JP7113907B2 - Composition, film, optical filter, solid-state imaging device, infrared sensor, method for manufacturing optical filter, camera module, compound, and dispersion composition - Google Patents

Description

TECHNICAL FIELD The present disclosure relates to compositions, films, optical filters, solid-state imaging devices, infrared sensors, optical filter manufacturing methods, camera modules, compounds, and dispersion compositions.

2. Description of the Related Art CCDs (charge-coupled devices) and CMOSs (complementary metal-oxide semiconductors), which are solid-state imaging devices for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. These solid-state imaging devices use silicon photodiodes that are sensitive to infrared rays in their light receiving portions. For this reason, an infrared cut filter is sometimes used to correct visibility.

Further, as conventional boron compounds, those described in Patent Documents 1 to 3 are known.

Patent Document 1 describes a salt of an anion represented by formula (1) and an onium cation derived from a dye capable of forming a salt with the anion.

（式（１）中、Ｚ^１及びＺ^２は、それぞれ独立に、１価のプロトン供与性置換基からプロトンを放出してなる置換基を２個有する基を表す。）

(In formula (1), Z ¹ and Z ² each independently represent a group having two substituents formed by releasing protons from a monovalent proton-donating substituent.)

Further, Patent Document 2 describes a toner composition containing a 5,5′-spirobi(5H-dibenzoborol) salt of a specific structure.

Furthermore, Patent Document 3 describes a boron compound with a specific structure that exhibits aggregation-induced luminescence (AIE).

JP 2014-37530 A U.S. Pat. No. 4,898,802 WO2017/080357

Conventionally, infrared cut filters have been used as flat films. In recent years, pattern formation of an infrared cut filter has been studied. For example, it is being considered to form and use each pixel of a color filter (for example, red pixel, blue pixel, green pixel, etc.) on an infrared cut filter.

However, the inventors of the present invention have found through investigation that infrared absorbing dyes used in infrared cut filters and the like do not have sufficient durability, particularly light resistance.

A problem to be solved by one embodiment of the present invention is to provide a composition having excellent light resistance.

Another object of the present invention is to provide a film, an optical filter, a solid-state imaging device, an infrared sensor, a method for producing an optical filter, and a camera module using the above composition. be.

A further problem to be solved by another embodiment of the present invention is to provide novel compounds.

Furthermore, the problem to be solved by another embodiment of the present invention is to provide a dispersion composition having excellent light resistance.

Means for solving the above problems include the following aspects.

<1> A composition comprising a compound having a structure represented by the following formula (1) and at least one compound selected from the group consisting of a binder and a curable compound.

In formula (1), X each independently represents a single bond or a linking group, Z ¹ and Z ² each independently represent a group forming an aliphatic ring or an aromatic ring, and from R ⁹ and R ¹⁰ A group having a dye structure is bonded or coordinated in at least one selected from the group consisting of R ⁹ or R ¹⁰ in which the group having a dye structure is not bonded or coordinated represents a substituent, R ⁹ and R ¹⁰ may combine with each other to form a ring with the boron atom.

<2> each X in formula (1) above is independently a single bond, -O-, -S-, -CH ₂ -, -N=, -CH=CH-, or -NR ¹¹ -; The composition according to <1>, wherein R ¹¹ represents a hydrogen atom, an alkyl group or an aryl group.

<3> The composition according to <1> or <2>, wherein the compound having the structure represented by formula (1) above is a compound represented by formula (2) below.

In formula (2), X represents a single bond or a linking group, R ¹ to R ⁸ each independently represent a hydrogen atom or a substituent, and at least one selected from the group consisting of R ⁹ and R ¹⁰ R ⁹ or R ¹⁰ to which a group having a dye structure is bonded or coordinated, and to which the group having a dye structure is not bonded or coordinated represents a substituent, and R ⁹ and R ¹⁰ are bonded to each other. may form a ring with the boron atom.

<4> X in the above formula (2) is a single bond, —O—, —S—, —CH ₂ —, —CH═CH—, or —NR ¹¹ —, R ¹¹ is a hydrogen atom, The composition according to <3>, which represents an alkyl group or an aryl group.

<5> The composition according to any one of <1> to <4>, wherein the compound having the structure represented by formula (1) has a maximum absorption wavelength of 650 nm to 1,500 nm.

<6> The dye structure in the group having the dye structure is a pyrrolopyrrole dye structure, a pyrromethene dye structure, a squarylium dye structure, a croconium dye structure, an indigo dye structure, an anthraquinone dye structure, a diimmonium dye structure, a phthalocyanine dye structure, and a naphthalocyanine dye. any one of <1> to <5>, which is at least one dye structure selected from the group consisting of a structure, a polymethine dye structure, a xanthene dye structure, a quinacridone dye structure, an azo dye structure, and a quinoline dye structure The described composition.

<7> The composition according to any one of <1> to <6>, which contains the curable compound and further contains a photopolymerization initiator.

<8> The composition according to any one of <1> to <7>, wherein the binder comprises a binder polymer.

<9> A film comprising the composition according to any one of <1> to <8> or formed by curing the composition.

<10> An optical filter having the film according to <9>.

<11> The optical filter according to <10>, which is an infrared cut filter or an infrared transmission filter.

<12> A solid-state imaging device having the film according to <9>.

<13> An infrared sensor comprising the film according to <9>.

<14> Applying the composition according to any one of <1> to <8> onto a support to form a composition layer; and patternwise exposing the composition layer; and a step of developing and removing the unexposed portion after the step of exposing to form a pattern.

<15> A step of applying the composition according to any one of <1> to <8> onto a support to form a composition layer, and curing the composition layer to form a cured layer. forming a photoresist layer on the cured layer; patterning the photoresist layer by exposing and developing to obtain a resist pattern; and drying the cured layer using the resist pattern as an etching mask. and etching.

<16> A camera module comprising a solid-state imaging device and the optical filter according to <10> or <11>.

<17> A compound represented by the following formula (P1).

In formula (P1), X ^P1 to X ^P6 each independently represent a single bond, -O-, -S-, -CH ₂ -, -N=, -CH=CH- or -NR ^P11 -, R ^P1 and R ^P2 each independently represent an alkyl group, an aryl group, a heteroaryl group, or a group represented by the following formula (P2), and R ^P3 to R ^P6 each independently represent a cyano group, an acyl group, an alkoxy represents a carbonyl group, an alkyl group, an arylsulfinyl group or a heteroaryl group, R ^P7 to R ^P10 each independently represents a hydrogen atom or a substituent, R ^P11 represents a hydrogen atom, an alkyl group or an aryl group, p1 to p4 each independently represents an integer of 0 to 4;

In formula (P2), X ^P11 represents a m-phenylene group, a p-phenylene group, a divalent condensed polycyclic aromatic ring group or a divalent heteroaromatic ring group in which two or more aromatic rings are condensed, and L ^P11 is represents a single bond or a divalent linking group, Y ^P11 represents a substituent, and * represents a linking site to the pyrrolopyrrole ring in formula (P1).

<18> A dispersion composition comprising a compound having a structure represented by the following formula (1) and at least one compound selected from the group consisting of solvents, binders and curable compounds.

In formula (1), X each independently represents a single bond or a linking group, Z ¹ and Z ² each independently represent a group forming an aliphatic ring or an aromatic ring, and from R ⁹ and R ¹⁰ A group having a dye structure is bonded or coordinated in at least one selected from the group consisting of R ⁹ or R ¹⁰ in which the group having a dye structure is not bonded or coordinated represents a substituent, R ⁹ and R ¹⁰ may combine with each other to form a ring with the boron atom.

According to one embodiment of the present invention, a composition having excellent light resistance can be provided.

Further, according to another embodiment of the present invention, it is possible to provide a film, an optical filter, a solid-state imaging device, an infrared sensor, a method for manufacturing an optical filter, and a camera module using the above composition.

Furthermore, according to other embodiments of the present invention, novel compounds can be provided.

Furthermore, according to another embodiment of the present invention, it is possible to provide a dispersion composition having excellent light resistance.

1 is a schematic diagram of an embodiment of an infrared sensor according to the present disclosure; FIG.

The content of the present disclosure will be described in detail below.

As used herein, "total solid content" refers to the total mass of components excluding the solvent from the total composition of the composition. Moreover, as described above, the “solid content” is the component excluding the solvent, and may be solid or liquid at 25° C., for example.

In the description of a group (atomic group) in the present specification, a description that does not indicate substitution or unsubstituted includes not only those having no substituents but also those having substituents. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In 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. Light used for exposure generally includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.

As used herein, the term "to" is used to include the numerical values before and after it as lower and upper limits.

In the present specification, "(meth)acrylate" represents both or either acrylate and methacrylate, "(meth)acryl" represents both or either acrylic and methacrylic, and "(meth) ) acryloyl” refers to either or both acryloyl and methacryloyl.

In the present specification, Me in the chemical formulas is a methyl group, Et is an ethyl group, Pr is a propyl group, Bu is a butyl group, Ac is an acetyl group, Bn is a benzyl group, and Ph is a phenyl group. show.

As used herein, the term "process" includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .

Further, in the present disclosure, "% by mass" and "% by weight" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

Furthermore, in the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.

Also, the transmittance in the present disclosure is the transmittance at 25° C. unless otherwise specified.

As used herein, the weight average molecular weight and number average molecular weight are defined as polystyrene equivalent values measured by gel permeation chromatography (GPC).

<Composition>

The composition according to the present disclosure includes a compound having a structure represented by formula (1) below and at least one compound selected from the group consisting of binders and curable compounds.

In formula (1), X each independently represents a single bond or a linking group, Z ¹ and Z ² each independently represent a group forming an aliphatic ring or an aromatic ring, and from R ⁹ and R ¹⁰ A group having a dye structure is bonded or coordinated in at least one selected from the group consisting of R ⁹ or R ¹⁰ in which the group having a dye structure is not bonded or coordinated represents a substituent, Also, R ⁹ and R ¹⁰ may combine with each other to form a ring together with the boron atom.

The composition according to this embodiment can be suitably used as a pattern-forming composition.

The pattern-forming composition may be either a negative pattern-forming composition or a positive pattern-forming composition. preferably an object.

Moreover, the composition according to the present embodiment can be suitably used as an infrared absorbing composition.

As described above, infrared absorbing dyes used in infrared cut filters and the like do not have sufficient light resistance, and are decomposed by light to reduce the infrared absorbing ability, and are obtained from compositions containing infrared absorbing dyes. Many of the cured films were insufficient in durability, particularly light resistance.

As a result of intensive studies by the present inventors, it was found that a composition having excellent light resistance can be provided by adopting the above configuration.

Although the action mechanism of this excellent effect is not clear, it is presumed as follows.

The compound having the structure represented by the formula (1) includes a boron complex having a dye structure, and the compound has a ring structure having a boron atom as a ring member, so that the dye structure associates, particularly J-associates. It is presumed that it becomes easier to wear and the light resistance improves.

Each component of the composition according to the present disclosure will be described below.

(Compound having a structure represented by formula (1))

A composition according to the present disclosure includes a compound having a structure represented by formula (1) above.

The compound having the structure represented by the above formula (1) may have only one structure represented by the above formula (1), or may have two or more structures. , From the viewpoint of heat resistance, it preferably has 1 to 4 structures represented by the above formula (1), more preferably 1 to 3, and 1 or 2 It is particularly preferred to have

Further, when there are two or more structures represented by the above formula (1), at least one selected from the group consisting of R ⁹ and R ¹⁰ in the two structures represented by the above formula (1) is bonded or The dye structure in the group having a dye structure by coordination may be the same dye structure or different dye structure, but from the viewpoint of light resistance and heat resistance, it is preferable that the dye structure is the same. preferable.

The molecular weight of the compound having the structure represented by the formula (1) is preferably 2,500 or less, more preferably 300 or more and 2,500 or less, and 400 or more and 2,000 or less. More preferably, it is particularly preferably 500 or more and 2,000 or less.

The compound having the structure represented by formula (1) above is preferably an infrared absorbing dye. The infrared absorbing dye means a material having absorption at least in the infrared region.

The compound having the structure represented by the above formula (1) preferably has a wavelength in the range of 650 nm to 1,500 nm, more preferably in the wavelength range of 680 nm to 1,300 nm, and has a wavelength of 700 nm to 1,100 nm. It is more preferable to have a maximum absorption wavelength in the range of .

The compound having the structure represented by the above formula (1) may be a pigment or a dye, but from the viewpoint of light resistance and heat resistance, it is preferably a pigment. Pigments are more preferred.

The dye structure in the group having a dye structure bonded or coordinated to at least one selected from the group consisting of R ⁹ and R ¹⁰ in the compound having the structure represented by the above formula (1) is lightfast, and , from the viewpoint of heat resistance, pyrrolopyrrole dye structure, pyrromethene dye structure, squarylium dye structure, croconium dye structure, indigo dye structure, anthraquinone dye structure, diimmonium dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, polymethine dye structure, xanthene It is preferably at least one dye structure selected from the group consisting of a dye structure, a quinacridone dye structure, an azo dye structure, and a quinoline dye structure, a pyrrolopyrrole dye structure, a pyrromethene dye structure, a squarylium dye structure, and an indigo dye structure. , and at least one dye structure selected from the group consisting of anthraquinone dye structures, and at least one dye structure selected from the group consisting of a pyrrolopyrrole dye structure, a pyrromethene dye structure, a squarylium dye structure, and an indigo dye structure. One type of dye structure is more preferred, and a pyrrolopyrrole dye structure is particularly preferred.

In addition, the portion other than the dye structure in the group having the dye structure is not particularly limited as long as it has an arbitrary structure, but structures such as those described in the specific examples described later are preferable.

The substituent of R ⁹ or R ¹⁰ to which the dye structure-containing group is not bonded or coordinated is preferably an alkyl group or an aryl group, more preferably an aryl group.

Further, when R ⁹ or R ¹⁰ is a substituent and the boron atom in the structure represented by the above formula (1) becomes a boron anion, it may have a counter cation. The counter cation is not particularly limited as long as it is a known cation.

The boron atom in the compound having the structure represented by the above formula (1) preferably has at least a coordinate bond from the viewpoint of light resistance and heat resistance, and has three covalent bonds and one coordinate bond. It is more preferable to have

In addition, from the viewpoint of light resistance and heat resistance, one of R ⁹ and R ¹⁰ in the compound having the structure represented by the above formula (1) is bonded to the dye structure by a covalent bond, and the other is coordinated. one is preferably a covalent bond with the dye structure, the other is more preferably a coordinate bond with a heteroatom, one is a covalent bond with the dye structure, The other is particularly preferably a coordinate bond with a nitrogen atom.

Moreover, the coordinate bond does not always need to be coordinated, and the coordinate bond may be temporarily lost due to thermal rotational or vibrational motion of the molecule.

The linking group for X in formula (1) is preferably an oxygen atom (O), a sulfur atom (S), an alkylene group, a nitrogen atom (N or NR ¹¹ ), an alkenylene group, and the like. R ¹¹ represents a hydrogen atom, an alkyl group or an aryl group.

The number of carbon atoms (number of carbon atoms) of the linking group in X in formula (1) is not particularly limited, but preferably has 0 to 8 carbon atoms, more preferably 0 to 2 carbon atoms, and 0 is more preferred.

Each X in formula (1) is independently a single bond, -O-, -S-, -CH ₂ -, -N=, -CH=CH-, or, from the viewpoint of light resistance and heat resistance, -NR ¹¹ - is preferred, and a single bond, -O-, -S-, -CH=CH- or -NR ¹¹ - is more preferred.

Further, in formula (1), the two Xs bonded to the boron atom are more preferably single bonds or -O- from the viewpoint of light resistance and heat resistance, and are single bonds. is particularly preferred.

Furthermore, in formula (1), X not bonded to a boron atom is particularly preferably a single bond, —O—, or —S— from the viewpoint of light resistance and heat resistance.

Moreover, the boron atom in the formula (1) is preferably a 5- or 6-membered ring member from the viewpoint of light resistance and heat resistance.

Z ¹ and Z ² in formula (1) are each independently preferably a group forming an aromatic ring, more preferably a group forming a benzene ring (=CH-CH=CH-CH=). preferable.

Moreover, Z ¹ and Z ² may have a substituent on the formed aliphatic ring or aromatic ring, but preferably have no substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, and a halogen atom.

Furthermore, Z ¹ and Z ² are preferably the same group from the viewpoint of light resistance and heat resistance.

In addition, the compound having the structure represented by the above formula (1) is preferably a compound having the structure represented by the following formula (2) from the viewpoint of light resistance and heat resistance.

In formula (2), X represents a single bond or a linking group, R ¹ to R ⁸ each independently represent a hydrogen atom or a substituent, and at least one selected from the group consisting of R ⁹ and R ¹⁰ R ⁹ or R ¹⁰ to which a group having a dye structure is bonded or coordinated and to which the group having a dye structure is not bonded or coordinated represents a substituent, and R ⁹ and R ¹⁰ are mutually It may be combined to form a ring with the boron atom.

