by gas adsorption according to the BET (Brunauer, Emmett and Teller) method. Determination of specific surface area of solids by adsorption).

The chromatic colorant preferably contains a pigment. The content of pigment in the chromatic colorant is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more. It is particularly preferable. Examples of pigments include those shown below.

Color Index (C.I.) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232 (methine type), 233 (quinoline type), 234 ( (aminoketone type), 235 (aminoketone type), 236 (aminoketone type), etc. (yellow pigments),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Above, orange pigment)
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294 (xanthene type, Organo Ultramarine, Bluish Red), 295 (monoazo type), 296 (diazo type), 297 (aminoketone type), etc. (red pigments),
C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine type), 65 (phthalocyanine type), 66 (phthalocyanine type), etc. (green pigments),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane type), 61 (xanthene type), etc. (purple pigments),
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 (monoazo type), 88 (methine type), etc. (the above are blue pigments).

In addition, as a green pigment, halogenated zinc phthalocyanine pigments have an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12, and an average of 2 to 5 chlorine atoms. You can also use 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 as a ligand described in International Publication No. 2012/102395, a phthalocyanine compound described in JP-A No. 2019-008014, A phthalocyanine compound, a phthalocyanine compound described in JP 2018-180023, a compound described in JP 2019-038958, a core-shell type dye described in JP 2020-076995, etc. can also be used.

Additionally, an aluminum phthalocyanine compound having a phosphorus atom can also be used as the blue pigment. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A No. 2012-247591 and paragraph number 0047 of JP-A No. 2011-157478.

In addition, as yellow pigments, compounds described in JP-A No. 2017-201003, compounds described in JP-A No. 2017-197719, and compounds described in paragraph numbers 0011-0062 and 0137-0276 of JP-A No. 2017-171912 are used. Compounds, compounds described in paragraph numbers 0010 to 0062, 0138 to 0295 of JP 2017-171913, compounds described in paragraph numbers 0011 to 0062, 0139 to 0190 of JP 2017-171914, JP 2017- Compounds described in paragraph numbers 0010 to 0065 and 0142 to 0222 of JP-A No. 171915, quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP-A No. 2013-054339, and paragraph numbers 0013 to 0058 of JP-A-2014-026228. The quinophthalone compound described in JP 2018-062644, the quinophthalone compound described in JP 2018-203798, the quinophthalone compound described in JP 2018-062578, and Japanese Patent No. 6432076. Quinophthalone compounds described in the publication, quinophthalone compounds described in JP2018-155881, quinophthalone compounds described in JP2018-111757, quinophthalone compounds described in JP2018-040835, JP2017- Quinophthalone compounds described in JP 2016-145282, quinophthalone compounds described in JP 2014-085565, quinophthalone compounds described in JP 2014-021139, JP 2014-021139; Quinophthalone compounds described in JP2013-209614, quinophthalone compounds described in JP2013-209435, quinophthalone compounds described in JP2013-181015, quinophthalone compounds described in JP2013-061622, Quinophthalone compounds described in JP2013-032486A, quinophthalone compounds described in JP2012-226110A, quinophthalone compounds described in JP2008-074987A, quinophthalone compounds described in JP2008-081565A Compounds, quinophthalone compounds described in JP 2008-074986, quinophthalone compounds described in JP 2008-074985, quinophthalone compounds described in JP 2008-050420, quinophthalone compounds described in JP 2008-031281 Quinophthalone compounds described in Japanese Patent Publication No. 48-032765, Quinophthalone compounds described in Japanese Patent Application Publication No. 2019-008014, Quinophthalone compounds described in Japanese Patent No. 6607427, Korean Published Patent No. 10-2014-0034963 Compounds described in Japanese Patent Publication No. 2017-095706, compounds described in Taiwan Patent Application Publication No. 201920495, compounds described in Japanese Patent No. 6607427, compounds described in Japanese Patent Application Publication No. 2020-033525 Compounds described in JP2020-033524A, compounds described in JP2020-033523A, compounds described in JP2020-033522A, compounds described in JP2020-033521A Compounds described in International Publication No. 2020/045200, compounds described in International Publication No. 2020/045199, and compounds described in International Publication No. 2020/045197 can also be used. Furthermore, polymerized versions of these compounds are 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 JP 2017-201384, a diketopyrrolopyrrole compound described in paragraph numbers 0016 to 0022 of Patent No. 6248838, Diketopyrrolopyrrole compounds described in International Publication No. 2012/102399, diketopyrrolopyrrole compounds described in International Publication No. 2012/117965, naphthol azo compounds described in JP2012-229344A, Patent No. 6516119 Red pigment described in the publication, red pigment described in Patent No. 6525101, brominated diketopyrrolopyrrole compound described in paragraph number 0229 of JP 2020-090632, Korean Published Patent No. 10-2019-0140741 Anthraquinone compounds described in the publication, anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140744, perylene compounds described in JP 2020-079396, etc. can also be used. Further, as a red pigment, a compound having a structure in which an aromatic ring group into which a group to which an oxygen atom, sulfur atom, or nitrogen atom is bonded is bonded to a diketopyrrolopyrrole skeleton may also be used. can.

Regarding the diffraction angles that various pigments preferably have, the descriptions in Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, and Japanese Patent Application Laid-open No. 2020-026503 can be referred to. Incorporated herein. In addition, as a pyrrolopyrrole pigment, the crystallite size in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight planes (±1±1±1) of the crystal lattice planes is 140 Å or less. It is also preferable to use one. Furthermore, it is also preferable to set the physical properties of the pyrrolopyrrole pigment as described in paragraphs 0028 to 0073 of JP-A-2020-097744.

Dyes can also be used as chromatic colorants. There are no particular restrictions on the dye, and any known dye can be used. For example, pyrazole azo dyes, anilinoazo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, and phenothiazines. Examples include pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, pyrromethene dyes, and the like.

Pigment multimers can also be used as chromatic colorants. The dye multimer is preferably a dye that is dissolved in a solvent. Further, the dye multimer may form particles. When the dye multimer is in the form of particles, it is usually used in a state of being dispersed in a solvent. The dye multimer in a particle state can be obtained, for example, by emulsion polymerization, and specific examples include the compound and manufacturing method described in JP-A No. 2015-214682. The dye multimer has two or more dye structures in one 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 contained 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 2,000 to 50,000. The lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. Dye multimers are described in JP 2011-213925, JP 2013-041097, JP 2015-028144, JP 2015-030742, WO 2016/031442, etc. Compounds can also be used.

Chromatic colorants include triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in JP 2020-117638, and International Publication No. 2020/174991. phthalocyanine compounds, isoindoline compounds or their salts described in JP-A No. 2020-160279, compounds represented by formula 1 described in Korean Published Patent No. 10-2020-0069442, Korean Published Patent No. 10- Compounds represented by formula 1 described in Korean Publication No. 2020-0069730, compounds represented by formula 1 described in Korean Publication Patent No. 10-2020-0069070, and compounds represented by formula 1 described in Korean Publication Patent No. 10-2020-0069067. Compound represented by formula 1 described in Korean Patent Publication No. 10-2020-0069062, halogenated zinc phthalocyanine pigment described in Patent No. 6809649, JP 2020-180176 Isoindoline compounds described in JP-A No. 2021-187913, phenothiazine compounds described in JP-A No. 2021-187913, halogenated zinc phthalocyanine described in International Publication No. 2022/004261, and halogenated compounds described in International Publication No. 2021/250883. Zinc phthalocyanine can be used. The other colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, in the rod-like structure, or in both structures.

When the resin 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 resin composition of the present invention. When the resin composition of the present invention contains two or more chromatic colorants, the total amount thereof is preferably within the above range.

When the resin composition of the present invention is used for an infrared cut filter, it is preferable that the resin composition of the present invention does not substantially contain a chromatic colorant. In addition, the case where the resin composition of the present invention does not substantially contain a chromatic colorant means that the content of the chromatic colorant in the total solid content of the resin composition of the present invention is 0.5% by mass or less. It is preferably 0.1% by mass or less, and more preferably does not contain a chromatic colorant.

<<Color material that transmits infrared rays and blocks visible light>>
The resin composition of the present invention can also contain a coloring material that transmits infrared rays and blocks visible light (hereinafter also referred to as a coloring material that blocks visible light). A resin composition containing a coloring material that blocks visible light is preferably used as a resin composition for forming an infrared transmission filter.

The coloring material that blocks visible light is preferably a coloring material that absorbs light in the wavelength range from violet to red. Further, the coloring material that blocks visible light is preferably a coloring material that blocks light in a wavelength range of 450 to 650 nm. Further, the coloring material that blocks visible light is preferably a coloring material that transmits light with a wavelength of 900 to 1500 nm. The coloring material that blocks visible light preferably satisfies at least one of the following requirements (A) and (B).
(A): Contains two or more types of chromatic colorants, and black color is formed by a combination of two or more types of chromatic colorants.
(B): Contains an organic black colorant.

Examples of the chromatic colorant include those mentioned above. Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. Examples of bisbenzofuranone compounds include compounds described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, and Japanese Patent Application Publication No. 2012-515234, and for example, as "Irgaphor Black" manufactured by BASF. available. Examples of perylene compounds include compounds described in paragraph numbers 0016 to 0020 of JP-A No. 2017-226821, C.I. I. Pigment Black 31, 32, etc. Examples of the azomethine compound include compounds described in JP-A-01-170601 and JP-A-02-034664, and are available as "Chromofine Black A1103" manufactured by Dainichiseika Kaisha, Ltd., for example.

When a black color is formed by a combination of two or more chromatic colorants, examples of the combination of chromatic colorants include the following embodiments (1) to (8).
(1) Embodiment containing a yellow colorant, a blue colorant, a purple colorant, and a red colorant.
(2) Embodiment containing a yellow colorant, a blue colorant, and a red colorant.
(3) Embodiment containing a yellow colorant, a purple colorant, and a red colorant.
(4) Embodiment containing a yellow colorant and a purple colorant.
(5) An embodiment containing a green colorant, a blue colorant, a purple colorant, and a red colorant.
(6) Embodiment containing a purple colorant and an orange colorant.
(7) Embodiment containing a green colorant, a purple colorant, and a red colorant.
(8) Embodiment containing a green colorant and a red colorant.

