WO2017170339A1

WO2017170339A1 - Composition, film, optical filter, laminate, solid-state imaging element, image display device and infrared sensor

Info

Publication number: WO2017170339A1
Application number: PCT/JP2017/012275
Authority: WO
Inventors: 峻輔北島; 佐々木　大輔; 和也尾田; 崇一郎長田
Original assignee: 富士フイルム株式会社
Priority date: 2016-03-30
Filing date: 2017-03-27
Publication date: 2017-10-05
Also published as: JP6705891B2; JPWO2017170339A1; TW201807149A

Abstract

Provided are: a composition which is capable of producing a film that has excellent light dispersion in a near-infrared region, while being suppressed in aggregation of near-infrared absorbing compounds; a film; an optical filter; a laminate; a solid-state imaging element; an image display device; and an infrared sensor. This composition contains: a near-infrared absorbing compound which has a π-conjugated plane containing a monocyclic or fused aromatic ring, while having a maximum absorption wavelength within the wavelength range of 650-1,000 nm; and an aggregation inhibitor which has at least one ring selected from among aromatic hydrocarbon rings and heterocyclic rings, while having no maximum absorption wavelength within the wavelength range of 650-1,000 nm.

Description

Composition, film, optical filter, laminate, solid-state imaging device, image display device, and infrared sensor

The present invention relates to a composition, a film, an optical filter, a laminate, a solid-state imaging device, an image display device, and an infrared sensor.

Films such as color filters and near-infrared cut filters have been manufactured using compositions containing color materials such as pigments and dyes.

Since dyes can save time and effort for dispersion as compared to pigments, compositions using dyes have the advantage of reducing the time and effort for producing the composition.

Patent Document 1 describes that a color filter is produced using a coloring composition containing a phthalocyanine compound having high solubility in an organic solvent and a compound having a pyridine ring substituted with a carboxyl group. . According to Patent Document 1, a phthalocyanine compound having a predetermined substituent (also referred to as a specific phthalocyanine compound) and a compound having a pyridine ring substituted with a carboxyl group (specific pyridine compound) are allowed to coexist. Is said to be able to suppress the formation of aggregates and agglomeration, and to produce a color filter excellent in luminance and the like.

Japanese Patent Laid-Open No. 2015-72440

In recent years, an attempt has been made to produce an optical filter such as a near-infrared cut filter using a composition containing a near-infrared absorbing compound having an absorption maximum wavelength in the wavelength range of 650 to 1,000 nm. In such an optical filter, further improvement in near-infrared spectrum such as light shielding property in the near-infrared region has been desired in recent years. One method for improving the near-infrared spectrum of an optical filter is to increase the concentration of a near-infrared absorbing compound in the film.

However, according to the study by the present inventors, it has been found that when a film is formed using a composition containing a near-infrared absorbing compound, the near-infrared absorbing compound tends to aggregate when the film is formed. Further, as the concentration of the near-infrared absorbing compound was increased, the near-infrared absorbing compound tended to aggregate more easily during film formation. When the size of the aggregates of near-infrared absorbing compounds in the film increases, the aggregates of the near-infrared absorbing compounds present in the film dissolve in the developer or the like during pattern formation when the film is patterned. Peeling or the like is likely to occur, and there is a possibility that a hole having the size of the aggregate of the near infrared ray absorbing compound may be formed at a location where the aggregate of the near infrared ray absorbing compound was present.

Note that Patent Document 1 is an application intended to produce a color filter using a colored composition containing a phthalocyanine compound, and there is no description or suggestion of a near-infrared absorbing compound.

Therefore, an object of the present invention is to provide a composition, a film, an optical filter, a laminate, a solid-state imaging device, and an image display device that are capable of producing a film that is excellent in near-infrared spectroscopy and in which aggregation of near-infrared absorbing compounds is suppressed. And providing an infrared sensor.