R ⁹ and R ¹⁰ in formula (2) have the same meanings as R ⁹ and R ¹⁰ in formula (1) above, and preferred embodiments are also the same.

X in formula (2) is a single bond, —O—, —S—, —CH ₂ —, —CH═CH—, or —NR ¹¹ — from the viewpoint of light resistance and heat resistance. is preferred, a single bond, -O- or -S- is more preferred, and a single bond is particularly preferred. R ¹¹ represents a hydrogen atom, an alkyl group or an aryl group.

R ¹ to R ⁸ in formula (2) are each independently preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group, more preferably a hydrogen atom or an alkyl group, and a hydrogen atom It is particularly preferred to have

Furthermore, the compound having the structure represented by the formula (1) is particularly preferably a compound represented by the following formula (P1) from the viewpoint of light resistance and heat resistance.

In formula (P1), X ^P1 to X ^P6 each independently represent a single bond, -O-, -S-, -CH ₂ -, -N=, -CH=CH- or -NR ^P11 -, R ^P1 and R ^P2 each independently represent an alkyl group, an aryl group, a heteroaryl group, or a group represented by the following formula (P2), and R ^P3 to R ^P6 each independently represent a cyano group, an acyl group, an alkoxy represents a carbonyl group, an alkyl group, an arylsulfinyl group or a heteroaryl group, R ^P7 to R ^P10 each independently represents a hydrogen atom or a substituent, R ^P11 represents a hydrogen atom, an alkyl group or an aryl group, p1 to p4 each independently represents an integer of 0 to 4;

In formula (P2), X ^P11 represents a m-phenylene group, a p-phenylene group, a divalent condensed polycyclic aromatic ring group or a divalent heteroaromatic ring group in which two or more aromatic rings are condensed, and L ^P11 is represents a single bond or a divalent linking group, Y ^P11 represents a substituent, and * represents a linking site to the pyrrolopyrrole ring in formula (P1).

X ^P1 , X ^P2 , X ^P4 and X ^P5 in formula (P1) are each independently a single bond or -O-, preferably a single bond, from the viewpoint of light resistance and heat resistance. is particularly preferred.

Moreover, X ^P1 , X ^P2 , X ^P4 and X ^P5 in formula (P1) are preferably the same group.

X ^P3 and X ^P6 in formula (P1) are each independently preferably a single bond, —O—, or —S— from the viewpoint of light resistance and heat resistance.

Also, X ^P3 and X ^P6 in formula (P1) are preferably the same group.

R ^P1 and R ^P2 in formula (P1) are each independently preferably an aryl group, a heteroaryl group, or a group represented by the above formula (P2), particularly an aryl group or a group represented by the above formula (P2) preferable.

In addition, the alkyl group, aryl group and heteroaryl group represented by R ^P1 and R ^P2 may have a substituent or may be unsubstituted. Substituents include alkoxy groups, hydroxy groups, halogen atoms, cyano groups, nitro groups, -OCOR ^11p , -SOR ^12p , -SO ₂ R ^13p and the like. R ^11p to R ^13p each independently represent a hydrocarbon group or a heteroaryl group. Further, examples of substituents include substituents described in paragraphs 0020 to 0022 of JP-A-2009-263614. Among them, preferred substituents are an alkoxy group, a hydroxy group, a cyano group, a nitro group, -OCOR ^11p , -SOR ^12p and -SO ₂ R ^13p .

Furthermore, the aryl group in R ^P1 and R ^P2 is an aryl group having an alkoxy group having a branched alkyl group as a substituent, an aryl group having a hydroxy group as a substituent, or a group represented by —OCOR ^11p as a substituent. It is preferably an aryl group having as. The branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms.

From the viewpoint of dispersibility, X ^P11 in formula (P2) is preferably an m-phenylene group, a p-phenylene group, a naphthylene group, a furandyl group, or a thiophenediyl group. A phenylene group or a naphthylene group is more preferred, an m-phenylene group or a p-phenylene group is even more preferred, and a p-phenylene group is particularly preferred.

From the viewpoint of dispersibility, L ^P11 in formula (P2) is preferably a divalent linking group.

From the viewpoint of dispersibility, the carbon number of the divalent linking group in L ^P11 is preferably 1 or more and 30 or less, more preferably 1 or more and 20 or less, and even more preferably 1 or more and 10 or less. .

From the viewpoint of dispersibility, the divalent linking group in L ^P11 is preferably an alkylene group, an ester bond, an ether bond, or an arylene group.

Furthermore, the divalent linking group in L ^P11 is preferably a group having an oxygen atom from the viewpoint of dispersibility, and is a group having at least one structure selected from the group consisting of an ester bond and an ether bond. is more preferred, and a group having an ester bond is even more preferred.

From the viewpoint of dispersibility, Y ^P11 in formula (P2) has an imide structure, an acid anhydride structure, a cyano group, an alkylsulfone group, an arylsulfone group, an alkylsulfoxide group, an arylsulfoxide group, a sulfonamide group, an amide group, a urethane group, a urea group, and a group having at least one structure selected from the group consisting of a hydroxy group. group, arylsulfoxide group, sulfonamide group, amide group, urethane group, and a group having at least one structure selected from the group consisting of urea group, N-substituted imide structure, acid anhydride having at least one structure selected from the group consisting of a cyano group, an alkylsulfone group, an arylsulfone group, an alkylsulfoxide group, an arylsulfoxide group, an N-disubstituted sulfonamide group, and an N-disubstituted amide group is more preferably a group, and a group having at least one structure selected from the group consisting of an N-substituted imide structure, an N-disubstituted sulfonamide group, and an N-disubstituted amide group is particularly preferred. , is most preferably a group having an N-substituted imide structure.

Moreover, ^YP11 preferably does not have an acidic group, a basic group, or a group having a salt structure, which will be described later with respect to the dye derivative.

From the viewpoint of dispersibility, Y ^P11 is preferably a group represented by any one of the following formulas Y-1 to Y-14, and any one of the following formulas Y-1 to Y-8. more preferably a group represented by the following formula Y-1 to Y-3, more preferably a group represented by any one of the following formula Y-1 or formula Y-2 is particularly preferred, and a group represented by formula Y-1 below is most preferred.

In formulas Y-1 to Y-14, R ^Y each independently represents a hydrogen atom, an alkyl group or an aryl group, and when two or more R ^Y are present in one formula, two R ^Y are alkylene groups. Alternatively, an alkylene group —O-alkylene group may form a ring, and * represents a linking site with L ^P11 in formula (P2).

From the viewpoint of dispersibility, R ^Y is preferably an alkyl group or an aryl group, more preferably an alkyl group, even more preferably an alkyl group having 1 to 8 carbon atoms, and a methyl group. is particularly preferred.

R ^P3 to R ^P6 in formula (P1) are each independently preferably a cyano group or a heteroaryl group from the viewpoint of infrared absorption.

From the viewpoint of infrared absorption, two of R ^P3 to R ^P6 are preferably cyano groups, and R ^P5 and R ^P6 are more preferably cyano groups.

From the viewpoint of infrared absorption, two of R ^P3 to R ^P6 are preferably heteroaryl groups, and R ^P3 and R ^P4 are more preferably heteroaryl groups.

The heteroaryl groups in R ^P3 to R ^P6 preferably have at least a nitrogen atom from the viewpoint of infrared absorption.

Further, the heteroaryl group for R ^P3 to R ^P6 is preferably a heteroaryl group in which a benzene ring or a naphthalene ring is condensed to a heteroaryl ring, from the viewpoint of infrared absorption, and a benzene ring is condensed to the heteroaryl ring. is more preferably a heteroaryl group having a benzoxazole ring structure, a benzothiazole ring structure, or a heteroaryl group having a quinoxaline ring structure, and a 2-quinoxalyl group or 6,7-dichloro A -2-quinoxalyl group is particularly preferred.

Furthermore, the heteroaryl ring in the heteroaryl group in R ^P3 to R ^P6 is preferably a 5- or 6-membered ring, and may be an oxazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring, or a pyrazine ring. More preferably, it is an oxazole ring, a thiazole ring, or a pyrazine ring.

Preferred heteroaryl groups for R ^P3 to R ^P6 include the groups shown below. Note that * represents a bonding site with a carbon-carbon double bond in formula (1).

R ^P7 to R ^P10 in formula (P1) are each independently preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group, and more preferably a hydrogen atom or an alkyl group. It is particularly preferred to have

p1 to p4 in formula (P1) are each independently preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Specific examples of the compound having the structure represented by formula (1) above preferably include the compounds used in the examples described later.

When the compound having the structure represented by the formula (1) is a pigment, preferably an infrared absorbing pigment, the compound having the structure represented by the formula (1) is particulate from the viewpoint of dispersibility. is preferred.

Further, when the compound having the structure represented by the above formula (1) is a pigment, preferably an infrared absorbing pigment, the volume average particle diameter of the compound having the structure represented by the above formula (1) is dispersible. From the viewpoint, it is preferably 1 nm or more and 500 nm or less, more preferably 1 nm or more and 100 nm or less, and even more preferably 1 nm or more and 50 nm or less.

The volume average particle size of the compound having the structure represented by formula (1) is measured using MICROTRAC UPA 150 manufactured by Nikkiso Co., Ltd.

In addition, the composition according to the present disclosure may contain one compound having a structure represented by formula (1) above, or may contain two or more compounds.

The content of the compound having the structure represented by the above formula (1) is preferably 1% by mass to 90% by mass with respect to the total solid content of the composition from the viewpoint of infrared absorption and dispersibility. . The lower limit is more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is more preferably 80% by mass or less, and even more preferably 70% by mass or less.

(binder)

The composition according to the present disclosure contains at least one compound selected from the group consisting of a binder and a curable compound, and preferably contains a binder from the viewpoint of film-forming properties.

Moreover, the binder is preferably a binder polymer from the viewpoint of film formability and dispersibility.

Moreover, a dispersant may be included as a binder polymer.

Specific examples of binder polymers include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, and polyarylene ether phosphine oxide resins. , polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, siloxane resins, and urethane resins.

One of these resins may be used alone, or two or more thereof may be mixed and used.

As the cyclic olefin resin, norbornene resin can be preferably used from the viewpoint of improving heat resistance.

Commercially available norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (for example, ARTON F4520). Commercially available polyimide resins include the Neoprim (registered trademark) series (for example, C3450) manufactured by Mitsubishi Gas Chemical Co., Inc., and the like.

Examples of epoxy resins include epoxy resins that are glycidyl etherified compounds of phenolic compounds, epoxy resins that are glycidyl etherified compounds of various novolac resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester-based Epoxy resins, glycidylamine-based epoxy resins, epoxy resins obtained by glycidylating halogenated phenols, condensation products of silicon compounds with epoxy groups and other silicon compounds, polymerizable unsaturated compounds with epoxy groups and other Examples include copolymers with other polymerizable unsaturated compounds.

In addition, as epoxy resins, Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (Japanese Oil Co., Ltd., epoxy group-containing polymer) and the like can also be used. As the urethane resin, 8UH-1006 and 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.) can also be used.

Further, as the binder polymer, resins described in Examples of International Publication No. 2016/088645, resins described in JP-A-2017-57265, resins described in JP-A-2017-32685, in particular Resins described in JP-A-2017-075248 and resins described in JP-A-2017-66240 can also be used, the contents of which are incorporated herein.

A resin having a fluorene skeleton can also be preferably used as the binder polymer. Regarding the resin having a fluorene skeleton, the description of US Patent Application Publication No. 2017/0102610 can be referred to, the content of which is incorporated herein.

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

The content of the binder polymer is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 60% by mass, based on the total solid content of the composition. The composition may contain only one kind of resin, or may contain two or more kinds of resins. When two or more types are included, the total amount is preferably within the above range.

- Dispersant -

Compositions according to the present disclosure may include a dispersant.

Dispersants include polymeric dispersants [e.g., resins having an amine group (polyamideamine and salts thereof), oligoimine resins, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formalin condensate] and the like.

Polymeric dispersants can be further classified into straight-chain polymers, terminal-modified polymers, graft-type polymers, and block-type polymers according to their structures.

As the polymer dispersant, a resin having an acid value of 60 mgKOH/g or more (more preferably, an acid value of 60 mgKOH/g or more and 300 mgKOH/g or less) can be suitably used.

Examples of terminal-modified polymers include polymers having a phosphate group at the end described in JP-A-3-112992, JP-A-2003-533455, etc., and JP-A-2002-273191, etc. Polymers having terminal sulfonic acid groups, and polymers having a partial skeleton of organic dyes and heterocycles described in JP-A-9-77994 and the like can be mentioned. Further, a polymer described in JP-A-2007-277514 in which two or more anchor moieties (acid group, basic group, partial skeleton of an organic dye, heterocyclic ring, etc.) to the surface of a pigment is introduced into the polymer terminal. It is preferable because it has excellent dispersion stability.

As the graft type polymer, for example, reaction products of poly(lower alkyleneimine) and polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, etc. , A reaction product of polyallylamine and polyester described in JP-A-9-169821, etc., a macromonomer described in JP-A-10-339949, JP-A-2004-37986, etc., and a copolymerization of a nitrogen atom monomer. Coalescence, JP-A-2003-238837, JP-A-2008-9426, graft-type polymer having a partial skeleton or heterocycle of an organic dye described in JP-A-2008-81732, JP-A-2010-106268 Examples thereof include copolymers of macromonomers and acid group-containing monomers described in publications and the like.

Known macromonomers can be used as the macromonomer used in producing the graft-type polymer by radical polymerization. acid methyl), AS-6 (polystyrene whose terminal group is a methacryloyl group), AN-6S (copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (polystyrene whose terminal group is a methacryloyl group Butyl acrylate), Plaxel FM5 (2-hydroxyethyl methacrylate with 5 molar equivalents of ε-caprolactone added by Daicel Chemical Industries, Ltd.), FA10L (2-hydroxyethyl acrylate with 10 molar equivalents of ε-caprolactone added) ), and polyester macromonomers described in JP-A-2-272009. Among these, polyester-based macromonomers, which are excellent in flexibility and solvent affinity, are particularly preferable from the viewpoint of the dispersibility and dispersion stability of pigment dispersions and the developability of compositions using pigment dispersions. Polyester macromonomers represented by the polyester macromonomers described in JP-A No. 2-272009 are most preferred.

As the block-type polymer, block-type polymers described in JP-A-2003-49110, JP-A-2009-52010, etc. are preferable.

The resin (dispersant) is also available as a commercial product. group-containing copolymer), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”, manufactured by EFKA “EFKA4047, 4050-4165 (polyurethane system), EFKA4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate) , 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)”, Ajinomoto Fine-Techno Co., Ltd. “Ajisper PB821, PB822, PB880, PB881”, Kyoeisha Chemical Co., Ltd. “Floren TG-710” (urethane oligomer)”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, Kusumoto Kasei Co., Ltd. “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid) , #7004 (polyether ester), DA-703-50, DA-705, DA-725”, manufactured by Kao Corporation “Demoll RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN- B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymeric polycarboxylic acid)”, “Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)”, “acetamine 86 ( Stearylamine Acetate)”, Nippon Lubrizol Co., Ltd. “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer with a functional part at the end) , 24000, 28000, 32000, 38500 (graft type polymer)”, Nikko Chemicals Co., Ltd. “Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)”, Kawaken Fine Chemical Co., Ltd. "Hinoact T-8000E", Shin-Etsu Chemical Co., Ltd. "Organosiloxane Polymer KP341", Morishita Sangyo Co., Ltd. " EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450”, manufactured by San Nopco Co., Ltd. “Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100”, manufactured by ADEKA Co., Ltd. “ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P- 123”, and “Ionet S-20” manufactured by Sanyo Chemical Industries, Ltd., and the like.

These resins may be used alone or in combination of two or more. Also, an alkali-soluble resin, which will be described later, can be used as a dispersant. Alkali-soluble resins include (meth)acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and carboxylic acid side chains. and resins obtained by modifying acid anhydrides to polymers having hydroxyl groups, and (meth)acrylic acid copolymers are particularly preferred. In addition, N-substituted maleimide monomer copolymers described in JP-A-10-300922, ether dimer copolymers described in JP-A-2004-300204, polymerizable groups described in JP-A-7-319161 Alkali-soluble resins containing are also preferred.

Among these, from the viewpoint of dispersibility, the resin preferably contains a resin having a polyester chain, and more preferably contains a resin having a polycaprolactone chain. The polyester chain interacts with R ¹ and R ² of the compound represented by formula (1), resulting in better dispersibility.

Moreover, the resin (preferably acrylic resin) preferably has a constitutional unit having an ethylenically unsaturated group from the viewpoint of dispersibility, transparency, and suppression of film defects caused by foreign substances.

Although the ethylenically unsaturated group is not particularly limited, it is preferably a (meth)acryloyl group.

Further, when the resin has an ethylenically unsaturated group, particularly a (meth)acryloyl group, in a side chain, the resin has a divalent linkage having an alicyclic structure between the main chain and the ethylenically unsaturated group. It is preferable to have a group.