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

When the resin composition of the present invention is used for an infrared cut filter, it is preferable that the resin composition of the present invention does not substantially contain a coloring material that blocks visible light. Note that the case where the resin composition of the present invention does not substantially contain a colorant that blocks visible light means that the content of the colorant that blocks visible light in the total solid content of the resin composition of the present invention is This means 0.5% by mass or less, preferably 0.1% by mass or less, and more preferably no coloring material that blocks visible light.

<<Surfactant>>
It is preferable that the resin composition of the present invention contains a surfactant. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. The surfactant is preferably a silicone surfactant or a fluorine surfactant. Examples of the surfactant include the surfactants described in paragraph numbers 0238 to 0245 of International Publication No. 2015/166779, the contents of which are incorporated herein.

Examples of fluorine-based surfactants include surfactants described in paragraph numbers 0060 to 0064 of JP 2014-041318 (corresponding paragraph numbers 0060 to 0064 of WO 2014/017669), and the like; Examples include the surfactants described in paragraph numbers 0117 to 0132 of Publication No. 132503 and the surfactants described in JP-A-2020-008634, the contents of which are incorporated herein. Commercially available fluorosurfactants include Megafac 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 (manufactured by DIC Corporation), Florado FC430, FC431, FC171 (manufactured by Sumitomo Corporation) 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by 3M Co., Ltd.), AGC Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), Ftergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 71 0FS, FTX-218 (all of which are manufactured by NEOS Co., Ltd.), and the like.

In addition, as fluorine-based surfactants, there are also acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the functional group containing a fluorine atom is cut off and the fluorine atom volatizes. It can be used suitably. Examples of such fluorine-based surfactants include the Megafac DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), An example is DS-21.

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 as the fluorinated surfactant. Examples of such fluorine-based surfactants include the fluorine-based surfactants described in JP-A No. 2016-216602, the content of which is incorporated herein.

A block polymer can also be used as the fluorosurfactant. As a fluorine-based surfactant, a (meth) having a repeating unit derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. Further, the fluorine-containing surfactants described in paragraph numbers 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-containing surfactant used in the present invention.
The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example 14,000. In the above compounds, % indicating the proportion of repeating units is mol%.

Furthermore, a fluoropolymer having an ethylenically unsaturated bond-containing group in its side chain can also be used as the fluorinated surfactant. Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A No. 2010-164965, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation, Examples include RS-72-K. Further, as the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 can also be used.

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

It is also preferable to use a fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant.
In formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, a represents 1 or 2, and X ^a+ represents an a-valent metal ion, a primary ammonium ion, or Represents a secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH ₄ ⁺ .

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), 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 (BASF Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.) (manufactured by Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) Examples include.

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

Anionic surfactants include dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyl ether disulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, 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 stearate, sodium oleate, t-octylphenoxyethoxypolyethoxyethyl Examples include sodium sulfate salt.

Examples of silicone surfactants include SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), TSF-4440, TSF-4300 , TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (manufactured by BYK-Chemie Co., Ltd.), and the like.

Moreover, a compound having the following structure can also be used as the silicone surfactant.

The content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and even more preferably 0.001 to 0.2% by mass based on the total solid content of the resin composition. preferable. The resin 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 resin composition of the present invention can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), Examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.), with p-methoxyphenol being preferred. The content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the resin composition. The resin composition may contain only one kind of polymerization inhibitor, or may contain two or more kinds of polymerization inhibitors. When two or more types are included, it is preferable that their total amount falls within the above range.

<<Silane coupling agent>>
The resin composition of the present invention can contain a silane coupling agent. In this specification, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Furthermore, the term "hydrolyzable group" refers to a substituent that is directly bonded to a silicon atom and can form 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, an acyloxy group, and an alkoxy group is preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups. (meth)acryloyl group and epoxy group are preferred. Examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A No. 2009-288703, and compounds described in paragraph numbers 0056 to 0066 of JP-A No. 2009-242604, the contents of which are incorporated herein by reference. Incorporated into the specification. 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 resin composition. The resin 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.

<<Ultraviolet absorber>>
The resin composition of the present invention can contain an ultraviolet absorber. Examples of the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, dibenzoyl compounds, and the like. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraphs 0052 to 0072 of JP2012-208374A, and paragraphs 0317 to 0317 of JP2013-068814A. 0334, paragraph numbers 0061 to 0080 of JP 2016-162946, paragraph numbers 0052 and 0074 of International Publication No. 2021/131355, and paragraph numbers 0022 to 0024 of International Publication No. 2021/132247. , the contents of which are incorporated herein. Commercially available UV absorbers include the Tinuvin series and Uvinul series manufactured by BASF. Furthermore, examples of the benzotriazole compound include the MYUA series manufactured by Miyoshi Yushi (Kagaku Kogyo Nippo, February 1, 2016). The ultraviolet absorbers include compounds described in paragraph numbers 0049 to 0059 of Patent No. 6268967, compounds described in paragraph numbers 0059 to 0076 of International Publication No. 2016/181987, and compounds described in International Publication No. 2020/137819. It is also possible to use a thioaryl group-substituted benzotriazole type ultraviolet absorber and a reactive triazine ultraviolet absorber described in JP-A No. 2021-178918. 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 resin composition. The resin 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 resin composition of the present invention can contain an antioxidant. Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. Examples of phenolic antioxidants include hindered phenol compounds. The phenolic antioxidant is preferably a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position). The above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms. Preferably, the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. As a phosphorus 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]dioxaphosphepine-2- yl)oxy]ethyl]amine, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and the like. Commercially available antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330, ADEKA STAB AO-412S, ADEKA STAB 2112, ADEKA STAB PEP-36, ADEKA STAB HP-10 (manufactured by ADEKA Co., Ltd.), and JP-650 (manufactured by Johoku Kagaku Kogyo Co., Ltd.). The antioxidants include compounds described in paragraph numbers 0023 to 0048 of Patent No. 6268967, compounds described in International Publication No. 2017/006600, compounds described in International Publication No. 2017/164024, and Korean Publication No. Compounds described in Patent No. 10-2019-0059371 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 resin composition. The resin 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 resin composition of the present invention may contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers, and other auxiliary agents (e.g., conductive particles, antifoaming agents, flame retardants, (leveling agents, peeling accelerators, fragrances, surface tension regulators, chain transfer agents, etc.) may also be included. By appropriately containing these components, properties such as film physical properties can be adjusted. These components are described, for example, in paragraphs 0183 and after of JP-A-2012-003225 (corresponding paragraph 0237 of U.S. Patent Application Publication No. 2013/0034812), and in paragraphs of JP-A-2008-250074. The descriptions of numbers 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated into the present specification. Furthermore, the resin composition of the present invention may contain a latent antioxidant, if necessary. A latent antioxidant is a compound whose moiety that functions as an antioxidant is protected with a protecting group, and is heated at 100 to 250°C or heated at 80 to 200°C in the presence of an acid/base catalyst. Examples include compounds that function as antioxidants by removing protective groups. Examples of the latent antioxidant include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219. Commercially available latent antioxidants include Adeka Arcles GPA-5001 (manufactured by ADEKA Co., Ltd.).

<Storage container>
The container for storing the resin composition of the present invention is not particularly limited, and any known container can be used. In addition, for the purpose of suppressing impurities from entering raw materials and resin compositions, we also use multilayer bottles with container inner walls made of 6 types and 6 layers of resin, and bottles with 7 layers of 6 types of resin as storage containers. It is also preferable to use Examples of such a container include the container described in JP-A No. 2015-123351. Further, the inner wall of the container is preferably made of glass, stainless steel, etc. for the purpose of preventing metal elution from the inner wall of the container, increasing stability of the resin composition over time, and suppressing component deterioration.

<Method for preparing resin composition>
The resin composition of the present invention can be prepared by mixing the above-mentioned components. When preparing a resin composition, the resin composition may be prepared by dissolving or dispersing all the components in a solvent at the same time, or, if necessary, two or more solutions or dispersions containing each component as appropriate may be prepared. may be prepared in advance and mixed at the time of use (at the time of application) to prepare a resin composition.

The preparation of the resin composition may include a process of dispersing the pigment. In the process of dispersing pigments, mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like. 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, ultrasonic dispersion, and the like. In addition, when pulverizing pigments in a sand mill (bead mill), it is preferable to use small-diameter beads or increase the filling rate of the beads, thereby increasing the pulverizing efficiency. Further, it is preferable to remove coarse particles by filtration, centrifugation, etc. after the pulverization treatment. In addition, the process and dispersion machine for dispersing pigments are described in ``Complete Works of Dispersion Technology, Published by Information Technology Corporation, July 15, 2005'' and ``Dispersion technology centered on suspension (solid/liquid dispersion system) and industrial The process and dispersion machine described in Paragraph No. 0022 of JP 2015-157893 A, "Practical Application Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be suitably used. Further, in the process of dispersing the pigment, the pigment may be subjected to a finer treatment in a salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling process, the descriptions in JP-A No. 2015-194521 and JP-A No. 2012-046629 can be referred to, for example. Bead materials used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. Moreover, an inorganic compound having a Mohs hardness of 2 or more can also be used for the beads. The resin composition may contain 1 to 10,000 ppm of the beads.

In preparing the resin composition, it is preferable to filter the resin composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration and the like can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (e.g. nylon-6, nylon-6,6), polyolefin resins (high density, ultra-high molecular weight) such as polyethylene, polypropylene (PP), etc. Examples include filters using materials such as polyolefin resin (including polyolefin resin). 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 even more preferably 0.05 to 0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. Regarding the pore size value of the filter, reference can be made to the nominal value of the filter manufacturer. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), Kitz Microfilter Co., Ltd., etc. can be used. .