The present inventor has conducted intensive studies on a near-infrared absorbing compound having a π-conjugated plane including a monocyclic or condensed aromatic ring and having an absorption maximum wavelength in the wavelength range of 650 to 1,000 nm. By using an infrared absorbing compound in combination with a compound having at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring and having no absorption maximum wavelength in the wavelength range of 650 to 1,000 nm, It has been found that aggregation of the above-mentioned near-infrared absorbing compound can be suppressed, and the present invention has been completed. The present invention provides the following.
<1> a near-infrared absorbing compound having a π-conjugated plane including a monocyclic or condensed aromatic ring and having an absorption maximum wavelength in the wavelength range of 650 to 1,000 nm;
A composition comprising an aggregation inhibitor having at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring and having no absorption maximum wavelength in the wavelength range of 650 to 1,000 nm.
<2> The composition according to <1>, wherein the aggregation inhibitor includes at least one ring selected from a benzene ring, a condensed ring including a benzene ring, and a nitrogen-containing heterocyclic ring.
<3> The aggregation inhibitor is a benzene ring, naphthalene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, Includes at least one ring selected from a benzoxazole ring, imidazoline ring, pyrazine ring, quinoxaline ring, pyrimidine ring, quinazoline ring, pyridazine ring, triazine ring, pyrrole ring, indole ring, isoindole ring, fluorene ring and carbazole ring <1> or <2>.
<4> The composition according to any one of <1> to <3>, wherein the π-conjugated plane of the near-infrared absorbing compound includes two or more monocyclic or condensed aromatic rings.
<5> The composition according to any one of <1> to <4>, wherein the near-infrared absorbing compound is at least one selected from a pyrrolopyrrole compound, a cyanine compound, and a squarylium compound.
<6> The composition according to any one of <1> to <5>, further comprising a resin.
<7> The composition according to any one of <1> to <6>, further comprising a polymerizable compound and a photopolymerization initiator.
<8> The composition according to any one of <1> to <7>, further comprising a colorant that transmits at least part of light in the near infrared region and shields light in the visible region.
<9> A film using the composition according to any one of <1> to <8>.
<10> An optical filter having the film according to <9>.
<11> The optical filter according to <10>, wherein the optical filter is a near-infrared cut filter or an infrared transmission filter.
<12> A pixel of the film according to <9>,
The optical filter according to <10> or <11>, having at least one pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless.
<13> A laminate having the film according to <9> and a color filter containing a chromatic colorant.
<14> A solid-state imaging device having the film according to <9>.
<15> An image display device having the film according to <9>.
<16> An infrared sensor having the film according to <9>.

According to the present invention, a composition, a film, an optical filter, a laminate, a solid-state imaging device, an image display device, and an infrared ray that are capable of producing a film excellent in near-infrared spectroscopy and suppressed from aggregation of near-infrared absorbing compounds. It became possible to provide a sensor.

It is the schematic which shows one Embodiment of an infrared sensor.

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the notation of a group (atomic group) in the present specification, the notation in which neither substitution nor substitution is described includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, “exposure” includes not only exposure using light, but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. The light used for exposure generally includes active rays or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, “(meth) allyl” represents allyl and methallyl, and “(meth) ) "Acryloyl" represents acryloyl and methacryloyl.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value measured by gel permeation chromatography (GPC).
In the present specification, near-infrared light refers to light (electromagnetic wave) having a maximum absorption wavelength region of 700 to 2,500 nm.
In this specification, the term “process” not only indicates an independent process, but also if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes, include.
In this specification, a dye means a compound that dissolves in a solvent. The dye used in the present invention has a solubility in 100 g of at least one solvent selected from cyclopentanone, cyclohexanone and propylene glycol monomethyl ether acetate at 23 ° C., preferably 1 g or more. Is more preferably 5 g or more.
In the present specification, the pigment means a compound that is difficult to dissolve in a solvent. For example, the pigment preferably has a solubility in 100 g of any of cyclopentanone, cyclohexanone, and propylene glycol monomethyl ether acetate at 23 ° C. of 0.1 g or less, more preferably 0.01 g or less. preferable.