The content of the dispersant is the compound represented by the formula (1), and when the compound represented by the formula (1) contains a pigment, dye, or pigment derivative other than the compound represented by the formula (1), the compound represented by the formula (1) , And, with respect to 100 parts by mass of the total content of pigments, dyes and pigment derivatives other than the compound represented by formula (1), it is preferably 1 part by mass to 100 parts by mass, and 5 parts by mass to 90 parts by mass. parts is more preferable, and 10 to 80 parts by mass is even more preferable.

- Alkali-soluble resin -

From the viewpoint of developability, the composition according to the present disclosure preferably contains an alkali-soluble resin as a binder polymer.

The alkali-soluble resin is a linear organic high-molecular-weight polymer that promotes alkali-solubility in at least one molecule (preferably, a molecule having an acrylic copolymer or a styrene-based copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having groups. From the viewpoint of heat resistance, polyhydroxystyrene-based resins, polysiloxane-based resins, acrylic resins, acrylamide-based resins, and acrylic/acrylamide copolymer resins are preferable. From the viewpoint of developing control, acrylic-based resins and acrylamide-based resins are preferred. , acrylic/acrylamide copolymer resins are preferred.

Groups that promote alkali solubility (hereinafter also referred to as acid groups) include, for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Any possible one is preferred, and (meth)acrylic acid is particularly preferred. Only one kind of these acid groups may be used, or two or more kinds thereof may be used. As the alkali-soluble resin, paragraphs 0558 to 0571 of JP-A-2012-208494 (paragraphs 0685 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and these contents are described in this specification. incorporated into the book.

The alkali-soluble resin is also preferably a resin having a structural unit represented by the following formula (ED).

In formula (ED), R ^{1 E1} and R ^{2 E2} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, and z represents 0 or 1.

The hydrocarbon group having 1 to 25 carbon atoms represented by R ^E1 and R ^E2 is not particularly limited, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. , t-butyl group, t-amyl group, stearyl group, lauryl group, linear or branched alkyl groups such as 2-ethylhexyl group; aryl groups such as phenyl group; cyclohexyl group, t-butylcyclohexyl group, di Alicyclic groups such as cyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group and 2-methyl-2-adamantyl group; substituted with alkoxy groups such as 1-methoxyethyl group and 1-ethoxyethyl group an alkyl group substituted with an alkyl group; an alkyl group substituted with an aryl group such as a benzyl group; and the like. Among these, primary or secondary hydrocarbon groups such as methyl group, ethyl group, cyclohexyl group, benzyl group, etc., which are difficult to be eliminated by acid or heat, are particularly preferred from the viewpoint of heat resistance.

Note that R ^E1 and R ^E2 may be the same type of substituents, or may be different substituents.

Examples of compounds forming structural units represented by formula (ED) include dimethyl-2,2′-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2′-[oxybis(methylene) ] Bis-2-propenoate, di(n-propyl)-2,2′-[oxybis(methylene)]bis-2-propenoate, di(n-butyl)-2,2′-[oxybis(methylene)]bis -2-propenoate, di(t-butyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-propenoate , etc. Among these, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate is particularly preferred.

The alkali-soluble resin may have a structural unit other than the structural unit represented by formula (ED).

Examples of monomers that form the above structural units include aryl (meth) acrylates, alkyl (meth) acrylates, and polyethyleneoxy (meth) acrylates that impart oil solubility from the viewpoint of ease of handling such as solubility in solvents. It is also preferable to contain it as a copolymerization component, and aryl (meth)acrylate or alkyl (meth)acrylate is more preferable.

In addition, from the viewpoint of alkali developability, monomers having a carboxyl group such as (meth)acrylic acid and itaconic acid containing an acidic group, monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride and itaconic anhydride It is preferable to contain a monomer having a carboxylic anhydride group such as an acid as a copolymerization component, and (meth)acrylic acid is more preferable.

The alkali-soluble resin is formed from, for example, a structural unit represented by the formula (ED), a structural unit formed from benzyl methacrylate, and at least one monomer selected from the group consisting of methyl methacrylate and methacrylic acid. A resin having a structural unit having

Regarding the resin having the structural unit represented by formula (ED), the descriptions in paragraphs 0079 to 0099 of JP-A-2012-198408 can be referred to, and the contents thereof are incorporated herein.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000. The lower limit is more preferably 5,000 or more, and even more preferably 7,000 or more. The upper limit is more preferably 45,000 or less, even more preferably 43,000 or less.

The acid value of the alkali-soluble resin is preferably 30-200 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, still more preferably 70 mgKOH/g or more. The upper limit is more preferably 150 mgKOH/g or less, still more preferably 120 mgKOH/g or less.

Incidentally, the acid value in the present disclosure shall be measured by the following method.

The acid value represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content. A measurement sample was dissolved in a mixed solvent of tetrahydrofuran/water = 9/1 (mass ratio), and a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.) was used to dilute the resulting solution to 25%. Neutralization titration is carried out with a 0.1 mol/L sodium hydroxide aqueous solution at °C. Using the inflection point of the titration pH curve as the titration end point, the acid value is calculated by the following formula.

A = 56.11 x Vs x 0.1 x f/w

A: Acid value (mgKOH/g)

Vs: Amount (mL) of 0.1 mol/L aqueous sodium hydroxide solution required for titration

f: titer of 0.1 mol/L sodium hydroxide aqueous solution

w: Measurement sample mass (g) (solid content conversion)

(Curable compound)

From the viewpoint of pattern formability, the composition according to the present disclosure preferably contains a curable compound, and more preferably contains a curable compound and further contains a photopolymerization initiator described later.

As the curable compound, a compound having a polymerizable group (hereinafter also referred to as "polymerizable compound") is preferable.

The curable compounds may be in any chemical form such as monomers, oligomers, prepolymers, polymers. As the curable compound, for example, paragraphs 0070 to 0191 of JP 2014-41318 (corresponding paragraphs 0071 to 0192 of WO 2014/017669), paragraphs 0045 to 0216 of JP 2014-32380, etc. can be referred to, and the contents thereof are incorporated in the specification of the present application.

Commercially available urethane resins having a methacryloyl group include 8UH-1006 and 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.).

The curable compound is preferably a polymerizable compound. The polymerizable compound may be a radically polymerizable compound or a cationically polymerizable compound. For example, compounds containing a polymerizable group such as an ethylenically unsaturated group and a cyclic ether group (epoxy, oxetane) may be used. mentioned. Among them, ethylenically unsaturated compounds are preferred.

As the ethylenically unsaturated group, a vinyl group, a styryl group, a (meth)acryloyl group, and a (meth)allyl group are preferred. The polymerizable compound may be a monofunctional compound having one polymerizable group, or may be a polyfunctional polymerizable compound having two or more polymerizable groups. is preferred, and a polyfunctional (meth)acrylate compound is more preferred. The film strength can be improved by including the polyfunctional polymerizable compound in the composition.

Curable compounds include monofunctional (meth)acrylate compounds, polyfunctional (meth)acrylate compounds (preferably tri- to hexafunctional (meth)acrylate compounds), polybasic acid-modified acrylic oligomers, epoxy resins, and polyfunctional epoxies. A resin etc. are mentioned.

As the curable compound, an ethylenically unsaturated compound can be preferably used. Examples of ethylenically unsaturated compounds can be referred to paragraphs 0033 to 0034 of JP-A-2013-253224, the contents of which are incorporated herein.

Examples of ethylenically unsaturated compounds include ethyleneoxy-modified pentaerythritol tetraacrylate (commercially available as NK Ester ATM-35E, manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available as KAYARAD D -330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.) dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E, Shin-Nakamura Chemical Co., Ltd. )) and structures in which these (meth)acryloyl groups are via ethylene glycol or propylene glycol residues are preferred. These oligomeric types can also be used.

Further, diglycerin EO (ethylene oxide)-modified (meth)acrylate (as a commercial product, M-460, manufactured by Toagosei Co., Ltd.) is preferable. Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT) and 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) are also preferred. These oligomeric types can also be used. Examples thereof include RP-1040 (manufactured by Nippon Kayaku Co., Ltd.).

The ethylenically unsaturated compound may have an acid group such as a carboxy group, a sulfonic acid group, or a phosphoric acid group.

Examples of ethylenically unsaturated compounds having an acid group include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids. A compound obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with an acid group by reacting a non-aromatic carboxylic acid anhydride is preferable, and particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol. or dipentaerythritol. Commercially available products include, for example, Aronix series M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The acid value of the ethylenically unsaturated compound having an acid group is preferably 0.1 mgKOH/g to 40 mgKOH/g. More preferably, the lower limit is 5 mgKOH/g or more. The upper limit is more preferably 30 mgKOH/g or less.

In the present disclosure, a compound having an epoxy group or an oxetanyl group can be used as the curable compound. Compounds having an epoxy group or an oxetanyl group include polymers having epoxy groups in side chains, and monomers or oligomers having two or more epoxy groups in the molecule. Examples thereof include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolak-type epoxy resin, cresol novolac-type epoxy resin, and aliphatic epoxy resin. Monofunctional or polyfunctional glycidyl ether compounds are also included, and polyfunctional aliphatic glycidyl ether compounds are preferred.

The weight average molecular weight is preferably 500 to 5,000,000, more preferably 1,000 to 500,000.

These compounds may be commercially available products, or may be obtained by introducing an epoxy group into the side chain of the polymer. Examples thereof include Cychromer P ACA 200M, ACA 230AA, ACA Z250, ACA Z251, ACA Z300, and ACA Z320 (manufactured by Daicel Chemical Industries, Ltd.).

Only one type of curable compound may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

The content of the curable compound is preferably 1% by mass to 90% by mass with respect to the total solid content of the composition. The lower limit is more preferably 5% by mass or more, still more preferably 10% by mass or more, and even more preferably 20% by mass or more. The upper limit is more preferably 80% by mass or less, and even more preferably 75% by mass or less.

(Polymerization initiator)

The composition according to the present disclosure preferably contains a polymerization initiator together with the curable compound.

The polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator, but is preferably a photopolymerization initiator.

Moreover, the polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator.

Examples of photoradical polymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like. Halogenated hydrocarbon compounds having a triazine skeleton include, for example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, compounds described in JP-A-53-133428, compounds described in German Patent No. 3337024; C. J. Schaefer et al. Org. Chem. ; 29, 1527 (1964), the compound described in JP-A-62-58241, the compound described in JP-A-5-281728, the compound described in JP-A-5-34920, the US patent Compounds described in No. 4,212,976 and the like can be mentioned.

From the viewpoint of exposure sensitivity, photoradical polymerization initiators include oxime compounds, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oximes. triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl-substituted coumarin compounds. Preferred are oxime compounds.

Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, compounds described in JP-A-2006-342166, and JP-A-2016-21012. Examples thereof include compounds described in publications. Also, J. C. S. Perkin II (1979, pp. 1653-1660), J. Am. C. S. Perkin II (1979, pp.156-162), Journal of Photopolymer Science and Technology (1995, pp.202-232), JP-A-2000-66385, JP-A-2000-80068, JP-A-2004- Also included are compounds described in JP-A-534797 and JP-A-2006-342166.

Commercially available products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (manufactured by BASF) are also suitable for use. In addition, TR-PBG-304 (manufactured by Changzhou Yuan Electronics New Materials Co., Ltd.), ADEKA Arkles NCI-831 (manufactured by ADEKA Co., Ltd.), ADEKA Arkles NCI-930 (manufactured by ADEKA Co., Ltd.), ADEKA OPTOMER N -1919 (manufactured by ADEKA Corporation) can also be used.

In addition, as oxime compounds other than the above, compounds described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N-position of the carbazole ring, and US Pat. compounds described in JP-A-2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye site, a ketoxime compound described in WO 2009/131189, a triazine skeleton and a compound described in US Pat. No. 7,556,910 containing an oxime skeleton in the same molecule, and having an absorption maximum at 405 nm and good sensitivity to a g-line light source. A compound or the like may also be used.

Preferably, for example, paragraphs 0274 to 0275 of JP-A-2013-29760 can be referred to, the contents of which are incorporated herein.

Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The oxime compound may be an oxime compound in which the NO bond of the oxime is in the (E) form, an oxime compound in which the NO bond of the oxime is in the (Z) form, or the (E) form. and the (Z) form.

In formula (OX-1), R 2 ^O1 and R ^{2 O2} each independently represent a monovalent substituent, R 2 ^O3 represents a divalent organic group, and Ar 2 ^O1 represents an aryl group.

In formula (OX-1), the monovalent substituent represented by R 2 ^O1 is preferably a monovalent nonmetallic atomic group.

Examples of monovalent nonmetallic atomic groups include alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heterocyclic groups, alkylthiocarbonyl groups, and arylthiocarbonyl groups. Moreover, these groups may have one or more substituents. In addition, the substituents described above may be further substituted with other substituents.

Examples of substituents include halogen atoms, aryloxy groups, alkoxycarbonyl groups or aryloxycarbonyl groups, acyloxy groups, acyl groups, alkyl groups, and aryl groups.

In formula (OX-1), the monovalent substituent represented by R ^{2 O2} is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of substituents include the substituents described above.

In formula (OX-1), the divalent organic group represented by R 2 ^O3 is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of substituents include the substituents described above.

A compound represented by the following formula (X-1) or (X-2) can also be used as the photopolymerization initiator.

In formula (X-1), R 1 ^X1 and R 1 ^X2 are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or , represents an arylalkyl group having 7 to 30 carbon atoms, and when R 1 ^X1 and R 1 ^X2 are phenyl groups, the phenyl groups may combine to form a fluorene group, and R 1 ^X3 and R 1 ^X4 are each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X ^A is a single bond or indicates a carbonyl group.

In formula (X-2), R ^X1 , R ^X2 , R ^X3 and R ^X4 have the same definitions as R ^X1 , R ^X2 , R ^X3 and R ^X4 in formula (X-1), and R ^X5 is -R ^X6 , -OR ^X6 , -SR ^X6 , -COR ^X6 , -CONR ^X6 R ^X6 , -NR ^X6 COR ^X6 , -OCOR ^X6 , -COOR ^X6 , -SCOR ^X6 , -OCSR ^X6 , -COSR ^X6 , -CSOR ^X6 , —CN represents a halogen atom or a hydroxyl group, and R ^X6 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic ring having 4 to 20 carbon atoms. group, X ^A represents a single bond or a carbonyl group, and xa represents an integer of 0-4.

In formulas (X-1) and (X-2) above, R ¹ and R ² are each independently preferably a methyl group, ethyl group, n-propyl group, i-propyl, cyclohexyl group or phenyl group. R ^X3 is preferably a methyl group, ethyl group, phenyl group, tolyl group or xylyl group. R ^X4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ^X5 is preferably a methyl group, ethyl group, phenyl group, tolyl group or naphthyl group. X ^A is preferably a single bond.

Specific examples of the compounds represented by formulas (X-1) and (X-2) include compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. The contents of which are incorporated herein.

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

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

The oxime compound preferably has a molar extinction coefficient at 365 nm or 405 nm of 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 300,000, from the viewpoint of sensitivity. More preferably 200,000.

The molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

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

Examples of —OC ₉ F ₁₇ in (C-12) above include the following groups.

An oxime compound having a fluorine atom can also be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, compounds described in JP-A-2013-164471 ( C-3) and the like. The contents of which are incorporated herein.

A photoacid generator is mentioned as a photocationic polymerization initiator. Examples of photoacid generators include diazonium salts, phosphonium salts, sulfonium salts, onium salt compounds such as iodonium salts, imidosulfonates, oximesulfonates, diazodisulfones, disulfones, and o-nitrobenzyl, which are decomposed by light irradiation to generate acids. Sulfonate compounds such as sulfonate can be mentioned. Details of the photocationic polymerization initiator can be referred to paragraphs 0139 to 0214 of JP-A-2009-258603, the contents of which are incorporated herein.

A commercial item can also be used for a photocationic polymerization initiator. Commercially available photocationic polymerization initiators include Adeka Arkles SP series (eg, Adeka Arkles SP-606) manufactured by ADEKA Corporation, IRGACURE250, IRGACURE270, and IRGACURE290 manufactured by BASF.

The polymerization initiator may be of one type or two or more types, and in the case of two or more types, the total amount is preferably within the above range.

The content of the polymerization initiator is preferably 0.01% by mass to 30% by mass with respect to the total solid content of the composition. The lower limit is more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. The upper limit is more preferably 20% by mass or less, and even more preferably 15% by mass or less.

(solvent)

A composition according to the present disclosure may contain a solvent.

The solvent is not particularly limited, and can be appropriately selected depending on the intended purpose as long as it can uniformly dissolve or disperse each component of the composition. For example, water and organic solvents can be used, and organic solvents are preferred.

Suitable examples of organic solvents include alcohols (e.g., methanol), ketones, esters, aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, and the like. . These may be used individually by 1 type, and may use 2 or more types together.

Among them, at least one organic solvent selected from the group consisting of esters having a cyclic alkyl group and ketones is preferred.

Specific examples of alcohols, aromatic hydrocarbons, and halogenated hydrocarbons include those described in paragraph 0136 of JP-A-2012-194534, etc., the contents of which are incorporated herein.