It is also preferable to use a fiber-like filter medium as the filter. Examples of fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers. 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 filters, different filters (for example, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed two or more times. Further, filters having different pore diameters within the above-mentioned range may be combined. Alternatively, only the dispersion liquid may be filtered with the first filter, and then filtered with the second filter after other components are mixed.

<Membrane>
Next, the membrane of the present invention will be explained. The membrane of the present invention is obtained from the resin composition of the present invention described above. The film of the present invention can be preferably used as an optical filter. Applications of the optical filter are not particularly limited, but include infrared cut filters, infrared transmission filters, and the like. Examples of the infrared cut filter include an infrared cut filter on the light receiving side of the solid-state image sensor (for example, an infrared cut filter for a wafer level lens, etc.), and an infrared cut filter on the back side of the solid-state image sensor (opposite side to the light receiving side). , infrared cut filters for environmental light sensors (for example, illuminance sensors that detect the illuminance and color tone of the environment in which the information terminal device is placed and adjust the color tone of the display, and color correction sensors that adjust the color tone). It will be done. In particular, it can be preferably used as an infrared cut filter on the light receiving side of a solid-state image sensor. Examples of the infrared transmission filter include a filter that can block visible light and selectively transmit infrared rays having a specific wavelength or more.

The film of the present invention may have a pattern or may be a film without a pattern (flat film). Further, the membrane of the present invention may be used by being laminated on a support, or the membrane of the present invention may be used by being peeled off from the support. Examples of the support include semiconductor base materials such as silicon substrates and transparent base materials.

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. Further, a partition wall that isolates each pixel may be formed on the semiconductor substrate. Examples of the partition wall include metals, metal oxides, black matrices, and the like. Further, an undercoat layer may be provided on the semiconductor substrate, if necessary, for improving adhesion with the upper layer, preventing substance diffusion, or flattening 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. Examples of resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymers, acrylic resins such as norbornene resins, polyacrylates, and polymethyl methacrylates, urethane resins, and vinyl chloride resins. , fluororesin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin, and the like. Examples of the glass include soda lime glass, borosilicate glass, alkali-free glass, quartz glass, and glass containing copper. Examples of glass containing copper include phosphate glass containing copper, fluorophosphate glass containing copper, and the like. A commercially available glass containing copper can also be used. Examples of commercially available glass containing copper include NF-50 (manufactured by AGC Techno Glass Co., Ltd.).

The thickness of the film of the present invention can be adjusted as appropriate depending on the purpose. The thickness of the film can be 200 μm or less, 150 μm or less, 120 μm or less, 20 μm or less, 10 μm or less, and 5 μm or less. You can also do it. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more.

When the film of the present invention is used as an infrared cut filter, it is preferable that the film of the present invention has a maximum absorption wavelength in a wavelength range of 650 to 1500 nm (preferably a wavelength of 660 to 1200 nm, more preferably a wavelength of 660 to 1000 nm). . Further, the average transmittance of light with a wavelength of 420 to 550 nm is preferably 50% or more, more preferably 70% or more, even more preferably 80% or more, and especially 85% or more. preferable. Further, the transmittance over the entire wavelength range of 420 to 550 nm is preferably 50% or more, more preferably 70% or more, and even more preferably 80% or more. Further, the film of the present invention preferably has a transmittance of 15% or less at at least one point in the wavelength range of 650 to 1500 nm (preferably wavelength 660 to 1200 nm, more preferably wavelength 660 to 1000 nm), and preferably 10% or less. The content is more preferably 5% or less, and even more preferably 5% or less. Furthermore, the film of the present invention preferably has an average absorbance of less than 0.030, more preferably less than 0.025, in the wavelength range of 420 to 550 nm, when the absorbance at the maximum absorption wavelength is 1.

When the film of the present invention is used as an infrared transmission filter, the film of the present invention preferably has, for example, any one of the following spectral properties (i1) to (i3).
(i1): The maximum value of 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 value of transmittance in the wavelength range of 1000 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in a wavelength range of 400 to 850 nm and transmit light with a wavelength exceeding 950 nm.
(i2): The maximum value of 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 value of transmittance in the wavelength range of 1100 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more). A film having such spectral characteristics can block light in a wavelength range of 400 to 950 nm and transmit light with a wavelength exceeding 1050 nm.
(i3): The maximum value of 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 value of transmittance in the wavelength range of 1200 to 1500 nm is 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 with a wavelength exceeding 1150 nm.

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 filter and is used in combination with a color filter, the color filter is preferably 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 form a laminate. In the laminate, the film of the present invention and the color filter may or may not be adjacent to each other in the thickness direction. When the film of the present invention and the color filter are not adjacent in the thickness direction, the film of the present invention may be formed on a support different from the support on which the color filter is formed, and the film of the present invention may be formed on a support different from the support on which the color filter is formed. Other members (for example, microlenses, flattening layers, etc.) constituting the solid-state imaging device may be interposed between the film and the color filter.

The film of the present invention is suitable for solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors) (the imaging section uses compound semiconductors such as InGaAs, organic semiconductors, quantum dots, etc. in addition to Si). It can be used in various devices such as infrared sensors, light emitting devices, optical communication devices (both transmitting and receiving), and image display devices.

<Membrane manufacturing method>
The film of the present invention can be manufactured through a step of applying the resin composition of the present invention.

Examples of the support include those mentioned above. As a method for applying the resin composition, a known method can be used. For example, drop casting method; slit coating method; spray method; roll coating method; spin coating method; casting coating method; slit and spin method; Various methods such as inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Examples include printing method; transfer method using a mold etc.; nanoimprint method. The application method for inkjet is not particularly limited, and for example, the method shown in "Expanding and Usable Inkjet - Infinite Possibilities Seen in Patents," Published February 2005, Sumibe Techno Research (especially from page 115). 133 pages), and methods described in JP-A No. 2003-262716, JP-A No. 2003-185831, JP-A No. 2003-261827, JP-A No. 2012-126830, JP-A No. 2006-169325, etc. Can be mentioned.

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

The film manufacturing method may further include a step of forming a pattern. Examples of the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method, and a pattern forming method using a photolithography method is preferable. Note that when the film of the present invention is used as a flat film, the step of forming a pattern may not be performed. Hereinafter, the process of forming a pattern will be described in detail.

(When forming a pattern using photolithography)
The pattern forming method using the photolithography method includes a step of exposing a resin composition layer formed by applying the resin composition of the present invention to light in a pattern (exposure step), and developing the unexposed portions of the resin composition layer. It is preferable to include a step of removing and forming a pattern (developing step). If necessary, a step of baking the developed pattern (post-bake step) may be provided. Each step will be explained below.

In the exposure step, the resin composition layer is exposed in a pattern. For example, the resin composition layer can be exposed in a pattern by exposing the resin composition layer to light through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. This allows the exposed portion to be cured.

Radiation (light) that can be used during exposure includes g-line, i-line, etc. Furthermore, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm). Furthermore, a long-wave light source of 300 nm or more can also be used.

Furthermore, during exposure, light may be exposed by continuous irradiation, or exposure may be performed by irradiation in pulses (pulse exposure). Note that pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and pauses in short cycles (for example, on the millisecond level or less).

The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J/cm ² , more preferably 0.05 to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being carried out in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially The exposure may be performed in an oxygen-free environment (in the absence of oxygen), or in a high oxygen atmosphere with an oxygen concentration of more than 21 volume % (for example, 22 volume %, 30 volume %, or 50 volume %). Further, the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000W/m ² to 100000W/m ² (for example, 5000W/m ² , 15000W/m ² , or 35000W/m ² ). I can do it. The oxygen concentration and the exposure illuminance may be appropriately combined. For example, the illumination intensity may be 10,000 W/m ² at an oxygen concentration of 10% by volume, or 20,000 W/m ² at an oxygen concentration of 35% by volume.

Next, the unexposed portions of the resin composition layer after exposure are removed by development to form a pattern. The unexposed portions of the resin composition layer can be removed by development using a developer. As a result, the unexposed portions of the resin composition layer in the exposure step are eluted into the developer, and only the photocured portions remain on the support. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. Furthermore, in order to improve the ability to remove residues, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

Examples of the developer include organic solvents, alkaline developers, and alkaline developers are preferably used. As the alkaline developer, an alkaline aqueous solution (alkaline developer) prepared 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, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, etc. Examples include alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. As for the alkali agent, compounds with a large molecular weight are preferable from the environmental and safety standpoints. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Moreover, the developer may further contain a surfactant. As the surfactant, nonionic surfactants are preferred. For convenience in transportation and storage, the developing solution may be manufactured as a concentrated solution and then diluted to a required concentration before use. The dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Further, rinsing is preferably performed by supplying a rinsing liquid to the developed resin composition layer while rotating the support on which the developed resin composition layer is formed. It is also preferable to move the nozzle that discharges the rinsing 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 to the peripheral edge, the nozzle may be moved while gradually decreasing its moving speed. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. The same effect can also be obtained by gradually reducing the rotational speed of the support while moving the nozzle from the center of the support to the peripheral edge.

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

(When forming a pattern using dry etching method)
Pattern formation by the dry etching method involves coating the resin composition on a support and curing the resin composition layer to form a cured material layer, and then forming a patterned photo on this cured material layer. This can be carried out by a method such as forming a resist layer, and then dry etching the cured material layer using an etching gas using the patterned photoresist layer as a mask. In forming the photoresist layer, it is preferable to perform a prebaking process. Regarding pattern formation by the dry etching method, the descriptions in paragraphs 0010 to 0067 of JP-A No. 2013-064993 can be referred to, and the contents thereof are incorporated into the present specification.

<Optical filter>
The optical filter of the present invention has the film of the present invention described above. Types of optical filters include infrared cut filters and infrared transmission filters.