<Composition>
The composition of the present invention comprises:
A near-infrared absorbing compound having a π-conjugated plane containing a monocyclic or condensed aromatic ring and having an absorption maximum wavelength in the wavelength range of 650 to 1,000 nm;
And an aggregation inhibitor having at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring and having no absorption maximum wavelength in the wavelength range of 650 to 1,000 nm.
According to the composition of the present invention, it is possible to produce a film that is excellent in near-infrared spectrum and in which aggregation of the near-infrared absorbing compound is suppressed. Moreover, according to this invention, even if the density | concentration of a near-infrared absorption compound is raised, aggregation of the near-infrared absorption compound in a film | membrane can be suppressed effectively. For this reason, according to this invention, the film | membrane with which aggregation of the near-infrared absorption compound was suppressed can be manufactured effectively, raising the density | concentration of a near-infrared absorption compound.
Although the detailed reason for the mechanism for obtaining such an effect is unknown, the mutual interaction between the aromatic hydrocarbon ring and / or the heterocyclic ring of the aggregation inhibitor and the aromatic ring in the π conjugate plane of the near-infrared absorbing compound. Presumably due to action. That is, the above-described interaction suppresses the association property of the J-aggregate of the near-infrared absorbing compound in the film, while appropriately maintaining the J-association property of the near-infrared absorbing compound, thereby reducing the aggregate size of the near-infrared absorbing compound. This is presumed to be due to the small size. Therefore, by using the composition of the present invention, it is possible to produce a film that is excellent in near-infrared spectrum and in which aggregation of near-infrared absorbing compounds is suppressed.
Hereinafter, each component of the composition of the present invention will be described.

<< Near-infrared absorbing compound >>
The composition of the present invention includes a near-infrared absorbing compound having a π-conjugated plane including a monocyclic or condensed aromatic ring and having an absorption maximum wavelength in the wavelength range of 650 to 1,000 nm. In the present invention, the aromatic ring includes an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

In the present invention, the near-infrared absorbing compound may be a pigment or a dye, but is preferably a dye. In the case where a dye type near-infrared absorbing compound is used, the effect of the present invention is particularly remarkably obtained.

In the present invention, the aromatic ring of the near-infrared absorbing compound includes a benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, quaterylene ring, acenaphthene ring, phenanthrene. Ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, Oxazole ring, benzoxazole ring, imidazoline ring, pyrazine ring, quinoxaline ring, pyrimidine ring, quinazoline ring, pyridazine ring, triazine ring, pyrrole ring, indole ring, isoindole ring, carbazole ring, And fused ring having these rings.

The π-conjugated plane of the near-infrared absorbing compound preferably contains 2 or more monocyclic or condensed aromatic rings, more preferably 3 or more, further preferably 4 or more, and more preferably 5 or more. It is particularly preferable to include it. The upper limit is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less.

In the present invention, the maximum absorption wavelength of the near-infrared absorbing compound is preferably in the range of 660 to 1,000 nm, more preferably in the range of 670 to 1,000 nm, and in the range of 700 to 1,000 nm. More preferably.

In this specification, “having a maximum absorption wavelength in the wavelength range of 650 to 1,000 nm” means the maximum absorbance in the wavelength range of 650 to 1,000 nm in the absorption spectrum of the near-infrared absorbing compound solution. It means that it has the wavelength which shows. Examples of the measurement solvent used for measuring the absorption spectrum of the near-infrared absorbing compound solution include chloroform, methanol, dimethyl sulfoxide, ethyl acetate, and tetrahydrofuran. In the case of a compound dissolved in chloroform, chloroform is used as a measurement solvent. For compounds that do not dissolve in chloroform, use methanol. Also, dimethyl sulfoxide is used when it does not dissolve in either chloroform or methanol.