Specific examples of esters, ketones, and ethers include those described in JP-A-2012-208494, paragraph 0497 (corresponding US Patent Application Publication No. 2012/0235099, paragraph 0609), and further , n-amyl acetate, ethyl propionate, dimethyl phthalate, ethyl benzoate, methyl sulfate, acetone, methyl isobutyl ketone, diethyl ether, ethylene glycol monobutyl ether acetate and the like.

Solvents include ethanol, methanol, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, N-methyl-2-pyrrolidone, ethyl cellosolve acetate, and ethyl lactate. , butyl acetate, cyclohexyl acetate, diethylene glycol dimethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate One or more are preferred.

The content of the solvent is preferably such that the total solid content of the composition is 10% by mass to 90% by mass. The lower limit is more preferably 15% by mass or more, and even more preferably 20% by mass or more. The upper limit is more preferably 80% by mass or less, and even more preferably 70% by mass or less.

The solvent may be of one kind or two or more kinds, and in the case of two or more kinds, the total amount is preferably within the above range.

(dye derivative)

The composition according to the present disclosure preferably further contains a dye derivative (hereinafter also simply referred to as "dye derivative") other than the compound having the structure represented by formula (1). By including the dye derivative, particularly when the compound having the structure represented by formula (1) is a pigment, the dispersibility of the compound having the structure represented by formula (1) is increased, and the compound represented by formula (1) Aggregation of compounds having the represented structure can be efficiently suppressed. The dye derivative is preferably a pigment derivative.

As the dye derivative, one having a structure in which a part of the dye is substituted with an acidic group, a basic group, or a group having a salt structure is preferable, and a dye derivative represented by the following formula (3) is more preferable. In the dye derivative represented by the following formula (3), the dye structure P is easily adsorbed to the surface of the compound having the structure represented by the formula (1), so it is represented by the formula (1) in the composition The dispersibility of the compound having the structure can be improved. In addition, when the composition contains a resin, the terminal portion X of the dye derivative is adsorbed to the resin through interaction with the adsorbing portion (such as a polar group) of the resin, so that the structure represented by formula (1) is It is possible to further improve the dispersibility of the compound having.

In formula ( ³ ), P3 represents a dye structure, L3 ^each independently represents a single bond or a linking group, and X3 ^each independently represents an acidic group, a basic group, or a group having a salt structure. , m represents an integer of 1 or more, and n represents an integer of 1 or more.

The dye structures in P3 are pyrrolopyrrole dye structure, squarylium dye structure, croconium dye structure, diimmonium dye structure, oxonol dye structure, diketopyrrolopyrrole dye structure, quinacridone dye structure, anthraquinone dye structure, ^{dianthraquinone} dye structure, benzoiso Consisting of an indole dye structure, a thiazine indigo dye structure, an azo dye structure, a quinophthalone dye structure, a phthalocyanine dye structure, a naphthalocyanine dye structure, a dioxazine dye structure, a pyromethene dye structure, a perylene dye structure, a perinone dye structure and a benzimidazolinone dye structure. At least one selected from the group is preferable, and at least one selected from the group consisting of a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, a quinacridone dye structure, a squarylium dye structure, a croconium dye structure and a benzimidazolinone dye structure is more Preferred are the pyrrolopyrrole dye structures. When the dye derivative has these dye structures, the dispersibility of the compound represented by formula (1) can be further improved.

Linking groups for L ³ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 A group consisting of one sulfur atom is preferred, and may be unsubstituted or may further have a substituent. Preferred substituents are alkyl groups, aryl groups, hydroxy groups and halogen atoms.

The linking group is an alkylene group, an arylene group, a nitrogen-containing heterocyclic group, -NR'-, -SO ₂ -, -S-, -O-, -CO-, -COO-, -CONR'-, or these are preferred, and alkylene groups, arylene groups, —SO ₂ —, —COO—, or groups in which two or more of these are combined are more preferred. R' represents a hydrogen atom, an alkyl group (preferably having 1 to 30 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms).

The number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-15, even more preferably 1-10. The alkylene group may have a substituent. The alkylene group may be linear, branched or cyclic. Moreover, the cyclic alkylene group may be monocyclic or polycyclic.

The arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, still more preferably 6 to 10 carbon atoms, and particularly preferably a phenylene group.

The nitrogen-containing heterocyclic group is preferably a 5- or 6-membered ring. The nitrogen-containing heterocyclic group is preferably a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring with 2 to 8 condensed numbers, more preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers. The number of nitrogen atoms contained in the nitrogen-containing heterocyclic group is preferably 1-3, more preferably 1 or 2. The nitrogen-containing heterocyclic group may contain heteroatoms other than the nitrogen atom. Examples of heteroatoms other than nitrogen atoms include oxygen atoms and sulfur atoms. The number of heteroatoms other than nitrogen atoms is preferably 0 to 3, more preferably 0 or 1.

Nitrogen-containing heterocyclic groups include a piperazine ring group, a pyrrolidine ring group, a pyrrole ring group, a piperidine ring group, a pyridine ring group, an imidazole ring group, a pyrazole ring group, an oxazole ring group, a thiazole ring group, a pyrazine ring group, and a morpholine ring. group, thiazine ring group, indole ring group, isoindole ring group, benzimidazole ring group, purine ring group, quinoline ring group, isoquinoline ring group, quinoxaline ring group, cinnoline ring group, carbazole ring group and the following formula (L-1 ) to formula (L-7).

* in the formula represents a bonding site with P ³ , L ³ or X ³ , and R represents a hydrogen atom or a substituent. A substituent T is mentioned as a substituent. Examples of the substituent T include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a thioalkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a carboxy group, an acetyl group, a cyano group, and a halogen. atoms (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. These substituents may further have a substituent.

Specific examples of the linking group include an alkylene group, an arylene group, —SO ₂ —, a group represented by formula (L-1) above, a group represented by formula (L-5) above, and —O— and alkylene. group, a group consisting of a combination of -NR'- and an alkylene group, a group consisting of a combination of -NR'- and -CO- and an alkylene group, -NR'- and -CO- and alkylene a group consisting of a combination of a group and an arylene group, a group consisting of a combination of -NR'-, -CO- and an arylene group, a group consisting of a combination of -NR'-, -SO ₂ - and an alkylene group, -NR' A group consisting of a combination of — and —SO ₂ —, an alkylene group and an arylene group, a group consisting of a combination of a group represented by the above formula (L-1) and an alkylene group, a group represented by the above formula (L-1) A group consisting of a combination of a group represented by the above formula (L-1) and an arylene group, a group consisting of a combination of a group represented by the above formula (L-1), —SO ₂ —, and an alkylene group, A group consisting of a combination of a group, -S- and an alkylene group, a group consisting of a combination of a group represented by the above formula (L-1), -O- and an arylene group, represented by the above formula (L-1) A group consisting of a combination of a group, -NR'-, -CO- and an arylene group, a group consisting of a combination of a group represented by the above formula (L-3) and an arylene group, an arylene group and -COO- and a group consisting of a combination of an arylene group, —COO— and an alkylene group.

In formula ( ³ ), X3 represents an acidic group, a basic group, or a group having a salt structure.

Examples of acidic groups include a carboxy group, a sulfo group, a phospho group, a sulfonimide group, and the like.

Basic groups include groups represented by formulas (X-3) to (X-8) described below.

Groups having a salt structure include salts of acidic groups and salts of basic groups described above. Atoms or atomic groups constituting the salt include metal atoms, tetrabutylammonium, and the like. As the metal atom, an alkali metal atom or an alkaline earth metal atom is more preferable. Alkali metal atoms include lithium, sodium, potassium and the like. Alkaline earth metal atoms include calcium, magnesium and the like.

X ³ is preferably at least one group selected from the group consisting of a carboxy group, a sulfo group, a sulfonimide group, and groups represented by any of the following formulas (X-1) to (X-11) .

In formulas (X-1) to (X-11), * represents a bonding site with L ³ in formula (3), and R ¹⁰⁰ to R ¹⁰⁶ each independently represent a hydrogen atom, an alkyl group, or an alkenyl group. or represents an aryl group, R ¹⁰⁰ and R ¹⁰¹ may be linked together to form a ring, and M represents an atom or atomic group constituting an anion and a salt.

Alkyl groups may be linear, branched or cyclic. The straight-chain alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 8 carbon atoms. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and still more preferably 3 to 8 carbon atoms. A cyclic alkyl group may be monocyclic or polycyclic. The number of carbon atoms in the cyclic alkyl group is preferably 3-20, more preferably 4-10, even more preferably 6-10.

The alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 2 to 4 carbon atoms.

The number of carbon atoms in the aryl group is preferably 6-18, more preferably 6-14, even more preferably 6-10.

R ¹⁰⁰ and R ¹⁰¹ may be linked together to form a ring. The ring may be an alicyclic ring or an aromatic ring. The ring may be monocyclic or polycyclic. When R ¹⁰⁰ and R ¹⁰¹ combine to form a ring, the linking group includes -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group and combinations thereof. It can be linked by a divalent linking group selected from the group consisting of. Specific examples include piperazine ring, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring and the like.

R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ each independently represent a halogen atom, a hydroxy group or a hydrocarbon group having 1 or more carbon atoms which may contain a substituent. The hydrocarbon group represented by R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Moreover, the aliphatic hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-30. The upper limit is preferably 20 or less, more preferably 10 or less, and even more preferably 5 or less. The aromatic hydrocarbon group preferably has 6 to 20 carbon atoms. The upper limit is preferably 18 or less, more preferably 15 or less, and even more preferably 12 or less. Substituents which the hydrocarbon groups represented by R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ may contain include halogen atoms, hydroxyl groups, carboxyl groups, alkoxy groups, phenoxy groups, acyl groups and sulfo groups. At least part of the hydrogen atoms in the alkoxy group may be substituted with halogen atoms. The aforementioned substituent is preferably a halogen atom or an alkoxy group in which at least a portion of the hydrogen atoms may be substituted with a halogen atom, more preferably a halogen atom. Moreover, as the halogen atom, a chlorine atom, a fluorine atom, or a bromine atom is preferable, and a fluorine atom is more preferable.

M represents an atom or atomic group that constitutes an anion and a salt. These include those described above, and the preferred ranges are also the same.

The upper limit of m represents the number of substituents that the dye structure P can take, and is preferably 10 or less, more preferably 5 or less. When m is 2 or more, multiple Ls and Xs may be different from each other.

n is preferably an integer of 1 to 3, more preferably 1 or 2. When n is 2 or more, multiple Xs may be different from each other.

Specific examples include the following groups.

The dye derivative is preferably a dye derivative represented by the following formula (4). A dye derivative represented by the following formula (4) is a compound in which P in formula (3) is a pyrrolopyrrole dye structure.

In formula (4), R ⁴³ to R ⁴⁶ each independently represent a cyano group, acyl group, alkoxycarbonyl group, alkylsulfinyl group, arylsulfinyl group or heteroaryl group, and R ⁴⁷ and R ⁴⁸ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR ⁴⁹ R ⁵⁰ or a metal atom, R ⁴⁷ may be covalently or coordinately bonded to R ⁴³ or R ⁴⁵ , and R ⁴⁸ is , R ⁴⁴ or R ⁴⁶ , and each of R ⁴⁹ and R ⁵⁰ is independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy a group, an aryloxy group, or a heteroaryloxy group, wherein R ⁴⁹ and R ⁵⁰ may combine to form a ring, and L ⁴¹ and L ⁴² are each independently a single bond, or an alkylene group, an arylene group, a nitrogen-containing heterocyclic group, —O—, —S—, —NR′—, —CO—, —SO ₂ —, or a linking group combining two or more of these, and R′ is hydrogen represents an atom, an alkyl group or an aryl group, X ⁴¹ and X ⁴² each independently represent an acidic group, a basic group or a group having a salt structure, n41 and n42 each independently represent an integer of 0 to 4 , n41 and n42 is 1 or more.

R ⁴³ to R ⁴⁸ in formula (4) have the same definitions as R ³ to R ⁸ in formula (1), and preferred embodiments are also the same.

X ⁴¹ and X ⁴² in formula (4) are synonymous with X ³ in formula (3), and the preferred embodiments are also the same.

In Formula (4), L ⁴¹ and L ⁴² have the same meanings as L ³ in Formula (3), and preferred embodiments are also the same. Furthermore, the following linking groups are particularly preferred from the viewpoints of synthetic suitability and visible transparency.

Further, L ⁴¹ preferably has 1 to 20 atoms forming a chain connecting X ⁴¹ and a benzene ring directly connected to the pyrrolopyrrole structure, which is the core structure of the pigment derivative. The lower limit is more preferably 2 or more, still more preferably 3 or more. The upper limit is more preferably 15 or less, still more preferably 10 or less. L ⁴² preferably has 1 to 20 atoms forming a chain connecting X ⁴² and a benzene ring directly connected to the pyrrolopyrrole structure, which is the core structure of the pigment derivative. The lower limit is more preferably 2 or more, still more preferably 3 or more. The upper limit is more preferably 15 or less, still more preferably 10 or less. According to this aspect, the dispersibility of the pigment can be further improved. Although the detailed reason is unknown, by increasing the distance between the pyrrolopyrrole structure, which is the core structure of the pigment derivative, and X ⁴¹ and X ⁴² , X ⁴¹ and X ⁴² are less susceptible to steric hindrance and resins and the like. It is presumed that the interaction between the two works more easily, and as a result, the dispersibility of the pigment can be improved.

The compound represented by formula (4) preferably has a solubility of 0 g/L to 0.1 g/L, more preferably 0 g/L to 0.01 g/L, in the solvent (25° C.) contained in the composition. is more preferable. According to this aspect, the dispersibility of the pigment can be further improved.

The compound represented by formula (1) is preferably a compound having a maximum absorption wavelength in the range of 700 nm to 1200 nm. Also, the ratio A1/A2 between the absorbance A1 at a wavelength of 500 nm and the absorbance A2 at the maximum absorption wavelength is preferably 0.1 or less, more preferably 0.05 or less.

Note that the absorbance of a compound in the present disclosure is a value obtained from the absorption spectrum of a solution of the compound. Chloroform, dimethylsulfoxide, tetrahydrofuran and the like are examples of the measurement solvent used for measuring the absorption spectrum of the solution of the compound represented by formula (4). When the compound represented by formula (4) dissolves in chloroform, chloroform is used as the measurement solvent. In addition, when it does not dissolve in chloroform but dissolves in dimethylsulfoxide or tetrahydrofuran, dimethylsulfoxide or tetrahydrofuran is used as the measurement solvent.

Specific examples of the dye derivative represented by formula (3) include the following (3-1) to (3-25). In the following formulas, m, m1, m2 and m3 each independently represent an integer of 1 or more.

Specific examples of the compound represented by Formula (4) include the following compounds. In the structural formulas below, Me represents a methyl group, Bu represents a butyl group, and Ph represents a phenyl group.

Ar-1 to Ar-31 and R-1 to R-7 in the table below are as follows. "*" in the structures shown below is a link.

In addition, the composition according to the present disclosure may contain one type of the dye derivative alone, or may contain two or more types thereof.

From the viewpoint of infrared absorption and dispersibility, the content of the dye derivative is preferably 0.1% by mass to 30% by mass, and 0.5% by mass to 25% by mass, based on the total solid content of the composition. % by mass is more preferred, and 1 to 20% by mass is even more preferred.

Further, the content of the dye derivative is preferably 1% by mass to 80% by mass with respect to the total mass of the compound represented by formula (1) from the viewpoint of infrared absorption and dispersibility. It is more preferably from 5% by mass to 50% by mass, and even more preferably from 5% by mass to 40% by mass.

(chromatic colorant, black colorant, colorant that blocks visible light)

The composition according to the present disclosure can contain at least one selected from the group consisting of chromatic colorants and black colorants (hereinafter, chromatic colorants and black colorants are collectively referred to as visible colorants. also called). In the present disclosure, chromatic colorants mean colorants other than white colorants and black colorants. The chromatic colorant is preferably a colorant that absorbs in a wavelength range of 400 nm or more and less than 650 nm.

- Chromatic coloring agent -

In the present disclosure, the chromatic colorant may be a pigment or a dye.

The average particle size (r) of the pigment preferably satisfies 20 nm≦r≦300 nm, more preferably 25 nm≦r≦250 nm, and even more preferably 30 nm≦r≦200 nm. The term "average particle size" as used herein means the average particle size of secondary particles in which the primary particles of the pigment are aggregated.

In addition, the particle size distribution of the secondary particles of the pigment that can be used (hereinafter also simply referred to as "particle size distribution") is such that the secondary particles falling within (average particle size ± 100) nm account for 70% by mass or more of the total, Preferably, it is 80% by mass or more. The particle size distribution of secondary particles can be measured using the scattering intensity distribution.

The average particle size of the primary particles is observed with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), the particle size is measured for 100 particles in a portion where the particles are not aggregated, and the average value is calculated. can be obtained by

The pigment is preferably an organic pigment. Moreover, the following can be mentioned as a pigment. However, the present disclosure is not limited to these.