In addition to the film of the invention described above, the optical filter of the invention may further include a copper-containing layer, a dielectric multilayer film, an ultraviolet absorbing layer, and the like. Examples of the ultraviolet absorbing layer include the absorbing layers described in paragraph numbers 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/099060. Examples of the dielectric multilayer film include the dielectric multilayer films described in paragraph numbers 0255 to 0259 of JP-A 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 (all manufactured by Schott Co., Ltd.), and CD5000 (manufactured by HOYA Co., Ltd.). Preferred base materials include transparent base materials made of materials such as glass and resin, and it is also preferred to form a film directly on various elements. Examples of resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymers, acrylic resins such as norbornene resins, polyacrylates, and polymethyl methacrylates, urethane resins, and vinyl chloride resins. , fluororesin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin, and the like. Examples of the glass include soda lime glass, borosilicate glass, alkali-free glass, quartz glass, and glass containing copper.

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

On the support, there is a transfer electrode made of polysilicon or the like and a plurality of photodiodes that constitute the light-receiving area of the solid-state image sensor, and a light-shielding material made of tungsten or the like with only the light-receiving part of the photodiode opened above the photodiode and the transfer electrode. The device has a device protective film made of silicon nitride or the like formed to cover the entire surface of the light shielding film and the photodiode light receiving part on the light shielding film, and has the film of the present invention on the device protective film. be. Furthermore, a configuration in which a light focusing means (for example, a microlens, etc., the same applies hereinafter) is provided on the device protective film and below the film of the present invention (on the side closer to the support), or a structure in which light is focused on the film of the present invention A configuration having a means or the like may be used. Further, the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned into, for example, a lattice shape by partition walls. 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 Nos. 2012-227478 and 2014-179577.

<Image display device>
The image display device of the present invention includes the film of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device. For definitions and details of image display devices, see, for example, "Electronic Display Devices (written by Akio Sasaki, published by Industrial Research Institute Co., Ltd., 1990)" and "Display Devices (written by Junaki Ibuki, published by Sangyo Tosho Co., Ltd., published in 1989). Publication)” etc. Further, liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994)". There is no particular restriction on the liquid crystal display device to which the present invention can be applied, and for example, the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology." The image display device may include a white organic EL element. The white organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, see Japanese Patent Application Laid-open No. 2003-045676, supervised by Akiyoshi Mikami, "The forefront of organic EL technology development - High brightness, high precision, long life, collection of know-how", Technical Information Association, It is described in pages 326-328, 2008, etc. The spectrum of white light emitted by the organic EL element 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 have a maximum emission peak in the red region (650 to 700 nm). The film of the present invention can also be used as an infrared transmitting film provided in an opening for infrared communication formed in a frame portion of a protective plate for a display device.

<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. EMBODIMENT OF THE INVENTION Hereinafter, one embodiment of the infrared sensor of this invention is described using drawings.

In FIG. 1, numeral 110 is a solid-state image sensor. An infrared cut filter 111 and an infrared transmission filter 114 are arranged on the imaging area of the solid-state image sensor 110. Furthermore, a color filter 112 is arranged on the infrared cut filter 111. A microlens 115 is arranged on the incident light hv side of the color filter 112 and the infrared transmission filter 114. A flattening layer 116 is formed to cover the microlens 115.

The infrared cut filter 111 can be formed using the resin composition of the present invention. The color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible region are formed, and there is no particular limitation, and a conventionally known color filter for forming pixels can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used. For example, the descriptions in paragraph numbers 0214 to 0263 of JP-A No. 2014-043556 can be referred to, and the contents thereof are incorporated herein. 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 resin composition of the present invention.

In the infrared sensor shown in FIG. 1, an infrared cut filter other than the infrared cut filter 111 (another infrared cut filter) may be further disposed on the flattening layer 116. Other infrared cut filters include those having a layer containing copper and/or a dielectric multilayer film. Details of these are mentioned above. Moreover, a dual band pass filter may be used as another infrared cut filter.

<Camera module>
The camera module of the present invention includes a solid-state image sensor and the above-described film of the present invention. Preferably, the camera module further includes a lens and a circuit that processes images obtained from the solid-state image sensor. The solid-state image sensor used in the camera module may be the solid-state image sensor according to the present disclosure described above, or may be a known solid-state image sensor. Further, as the lens used in the camera module and the circuit that processes the image obtained from the solid-state image sensor, known ones can be used. As an example of the camera module, camera modules described in JP-A No. 2016-006476 and JP-A No. 2014-197190 can be referred to, and the contents thereof are incorporated into this specification.

<Light emitting element>
The film of the present invention can also be used in light emitting devices. The structure of the light emitting element is not particularly limited as long as it functions as a light emitting element, and light emitting diodes (LEDs), organic light emitting diodes (OLEDs), quantum dot light emitting diodes (QLEDs), vertical cavity surface emitting lasers ( VICSEL), etc. The film of the present invention may be formed directly on the light emitting element, or may be placed on the light emitting path.

<Optical communication device>
The film of the present invention can also be used in optical communication devices. The configuration of the optical communication element is not particularly limited as long as it functions as an optical communication element, and may be either a transmitting element or a receiving element. Examples of the optical communication device include an infrared remote control, an infrared transceiver, an optical interposer, and an optical interconnection. The film of the present invention may be formed directly on the receiving element, directly on the transmitting element, or placed on the transmitting/receiving path.

The present invention will be explained in more detail with reference to Examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention.

<Measurement of weight average molecular weight>
The weight average molecular weight of the resin was measured using HPC-8220GPC (manufactured by Tosoh Corporation) as a measuring device, TSKguardcolumn SuperHZ-L as a guard column, and TSKgel SuperHZM-M, TSKgel SuperHZ4000, TSKgel SuperH as a column. Column directly connected to Z3000 and TSKgel SuperHZ2000 , set the column temperature to 40°C, inject 10 μL of a tetrahydrofuran solution with a sample concentration of 0.1% by mass into the column, flow tetrahydrofuran as an elution solvent at a flow rate of 0.35 mL per minute, and perform RI (differential refractive index). A sample peak was detected using a detection device, and calculations were made using a calibration curve prepared using standard polystyrene.

<Synthesis example of compound>
(Synthesis Example 1) Synthesis of compound 033

-Synthesis process of compound 033K-
10.0 g (63.7 mmol) of bromobenzene, 8.78 g (65.0 mmol; 1.02 eq.) of 2,4,6-trimethylaniline, 9.18 g (95.5 mmol; 1. 5 eq.) and 30 mL of toluene were mixed. Next, after repeating the operation of degassing under reduced pressure and replacing with nitrogen three times, 0.286 g (1.27 mmol; 0.02 eq.) of palladium acetate and 0.924 g of tri-t-butylphosphonium tetrafluoroborate were added. (3.18 mmol; 0.05 eq.) was added. Next, the operation of degassing under reduced pressure and replacing with nitrogen was repeated three times, followed by reaction at 120° C. for 4 hours under a nitrogen flow. After cooling, water was added, ethyl acetate (EtOAc) was added, and the layers were separated. The obtained organic layer was washed with brine, dried over MgSO ₄ , concentrated under reduced pressure, and purified by silica gel column chromatography (developing solvent: hexane) to obtain 12.05 g of compound 033K. The yield was 90%.
TLC (Thin-Layer Chromatography) R _f value = 0.26 (hexane)
¹ H NMR (CDCl ₃ ) d 2.17 (s, 3H), 2.18 (s, 3H), 2.30 (s, 3H), 5.09 (s, 1H), 6.47-6. 49 (m, 2H), 6.72 (t, J=7.2Hz, 1H), 6.94 (s, 2H), 7.14 (t, J=7.2Hz, 2H).

-Synthesis process of compound 033A-
4.19 g (19.8 mmol) of compound 033K was dissolved in 49.6 mL of dehydrated DMF (N,N-dimethylformamide), and 0.952 g (23.8 mmol; 1.2 eq. ) was added little by little and stirred in a water bath for 30 minutes. Under ice cooling, 4.77 g (23.8 mmol; 1.2 eq.) of ethyl p-toluenesulfonate was added little by little, and the mixture was reacted in an oil bath at 90° C. for 2 hours and at 100° C. for 3 hours. After cooling, water was added, ethyl acetate was added, and the layers were separated. The obtained organic layer was washed three times with water, washed with brine, dried over Na ₂ SO ₄ , concentrated under reduced pressure, and purified by silica gel column chromatography (developing solvent: hexane) to obtain 4.05 g of compound 033A. Ta. The yield was 85%.
TLC R _f value = 0.55 (hexane)
^1H NMR ( _CDCl3 ) d 1.20 (t, J=7.2Hz, 3H), 2.06 (s, 6H), 2.31 (s, 3H), 3.57 (q, J=7 .2Hz, 2H), 6.39-6.41 (m, 2H), 6.61-6.65 (m, 1H), 6.95 (s, 2H), 7.14 (t, J=7 .6Hz, 2H).
^13C NMR ( _CDCl3 ) d 13.23, 18.31, 20.97, 45.30, 111.16, 115.68, 129.16, 129.60, 136.34, 137.85, 140. 30, 147.64.

-Synthesis process of compound 033B-
9.49 g (39.6 mmol) of compound 033A was dissolved in 198 mL of dehydrated DMF, and 7.06 g (39.6 mmol; 1.0 eq.) of N-bromosuccinimide was dissolved in 23.8 mL of dehydrated DMF under ice cooling. The dissolved solution was added dropwise over 40 minutes, and the mixture was stirred in an ice bath for 30 minutes and at room temperature for 3 hours. Under ice cooling, 100 mL of water was added, and 200 mL of ethyl acetate and 100 mL of water were added to separate the layers. The obtained organic layer was washed twice with water, washed with brine, dried over Na ₂ SO ₄ , concentrated under reduced pressure, and purified by silica gel column chromatography (developing solvent: hexane) to obtain 12.31 g of compound 033B. Ta. The yield was 98%.
TLC R _f value = 0.62 (hexane)
^1H NMR ( _CDCl3 ) d 1.19 (t, J=7.2Hz, 3H), 2.04 (s, 6H), 2.31 (s, 3H), 3.52 (q, J=7 .2Hz, 2H), 6.20-6.35 (m, 2H), 6.95 (s, 2H), 7.19 (d, J=8.8Hz, 2H).
^13C NMR ( _CDCl3 ) d 13.01, 18.20, 20.96, 45.44, 107.52, 112.85, 129.72, 131.82, 136.69, 137.59, 139. 75, 146.70.