In the present invention, in the near-infrared absorbing compound, 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 0.08 or less, more preferably 0.04 or less. preferable. According to this aspect, it is easy to produce a film having excellent visible transparency and infrared shielding properties from the composition of the present invention. The absorbance A1 at a wavelength of 500 nm and the absorbance A2 at the maximum absorption wavelength are values obtained from an absorption spectrum of a near-infrared absorbing compound solution.

In the present invention, it is also preferable to use at least two compounds having different maximum absorption wavelengths as the near-infrared absorbing compound. According to this aspect, the waveform of the absorption spectrum of the film is wider than when one kind of near-infrared absorbing compound is used, and near-infrared rays in a wide wavelength range can be shielded. When using at least two compounds having different maximum absorption wavelengths, the first near-infrared absorbing compound having the maximum absorption wavelength in the wavelength range of 650 to 1,000 nm, and the maximum absorption wavelength of the first near-infrared absorbing compound At least a second near-infrared absorbing compound having a maximum absorption wavelength in a wavelength range of 650 to 1000 nm, the maximum absorption wavelength of the first near-infrared absorption compound, and the second near-infrared absorption The difference from the maximum absorption wavelength of the compound is preferably 1 to 150 nm.

In the present invention, the near-infrared absorbing compound is a pyrrolopyrrole compound, cyanine compound, squarylium compound, phthalocyanine compound, naphthalocyanine compound, quaterylene compound, merocyanine compound, croconium compound, oxonol compound, diimonium compound, dithiol compound, triarylmethane compound, At least one selected from a pyromethene compound, an azomethine compound, an anthraquinone compound and a dibenzofuranone compound is preferable, and at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound and a quaterrylene compound is more preferable. At least one selected from a pyrrolopyrrole compound, a cyanine compound, and a squarylium compound But more preferably, pyrrolo-pyrrole compounds are particularly preferred.
Examples of the pyrrolopyrrole compound include compounds described in paragraph Nos. 0016 to 0058 of JP-A-2009-263614. Examples of the phthalocyanine compound include oxytitanium phthalocyanine pigments. As the phthalocyanine compound, naphthalocyanine compound, imonium compound, cyanine compound, squarylium compound, and croconium compound, the compounds described in paragraph Nos. 0010 to 0081 of JP 2010-1111750 A may be used. Incorporated into. In addition, as for the cyanine compound, for example, “functional pigment, Nobu Okawara / Ken Matsuoka / Kojiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein. .

(Pyrrolopyrrole compound)
As the pyrrolopyrrole compound used as the near-infrared absorbing compound, a compound represented by the following formula (I) is preferable.

In formula (I), A ¹ and A ² each independently represent a heteroaryl group,
B ¹ and B ² each independently represent a —BR ¹ R ² group, R ¹ and R ² each independently represent a substituent, and R ¹ and R ² may be bonded to each other to form a ring ,
C ¹ and C ² each independently represents an alkyl group, an aryl group, or a heteroaryl group,
D ¹ and D ² each independently represent a substituent.

In formula (I), A ¹ and A ² each independently represents a heteroaryl group. A ¹ and A ² may be the same group or different groups. A ¹ and A ² are preferably the same group.
The heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having a condensation number of 2 to 8, more preferably a single ring or a condensed ring having a condensation number of 2 to 4. . The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, still more preferably 3 to 12, and particularly preferably 3 to 10. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring.

The heteroaryl group is preferably a group represented by the following formula (A-1) and a group represented by the following formula (A-2).