Color Index (C.I.) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. (above, yellow pigment),

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

C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, 294 (xanthene , Organo Ultamarine, Bluish Red) etc. (above, red pigment),

C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigment),

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (the above are 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), 88 (methine/polymethine system), etc. (above, blue pigments);

These pigments can be used alone or in various combinations.

The dye is not particularly limited, and known dyes can be used. Chemical structures include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based and pyrromethene-based dyes can be used. Multimers of these dyes may also be used. In addition, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.

As the dye, at least one of acid dyes and derivatives thereof may be preferably used. In addition, at least one of direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and derivatives thereof can also be usefully used.

Specific examples of acid dyes are listed below, but are not limited thereto. Examples include the following dyes and derivatives of these dyes.

acid alizarin violet N,

acid blue 1,7,9,15,18,23,25,27,29,40-45,62,70,74,80,83,86,87,90,92,103,112,113,120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1,

acid chrome violet K,

acid Fuchsin; acid green 1, 3, 5, 9, 16, 25, 27, 50,

acid orange 6,7,8,10,12,50,51,52,56,63,74,95,

acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274,

acid violet 6B, 7, 9, 17, 19,

acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243,

Food Yellow 3

In addition to the above, azo-based, xanthene-based, and phthalocyanine-based acid dyes are also preferred, such as C.I. I. Solvent Blue 44, 38; C.I. I. Acid dyes such as Solvent orange 45; Rhodamine B and Rhodamine 110, and derivatives of these dyes are also preferably used.

Among them, as dyes, triarylmethane-based, anthraquinone-based, azomethine-based, benzylidene-based, oxonol-based, cyanine-based, phenothiazine-based, pyrrolopyrazole-azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based, and pyrazoleazo-based dyes , anilinoazo, pyrazolotriazole azo, pyridone azo, anthrapyridone, and pyrromethene.

Furthermore, pigments and dyes may be used in combination.

-Black colorant-

As the black colorant, an organic black colorant is preferred. In the present disclosure, a black coloring agent as a coloring agent that blocks visible light means a material that absorbs visible light but transmits at least part of infrared rays. Therefore, in the present disclosure, the black colorant as a colorant that blocks visible light does not include carbon black and titanium black. A bisbenzofuranone compound, an azomethine compound, a perylene compound, an azo compound, or the like can also be used as a black colorant for blocking visible light.

Examples of the bisbenzofuranone compound include those described in JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, and the like. For example, it is available as "Irgaphor Black" manufactured by BASF.

As a perylene compound, C.I. I. Pigment Black 31, 32 and the like.

Examples of azomethine-based compounds include those described in JP-A-1-170601 and JP-A-2-34664. . Although the azo compound is not particularly limited, a compound represented by the following formula (A-1) and the like can be preferably mentioned.

- Colorant that blocks visible light -

When the composition according to the present disclosure is used to manufacture an infrared transmitting filter that transmits infrared rays in the region not absorbed by the infrared absorbing dye contained therein, it preferably contains a coloring agent that blocks visible light.

The colorant that blocks visible light preferably exhibits black, gray, or a color close thereto by combining a plurality of colorants.

Moreover, the coloring agent that blocks visible light is preferably a material that absorbs light in the wavelength range from violet to red.

Further, the coloring agent that blocks visible light is preferably a coloring agent that blocks light in the wavelength range of 450 nm to 650 nm.

In the present disclosure, the colorant that blocks visible light preferably satisfies at least one of the following requirements (1) and (2), and more preferably satisfies requirement (1).

(1): An embodiment containing two or more chromatic colorants.

(2): An embodiment containing a black colorant.

Further, in the present disclosure, a black coloring agent as a coloring agent that blocks visible light means a material that absorbs visible light but transmits at least part of infrared rays. Therefore, in the present disclosure, organic black colorants as colorants that block visible light do not include black colorants that absorb both visible light and infrared rays, such as carbon black and titanium black.

The colorant that blocks visible light has a ratio of A/B, which is the ratio of the minimum absorbance value A in the wavelength range of 450 nm to 650 nm and the absorbance minimum value B in the wavelength range of 900 nm to 1,300 nm, to 4. 0.5 or more is preferable.

The above characteristics may be satisfied by one type of material or may be satisfied by a combination of multiple materials. For example, in the case of the above aspect (1), it is preferable that a plurality of chromatic colorants be combined to satisfy the above spectral characteristics.

When two or more chromatic colorants are included as colorants that block visible light, the chromatic colorants include a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant. It is preferably a colorant selected from

When two or more chromatic colorants are combined to form a colorant that blocks visible light, examples of combinations of chromatic colorants include the following.

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

(6) Embodiment containing purple colorant and orange colorant

(7) Embodiment containing a green colorant, a purple colorant and a red colorant

(8) Aspect containing a green colorant and a red colorant

As a specific example of the above aspect (1), C.I. I. Pigment Yellow 139 or 185 and C.I. I. Pigment Blue 15:6 and C.I. I. Pigment Violet 23 and C.I. I. and Pigment Red 254 or 224.

As a specific example of the above aspect (2), C.I. I. Pigment Yellow 139 or 185 and C.I. I. Pigment Blue 15:6 and C.I. I. and Pigment Red 254 or 224.

As a specific example of the above aspect (3), C.I. I. Pigment Yellow 139 or 185 and C.I. I. Pigment Violet 23 and C.I. I. and Pigment Red 254 or 224.

As a specific example of the above aspect (4), C.I. I. Pigment Yellow 139 or 185 and C.I. I. and Pigment Violet 23.

As a specific example of the aspect (5) above, C.I. I. Pigment Green 7 or 36 and C.I. I. Pigment Blue 15:6 and C.I. I. Pigment Violet 23 and C.I. I. and Pigment Red 254 or 224.

As a specific example of the above aspect (6), C.I. I. Pigment Violet 23 and C.I. I. and Pigment Orange 71.

Specific examples of (7) above include C.I. I. Pigment Green 7 or 36 and C.I. I. Pigment Violet 23 and C.I. I. and Pigment Red 254 or 224.

Specific examples of (8) above include C.I. I. Pigment Green 7 or 36 and C.I. I. and Pigment Red 254 or 224.

Examples of the ratio (mass ratio) of each colorant include the following.

When the composition according to the present disclosure contains a visible colorant, the content of the visible colorant is preferably 0.01% by mass to 50% by mass based on the total solid content of the composition. The lower limit is more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 15% by mass or less.

The content of the visible coloring agent is preferably 10 parts by mass to 1,000 parts by mass, more preferably 50 parts by mass to 800 parts by mass, with respect to 100 parts by mass of the infrared absorbing dye.

(Silane coupling agent)

A composition according to the present disclosure may contain a silane coupling agent. In the present disclosure, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction. Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Moreover, functional groups other than hydrolyzable groups are preferably groups that interact or form bonds with resins or the like to exhibit affinity. Examples thereof include vinyl group, styryl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group, isocyanate group and the like, and (meth)acryloyl group and epoxy group are preferred. As the silane coupling agent, compounds described in paragraphs 0018 to 0036 of JP-A-2009-288703, compounds described in paragraphs 0056-0066 of JP-A-2009-242604, paragraph 0229 of WO 2015/166779 0236, the contents of which are incorporated herein.

The content of the silane coupling agent is preferably 0.01% by mass to 15.0% by mass, more preferably 0.05% by mass to 10.0% by mass, relative to the total solid content of the composition. . Only one kind of silane coupling agent may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount is preferably within the above range.

(Surfactant)

The composition according to the present disclosure may contain a surfactant from the viewpoint of further improving coatability. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. Surfactants can be referred to paragraphs 0238-0245 of WO2015/166779, the contents of which are incorporated herein.

By including a fluorine-based surfactant in the composition according to the present disclosure, the liquid properties (especially fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved. be able to. In addition, it is possible to form a uniform-thickness film with little unevenness in thickness more favorably.

The fluorine atom content in the fluorosurfactant is preferably 3% to 40% by mass, more preferably 5% to 30% by mass, and particularly preferably 7% to 25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the composition.

Specifically, as the fluorosurfactant, the surfactant described in paragraphs 0060 to 0064 of JP-A-2014-41318 (paragraphs 0060-0064 of the corresponding WO 2014/17669), etc., JP 2011 -132503, paragraphs 0117-0132, the contents of which are incorporated herein. Commercially available fluorosurfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (the above, DIC Ltd.), Florado FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC- 381, SC-383, S-393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like.

In addition, the fluorosurfactant has a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing a fluorine atom is cleaved and the fluorine atom is volatilized. Acrylic compounds are also suitable. Available. Examples of such fluorine-based surfactants include Megafac DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), such as Megafac DS. -21.

A block polymer can also be used as the fluorosurfactant. Examples thereof include compounds described in JP-A-2011-89090. The fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.

The weight average molecular weight of the block polymer is preferably 3,000 to 50,000.

A fluoropolymer having an ethylenically unsaturated group in a side chain can also be used as the fluorosurfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, such as Megafac RS-101, RS-102, RS-718K and RS manufactured by DIC Corporation. -72-K and the like. Compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used as the fluorine-based surfactant.

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 company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.) Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto Oil Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.) etc.

The content of the surfactant is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass, based on the total solid content of the composition. Only one type of surfactant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

(Ultraviolet absorber)

The composition according to the present disclosure preferably contains an ultraviolet absorber. Examples of the ultraviolet absorber include conjugated diene compounds and diketone compounds, with conjugated diene compounds being preferred. The conjugated diene compound is more preferably a compound represented by the following formula (UV-1).

In formula (UV-1), R ^U1 and R ^U2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ^U1 and R ^U2 are They may be the same or different, but they do not represent a hydrogen atom at the same time.

R ^U1 and R ^U2 may form a cyclic amino group together with the nitrogen atom to which R ^U1 and R ^U2 are bonded. The cyclic amino group includes, for example, a piperidino group, a morpholino group, a pyrrolidino group, a hexahydroazepino group, a piperazino group and the like.

R ^U1 and R ^U2 are each independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 5 carbon atoms.

R ^U3 and R ^U4 represent electron-withdrawing groups. R ^U3 and R ^U4 are preferably acyl group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group or sulfamoyl group, acyl group, carbamoyl A group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group or a sulfamoyl group is more preferred. Also, R ^U3 and R ^U4 may combine with each other to form a cyclic electron-withdrawing group. Examples of the cyclic electron-withdrawing group formed by bonding R ³ and R ⁴ together include a 6-membered ring containing two carbonyl groups.

At least one of R ^U1 , R ^U2 , R ^U3 and R ^U4 may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with other monomers.

Description of the substituents of the ultraviolet absorber represented by formula (UV-1) can be referred to paragraphs 0320 to 0327 of JP-A-2013-68814, the contents of which are incorporated herein. Examples of commercially available UV absorbers represented by formula (UV-1) include UV503 (manufactured by Daito Kagaku Co., Ltd.).

The diketone compound used as the ultraviolet absorber is preferably a compound represented by the following formula (UV-2).

In formula (UV-2), R ¹⁰¹ and R ¹⁰² each independently represent a substituent, m1 and m2 each independently represent an integer of 0-4. Substituents include alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heteroaryloxycarbonyl groups, acyloxy groups, amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heteroarylthio group, alkylsulfonyl group, aryl sulfonyl group, heteroarylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, heteroarylsulfinyl group, ureido group, phosphoramide group, mercapto group, sulfo group, carboxy group, nitro group, hydroxamic acid group, sulfino group, hydrazino group , an imino group, a silyl group, a hydroxy group, a halogen atom, a cyano group, etc., and an alkyl group or an alkoxy group is preferred.

The number of carbon atoms in the alkyl group is preferably 1-20. Alkyl groups include straight-chain, branched, and cyclic groups, preferably straight-chain or branched, and more preferably branched.

The number of carbon atoms in the alkoxy group is preferably 1-20. The alkoxy group may be linear, branched or cyclic, preferably linear or branched, more preferably branched.

A combination in which one of R ¹⁰¹ and R ¹⁰² is an alkyl group and the other is an alkoxy group is preferred.

m1 and m2 are each independently preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1.

Compounds represented by formula (UV-2) include the following compounds.

Ubinal A (manufactured by BASF) can also be used as the ultraviolet absorber. Further, the ultraviolet absorber can be an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, an ultraviolet absorber such as a triazine compound, and specific examples are described in JP-A-2013-68814. compound. As the benzotriazole compound, the MYUA series manufactured by Miyoshi Oil Co., Ltd. (Chemical Daily, February 1, 2016) may be used.

The content of the ultraviolet absorber is preferably 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass, based on the total solid content of the composition.

(Polymerization inhibitor)

A composition according to the present disclosure may 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), 2,2′-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred. In addition, the polymerization inhibitor may function as an antioxidant. The content of the polymerization inhibitor is preferably 0.01% by mass to 5% by mass with respect to the total solid content of the composition.

(other ingredients)

The composition according to the present disclosure may optionally contain sensitizers, cross-linking agents, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliary agents (e.g., conductive particles, fillers, erasers, etc.). foaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately containing these components, it is possible to adjust properties such as stability and film physical properties of the desired optical filter such as an infrared cut filter. These components, for example, JP 2012-3225 from paragraph 0183 (corresponding US Patent Application Publication No. 2013/0034812 paragraph 0237) described, JP 2008-250074 paragraph 0101 ~ Descriptions such as 0104 and 0107 to 0109 can be referred to, and the contents thereof are incorporated herein.

Examples of antioxidants that can be used include phenol compounds, phosphorus compounds (eg compounds described in paragraph 0042 of JP-A-2011-90147), thioether compounds, and the like. Commercially available products include, for example, Adekastab series manufactured by ADEKA Corporation (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO- 330, etc.). The content of the antioxidant is preferably 0.01% by mass to 20% by mass, more preferably 0.3% by mass to 15% by mass, based on the total solid content of the composition. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

(Preparation of composition)

A composition according to the present disclosure can be prepared by mixing the components described above. Moreover, it is preferable to filter with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyethylene, polyolefin resins such as polypropylene (PP) (high density, ultra high molecular weight including) and the like. Among these materials, polypropylene (including high-density polypropylene) or nylon is preferred.

The pore size of the filter is preferably 0.01 μm to 7.0 μm, more preferably 0.01 μm to 3.0 μm, even more preferably 0.05 μm to 0.5 μm. By setting the amount within this range, it becomes possible to reliably remove fine foreign matter that hinders the preparation of a uniform and smooth composition in the subsequent steps. In addition, it is also preferable to use a fiber-like filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber, etc. Specifically, Roki Techno's SBP type series (SBP008, etc.), TPR type series (TPR002 , TPR005, etc.), SHPX type series (SHPX003, etc.) filter cartridges can be used.

When using filters, different filters may be combined. At that time, the filtration with the first filter may be performed only once, or may be performed two or more times.

Also, the first filters having different pore diameters within the range described above may be combined. The pore size here can refer to the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by Nippon Pall Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd., or Kitz Micro Filter Co., Ltd., for example. .

(Use of composition)

Since the composition according to the present disclosure can be liquid, for example, a film can be easily produced by applying the composition according to the present disclosure to a substrate or the like and drying it.

When forming a film by coating, the viscosity of the composition according to the present disclosure is preferably 1 mPa·s to 100 mPa·s from the viewpoint of coatability. The lower limit is more preferably 2 mPa·s or more, and even more preferably 3 mPa·s or more. The upper limit is more preferably 50 mPa·s or less, still more preferably 30 mPa·s or less, and particularly preferably 15 mPa·s or less.

The total solid content of the composition according to the present disclosure varies depending on the coating method, but is preferably, for example, 1% by mass to 50% by mass. More preferably, the lower limit is 10% by mass or more. The upper limit is more preferably 30% by mass or less.

Applications of the composition according to the present disclosure are not particularly limited. For example, it can be preferably used for forming an infrared cut filter or the like. For example, it can be preferably used as an infrared cut filter on the light receiving side of a solid-state image sensor (for example, for an infrared cut filter for a wafer level lens), an infrared cut filter on the back side of the solid-state image sensor (the side opposite to the light receiving side), and the like. can. In particular, it can be preferably used as an infrared cut filter on the light receiving side of a solid-state imaging device. Further, by adding a coloring agent that blocks visible light to the composition according to the present disclosure, it is possible to form an infrared transmission filter capable of transmitting infrared rays having a specific wavelength or higher. For example, it is possible to form an infrared transmission filter capable of blocking light with a wavelength of 400 nm to 900 nm and transmitting infrared light with a wavelength of 900 nm or more.

Also, the composition according to the present disclosure is preferably stored in a container.

As a storage container, it is also possible to use a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resin, or a bottle whose inner wall is made of 6 types of resin in 7 layers, in order to prevent impurities from entering the raw materials and compositions. preferable. Examples of these containers include containers described in JP-A-2015-123351.

<Membrane>

A film according to the present disclosure is a film comprising or cured from the composition according to the present disclosure. Moreover, when the composition contains a solvent, drying may be performed. A film according to the present disclosure can be preferably used as an infrared cut filter. It can also be used as a heat ray shielding filter or an infrared transmitting filter. The membrane according to the present disclosure may be used by being laminated on a support, or may be used by peeling from the support. A film according to the present disclosure may have a pattern or may be a film without a pattern (flat film).