- Compound 033C synthesis step 5.00 g (15.7 mmol) of compound 033B was dissolved in 100 mL of 4-methyltetrahydropyran, 4.99 g (19.6 mmol; 1.25 eq.) of bis(pinacolato)diboron, and potassium acetate. 1.93g (19.6mmol; 1.25eq.) of Next, the operation of degassing under reduced pressure and replacing with nitrogen was repeated three times to obtain 0.575 g (0.79 mmol; 5 mol%) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (dppf). was added. Next, the operation of degassing under reduced pressure and then replacing with nitrogen was repeated three times, and the reaction was carried out at 100° C. for 45 hours under a nitrogen flow. After cooling, water and ethyl acetate were added to separate the layers. The obtained organic layer was washed with brine, dried with Na ₂ SO ₄ , concentrated under reduced pressure, and purified by silica gel column chromatography (developing solvent: hexane: ethyl acetate = 9:1 (mass ratio)) to obtain compound 033C. 2.90g was obtained. The yield was 51%.
TLC R _f value = 0.57 (hexane: ethyl acetate = 9:1 (mass ratio))
^1H NMR ( _CDCl3 ) d 1.21 (t, J=7.2Hz, 3H), 1.30 (s, 12H), 2.04 (s, 6H), 2.32 (s, 3H), 3.52 (q, J=7.2Hz, 2H), 6.00-6.90 (br, 2H), 6.96 (s, 2H), 7.60-7.70 (br, 2H).
^13C NMR ( _CDCl3 ) d 13.05, 18.21, 20.96, 24.83, 45.46, 83.08, 127.71, 129.64, 134.73, 136.32, 136. 56, 137.50, 139.82, 150.02.

-Synthesis process of compound 4D-
Compound 4D was synthesized by the method described in the literature (Angew. Chem. Int. Ed., 2013, Vol. 52, pp. 8990-8994).

-Synthesis process of compound 033E-
After dissolving 2.0 g (5.05 mmol) of compound 4D in 105 mL of dehydrated diethyl ether and 34.8 mL of dehydrated THF (tetrahydrofuran), it was cooled in a dry ice-acetone bath, and n-butyllithium (BuLi) ( 6.82 mL (10.9 mmol; 2.16 eq.) of 1.6 mol/L) was added dropwise at an internal temperature of −74° C. or below, and the mixture was stirred as it was for 2 hours. A solution of 1.28 g (5.05 mmol; 1.0 eq.) of dichlorodiphenylsilane (Ph ₂ SiCl ₂ ) dissolved in 14 mL of dehydrated diethyl ether was added dropwise over 1 hour at an internal temperature of -75°C or lower, and then left as is. The mixture was stirred for 1 hour, and the mixture was stirred while being slowly heated to 0° C. over 6 hours while immersed in a cold bath. 50 mL of water was added, and ethyl acetate was added to separate the layers. The obtained organic layer was washed with brine, dried with Na ₂ SO ₄ , concentrated under reduced pressure, and purified by silica gel column chromatography (developing solvent: hexane: ethyl acetate = 19:1 (mass ratio)) to obtain compound 033E. 0.80g was obtained. The yield was 38%.
TLC R _f = 0.24 (hexane: ethyl acetate = 19:1 (mass ratio))
¹ H NMR (CDCl ₃ ) d 4.37 (s, 4H), 7.16 (d, J=5.2Hz, 2H), 7.32-7.36 (m, 4H), 7.37-7 .42 (m, 4H), 7.58 (dd, J=1.2 and 8.0Hz, 4H).
^13C NMR ( _CDCl3 ) d 66.20, 104.79, 126.36, 128.07, 129.99, 131.42, 133.29, 133.79, 135.60, 155.25.
²⁹ Si NMR (CDCl ₃ ) d -33.27.

-Synthesis process of compound 033F-
After dissolving 0.50 g (1.2 mmol) of compound 033E in 12 mL of dehydrated THF, it was cooled in a dry ice-acetone bath, and 3.6 mL (3.2 mmol) of a toluene solution (1 mol/L) of lithium diisopropylamide (LDA) was dissolved. .6 mmol; 3.0 eq.) was added dropwise at an internal temperature of -76°C or lower, and the mixture was stirred for 2 hours. A solution of 0.86 g (2.6 mmol; 2.2 eq.) of 1,2-dibromotetrachloroethane dissolved in 2 mL of dehydrated THF was added dropwise, and the mixture was stirred overnight while slowly raising the temperature while immersed in a cold bath. 10 mL of water was added, and ethyl acetate was added to separate the layers. The obtained organic layer was washed with brine, dried with Na ₂ SO ₄ , concentrated under reduced pressure, added hexane and ethyl acetate and subjected to ultrasonic dispersion, filtered, washed with hexane, and dried under reduced pressure (60 ° C.). , 0.56 g of compound 033F was obtained. The yield was 81%.
¹ H NMR (CDCl ₃ ) d 4.30 (s, 4H), 7.04 (s, 2H), 7.36-7.43 (m, 4H), 7.44-7.46 (m, 2H) ), 7.54-7.56 (m, 4H).
^13C NMR ( _CDCl3 ) d 66.28, 103.75, 114.31, 128.30, 130.45, 131.90, 133.78, 135.11, 135.55, 155.71.
²⁹ Si NMR (CDCl ₃ ) d -34.72.

-Synthesis process of compound 033G-
0.859 g (1.49 mmol) of compound 033F, 1.20 g (3.28 mmol; 2.2 eq.) of compound 033C, 1.17 g (3.58 mmol; 2.4 eq.) of cesium carbonate, 4-methyltetrahydro 85.9 mL of pyran and 8.59 mL of water were mixed. Next, after repeating the operation of degassing under reduced pressure and replacing with nitrogen three times, (2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2- 0.133 g (0.149 mmol; 0.1 eq.) of (2'-amino-1,1'-biphenyl)] palladium methanesulfonate (XPhos Pd G3) was added. Next, the operation of degassing under reduced pressure and then replacing with nitrogen was repeated three times, followed by a reaction at 110° C. for 8 hours under a nitrogen flow. After cooling, ethyl acetate was added and the mixture was separated. The obtained organic layer was washed with brine, dried with Na ₂ SO ₄ , concentrated under reduced pressure, and purified by silica gel column chromatography (developing solvent: hexane: ethyl acetate = 4:1 (mass ratio)) to obtain compound 033G. Obtained. The obtained compound 033G was used as it was in the next step.
TLC R _f value = 0.61 (hexane: ethyl acetate = 4:1 (mass ratio))
^1H NMR ( _CDCl3 ) d 1.20 (t, J=7.2Hz, 6H), 2.05 (s, 12H), 2.32 (s, 6H), 3.58 (q, J=7 .2Hz, 4H), 4.38 (s, 4H), 6.20-6.50 (m, 4H), 6.95 (s, 4H), 7.09 (s, 2H), 7.31- 7.39 (m, 10H), 7.62-7.64 (m, 4H).
^13C NMR ( _CDCl3 ) d 13.15, 18.27, 20.98, 45.46, 66.15, 77.22, 104.92, 111.34, 121.93, 124.64, 127. 44, 128.02, 129.66, 133.62, 134.79, 135.72, 136.58, 137.63, 139.88, 146.62, 147.43, 151.90.

-Synthesis process of compound 033H-
Compound 033G was dissolved in 40 mL of methylene chloride, 2.56 mL (10.2 mmol 6.9 eq.) of hydrogen chloride (4 mol/L 1,4-dioxane solution) was added, and the mixture was stirred at room temperature overnight. The mixture was neutralized with saturated sodium bicarbonate solution and separated. The resulting aqueous layer was extracted with CH ₂ Cl ₂ , the organic layer was dried over Na ₂ SO ₄ , concentrated under reduced pressure, concentrated and recrystallized from CH ₂ Cl ₂ -methanol, filtered, washed with methanol, 0.98 g of compound 033H was obtained. The yield was 77% (from compound 033F).
TLC R _f value = 0.54 (hexane: ethyl acetate = 4:1 (mass ratio))
^1H NMR ( _CDCl3 ) d 1.22 (t, J=7.2Hz, 6H), 2.06 (s, 12H), 2.32 (s, 6H), 3.61 (q, J=7 .2Hz, 4H), 6.20-6.50(m, 4H), 6.96(s, 4H), 7.35-7.44(m, 12H), 7.62-7.64(m , 4H).
^13C NMR ( _CDCl3 ) d 13.06, 18.22, 20.98, 45.57, 77.22, 104.92, 111.41, 121.10, 126.17, 127.88, 128. 32, 129.74, 132.14, 135.61, 136.83, 137.40, 139.53, 143.58, 148.44, 154.71, 175.72.
²⁹ Si NMR (CDCl ₃ ) d -34.78.