In the formula (A-1), X ¹ each independently represents O, S, NR ^X1 or CR ^X2 R ^X3 , R ^X1 to R ^X3 each independently represent a hydrogen atom or a substituent, and R 1 ³ and R ⁴ each independently represent a hydrogen atom or a substituent, and R ³ and R ⁴ may be bonded to each other to form a ring. * Represents a bonding position with the formula (I).
The substituents represented by R ³ , R ⁴ and R ^X1 to R ^X3 are alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acyl groups, alkoxycarbonyl groups, aryls. Oxycarbonyl group, heteroaryloxycarbonyl group, acyloxy group, amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, Arylthio group, heteroarylthio group, alkylsulfonyl group, arylsulfonyl group, heteroarylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, heteroarylsulfinyl group, urea Group, phosphoric acid amide group, mercapto group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, silyl group, hydroxyl group, halogen atom, cyano group, etc. Groups, aryl groups and halogen atoms are preferred.
The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described above, and examples thereof include a halogen atom and an aryl group.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described above, and examples include a halogen atom and an alkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The ring formed by combining R ³ and R ⁴ is preferably an aromatic ring. When R ³ and R ⁴ form a ring, the group represented by the formula (A-1) is a group represented by the formula (A-1-1) or a group represented by the formula (A-1-2). And the like.

In the formula, each of X ¹ independently represents O, S, NR ^X1 or CR ^X2 R ^X3 , each of R ^X1 to R ^X3 independently represents a hydrogen atom or a substituent, and R ¹⁰¹ to R ¹⁰⁹ represent Each independently represents a hydrogen atom or a substituent. * Represents a bonding position with the formula (I).

In formula (A-2), Y ¹ to Y ⁴ each independently represent N or CR ^Y1 , at least two of Y ¹ to Y ⁴ are CR ^Y1 , and R ^Y1 represents a hydrogen atom or a substituent And adjacent R ^Y1 may be bonded to each other to form a ring. * Represents a bonding position with the formula (I).
Examples of the substituent represented by R ^Y1 include the substituents described above, and an alkyl group, an aryl group, and a halogen atom are preferable. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described above, and examples thereof include a halogen atom and an aryl group.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-described substituents, and examples thereof include a halogen atom and an alkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

At least two of Y ¹ to Y ⁴ are CR ^Y1 , and adjacent R ^Y1 may be bonded to each other to form a ring. The ring formed by combining adjacent R ^Y1 is preferably an aromatic ring. When adjacent R ^Y1 form a ring, examples of the group represented by the formula (A-2) include groups represented by the formulas (A-2-1) to (A-2-5). .

In the formula, R ²⁰¹ to R ²²⁷ each independently represent a hydrogen atom or a substituent, and * represents a bonding position with the formula (I).

Specific examples of A ¹ and A ² include the following. In the following, Bu represents a butyl group.

In formula (I), B ¹ and B ² each independently represent a —BR ¹ R ² group, and R ¹ and R ² each independently represent a substituent. R ¹ and R ² may combine with each other to form a ring. Examples of the substituent include the groups described above for A ¹ and A ^2. A halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or a heteroaryl group is preferable, and a halogen atom, an aryl group or a heteroaryl group is preferable. Are more preferable, and an aryl group or a heteroaryl group is more preferable. R ¹ and R ² may be the same group or different groups. R ¹ and R ² are preferably the same group. B ¹ and B ² may be the same group or different groups. B ¹ and B ² are preferably the same group.

As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom is particularly preferable.
The alkyl group preferably has 1 to 40 carbon atoms. For example, the lower limit is more preferably 3 or more. For example, the upper limit is more preferably 30 or less, and further preferably 25 or less. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
The alkenyl group preferably has 2 to 40 carbon atoms. For example, the lower limit is preferably 3 or more, more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The alkenyl group may be linear, branched or cyclic.
The alkoxy group preferably has 1 to 40 carbon atoms. For example, the lower limit is more preferably 3 or more. For example, the upper limit is more preferably 30 or less, and further preferably 25 or less. The alkoxy group may be linear, branched or cyclic.
The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom. About these details, what was mentioned above is mentioned.
The heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, still more preferably 3 to 12, and particularly preferably 3 to 5. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom. About these details, what was mentioned above is mentioned.