"Drying" in the present disclosure may be achieved by removing at least a portion of the solvent, and it is not necessary to completely remove the solvent, and the amount of solvent to be removed can be set as desired.

Further, the above-mentioned curing may be performed as long as the hardness of the film is improved, but curing by polymerization is preferable.

The thickness of the film according to the present disclosure can be appropriately adjusted depending on the purpose. The thickness of the film is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the thickness of the film is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.

The film according to the present disclosure preferably has a maximum absorption wavelength in the wavelength range of 650 nm to 1,500 nm, more preferably has a maximum absorption wavelength in the wavelength range of 680 nm to 1,300 nm, and a wavelength of 700 nm to 1,100 nm. It is more preferable to have a maximum absorption wavelength in the range of .

When the film according to the present disclosure is used as an infrared cut filter, the film according to the present disclosure preferably satisfies at least one of the following (1) to (4), and (1) to (4) It is more preferable to satisfy all the conditions.

(1) The transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 80% or more, even more preferably 85% or more, and particularly preferably 90% or more.

(2) The transmittance at a wavelength of 500 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.

(3) The transmittance at a wavelength of 600 nm is preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, and particularly preferably 95% or more.

(4) The transmittance at a wavelength of 650 nm is preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, and particularly preferably 95% or more.

Films according to the present disclosure can also be used in combination with color filters containing chromatic colorants. A color filter can be produced using a coloring composition containing a chromatic colorant. Examples of the chromatic colorant include the chromatic colorants described in the section of the composition according to the present disclosure. The coloring composition can further contain a resin, a polymerizable compound, a polymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber, and the like. These details include the materials described above and can be used.

When a film according to the present disclosure and a color filter are used in combination, it is preferred that the color filter is arranged in the optical path of the film according to the present disclosure. For example, a film according to the present disclosure and a color filter can be laminated and used as a laminate. In the laminate, the film and the color filter according to the present disclosure may or may not be adjacent in the thickness direction. When the film according to the present disclosure and the color filter are not adjacent in the thickness direction, the film according to the present disclosure may be formed on a support other than the support on which the color filter is formed. Other members (for example, microlenses, planarization layers, etc.) that constitute the solid-state imaging device may be interposed between the disclosed film and the color filter.

In the present disclosure, an infrared cut filter means a filter that transmits light with wavelengths in the visible region (visible light) and blocks at least part of light with wavelengths in the near-infrared region (infrared rays). The infrared cut filter may transmit all light of wavelengths in the visible region, and among the light of wavelengths in the visible region, it allows light in a specific wavelength region to pass and blocks light in a specific wavelength region. can be anything. In addition, in the present disclosure, a color filter means a filter that allows light in a specific wavelength region to pass through and blocks light in a specific wavelength region among light with wavelengths in the visible region. Further, in the present disclosure, an infrared transmission filter means a filter that blocks visible light and transmits at least part of infrared light.

The film according to the present disclosure can be used in various devices such as solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal-oxide semiconductors), infrared sensors, and image display devices.

<Method for producing membrane>

Next, a method for manufacturing a film according to the present disclosure will be described. A film according to the present disclosure can be manufactured through a step of applying a composition according to the present disclosure.

In the method of manufacturing a membrane according to the present disclosure, the composition is preferably applied onto a support. Examples of the support include substrates made of materials such as silicon, non-alkali glass, soda glass, Pyrex (registered trademark) glass, and quartz glass. An organic film, an inorganic film, or the like may be formed on these substrates. Materials for the organic film include, for example, the resins described above. A substrate made of the above-described resin can also be used as the support. Moreover, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support. In some cases, the support also has a black matrix that isolates each pixel. If necessary, the support may be provided with an undercoat layer for improving adhesion to the upper layer, preventing diffusion of substances, or planarizing the surface of the substrate. Moreover, when a glass substrate is used as the support, it is preferable to form an inorganic film on the glass substrate or dealkalize the glass substrate before use. According to this aspect, it is easy to manufacture a film in which the generation of foreign matter is further suppressed.

As a method for applying the composition, a known method can be used. For example, drop method (drop cast); slit coating method; spray method; roll coating method; spin coating method (spin coating); methods described in publications); inkjet (e.g., on-demand method, piezo method, thermal method), discharge system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Examples include various printing methods; transfer methods using molds and the like; nanoimprinting methods and the like. The application method for inkjet is not particularly limited. 133 page), and methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. mentioned.

The composition layer formed by applying the composition may be dried (pre-baked). If the pattern is formed by a low temperature process, prebaking may not be performed. When pre-baking is performed, the pre-baking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower. The lower limit is, for example, preferably 50° C. or higher, more preferably 80° C. or higher. By setting the pre-baking temperature to 150° C. or lower, for example, when the photoelectric conversion film of the image sensor is made of an organic material, these characteristics can be maintained more effectively.

The prebaking time is preferably 10 seconds to 3,000 seconds, more preferably 40 seconds to 2,500 seconds, and even more preferably 80 seconds to 220 seconds. Drying can be performed using a hot plate, an oven, or the like.

The film manufacturing method according to the present disclosure 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. Note that when the film according to the present disclosure is used as a flat film, the step of forming a pattern may not be performed. The process of forming the pattern will be described in detail below.

- Pattern formation by photolithography -

The pattern formation method by photolithography includes a step of patternwise exposing the composition layer formed by applying the composition according to the present disclosure (exposure step), and developing and removing the unexposed portion of the composition layer. and a step of forming a pattern (developing step). If necessary, a step of baking the developed pattern (post-baking step) may be provided. Each step will be described below.

<<Exposure process>>

In the exposure step, the composition layer is exposed patternwise. For example, the composition layer can be pattern-exposed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure device such as a stepper. Thereby, the exposed portion can be cured. As the radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are preferable, and i-line is more preferable. The irradiation amount (exposure amount) is, for example, preferably 0.03 J/cm ² to 2.5 J/cm ² , more preferably 0.05 J/cm ² to 1.0 J/cm ² , and 0.08 J/cm ² to 0.5 J/cm ² is particularly preferred. The oxygen concentration at the time of exposure can be selected as appropriate. ), or in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (eg, 22% by volume, 30% by volume, 50% by volume). The exposure illuminance can be set as appropriate, and is preferably 1,000 W/m ² to 100,000 W/m ² (eg, 5,000 W/m ² , 15,000 W/m ² , 35,000 W/m 2 m ² ). Oxygen concentration and exposure illuminance may be appropriately combined. For example, illuminance of 10,000 W/m ² at oxygen concentration of 10% by volume and illuminance of 20,000 W/m ² at oxygen concentration of 35% by volume.

<<development process>>

Next, an unexposed portion of the composition layer after exposure is removed by development to form a pattern. The development and removal of the composition layer in the unexposed area can be carried out using a developer. As a result, the unexposed portion of the composition layer in the exposure step is eluted into the developer, leaving only the photocured portion on the support. As the developing solution, an alkaline developing solution that does not damage the underlying solid-state imaging device, circuits, and the like is desirable. The temperature of the developer is preferably 20° C. to 30° C., for example. The development time is preferably 20 seconds to 180 seconds. Further, in order to improve the residue removability, the step of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.

Alkaline agents used in the developer include, for example, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Organic alkalis such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate. As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 1% by mass. Moreover, you may use surfactant for a developer. Examples of surfactants include the surfactants described in the composition above, and nonionic surfactants are preferred. From the viewpoint of transportation and storage convenience, the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 times to 100 times. In the case of using such a developer comprising an alkaline aqueous solution, it is preferable to wash (rinse) with pure water after development.

Heat treatment (post-baking) can also be performed after drying after development. Post-baking is a post-development heat treatment for complete curing of the film. When post-baking is performed, the post-baking temperature is preferably 100° C. to 240° C., for example. From the viewpoint of film hardening, 200° C. to 230° C. is more preferable. When an organic electroluminescence (organic EL) element is used as the light source, or when the photoelectric conversion film of the image sensor is made of an organic material, the post-bake temperature is preferably 150° C. or less, more preferably 120° C. or less. It is preferably 100° C. or lower, more preferably 90° C. or lower. The lower limit can be, for example, 50° C. or higher. Post-baking should be performed continuously or batchwise using a heating means such as a hot plate, convection oven (hot air circulating dryer), high-frequency heater, etc. so that the film after development satisfies the above conditions. can be done. Further, when a pattern is formed by a low-temperature process, post-baking may not be performed, and a step of exposing again (post-exposure step) may be added.

- Pattern formation by dry etching -

Pattern formation by a dry etching method involves curing a composition layer formed by coating a composition on a support or the like to form a cured layer, and then forming a photoresist layer patterned on the cured layer. is formed, and then dry etching is performed on the cured product layer using an etching gas using the patterned photoresist layer as a mask. In forming the photoresist layer, it is preferable to further perform a pre-baking process. In particular, as a photoresist forming process, a mode in which heat treatment after exposure and heat treatment (post-baking treatment) after development are performed is desirable. Regarding pattern formation by a dry etching method, the descriptions in paragraphs 0010 to 0067 of JP-A-2013-64993 can be referred to, and the contents thereof are incorporated herein.

<Optical filter and laminate>

An optical filter according to the present disclosure has a film according to the present disclosure.

The optical filter according to the present disclosure can be preferably used as at least one optical filter selected from the group consisting of an infrared cut filter and an infrared transmission filter, and more preferably used as an infrared cut filter.

An embodiment having a film according to the present disclosure and pixels selected from the group consisting of red, green, blue, magenta, yellow, cyan, black and colorless is also a preferred embodiment of the optical filter according to the present disclosure.

A laminate according to the present disclosure is a laminate having the film according to the present disclosure and a color filter containing a chromatic colorant.

An infrared cut filter according to the present disclosure has a membrane according to the present disclosure.

Note that the infrared cut filter according to the present disclosure may be a filter that cuts only infrared light with a partial wavelength in the infrared region, or a filter that cuts the entire infrared region. A near-infrared cut filter is an example of a filter that cuts only infrared light with a partial wavelength in the infrared region. The near-infrared rays include infrared rays with a wavelength of 750 nm to 2,500 nm.

In addition, the infrared cut filter according to the present disclosure is preferably a filter that cuts infrared rays in the wavelength range of 750 nm to 1,000 nm, more preferably a filter that cuts infrared rays in the wavelength range of 750 nm to 1,200 nm. More preferably, it is a filter that cuts infrared rays with a wavelength of 750 nm to 1,500 nm.

The infrared cut filter according to the present disclosure may further have a layer containing copper, a dielectric multilayer film, an ultraviolet absorption layer, etc., in addition to the above films. Since the infrared cut filter according to the present disclosure further has at least a copper-containing layer or a dielectric multilayer film, it is easy to obtain an infrared cut filter with a wide viewing angle and excellent infrared shielding properties. Further, since the infrared cut filter according to the present disclosure further includes an ultraviolet absorbing layer, it can be an infrared cut filter having excellent ultraviolet shielding properties. As the ultraviolet absorbing layer, for example, the absorbing layers described in paragraphs 0040 to 0070 and 0119 to 0145 of WO 2015/099060 can be considered, the contents of which are incorporated herein. As for the dielectric multilayer film, descriptions in paragraphs 0255 to 0259 of JP-A-2014-41318 can be referred to, and the contents thereof are incorporated herein. 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 be used. Copper-containing glass substrates include copper-containing phosphate glass, copper-containing fluorophosphate glass, and the like. Commercially available copper-containing glasses include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (manufactured by Schott), CD5000 (manufactured by HOYA Corporation), and the like.

The infrared cut filter according to the present disclosure can be used in various devices such as solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal-oxide semiconductors), infrared sensors, and image display devices.

The infrared cut filter according to the present disclosure is a film pixel (pattern) obtained using the composition according to the present disclosure, and at least selected from the group consisting of red, green, blue, magenta, yellow, cyan, black and colorless. A mode having one kind of pixels (pattern) is also a preferred mode.

The method for producing the optical filter according to the present disclosure is not particularly limited, but includes the steps of applying the composition of the present disclosure onto a support to form a composition layer, and exposing the composition layer in a pattern. and developing and removing the unexposed areas to form a pattern, or applying a composition according to the present disclosure onto a support to form a composition layer and curing to form a layer forming a photoresist layer on the layer; patterning the photoresist layer by exposing and developing to obtain a resist pattern; and drying the layer using the resist pattern as an etching mask. A method including an etching step is preferred.

As each step in the method for manufacturing an optical filter according to the present disclosure, each step in the method for manufacturing a film according to the present disclosure can be referred to.

<Solid-state image sensor>

A solid-state imaging device according to the present disclosure has a film according to the present disclosure. The configuration of the solid-state imaging device is not particularly limited as long as it has a film according to the present disclosure and functions as a solid-state imaging device. For example, the following configuration can be mentioned.

A plurality of photodiodes constituting the light receiving area of the solid-state imaging device and transfer electrodes made of polysilicon or the like are provided on the support, and light shielding made of tungsten or the like with only the light receiving portions of the photodiodes being opened on the photodiodes and the transfer electrodes. a film, a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving part, and a film according to the present disclosure on the device protective film is. Furthermore, on the device protective film, under the film according to the present disclosure (on the side close to the support), a light collecting means (for example, a microlens, etc.; the same shall apply hereinafter), or on the film according to the present disclosure A configuration having a condensing means or the like may also be used. A color filter used in a solid-state imaging device may have a structure in which a film forming each pixel is embedded in a space partitioned, for example, in a grid pattern by partition walls. The partition in this case preferably has a lower refractive index than each pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478 and JP-A-2014-179577.

<Image display device>

An image display device according to the present disclosure has a film according to the present disclosure. Examples of image display devices include liquid crystal display devices and organic electroluminescence (organic EL) display devices. For the definition and details of the image display device, see, for example, "Electronic display device (authored by Akio Sasaki, published by Kogyo Choukai Co., Ltd., 1990)" and "Display device (authored by Junsho Ibuki, published by Sangyo Tosho Co., Ltd., 1989). )”, etc. Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994)". There is no particular limitation on the liquid crystal display device that can be applied to the present disclosure, and for example, it can be applied to liquid crystal display devices of various types described in the above-mentioned "next-generation liquid crystal display technology". The image display device may have a white organic EL element. A white organic EL device preferably has a tandem structure. Regarding the tandem structure of organic EL elements, see Japanese Patent Application Laid-Open No. 2003-45676, supervised by Akiyoshi Mikami, "Forefront of Organic EL Technology Development -High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association, 326-328, 2008, and others. The spectrum of white light emitted by the organic EL device preferably has strong maximum emission peaks in the blue region (430 nm-485 nm), green region (530 nm-580 nm) and yellow region (580 nm-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferred.

<Infrared sensor>

An infrared sensor according to the present disclosure has a membrane according to the present disclosure. The configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. An embodiment of an infrared sensor according to the present disclosure will be described below with reference to the drawings.

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

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

The color filter 112 is a color filter formed with pixels that transmit and absorb light of a specific wavelength in the visible region, and is not particularly limited, and conventionally known color filters for forming pixels can be used. For example, a color filter having red (R), green (G), and blue (B) pixels is used. For example, the description of paragraphs 0214 to 0263 of JP-A-2014-43556 can be taken into consideration, and this content is incorporated herein.

The characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used. For example, when the emission wavelength of the infrared LED is 850 nm, the infrared transmission filter 114 preferably has a maximum light transmittance of 30% or less in the wavelength range of 400 nm to 650 nm in the thickness direction of the film. % or less, more preferably 10% or less, and particularly preferably 0.1% or less. The transmittance preferably satisfies the above conditions over the entire wavelength range of 400 nm to 650 nm.

In the infrared transmission filter 114, the minimum value of the light transmittance in the thickness direction of the film in the wavelength range of 800 nm or more (preferably 800 nm to 1,300 nm) is preferably 70% or more, preferably 80% or more. More preferably, it is 90% or more. The above transmittance preferably satisfies the above conditions in a part of the wavelength range of 800 nm or longer, and more preferably satisfies the above conditions at a wavelength corresponding to the emission wavelength of the infrared LED.

The film thickness of the infrared transmission filter 114 is preferably 100 μm or less, more preferably 15 μm or less, even more preferably 5 μm or less, and particularly preferably 1 μm or less. The lower limit is preferably 0.1 μm. If the film thickness is within the above range, the film can satisfy the spectral characteristics described above.

A method for measuring the spectral characteristics, film thickness, etc. of the infrared transmission filter 114 will be described below.

The film thickness is measured using a stylus profilometer (DEKTAK150 manufactured by ULVAC) on the dried substrate having the film.

The spectral characteristics of the film are the values obtained by measuring the transmittance in the wavelength range of 300 nm to 1,300 nm using an ultraviolet-visible-near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

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

In the infrared sensor shown in FIG. 1 , an infrared cut filter (another infrared cut filter) different from the infrared cut filter 111 may be further arranged on the planarization layer 116 . Other infrared cut filters include those having at least a layer containing copper or a dielectric multilayer film. These details are given above. A dual bandpass filter may be used as another infrared cut filter.