-Synthesis process of compound 033I-
After adding 3 mg of iodine to 0.052 g (2.1 mmol; 12 eq.) of magnesium and 1.5 mL of dehydrated THF and heating to about 40°C, 0.05 g (2.1 mmol; 12 eq.) of 2-bromo-1,3-dimethoxybenzene was added. A solution of 38 g (1.8 mmol; 10 eq.) dissolved in 1.5 mL of dehydrated THF was slowly added dropwise at an internal temperature of 40°C or higher, stirred in an oil bath at 60°C for 4 hours, and then cooled to room temperature to form a Grignard reagent solution. was prepared. 0.15 g (0.18 mmol) of compound 033H was dissolved in 1.5 mL of dehydrated THF, and the prepared Grignard reagent solution was added dropwise in an ice bath at an internal temperature of 4° C. or lower, followed by stirring in an oil bath at 50° C. for 5 hours. . After cooling, the reaction solution was concentrated under reduced pressure, and a saturated aqueous ammonium chloride solution and CH ₂ Cl ₂ were added to separate the layers. The obtained organic layer was washed with brine, dried with Na ₂ SO ₄ , concentrated under reduced pressure, and purified by silica gel column chromatography (developing solvent: hexane: ethyl acetate = 4:1 (mass ratio)) to obtain compound 033I. 0.096g was obtained. The yield was 55%.
TLC R _f value = 0.32 (hexane: ethyl acetate = 4:1 (mass ratio))
¹ H NMR (CD ₂ Cl ₂ ) d 1.21 (t, J=7.2Hz, 6H), 1.29-1.34 (br, 1H), 2.06 (s, 12H), 2.33 (s, 6H), 3.59 (q, J=7.2Hz, 4H), 3.60 (s, 6H), 6.20-6.60 (br, 4H), 6.69-6.71 (m, 2H), 6.99 (s, 4H), 7.15 (s, 2H), 7.32-7.37 (m, 5H), 7.38-7.45 (m, 6H), 7.71-7.80 (m, 4H).
^13C NMR (CD ₂ Cl ₂ ) d 13.26, 18.36, 21.06, 45.76, 56.97, 75.97, 107.02, 111.63, 122.40, 123.48, 127.40, 128.34, 128.41, 129.91, 129.94, 130.04, 130.50, 135.94, 136.04, 136.97, 137.95, 140.18, 144. 79, 147.70, 158.53, 159.98.

-Synthesis process of compound 033J-
0.096 g (0.097 mmol) of compound 033I was dissolved in 5 mL of methylene chloride, and 0.19 mL (0.78 mmol; 8 eq.) of hydrogen chloride (4 mol/L 1,4-dioxane solution) was added. Stirred at room temperature for 30 minutes. 5 mL of dilute hydrochloric acid (6 mol/L) and CH ₂ Cl ₂ were added and stirred to separate the layers. The obtained organic layer was washed with water until the pH of the aqueous layer became 7, dried over Na ₂ SO ₄ and concentrated under reduced pressure to obtain 0.10 g of Compound 033J. The obtained compound 033J was used as it was in the next step.
TLC R _f value = 0.00 (hexane: ethyl acetate = 4:1 (mass ratio))
MS (LDI): m/z 969.38 ([M-Cl] ⁺ ).

-Synthesis process of compound 033-
Compound 033J was added to 10 mL of methylene chloride and suspended, and then 0.0310 g (0.097 mmol; 1.0 eq.) of potassium bis(trifluoromethanesulfonyl)imide (Tf ₂ N ⁻ K ⁺ ) was added to water. The mixture was dissolved in 1 mL and added, stirred at room temperature for 50 minutes, and separated. The obtained organic layer was concentrated under reduced pressure and subjected to silica gel column chromatography (initial developing solution was hexane:ethyl acetate = 4:1 (mass ratio), and then the developing solution was CH ₂ Cl ₂ :ethyl acetate = 4: 1 (mass ratio)) to obtain 0.092 g of Compound 033. The yield was 76% (from compound 033I).
TLC R _f value = 0.73 (CH ₂ Cl ₂ : ethyl acetate = 4:1 (mass ratio))
^1H NMR ( _CDCl3 ) d 1.23 (t, J=7.2Hz, 6H), 2.02 (s, 12H), 2.32 (s, 6H), 3.69 (q, J=7 .2Hz, 4H), 3.77(s, 6H), 5.80-6.20(br, 4H), 6.69(q, J=8.8Hz, 2H), 6.97(s, 4H) ), 7.30-7.43 (br, 2H), 7.45-7.63 (m, 8H), 7.66-7.76 (m, 5H), 7.82 (s, 2H).
^13C NMR ( _CDCl3 ) d 12.75, 18.04, 20.98, 46.39, 56.31, 77.23, 104.16, 111.41, 114.65, 120.03 (q, J=321.8Hz), 120.53, 129.00, 129.71, 129.98, 131.48, 133.10, 134.62, 135.52, 136.23, 137.90, 138.13 , 147.20, 148.23, 151.21, 152.18, 157.86, 167.74.
²⁹ Si NMR (CDCl ₃ ) d -32.71.
¹⁹ F NMR (CDCl ₃ ) d -78.62.
MS (LDI): m/z 969.37 ([M-Tf ₂ N] ⁺ ), 279.93 (Tf ₂ N ^- ).
Maximum absorption wavelength = 995 nm (CH ₂ Cl ₂ ) e 1.35×10 ⁵ L/mol・cm

(Synthesis Example 2) Synthesis of Compound 034 Compound 034 was synthesized in the same manner as in Synthesis Example 1, except that in the synthesis step of Compound 033E, dichlorodiphenylsilane was changed to an equimolar amount of dichlorodimethylsilane.
MS (LDI): m/z 845.37 ([M−Tf ₂ N] ⁺ ), 279.92 (Tf ₂ N ⁻ ).
Maximum absorption wavelength = 928 nm (CH ₂ Cl ₂ )

(Synthesis Example 3) Synthesis of Compound 035 Compound 035 was synthesized in the same manner as in Synthesis Example 1, except that in the synthesis step of Compound 033E, dichlorodiphenylsilane was replaced with an equimolar amount of dichlorodiethylsilane.
MS (LDI): m/z 873.39 ([M−Tf ₂ N] ⁺ ), 279.91 (Tf ₂ N ⁻ ).
Maximum absorption wavelength = 909 nm (CH ₂ Cl ₂ )

(Synthesis Example 4) Synthesis of Compound 036 Compound 036 was synthesized in the same manner as in Synthesis Example 1, except that in the synthesis step of Compound 033B, Compound 033A was changed to an equimolar amount of diethylaniline.
MS (LDI): m/z 789.30 ([M-Tf ₂ N] ⁺ ), 279.92 (Tf ₂ N ^- ).
Maximum absorption wavelength = 915 nm (CH ₂ Cl ₂ )

(Synthesis Example 5) Synthesis of Compound 037 In the synthesis step of Compound 033I, the same procedure as in Synthesis Example 1 was performed except that 2-bromo-1,3-dimethoxybenzene was changed to an equimolar amount of 2-bromomesitylene. 037 was synthesized.
MS (LDI): m/z 951.43 ([M−Tf ₂ N] ⁺ ), 279.93 (Tf ₂ N ⁻ ).
Maximum absorption wavelength = 1037 nm (CH ₂ Cl ₂ )

(Synthesis Example 6) Synthesis of Compound 038 Compound 038 was produced by performing the same operation as in Synthesis Example 1, except that in the synthesis step of Compound 033I, 2-bromo-1,3-dimethoxybenzene was changed to an equimolar amount of bromobenzene. Synthesized.
MS (LDI): m/z 909.35 ([M−Tf ₂ N] ⁺ ), 279.93 (Tf ₂ N ⁻ ).
Maximum absorption wavelength = 1021 nm (CH ₂ Cl ₂ )

(Synthesis Example 7) Synthesis of Compound 039 In the synthesis step of Compound 033, Compound 039 was produced by performing the same operation as in Synthesis Example 1 except that potassium bis(trifluoromethanesulfonyl)imide was replaced with an equimolar amount of potassium trifluoroacetate. Synthesized.
MS (LDI): m/z 845.37 ([M- CF ₃ CO ₂ ] ⁺ ), 113.00 (CF ₃ CO ₂ ^- ).
Maximum absorption wavelength = 996 nm (CH ₂ Cl ₂ )

(Synthesis Example 8) Synthesis of Compound 040 Compound 040 was obtained by performing the same operation as in Synthesis Example 1, except that in the synthesis step of Compound 033, potassium bis(trifluoromethanesulfonyl)imide was replaced with an equimolar amount of sodium trifluoromethanesulfonate. was synthesized.
MS (LDI): m/z 845.37 ([M- CF ₃ SO ₃ ] ⁺ ), 148.95 (CF ₃ SO ₃ ^- ).
Maximum absorption wavelength = 995 nm (CH ₂ Cl ₂ )

(Synthesis Example 9) Synthesis of Compound 041 Compound 041 was obtained by performing the same operation as in Synthesis Example 1, except that in the synthesis step of Compound 033, potassium bis(trifluoromethanesulfonyl)imide was replaced with an equimolar amount of potassium hexafluorophosphate. was synthesized.
MS (LDI): m/z 845.37 ([M- PF ₆ ] ⁺ ), 144.97 (PF ₆ ^- ).
Maximum absorption wavelength = 994 nm (CH ₂ Cl ₂ )

(Synthesis Example 10) Synthesis of Compound 042 Same as Synthesis Example 1 except that in the synthesis step of Compound 033, potassium bis(trifluoromethanesulfonyl)imide was replaced with an equimolar amount of lithium tetrakis(pentafluorophenyl)borate ethyl etherate. Compound 042 was synthesized by performing the following operations.
MS (LDI): m/z 845.37 ([MB(C ₆ F ₅ ) ₄ ] ⁺ ), 678.97 (B(C ₆ F ₅ ) ₄ ⁻ ).
Maximum absorption wavelength = 995 nm (CH ₂ Cl ₂ )

(Synthesis Example 11) Synthesis of Compound 043 In the synthesis step of Compound 033, the same procedure as Synthesis Example 1 was performed except that potassium bis(trifluoromethanesulfonyl)imide was replaced with an equimolar amount of potassium tris(trifluoromethanesulfonyl)methanide. Compound 043 was synthesized.
MS (LDI): m/z 845.37 ([MC(SO ₂ CF ₃ ) ₃ ] ⁺ ), 410.88 (C(SO ₂ CF ₃ ) ₃ ⁻ ).
Maximum absorption wavelength = 997 nm (CH ₂ Cl ₂ )