R ¹ and R ² of the —BR ¹ R ² group may be bonded to each other to form a ring. Examples thereof include the structures shown in the following (B-1) to (B-4). In the following, R represents a substituent, R ^a1 to R ^a4 each independently represents a hydrogen atom or a substituent, m1 to m3 each independently represents an integer of 0 to 4, and * represents a formula This represents the binding position with (I). Examples of the substituent represented by R and R ^a1 to R ^a4 include the substituents described for R ¹ and R ² , and a halogen atom and an alkyl group are preferable.

Specific examples of B ¹ and B ² include the following. In the following, Me represents a methyl group and Bu represents a butyl group.

In formula (I), C ¹ and C ² each independently represents an alkyl group, an aryl group, or a heteroaryl group. C ¹ and C ² may be the same group or different groups. C ¹ and C ² are preferably the same group. C ¹ and C ² are each independently preferably an aryl group or a heteroaryl group, and more preferably an aryl group.
The alkyl group preferably has 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 25 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably branched.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. A phenyl group or a naphthyl group is particularly preferred.
The heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom constituting the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12.

The alkyl group, aryl group, and heteroaryl group described above may have a substituent or may be unsubstituted. It preferably has a substituent.
Examples of the substituent include a hydrocarbon group which may contain an oxygen atom, an amino group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a heteroaryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group. Group, arylthio group, heteroarylthio group, alkylsulfonyl group, arylsulfonyl group, heteroarylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, heteroarylsulfinyl group, ureido group, phosphoric acid amide group, mercapto group, sulfo group, Examples thereof include a carboxyl group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, a silyl group, a hydroxyl group, a halogen atom, and a cyano group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group.
The alkyl group preferably has 1 to 40 carbon atoms. The lower limit is more preferably 3 or more, further preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably branched. The branched alkyl group preferably has 3 to 40 carbon atoms. For example, the lower limit is more preferably 5 or more, still more preferably 8 or more, and still more preferably 10 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The number of branches of the branched alkyl group is preferably 2 to 10, for example, and more preferably 2 to 8.
The alkenyl group preferably has 2 to 40 carbon atoms. For example, the lower limit is preferably 3 or more, more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The alkenyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably branched. The branched alkenyl group preferably has 3 to 40 carbon atoms. For example, the lower limit is more preferably 5 or more, still more preferably 8 or more, and still more preferably 10 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The number of branches of the branched alkenyl group is preferably 2 to 10, and more preferably 2 to 8.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
Examples of the hydrocarbon group containing an oxygen atom include a group represented by ^{-LR x1} .
L represents —O—, —CO—, —COO—, —OCO—, — (OR ^x2 ) _m — or — (R ^x2 O) _m —. R ^x1 represents an alkyl group, an alkenyl group, or an aryl group. R ^x2 represents an alkylene group or an arylene group. m represents an integer of 2 or more, and the m R ^x2 may be the same or different.
L is preferably —O—, — (OR ^x2 ) _m — or — (R ^x2 O) _m —, more preferably —O—.
The alkyl group, alkenyl group and aryl group represented by R ^x1 have the same ^{meanings as} described above, and the preferred ranges are also the same. R ^x1 is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
The alkylene group represented by R ^x2 preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms. The alkylene group may be linear, branched or cyclic, but is preferably linear or branched. The number of carbon atoms of the arylene group represented by R ^x2 is preferably 6 to 20, and more preferably 6 to 12. R ^x2 is preferably an alkylene group.
m represents an integer of 2 or more, preferably 2 to 20, and more preferably 2 to 10.