Also, the absorption wavelengths of the infrared transmission filter and the infrared cut filter used in the present disclosure are appropriately combined according to the light source used.

(The camera module)

A camera module according to the present disclosure has a solid-state imaging device and an infrared cut filter according to the present disclosure.

Also, the camera module according to the present disclosure preferably further includes a lens and a circuit for processing an image obtained from the solid-state imaging device.

The solid-state imaging device used in the camera module according to the present disclosure may be the solid-state imaging device according to the present disclosure or a known solid-state imaging device.

Also, known lenses can be used as the lens used in the camera module according to the present disclosure and as a circuit for processing the image obtained from the solid-state imaging device.

As an example of the camera module, the camera module described in JP-A-2016-6476 or JP-A-2014-197190 can be considered, the contents of which are incorporated herein.

(Compound)

The compound according to the present disclosure is a compound having a structure represented by the above formula (1), and from the viewpoint of light resistance and heat resistance, it is preferably a compound represented by the following formula (P1).

A compound according to the present disclosure can be suitably used as an infrared absorbing dye.

In formula (P1), X ^P1 to X ^P6 each independently represent a single bond, -O-, -S-, -CH ₂ -, -N=, -CH=CH- or -NR ^P11 -, R ^P1 and R ^P2 each independently represent an alkyl group, an aryl group, a heteroaryl group, or a group represented by the following formula (P2), and R ^P3 to R ^P6 each independently represent a cyano group, an acyl group, an alkoxy represents a carbonyl group, an alkyl group, an arylsulfinyl group or a heteroaryl group, R ^P7 to R ^P10 each independently represents a hydrogen atom or a substituent, R ^P11 represents a hydrogen atom, an alkyl group or an aryl group, p1 to p4 each independently represents an integer of 0 to 4;

In formula (P2), X ^P11 represents a m-phenylene group, a p-phenylene group, a divalent condensed polycyclic aromatic ring group in which two or more aromatic rings are condensed, or a divalent heteroaromatic ring group, and L ^P11 is represents a single bond or a divalent linking group, Y ^P11 represents a substituent, and * represents a linking site to the pyrrolopyrrole ring in formula (P1).

The compound having the structure represented by formula (1) in the compound according to the present disclosure and the compound represented by formula (P1) have the structure represented by formula (1) described above in the composition according to the present disclosure. and the compound represented by the formula (P1) are synonymous, respectively, and preferred embodiments are also the same.

The method for producing the compound according to the present disclosure is not particularly limited, and the compound can be produced as appropriate with reference to known production methods.

For example, a method of producing by reacting a compound having a dye structure with a boron compound is suitable.

(Dispersion composition)

The dispersion composition according to the present disclosure contains a compound having a structure represented by formula (1) below and at least one compound selected from the group consisting of solvents, binders and curable compounds.

In formula (1), X each independently represents a single bond or a linking group, Z ¹ and Z ² each independently represent a group forming an aliphatic ring or an aromatic ring, and from R ⁹ and R ¹⁰ A group having a dye structure is bonded or coordinated in at least one selected from the group consisting of R ⁹ or R ¹⁰ in which the group having a dye structure is not bonded or coordinated represents a substituent, Also, R ⁹ and R ¹⁰ may combine with each other to form a ring together with the boron atom.

The compound, solvent, binder and curable compound having the structure represented by the above formula (1) in the dispersion composition according to the present disclosure are the structures represented by the above formula (1) in the composition according to the present disclosure. are synonymous with compounds having

In addition, the composition according to the present disclosure can suitably contain the above-described components as components other than those described above.

When the compound having the structure represented by formula (1) is a pigment, the dispersion composition according to the present disclosure preferably contains a dispersant from the viewpoint of dispersibility and dispersion stability.

Further, when the compound having the structure represented by the above formula (1) is a pigment, the dispersion composition according to the present disclosure preferably contains a pigment derivative from the viewpoint of dispersibility and dispersion stability, More preferably, it contains a pigment derivative.

The dispersant and the dye derivative in the dispersion composition according to the present disclosure are synonymous with the dispersant and the dye derivative described above in the composition according to the present disclosure, respectively, and preferred embodiments are also the same.

EXAMPLES The present disclosure will be described more specifically with reference to examples below. Materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present disclosure. Accordingly, the scope of the present disclosure is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

(Synthesis example 1)

PPB-A-2 was synthesized by the method shown in the scheme below. Details are given below.

<Synthesis of Intermediate-2>

10.52 g of 5,5-dimethyl-5H-dibenzo[b,d]silole was added to the flask, and the inside of the flask was replaced with nitrogen. 25 g of boron tribromide was added thereto and stirred at 50° C. for 24 hours. After the reaction solution was cooled to room temperature and further cooled to -30°C, 100 mL of separately prepared ice water and 150 mL of ethyl acetate (EtOAc) were added dropwise while maintaining the internal temperature below -10°C. After stirring this solution for 20 minutes, liquid separation operation was performed, and the obtained organic layer was washed with 100 mL of brine. After the organic layer was dried with magnesium sulfate, it was filtered to remove salts, and 2.9 g of ethanolamine was added to the obtained filtrate and concentrated. After adding 100 mL of hexane to the concentrated liquid and stirring, the hexane was removed by decanting, and after adding 100 mL of hexane again and stirring, the hexane was removed by decanting. 30 mL of water/methanol (1:1 solution) was added to the resulting residue and stirred for 30 minutes. By filtering this solution, 4.1 g of Intermediate-2 was obtained.

<Synthesis of Intermediate-3>

Synthesized with reference to the descriptions in International Publication No. 2018/020861 and Japanese Patent No. 6329626.

<Synthesis of PPB-A-2>

1.04 g of intermediate-2 and 8 mL of o-dichlorobenzene were added to the flask, and the inside of the flask was replaced with nitrogen. 1.48 g of titanium tetrachloride was added dropwise thereto and stirred at 40° C. for 30 minutes. 0.5 g of Intermediate-3 was added to this solution and washed with 2 mL of o-dichlorobenzene. The reaction solution was stirred at 40°C for 20 minutes, then at 85°C for 1 hour, and further stirred at 125°C for 2.5 hours. The reaction solution was cooled to room temperature, 20 mL of hexane was added, and the mixture was stirred for 30 minutes. This solution was filtered to obtain 1.0 g of PPB-A-2.

¹ H-NMR (dTHF): δ = 6.03 (d, 4H), 6.13 (d, 4H), 7.00-7.60 (m, 16H), 8.13 (s, 2H), 8.24 (s, 2H), 8.63 (brs, 2H), 9.14 (s, 2H).

The λmax of PPB-A-2 was 898 nm in tetrahydrofuran (THF).

(Synthesis example 2)

PPB-C-4 was synthesized by the method shown in the scheme below. Details are given below.

<Synthesis of Intermediate-5>

In a nitrogen atmosphere, 8.3 g of trimethoxyborane, 400 mL of acetonitrile and 14.9 g of 2,2'-dihydroxybiphenyl were added to the flask and stirred at 60°C for 1 hour. 4.9 g of ethanolamine was added to this solution and stirred for 2 hours. After the solution was cooled to room temperature, it was filtered and washed with 100 mL of acetonitrile. The resulting filter cake was dried to obtain 16 g of Intermediate-5.

<Synthesis of Intermediate-6>

Synthesized with reference to the descriptions in International Publication No. 2018/020861 and Japanese Patent No. 6329626.

<Synthesis of PPB-C-4>

3.2 g of Intermediate-5 and 25 g of dehydrated toluene were added to the flask, and the inside of the flask was replaced with nitrogen. 3.58 g of titanium tetrachloride was added dropwise to this solution and stirred at 30° C. for 30 minutes. 2.5 g of Intermediate-6 was added to this reaction solution, and the mixture was stirred under reflux with heating for 2.5 hours. After cooling this reaction liquid to room temperature, 100 mL of water and 100 mL of chloroform were added, liquid separation operation was performed, and the obtained organic layer was wash|cleaned by 100 mL of saturated multistory water. The organic layer was dried over magnesium sulfate, filtered to remove salts, and the obtained filtrate was concentrated. The concentrate was purified by silica gel column chromatography (solvent: chloroform) to obtain 1.05 g of PPB-C-4.

¹ H-NMR (heavy chloroform): δ = 7.32 to 7.46 (m, 6H), 7.03 to 7.18 (m, 6H), 6.80 to 7.02 (m, 12H), 6.59-6.71 (m, 4H), 6.31-6.47 (m, 4H), 3.34-3.89 (m, 4H), 0.60-1.89 (m, 78H) ).

The λmax of PPB-C-4 was 696 nm in chloroform.

Compounds used in Examples and Comparative Examples other than those described above are shown below.

Note that * in the following structure represents a bonding portion with -O-.

<Dyes and dye derivatives>

SQ-D-1 is a compound described in JP-A-2017-165857.

<Dispersion resin>

D-1: Resin having the following structure (acid value = 100 mg KOH / g, weight average molecular weight = 37,600, the numerical value attached to the main chain represents the molar ratio of the repeating unit, and the numerical value attached to the side chain is the number of repeating units. represents a number.)

D-2: Resin having the following structure (acid value = 32.3 mgKOH/g, amine value = 45.0 mgKOH/g, weight average molecular weight = 22,900, the numerical value attached to the main chain represents the molar ratio of the repeating unit, The number attached to the side chain represents the number of repeating units.)

<Resin>

E-1: Acrybase FF-426 (manufactured by Fujikura Kasei Co., Ltd., alkali-soluble resin)

E-2: ARTON F4520 (manufactured by JSR Corporation, cyclic polyolefin resin)

E-3: Resin having the following structure (Mw = 40,000, acid value 100 mgKOH/g, the numerical value attached to the main chain represents the mass ratio of repeating units. Alkali-soluble resin.)

<Photoinitiator>

<Polymerizable compound>

M-1: Aronix M-305 (manufactured by Toagosei Co., Ltd., a mixture of the following two compounds. The triacrylate content is 55% 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)

<Solvent>

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

CYP: Cyclopentanone

<Preparation of pigment dispersion>

10 parts by mass of the pigment described in Table 3 or Table 5 below, 3 parts by mass of the derivative described in Table 3 or Table 5 below, 7.8 parts by mass of the dispersant described in Table 3 or Table 5 below, propylene glycol methyl ether acetate ( 150 parts by mass of PGMEA) and 230 parts by mass of zirconia beads with a diameter of 0.3 mm were mixed, dispersed for 5 hours using a paint shaker, and the beads were separated by filtration to produce a dispersion.

<Evaluation of dispersibility>

-viscosity-

Using an E-type viscometer, the viscosity of the dispersion at 25° C. was measured at a rotation speed of 1,000 rpm and evaluated according to the following criteria.

A: 1 mPa s or more and 15 mPa s or less

B: more than 15 mPa s and 30 mPa s or less

C: more than 30 mPa s

-Particle size-

The average particle size of the pigment in the dispersion was measured on a volume basis using MICROTRACUPA 150 manufactured by Nikkiso Co., Ltd.

A: The average particle size of the pigment is 1 nm or more and 50 nm or less

B: The average particle size of the pigment is more than 50 nm and 100 nm or less

C: the average particle size of the pigment exceeds 100 nm

(Examples 1 to 39 and Comparative Examples 1 to 3)

<Evaluation method for pigment-type examples and comparative examples>

<<Preparation of curable composition 1>>

A curable composition was prepared by mixing the following components.

- Composition of curable composition -

- The dispersion liquid obtained above: 55 parts by mass

・Resin: 7.0 parts by mass

・Polymerizable compound: 4.5 parts by mass

・Photopolymerization initiator: 0.8 parts by mass

· Polymerization inhibitor (p-methoxyphenol): 0.001 parts by mass

Surfactant (the following mixture (Mw = 14,000). In the following formula, % indicating the proportion of repeating units is mass%.): 0.03 parts by mass

· Ultraviolet absorber (UV-503, manufactured by Daito Chemical Co., Ltd.): 1.3 parts by mass

・Solvent: 31 parts by mass

<<Preparation of cured film 1>>

The curable composition was applied onto a glass substrate by spin coating, and then heated at 100° C. for 2 minutes using a hot plate to obtain a composition layer. The obtained composition layer was exposed with an exposure dose of 500 mJ/cm ² using an i-line stepper. Then, the exposed composition layer was subjected to curing treatment at 220° C. for 5 minutes using a hot plate to obtain a cured film having a thickness of 0.7 μm.

<<Evaluation of heat resistance>>

The obtained film was heated at 260° C. for 300 seconds using a hot plate. The transmittance of the film before and after heating to light with a wavelength of 400 nm to 1200 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). In the wavelength range of 400 nm to 1200 nm, the change in transmittance at the wavelength at which the change in transmittance before and after heating was the largest was calculated from the following formula, and the change in transmittance was evaluated according to the following criteria.

Change in transmittance = | (transmittance after heating - transmittance before heating) |

A: transmittance change is less than 3%

B: Transmittance change is 3% or more and less than 5%

C: transmittance change is 5% or more

In addition, regarding the absorbance at the maximum absorption wavelength before and after heating, the residual rate was calculated from the following formula, and the residual rate was evaluated according to the following criteria.

Residual rate (%) = {(absorbance after heating) ÷ (absorbance before heating)} × 100

A: Residual rate is over 95% and 100% or less

B: Residual rate is over 80% and 95% or less

C: Residual rate is 80% or less

<<Evaluation of light resistance>>

The resulting film was set in a discoloration tester equipped with a super xenon lamp (100,000 lux), and irradiated with light of 100,000 lux for 50 hours without using an ultraviolet cut filter. Next, the transmission spectrum of the film after light irradiation was measured using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). In the wavelength range of 400 nm to 1200 nm, the transmittance change at the wavelength at which the change in transmittance before and after light irradiation was the largest was calculated from the following formula, and the heat resistance was evaluated according to the following criteria.

Transmittance change =|(Transmittance after light irradiation-Transmittance before light irradiation)|

A: transmittance change is less than 3%

B: Transmittance change is 3% or more and less than 5%

C: transmittance change is 5% or more

In addition, regarding the absorbance at the maximum absorption wavelength before and after light irradiation, the residual rate was calculated from the following formula and evaluated according to the following criteria.

Residual rate (%) = {(absorbance after light irradiation) ÷ (absorbance before light irradiation)} × 100

A: Residual rate is over 95% and 100% or less

B: Residual rate is over 80% and 95% or less

C: Residual rate is 80% or less

<Evaluation method for dye-type examples and comparative examples>

<<Preparation of dye solution>>

A dye solution was prepared by mixing 2.34 parts by weight of the dye shown in Table 3 or 5 below and 72.2 parts by weight of a solvent.

<<Preparation of curable composition 2>>

A curable composition was prepared by mixing the following components.

- Composition of curable composition -

・ Pigment solution: 74.5 parts by mass

・Resin (30% cyclopentanone solution): 20.1 parts by mass

- Polymerizable compound: 1.3 parts by mass

・Photopolymerization initiator: 1.4 parts by mass

· Polymerization inhibitor (p-methoxyphenol): 0.001 parts by mass

・ Megafac RS-72-K (fluorosurfactant, manufactured by DIC Corporation): 2.6 parts by mass

<<Preparation of curable composition 3>>

A curable composition was prepared by mixing the following components.

- Composition of curable composition -

・ Pigment solution: 74.5 parts by mass

・ Epoxy resin (30% cyclopentanone solution): 20.1 parts by mass

・ Epoxy curing agent: 0.05 parts by mass

The details of the epoxy resins and epoxy curing agents used in Examples and Comparative Examples are shown below.

-Epoxy resin-

F-1: Glycidyl methacrylate skeleton random polymer (manufactured by NOF Corporation, Marproof G-0150M, weight average molecular weight 10,000)

F-2: EPICLON HP-4700 (manufactured by DIC Corporation, naphthalene type epoxy resin)

F-3: JER1031S (manufactured by Mitsubishi Chemical Corporation, polyfunctional epoxy resin)

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

- Epoxy curing agent -

G-1: trimellitic acid

G-2: pyromellitic anhydride

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

G-4: pentaerythritol tetrakis (3-mercaptopropionate)

<<Preparation of cured film 2>>

Each curable composition prepared above was applied to a glass substrate by spin coating, then heated (pre-baked) at 80° C. for 10 minutes using a hot plate, and then heated at 150° C. for 3 hours to obtain a thickness. A film with a thickness of 0.7 μm was obtained.

<<Evaluation of heat resistance and light resistance>>

Heat resistance and light resistance were evaluated in the same manner as above.

The evaluation results are collectively shown in Tables 4 and 6.

From the results shown in Tables 4 and 6, it is clear that the compositions according to the present disclosure are superior in light resistance to the compositions of the comparative examples. Furthermore, it can be seen that the composition according to the present disclosure is also excellent in heat resistance.

Moreover, in Example 1, the same results as in Example 1 were obtained even when no polymerization inhibitor was added.

In Example 1, the same results as in Example 1 were obtained even when no surfactant was added.