(Synthesis Example 12) Synthesis of Compound 044 In the synthesis step of Compound 033, potassium bis(trifluoromethanesulfonyl)imide was added to 0.5 equivalent of 1,1,2,2,3,3-hexafluoropropane based on Compound 033J. Compound 044 was synthesized in the same manner as in Synthesis Example 1 except that potassium -1,3-disulfonate was used.
MS (LDI): m/z 845.37 ([cation part]), 154.96 ([anion part]/2).
Maximum absorption wavelength = 995 nm (CH ₂ Cl ₂ )

(Synthesis Example 13) Synthesis of Compound 045 Compound 045 was synthesized in the same manner as in Synthesis Example 1 except that dichlorodiphenylsilane was changed to an equimolar amount of thionyl chloride.
MS (LDI): m/z 835.32 ([M−Tf ₂ N] ⁺ ), 279.92 (Tf ₂ N ⁻ ).
Maximum absorption wavelength = 1037 nm (CH ₂ Cl ₂ )

(Synthesis Example 14) Synthesis of Compound 046 Compound 046 was synthesized in the same manner as in Synthesis Example 4 except that dichlorodiphenylsilane was changed to an equimolar amount of thionyl chloride.
MS (LDI): m/z 655.20 ([M-Tf ₂ N] ⁺ ), 279.91 (Tf ₂ N ^- ).
Maximum absorption wavelength = 932 nm (CH ₂ Cl ₂ )

(Synthesis Example 15) Synthesis of Compound 047 Compound 045 was synthesized in the same manner as in Synthesis Example 5 except that dichlorodiphenylsilane was changed to an equimolar amount of thionyl chloride.
MS (LDI): m/z 817.35 ([M-Tf ₂ N] ⁺ ), 279.91 (Tf ₂ N ^- ).
Maximum absorption wavelength = 973 nm (CH ₂ Cl ₂ )

(Synthesis Example 16) Synthesis of Compound 048 Compound 045 was synthesized in the same manner as in Synthesis Example 6 except that dichlorodiphenylsilane was changed to an equimolar amount of thionyl chloride.
MS (LDI): m/z 775.27 ([M−Tf ₂ N] ⁺ ), 279.92 (Tf ₂ N ⁻ ).
Maximum absorption wavelength = 1067 nm (CH ₂ Cl ₂ )

(Synthesis Example 17) Synthesis of Compound 049 Compound 049 was synthesized in the same manner as in Synthesis Example 13, except that potassium bis(trifluoromethanesulfonyl)imide was replaced with an equimolar amount of potassium hexafluorophosphate. did.
MS (LDI): m/z 835.32 ([M- CF ₃ CO ₂ ] ⁺ ), 113.00 (CF ₃ CO ₂ ^- ).
Maximum absorption wavelength = 1038 nm (CH ₂ Cl ₂ )

(Synthesis Example 18) Synthesis of Compound 050 Synthesis of Compound 050 was performed in the same manner as in Synthesis Example 13, except that potassium bis(trifluoromethanesulfonyl)imide was replaced with an equimolar amount of sodium trifluoromethanesulfonate. did.
MS (LDI): m/z 835.32 ([M- CF ₃ SO ₃ ] ⁺ ), 148.95 (CF ₃ SO ₃ ^- ).
Maximum absorption wavelength = 1036 nm (CH ₂ Cl ₂ )

(Synthesis Example 19) Synthesis of Compound 051 Compound 051 was synthesized in the same manner as in Synthesis Example 13, except that potassium bis(trifluoromethanesulfonyl)imide was replaced with an equimolar amount of sodium trifluoromethanesulfonate. did.
MS (LDI): m/z 835.32 ([M- PF ₆ ] ⁺ ), 144.97 (PF ₆ ^- ).
Maximum absorption wavelength = 1037 nm (CH ₂ Cl ₂ )

(Synthesis Example 20) Synthesis of Compound 052 The same procedure as in Synthesis Example 13 except that potassium bis(trifluoromethanesulfonyl)imide was replaced with an equimolar amount of lithium tetrakis(pentafluorophenyl)borate ethyl etherate. Compound 052 was synthesized.
MS (LDI): m/z 835.32 ([MB(C ₆ F ₅ ) ₄ ] ⁺ ), 678.97 (B(C ₆ F ₅ ) ₄ ⁻ ).
Maximum absorption wavelength = 1038 nm (CH ₂ Cl ₂ )

(Synthesis Example 21) Synthesis of Compound 053 The same procedure as in Synthesis Example 13 was performed except that potassium bis(trifluoromethanesulfonyl)imide was replaced with an equimolar amount of potassium tris(trifluoromethanesulfonyl)methanide. 053 was synthesized.
MS (LDI): m/z 835.31 ([MC(SO ₂ CF ₃ ) ₃ ] ⁺ ), 410.88 (C(SO ₂ CF ₃ ) ₃ ⁻ ).
Maximum absorption wavelength = 1036 nm (CH ₂ Cl ₂ )

(Synthesis Example 22) Synthesis of Compound 054 Compound 054 was synthesized in the same manner as in Synthesis Example 12, except that dichlorodiphenylsilane was changed to an equimolar amount of thionyl chloride.
MS (LDI): m/z 835.32 ([cation part]), 154.96 ([anion part]/2).
Maximum absorption wavelength = 1038 nm (CH ₂ Cl ₂ )

<Production of pigment dispersion>
The materials shown in the table below were blended in the proportions shown in the table below to obtain a mixture with a total amount of 10 g. This mixture was mixed and dispersed for 3 hours using zirconia beads with a diameter of 0.3 mm in a bead mill (high pressure dispersion machine with vacuum mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.)), and each pigment was mixed and dispersed. A dispersion was prepared. The solid content concentration of the pigment dispersion was adjusted by adjusting the amount of solvent added.

Details of the materials listed in the table are as follows.

(pigment)
017, 018: Compounds 017, 018 (infrared absorbing pigments) shown in the specific examples of the specific infrared absorbing pigments mentioned above
IR101 to IR103: Compounds with the following structure (infrared absorbing dyes)
PB15:6: C. I. Pigment Blue 15:6 (blue colorant)
PR254: C. I. Pigment Red 254 (red colorant)

(pigment derivative)
Syn-001, Syn-002: Compounds with the following structure

(dispersant)
Dis-001: Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 25,000)
Dis-002: Resin with the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 9800)

(solvent)
S-001: Propylene glycol monomethyl ether acetate

<Manufacture of resin composition>
Materials other than the solvents shown in the table below are mixed in the proportions shown in the table below, the solvents shown in the table below are added to adjust the solid content concentration to 20% by mass, and the mixture is stirred to form nylon with a pore size of 0.45 μm. filter (manufactured by Nippon Pall Co., Ltd.) to produce a resin composition. The numerical values in the blending amount column in the table are values in parts by mass in terms of solid content.

Details of the materials listed in the table above are as follows.

(Pigment dispersion)
D001, D002, D101-D105: Pigment dispersion liquid D001, D002, D101-D105 described above

(color material)
001, 002, 008, 009, 016, 021, 022, 023, 025 to 054: Compounds 001, 002, 008, 009, 016, 021, 022, 023, 025 shown in the specific examples of the specific infrared absorbing dye mentioned above ～054
IR001 to IR007: Compounds with the following structure (infrared absorbing dyes)

(resin)
B001: Polymethyl methacrylate (weight average molecular weight 24,000, dispersity 1.8)
B002: Random copolymer of benzyl methacrylate and methacrylic acid (benzyl methacrylate: methacrylic acid = 60:40 (mole ratio), weight average molecular weight 20000, dispersity 1.9)
B003: Resin with the following structure (the numbers added to the main chain are the molar ratio of repeating units, weight average molecular weight 15000, dispersity 2.1)
B004: Resin with the following structure (weight average molecular weight 25,000, degree of dispersion 2.2, glass transition temperature 310°C)

(Polymerizable compound)
M-1: Aronix M-305 (manufactured by Toagosei 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)
M-4: EPICLON N-695 (manufactured by DIC Corporation, o-cresol novolac type epoxy compound)

(Photopolymerization initiator)
C-1: Irgacure OXE01 (manufactured by BASF, oxime ester compound)
C-2: Irgacure OXE02 (manufactured by BASF, oxime ester compound)

(surfactant)
F-1: Megafac RS-72-K (manufactured by DIC Corporation, fluorine-based surfactant)
F-2: Compound with the following structure (weight average molecular weight 14,000, the numerical value of % indicating the proportion of repeating units is mol%)
F-3: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane modified with carbinol at both ends, hydroxyl value 62 mgKOH/g, silicone surfactant)

(Polymerization inhibitor)
G-1: p-methoxyphenol

(Ultraviolet absorber)
U-1: Uvinul3050 (manufactured by BASF)

(solvent)
S-001: Propylene glycol monomethyl ether acetate S-002: Propylene glycol monomethyl ether

<Membrane production>
(Production Example 1) Method for producing a film using the resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 The resin composition was placed on a glass substrate or an 8 inch (1 inch = 2.54 cm) silicon wafer, Spin coating was applied so that the film thickness after film formation was 1.5 μm. Next, using a hot plate, the mixture was heated at 100° C. for 1 minute to produce a membrane.

(Production Example 2) Method for producing a film using the resin composition of Example 3 The resin composition was deposited on a glass substrate or an 8-inch (1 inch = 2.54 cm) silicon wafer so that the film thickness after film formation was 1. The coating was applied by spin coating to a thickness of .5 μm. Then, using a hot plate, the mixture was heated at 200° C. for 10 minutes to produce a membrane.