The substituent which the alkyl group, aryl group and heteroaryl group may have is preferably a group having a branched alkyl structure. The substituent is preferably a hydrocarbon group that may contain an oxygen atom, and more preferably a hydrocarbon group containing an oxygen atom. The hydrocarbon group containing an oxygen atom is preferably a group represented by —O—R ^x1 . R ^x1 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and particularly preferably a branched alkyl group. That is, the substituent is more preferably an alkoxy group, and particularly preferably a branched alkoxy group. When the substituent is an alkoxy group, a film having excellent heat resistance and light resistance can be easily obtained. The alkoxy group preferably has 1 to 40 carbon atoms. For example, the lower limit is preferably 3 or more, more preferably 5 or more, still more preferably 8 or more, and particularly preferably 10 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The alkoxy group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably branched. The number of carbon atoms of the branched alkoxy group is preferably 3 to 40. For example, the lower limit is more preferably 5 or more, still more preferably 8 or more, and still more preferably 10 or more. The upper limit is more preferably 35 or less, and even more preferably 30 or less. The number of branched alkoxy groups is preferably 2 to 10, more preferably 2 to 8.

Specific examples of C ¹ and C ² include the following. In the following, Me represents a methyl group and Bu represents a butyl group.

In formula (I), D ¹ and D ² each independently represent a substituent. D ¹ and D ² may be the same group or different groups. D ¹ and D ² are preferably the same group.
Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, Acyloxy group, amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heteroarylthio group, alkylsulfonyl Group, arylsulfonyl group, heteroarylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, heteroarylsulfinyl group, ureido group, phosphoric acid amide group, Mercapto group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, sulfino group, a hydrazino group, an imino group, a silyl group, a hydroxyl group, a halogen atom, and a cyano group. D ¹ and D ² are preferably electron withdrawing groups.

A substituent having a positive Hammett constant σ _p value (sigma para value) acts as an electron-attracting group. In the present invention, a substituent having a Hammett's σ _p value of 0.2 or more can be exemplified as an electron withdrawing group. The σ _p value of the substituent is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80 or less. Specific examples of the electron withdrawing group include a cyano group (0.66), a carboxyl group (—COOH: 0.45), an alkoxycarbonyl group (for example, —COOMe: 0.45), an aryloxycarbonyl group (for example, , —COOPh: 0.44), a carbamoyl group (eg, —CONH ₂ : 0.36), an alkylcarbonyl group (eg, —COMe: 0.50), an arylcarbonyl group (eg, —COPh: 0.43) An alkylsulfonyl group (for example, —SO ₂ Me: 0.72), an arylsulfonyl group (for example, —SO ₂ Ph: 0.68), and the like. A cyano group, an alkylcarbonyl group, an alkylsulfonyl group and an arylsulfonyl group are preferred, and a cyano group is more preferred. Here, Me represents a methyl group, Ph represents a phenyl group, and the numerical values in parentheses are σ _p values. As for Hammett's σ _p value, paragraph numbers 0024 to 0025 of JP-A-2009-263614 can be referred to, the contents of which are incorporated herein.

Specific examples of D ¹ and D ² include the following.

The pyrrolopyrrole compound is preferably a compound represented by the following formula (II) or a compound represented by the following formula (III). According to this aspect, it is easy to form a pattern having excellent infrared shielding properties and light resistance.

In the formula (II), X ¹ and X ² each independently represent O, S, NR ^X1 or CR ^X2 R ^X3 , R ^X1 to R ^X3 each independently represent a hydrogen atom or a substituent,
R ³ to R ⁶ each independently represents a hydrogen atom or a substituent,
R ³ and R ⁴ , or R ⁵ and R ⁶ may combine with each other to form a ring,
B ¹ and B ² each independently represent a —BR ¹ R ² group, R ¹ and R ² each independently represent a substituent, and R ¹ and R ² may be bonded to each other to form a ring. Often,
C ¹ and C ² each independently represents an alkyl group, an aryl group, or a heteroaryl group,
D ¹ and D ² each independently represent a substituent.