In Example 1, even when 1/2 mass of Dispersion 1 was replaced with Dispersion 3, the same results as in Example 1 were obtained.

(Examples 101 to 139)

Using the compositions obtained in Examples 1 to 39, a 2 μm square pattern (infrared cut filter) was formed by the following method.

<In the case of the above composition preparation method 1 or 2>

The compositions obtained in Examples 1 to 22 or 27 to 38 were applied by spin coating so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it was heated at 100° C. for 2 minutes. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed at 1,000 mJ/cm ² through a 2 μm square dot pattern mask. Then, using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH), puddle development was performed at 23° C. for 60 seconds. After that, it was rinsed with a spin shower and then washed with pure water. Then, a hot plate was used to heat at 200° C. for 5 minutes to form a 2 μm square pattern (infrared cut filter).

<In the case of the above composition preparation method 3>

The composition obtained in Examples 23 to 26 or 39 was applied onto a silicon wafer by spin coating so that the film thickness after film formation was 1.0 μm. After that, using a hot plate, it was heated at 100° C. for 2 minutes. Then, using a hot plate, it was heated at 200° C. for 5 minutes. Then, a 2 μm square pattern (infrared cut filter) was formed by dry etching.

Next, the red composition was applied onto the pattern of the infrared cut filter by a spin coating method so that the film thickness after forming the film would be 1.0 μm. Then, using a hot plate, it was heated at 100° C. for 2 minutes. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed at 1,000 mJ/cm ² through a 2 μm square dot pattern mask. Then, using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH), puddle development was performed at 23° C. for 60 seconds. After that, it was rinsed with a spin shower and then washed with pure water. Then, the red composition was patterned on the pattern of the infrared cut filter by heating at 200° C. for 5 minutes using a hot plate. Similarly, the Green composition and the Blue composition were sequentially patterned to form red, green and blue colored patterns (Bayer patterns).

Note that the Bayer pattern means one red element, two green elements, and one blue element, as disclosed in US Pat. No. 3,971,065. ) elements, but in this example one Red element, one Green element, and one Blue element. ) elements and a 2×2 array of filter elements with one infrared-transmitting filter element was formed in a Bayer pattern.

Next, a composition for forming an infrared transmission filter (composition 100 or composition 101 below) was applied onto the pattern-formed film by a spin coating method so that the film thickness after forming the film would be 2.0 μm. Then, using a hot plate, it was heated at 100° C. for 2 minutes. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed at 1,000 mJ/cm ² through a 2 μm square Bayer pattern mask. Then, using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH), puddle development was performed at 23° C. for 60 seconds. After that, it was rinsed with a spin shower and then washed with pure water. Next, by heating at 200° C. for 5 minutes using a hot plate, patterning of an infrared transmission filter was performed in the missing portions where the colored pattern was not formed in the Bayer pattern of the infrared cut filter. This was incorporated into a solid-state imaging device according to a known method.

The obtained solid-state imaging device was irradiated with infrared light from an infrared light emitting diode (infrared LED) under a low illuminance environment (0.001 lux (Lux)), an image was captured, and image performance was evaluated. Images could be clearly recognized even in a low illuminance environment when any of the compositions obtained in Examples 1 to 32 were used.

The Red composition, Green composition, Blue composition, and composition for forming an infrared transmission filter used in Examples 101 to 139 are as follows.

- Red composition -

After mixing and stirring the following components, the mixture was filtered through a nylon filter having a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a red composition.

Red pigment dispersion: 51.7 parts by mass

Resin 4 (40% by mass PGMEA solution): 0.6 parts by mass

Polymerizable compound 4: 0.6 parts by mass

Photoinitiator 1: 0.3 parts by mass

Surfactant 1: 4.2 parts by mass

PGMEA: 42.6 parts by mass

- Green composition -

After mixing and stirring the following components, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a green composition.

Green pigment dispersion: 73.7 parts by mass

Resin 4 (40% by mass PGMEA solution): 0.3 parts by mass

Polymerizable compound 1: 1.2 parts by mass

Photoinitiator 1: 0.6 parts by mass

Surfactant 1: 4.2 parts by mass

Ultraviolet absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.): 0.5 parts by mass

PGMEA: 19.5 parts by mass

-Blue composition-

After mixing and stirring the following components, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a Blue composition.

Blue pigment dispersion: 44.9 parts by mass

Resin 4 (40% by mass PGMEA solution): 2.1 parts by mass

Polymerizable compound 1: 1.5 parts by mass

Polymerizable compound 4: 0.7 parts by mass

Photopolymerization initiator 1: 0.8 parts by mass

Surfactant 1: 4.2 parts by mass

PGMEA: 45.8 parts by mass

-Composition for forming an infrared transmission filter-

After mixing and stirring the components in the following composition, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a composition for forming an infrared transmission filter.

<Composition 100>

Pigment dispersion liquid 1-1: 46.5 parts by mass

Pigment dispersion liquid 1-2: 37.1 parts by mass

Polymerizable compound 5: 1.8 parts by mass

Resin 4: 1.1 parts by mass

Photoinitiator 2: 0.9 parts by mass

Surfactant 1: 4.2 parts by mass

Polymerization inhibitor (p-methoxyphenol): 0.001 part by mass

Silane coupling agent: 0.6 parts by mass

PGMEA: 7.8 parts by mass

<Composition 101>

Pigment dispersion liquid 2-1: 1,000 parts by mass

Polymerizable compound (dipentaerythritol hexaacrylate): 50 parts by mass

Resin: 17 parts by mass

Photopolymerization initiator (1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime)): 10 parts by mass

PGMEA: 179 parts by mass

Alkali-soluble polymer F-1: 17 parts by mass (solid content concentration 35 parts by mass)

<Synthesis example of alkali-soluble polymer F-1>

In a reaction vessel, 14 parts of benzyl methacrylate, 12 parts of N-phenylmaleimide, 15 parts of 2-hydroxyethyl methacrylate, 10 parts of styrene and 20 parts of methacrylic acid are dissolved in 200 parts of propylene glycol monomethyl ether acetate. 3 parts of azoisobutyronitrile and 5 parts of α-methylstyrene dimer are charged. After purging the interior of the reaction vessel with nitrogen, the mixture was heated at 80° C. for 5 hours with stirring and nitrogen bubbling to obtain a solution containing alkali-soluble polymer F-1 (solid concentration: 35% by mass). This polymer had a polystyrene equivalent weight average molecular weight of 9,700, a number average molecular weight of 5,700, and an Mw/Mn ratio of 1.70.

<Pigment Dispersion Liquid 2-1>

C. I. Pigment Black 32, 60 parts, C.I. I. Pigment Blue 15:6, 20 parts, C.I. I. 20 parts of Pigment Yellow 139, 80 parts of Solsperse 76500 manufactured by Nippon Lubrizol Co., Ltd. (solid concentration: 50% by mass), 120 parts of solution containing alkali-soluble polymer F-1 (solid concentration: 35% by mass) and 700 parts of propylene glycol monomethyl ether acetate were mixed and dispersed for 8 hours using a paint shaker to obtain a colorant dispersion liquid 2-1.

Raw materials used for the Red composition, the Green composition, the Blue composition, and the composition for forming an infrared transmission filter are as follows.

・Red pigment dispersion

C. I. Pigment Red 254, 9.6 parts by mass, C.I. I. A mixture of 4.3 parts by mass of Pigment Yellow 139, 6.8 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by mass of PGMEA was passed through a bead mill (zirconia beads with a diameter of 0.3 mm). ) for 3 hours to prepare a pigment dispersion. Further, dispersion treatment was carried out using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism under a pressure of 2,000 kg/cm ³ and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a red pigment dispersion.

・Green pigment dispersion

C. I. Pigment Green 36, 6.4 parts by mass, C.I. I. A mixture of 5.3 parts by weight of Pigment Yellow 150, 5.2 parts by weight of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by weight of PGMEA was prepared in a bead mill (zirconia beads 0.3 mm diameter). A pigment dispersion was prepared by mixing and dispersing for 3 hours. Further, dispersion treatment was carried out using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism under a pressure of 2,000 kg/cm ³ and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a green pigment dispersion.

・Blue pigment dispersion

C. I. Pigment Blue 15:6, 9.7 parts by mass, C.I. I. A mixture of 2.4 parts by mass of Pigment Violet 23, 5.5 parts of a dispersant (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts of PGMEA was milled with a bead mill (zirconia beads 0.3 mm diameter). A pigment dispersion was prepared by mixing and dispersing for hours. Further, dispersion treatment was carried out using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism under a pressure of 2,000 kg/cm ³ and a flow rate of 500 g/min. This dispersion treatment was repeated 10 times to obtain a blue pigment dispersion.

・ Pigment dispersion liquid 1-1

A mixed liquid having the following composition was mixed and dispersed for 3 hours in a bead mill (high-pressure disperser NANO-3000-10 with decompression mechanism (manufactured by Nippon BEE Co., Ltd.)) using 0.3 mm diameter zirconia beads. Thus, a pigment dispersion liquid 1-1 was prepared.

-Mixed pigment consisting of a red pigment (C.I. Pigment Red 254) and a yellow pigment (C.I. Pigment Yellow 139): 11.8 parts by mass

・ Resin (Disperbyk-111, manufactured by BYK Chemie): 9.1 parts by mass

・PGMEA: 79.1 parts by mass

・ Pigment dispersion liquid 1-2

A mixed liquid having the following composition was mixed and dispersed for 3 hours in a bead mill (high-pressure disperser NANO-3000-10 with decompression mechanism (manufactured by Nippon BEE Co., Ltd.)) using 0.3 mm diameter zirconia beads. Thus, a pigment dispersion 1-2 was prepared.

- Mixed pigment consisting of a blue pigment (C.I. Pigment Blue 15:6) and a purple pigment (C.I. Pigment Violet 23): 12.6 parts by mass

・ Resin (Disperbyk-111, manufactured by BYK Chemie): 2.0 parts by mass

・Resin A: 3.3 parts by mass

・Cyclohexanone: 31.2 parts by mass

・PGMEA: 50.9 parts by mass

Resin A: Structure below (Mw = 14,000, the ratio in each structural unit is the molar ratio.)

- Polymerizable compound 1: KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

- Polymerizable compound 4: the following structure

-Polymerizable compound 5: the following structure (a mixture of the left compound and the right compound in a molar ratio of 7:3)

- Resin 4: The following structure (acid value: 70 mg KOH/g, Mw = 11,000, the ratio in each structural unit is the molar ratio.)

- Photopolymerization initiator 1: IRGACURE-OXE01 (1-[4-(phenylthio)]-1,2-octanedione-2-(O-benzoyloxime), manufactured by BASF)

- Photoinitiator 2: the following structure

- Surfactant 1: 1 wt% PGMEA solution of the following mixture (Mw = 14,000). In the following formulas, the unit of % (62% and 38%) indicating the ratio of structural units is % by mass.

• Silane coupling agent: A compound having the following structure. In the structural formulas below, Et represents an ethyl group.

(Example 201)

After the following components were mixed and stirred, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a pattern forming composition of Example 201.

Pattern-forming composition of Example 1: 22.67 parts by mass

Pigment dispersion liquid 2-1: 51.23 parts by mass

Using the pattern forming composition of Example 201, heat resistance, pattern shape, and development residue were evaluated in the same manner as in Example 1. As a result, the same effects as in Example 1 were obtained. In addition, the cured film obtained using the pattern forming composition of Example 201 blocks light with wavelengths in the visible region and transmits at least part of light with wavelengths in the near infrared region (near infrared rays). I was able to

(Example 202)

After the following components were mixed and stirred, the mixture was filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a pattern forming composition of Example 202.

Pattern-forming composition of Example 1: 36.99 parts by mass

Pigment dispersion liquid 1-1: 46.5 parts by mass

Pigment dispersion liquid 1-2: 37.1 parts by mass

Using the pattern forming composition of Example 202, heat resistance, pattern shape, and development residue were evaluated in the same manner as in Example 1. As a result, the same effects as in Example 1 were obtained. In addition, the cured film obtained using the pattern forming composition of Example 202 blocks light with wavelengths in the visible region and transmits at least part of light with wavelengths in the near infrared region (near infrared rays). I was able to

(Example 301)

Infrared shielding properties, heat resistance, pattern shape, Also, the same effect as in Examples 1 to 39 can be obtained even when the development residue is evaluated.

(Example 302)

The same heat resistance, pattern The same effect as in Examples 201 and 202 can be obtained by evaluating the shape and development residue.

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

Claims (15)

a compound having a structure represented by the following formula ( 2 );
At least one compound selected from the group consisting of a binder and a curable compound ,
A dye structure in a group having a dye structure bonded or coordinated in at least one selected from the group consisting of R ⁹ and R ¹⁰ in a compound having a structure represented by the formula (2) is a pyrrolopyrrole dye structure , squarylium dye structure, croconium dye structure, indigo dye structure, anthraquinone dye structure, diimmonium dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, polymethine dye structure, xanthene dye structure, quinacridone dye structure, azo dye structure, and quinoline dye at least one dye structure selected from the group consisting of structures
Composition.

^In formula (2), ^X represents a single bond or a divalent linking group, R ¹ to R ⁸ each independently represent a hydrogen atom or a substituent, and at least R ⁹ or R ¹⁰ to which a group having a dye structure is bonded or coordinated in one and to which the group having a dye structure is not bonded or coordinated represents a substituent, and R ⁹ and R ¹⁰ may combine with each other to form a ring with the boron atom. The composition according to claim ¹ , wherein X in formula (2) is a single bond, O, S, _CH2 , -CH=CH-, or NR11 . R ¹¹ represents a hydrogen atom, an alkyl group or an aryl group. 3. The composition according to claim 1, wherein the compound having the structure represented by formula ( 2 ) has a maximum absorption wavelength of 650 nm to 1,500 nm. The composition according to any one of claims 1 to 3 , comprising the curable compound and further comprising a photopolymerization initiator. The composition according to any one of claims 1 to 4 , comprising a binder polymer as the binder. A film comprising the composition according to any one of claims 1 to 5 , or a film formed by curing the composition. An optical filter comprising the film according to claim 6 . 8. The optical filter according to claim 7 , which is an infrared cut filter or an infrared transmission filter. A solid-state imaging device comprising the film according to claim 6 . An infrared sensor comprising the film according to claim 6 . applying the composition according to any one of claims 1 to 5 onto a support to form a composition layer;
A method for producing an optical filter, comprising the steps of patternwise exposing the composition layer and removing the unexposed portion by development to form a pattern. applying the composition according to any one of claims 1 to 5 onto a support to form a composition layer and curing to form a layer;
forming a photoresist layer on said layer;
patterning the photoresist layer by exposing and developing to obtain a resist pattern;
A method for manufacturing an optical filter, comprising the step of dry-etching the layer using the resist pattern as an etching mask. A camera module comprising a solid-state imaging device and the optical filter according to claim 7 or 8 . A compound represented by the following formula (P1).

In formula (P1), X ^P1 , X ^P2 , X ^P4 and X ^P5 each represent a single bond, X ^P3 and X ^P6 each independently represent a single bond, O, S, CH ₂ , N, -CH=CH- Alternatively, NR ^P11 , R ^P1 and R ^P2 each independently represent an alkyl group, an aryl group, a heteroaryl group, or a group represented by the following formula (P2), and R ^P3 to R ^P6 each independently a cyano group, an acyl group, an alkoxycarbonyl group, an alkyl group, an arylsulfinyl group or a heteroaryl group; R ^P7 to R ^P10 each independently represent a hydrogen atom or a substituent; R ^P11 is a hydrogen atom or an alkyl group; or represents an aryl group, and p1 to p4 each independently represents an integer of 0 to 4.

In formula (P2), X ^P11 represents a m-phenylene group, a p-phenylene group, a divalent condensed polycyclic aromatic ring group in which two or more aromatic rings are condensed, or a divalent heteroaromatic ring group, and L ^P11 is represents a single bond or a divalent linking group, Y ^P11 represents a substituent, and * represents a linking site to the pyrrolopyrrole ring in formula (P1). a compound having a structure represented by the following formula ( 2 );
At least one compound selected from the group consisting of solvents, binders and curable compounds ,
A dye structure in a group having a dye structure bonded or coordinated in at least one selected from the group consisting of R ⁹ and R ¹⁰ in a compound having a structure represented by the formula (2) is a pyrrolopyrrole dye structure , squarylium dye structure, croconium dye structure, indigo dye structure, anthraquinone dye structure, diimmonium dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, polymethine dye structure, xanthene dye structure, quinacridone dye structure, azo dye structure, and quinoline dye at least one dye structure selected from the group consisting of structures
dispersion composition.

^In formula (2), ^X represents a single bond or a divalent linking group, R ¹ to R ⁸ each independently represent a hydrogen atom or a substituent, and at least R ⁹ or R ¹⁰ to which a group having a dye structure is bonded or coordinated in one and to which the group having a dye structure is not bonded or coordinated represents a substituent, and R ⁹ and R ¹⁰ may combine with each other to form a ring with the boron atom.

Images