(Production Example 3) Method for producing a film using the resin compositions of Examples 4 to 53 The resin composition was deposited on a glass substrate or an 8 inch (1 inch = 2.54 cm) silicon wafer, and the film thickness after film formation was determined. The film was spin-coated to a thickness of 1.5 μm, and the entire surface was exposed using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.) at an exposure dose of 1000 mJ/cm ² . Next, using a hot plate, the mixture was heated at 200° C. for 2 minutes to produce a membrane.

<Evaluation of spectral characteristics>
(Evaluation of near-infrared shielding properties)
For the glass substrate on which the above film was formed, the transmittance in the wavelength range of 400 to 2000 nm was measured using an ultraviolet-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Tech Corporation). The average value (T) of transmittance in the range of 1000 to 1400 nm was determined. Near-infrared shielding properties were evaluated based on the following criteria.
A:T<5%
B: 5%≦T<10%
C: 10%≦T

(Evaluation of rectangularity of light shielding area in near-infrared region)
The transmittance of the glass substrate on which the above film was formed was measured in the wavelength range of 400 to 2000 nm using an ultraviolet-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Tech Corporation).
In the wavelength range of 700 to 1800 nm, the wavelength at which the transmittance is 20% (λ _L20 ) and the wavelength at which the transmittance is 90% (λ _L90 ), which is on the longer wavelength side than the maximum absorption wavelength, and the maximum absorption The wavelength at which the transmittance is 20% (λ _S20 ) and the wavelength at which the transmittance is 90% (λ _S90 ), which are shorter than the wavelength, are determined, and the rectangularity of each light-shielding area is determined using the following criteria. was evaluated.

-Evaluation criteria for the rectangularity of the light blocking area on the short wavelength side (rectangularity on the short wavelength side)-
A: λ _S90 - λ _S20 <150nm
B: 150nm≦λ _S90 -λ _S20 <200nm
C: 200nm≦λ _S90 -λ _S20

-Evaluation criteria for the rectangularity of the light shielding area on the long wavelength side (rectangularity on the long wavelength side)-
A: λ _L20 - λ _L90 <150nm
B: 150nm≦λ _L20 -λ _L90 <200nm
C: 200nm≦λ _L20 -λ _L90

<Evaluation of light resistance>
The transmittance of the glass substrate on which the above film was formed was measured in the wavelength range of 400 to 2000 nm using an ultraviolet-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Tech Corporation).
Next, the glass substrate on which the above film was formed was irradiated with a xenon lamp at 100,000 lux for 20 hours (equivalent to 2 million lux·h), and the transmittance of the film after irradiation with the xenon lamp was measured.
The amount of change in transmittance (ΔT) at each wavelength in the wavelength range of 800 to 2000 nm before and after irradiation with a xenon lamp is determined, and the light resistance is evaluated using the following criteria based on the largest value of ΔT in the entire measurement wavelength range. did. The smaller the value of ΔT, the better the light resistance.
Amount of change in transmittance (ΔT) = |Transmittance of the film before irradiation with the xenon lamp - Transmittance of the film after irradiation with the xenon lamp |
A:ΔT<3%
B: 3≦ΔT<5%
C: 5≦ΔT%

<Evaluation of heat resistance>
The transmittance of the glass substrate on which the above film was formed was measured in the wavelength range of 400 to 2000 nm using an ultraviolet-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Tech Corporation).
Next, the glass substrate on which the above film was formed was heated at 200° C. for 10 minutes using a hot plate.
The amount of change in transmittance (ΔT) at each wavelength in the wavelength range of 800 to 2000 nm before and after heating was determined, and the heat resistance was evaluated using the following criteria based on the largest value of ΔT in the entire measurement wavelength range. The smaller the value of ΔT, the better the heat resistance.
Amount of change in transmittance (ΔT) = | Transmittance of membrane before heating - Transmittance of membrane after heating |
A:ΔT<5%
B: 5≦ΔT<10%
C: 10≦ΔT%

As shown in the table above, the examples were excellent in evaluation of light resistance and heat resistance. Furthermore, the examples had excellent evaluation of rectangularity on the long wavelength side, had a steep slope of transmittance on the long wavelength side with respect to the maximum absorption wavelength, and had excellent contrast between transmittance and light shielding properties.
Further, for the films obtained using the resin compositions of Examples 28 and 53, the average transmittance in the wavelength range of 400 to 1000 nm was less than 5%.

The resin compositions of Examples 4 to 53 were spin-coated onto a glass substrate or an 8-inch (1 inch = 2.54 cm) silicon wafer so that the film thickness after film formation was 1.5 μm, and then hot-coated. The plate was heated at 100° C. for 2 minutes. Next, using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), a 2 μm Bayer pattern was exposed through a mask at an exposure dose of 1000 mJ/cm ² . Next, paddle development was performed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, after rinsing with a spin shower and further rinsing with pure water, a pattern was formed by heating on a hot plate at 200° C. for 5 minutes. When the obtained pattern was observed under a microscope, it was found that a Bayer pattern was formed.

110: solid-state image sensor, 111: infrared cut filter, 112: color filter, 114: infrared transmission filter, 115: microlens, 116: flattening layer

Claims

at least one infrared absorbing dye A selected from a dye A1 represented by formula (1) and a dye multimer A2 containing two or more dye structures derived from the dye A1 in one molecule;
A resin composition comprising a resin;
In formula (1), L 101 is -P(=O)(R L101 )-, -P(=S)(R L102 )-, -Si(R L103 )(R L104 )-, -B(R L105 )-, -S(=O) 2 - or -S(=O)-, R L101 to R L105 each independently represent a hydrogen atom or a substituent, and R L103 and R L104 are bonded. may form a ring,
X 101 to X 103 each independently represent a nitrogen atom or -CR X101 -, R X101 represents a hydrogen atom or a substituent,
L 102 and L 103 each independently represent a sulfur atom or -X 104 =X 105 -, X 104 and X 105 each independently represent a nitrogen atom or -CR X102 -, and R , represents a hydrogen atom or a substituent,
Ar 101 and Ar 102 each independently represent -(CR Ar101 = CR Ar102 ) n101 -, an arylene group, a heterocyclic group, or a group combining two or more of these groups, and R Ar101 and R Ar102 each represent independently represents a hydrogen atom or a substituent, n101 represents an integer of 1 to 3,
Y 101 and Y 102 each independently represent -OR Y101 , -NR Y102 RY103 or -SR Y104, and R Y101 to R Y104 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl represents a group, an aryl group or a heteroaryl group, and R Y102 and R Y103 may be bonded via a single bond or a divalent linking group to form a ring,
Ar 101 and X 101 may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar 101 and Y 101 may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar 102 and X 102 may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Ar 102 and Y 102 may be bonded via a single bond or a divalent linking group to form a 5-membered ring or a 6-membered ring,
Z 1 represents a counter ion,
p1 represents an integer from 0 to 5,
q1 represents an integer from 1 to 5.
In the formula (1), X 103 is -CR X101 -, R X101 is a hydrogen atom or a substituent,
The resin composition according to claim 1, wherein L 102 and L 103 are each a sulfur atom.
In the formula (1), X 103 is -CR X101 -, R X101 is a hydrogen atom or a substituent,
L 102 and L 103 are each a sulfur atom,
The resin composition according to claim 1, wherein L 101 is -P(=O)(R L101 )-, and R L101 is a hydrogen atom or a substituent.
In the formula (1), X 103 is -CR X101 -, R X101 is a hydrogen atom or a substituent,
L 102 and L 103 are each a sulfur atom,
L 101 is -P(=O)(R L101 )-, R L101 is a hydrogen atom or a substituent,
Y 101 and Y 102 are each independently -NR Y102 R Y103 , and R Y102 and R Y103 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. The resin composition according to claim 1, wherein R Y102 and R Y103 may be bonded via a single bond or a divalent linking group to form a ring.
In the formula (1), X 103 is -CR X101 -, R X101 is a hydrogen atom or a substituent,
L 102 and L 103 are each a sulfur atom,
L 101 is -Si(R L103 )(R L104 )- or -S(=O)-, and R L103 and R L104 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, is an aryl group or a heteroaryl group,
Y 101 and Y 102 are each independently -NR Y102 R Y103 , and R Y102 and R Y103 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. The resin composition according to claim 1, wherein R Y102 and R Y103 may be bonded via a single bond or a divalent linking group to form a ring.
The resin composition according to any one of claims 1 to 5, further comprising an infrared absorbing agent other than the infrared absorbing dye A.
The resin composition according to claim 6, wherein the maximum absorption wavelength of the infrared absorbing agent other than the infrared absorbing dye A is on the shorter wavelength side than the maximum absorption wavelength of the infrared absorbing dye A.
The resin composition according to any one of claims 1 to 5, wherein the maximum absorption wavelength of the infrared absorbing dye A is in a wavelength range of 700 to 1800 nm.
The resin composition according to any one of claims 1 to 5, further comprising a polymerizable compound and a photopolymerization initiator.
A film obtained using the resin composition according to any one of claims 1 to 5.
An optical filter comprising the film according to claim 10.
A solid-state imaging device comprising the film according to claim 10.
An image display device comprising the film according to claim 10.
An infrared sensor comprising the film according to claim 10.
A camera module comprising the membrane according to claim 10.
A compound represented by formula (4);
In the formula, Ar 401 represents an aryl group or a heteroaryl group,
R 401 to R 404 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group,
R 405 and R 406 each independently represent an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group or a cyano group,
R 407 and R 408 each independently represent an alkyl group or an aryl group,
n401 and n402 each independently represent an integer from 0 to 4,
q4 represents 1 or 2,
Z 4 represents a q4-valent counteranion.
A compound represented by formula (5);
In the formula, Ar 501 represents an aryl group or a heteroaryl group,
R 501 to R 504 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group,
R 505 and R 506 each independently represent an alkyl group, an aryl group, a heteroaryl group, an aryloxy group, a heteroaryloxy group, an alkoxy group or a cyano group,
n 501 and n 502 each independently represent an integer from 0 to 4,
q5 represents 1 or 2,
Z 5 represents a q5-valent counteranion.