^{^{^{^{B 1, B 2, C 1}}}} , C 2, D 1 and ^{D 2} of formula (II) has the same meaning as ^{^{^{^{B 1, B 2, C 1}}}} , C 2, D 1 and ^{D 2} of formula (I) The preferable range is also the same. X ¹ , X ² and R ³ to R ^{6 in} formula (II) have the same meanings as X ¹ , R ³ and R ^{4 in} formula (A-1) described above, and preferred ranges are also the same.

In formula (III), Y ¹ to Y ⁸ each independently represent N or CR ^Y1 , at least two of Y ¹ to Y ⁴ are CR ^Y1 , and at least two of Y ⁵ to Y ⁸ are CR ^{Y 1} , R ^Y1 represents a hydrogen atom or a substituent, and adjacent R ^Y1 may be bonded to each other to form a ring;
B ¹ and B ² each independently represent a —BR ¹ R ² group, R ¹ and R ² each independently represent a substituent, and R ¹ and R ² may be bonded to each other to form a ring. Often,
C ¹ and C ² each independently represents an alkyl group, an aryl group, or a heteroaryl group,
D ¹ and D ² each independently represent a substituent.

^{^{^{^{B 1, B 2, C 1}}}} , C 2, D 1 and ^{D 2} of formula (III) has the same meaning as ^{^{^{^{B 1, B 2, C 1}}}} , C 2, D 1 and ^{D 2} of formula (I) The preferable range is also the same. Y ¹ to Y ^{8 in} the formula (III) have the same meanings as Y ¹ to Y ⁴ in the formula (A-2) described above, and preferred ranges are also the same.

Specific examples of the pyrrolopyrrole compound include the following compounds. In the following structural formulas, Ph represents a phenyl group, Me represents a methyl group, and Bu represents a butyl group. Specific examples of the pyrrolopyrrole compound include the compounds described in paragraph numbers 0049 to 0058 of JP-A-2009-263614, the contents of which are incorporated herein.

(Squarylium compound)
In the present invention, the squarylium compound used as the near-infrared absorbing compound is preferably a compound represented by the following formula (1).

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

In formula (2), Z ¹ represents a nonmetallic atomic group forming a nitrogen-containing heterocyclic ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a wavy line represents Represents a connecting hand with the formula (1).

A ¹ and A ² in Formula (1) each independently represent an aryl group, a heteroaryl group, or a group represented by Formula (2), and a group represented by Formula (2) is preferable.
The number of carbon atoms of the aryl group represented by A ¹ and A ² is preferably 6 to 48, more preferably 6 to 24, and even more preferably 6 to 12. Specific examples include a phenyl group and a naphthyl group.
The heteroaryl group represented by A ¹ and A ² is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, still more preferably a single ring or a condensed ring having 2 to 4 condensations, a single ring or A condensed ring having a condensation number of 2 or 3 is particularly preferred. As a hetero atom contained in a heterocyclic group, a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, and a nitrogen atom and a sulfur atom are preferable. The number of heteroatoms is preferably 1 to 3, and more preferably 1 to 2. Specific examples include a heteroaryl group derived from a monocyclic or polycyclic aromatic ring such as a 5-membered or 6-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom.

The aryl group and heteroaryl group may have a substituent. When the aryl group and heteroaryl group have two or more substituents, the plurality of substituents may be the same or different.

Examples of the substituent include a halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aralkyl group, —OR ¹⁰ , —COR ¹¹ , —COOR ¹² , —OCOR ¹³ , — NR ¹⁴ R ¹⁵ , —NHCOR ¹⁶ , —CONR ¹⁷ R ¹⁸ , —NHCONR ¹⁹ R ²⁰ , —NHCOOR ²¹ , —SR ²² , —SO ₂ R ²³ , —SO ₂ OR ²⁴ , —NHSO ₂ R ²⁵ , and —SO ₂ NR ²⁶ R ²⁷ is exemplified. R ¹⁰ to R ²⁷ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. When R ^{12 of} —COOR ¹² is hydrogen (that is, a carboxyl group), the hydrogen atom may be dissociated or may be in a salt state. When R ^{24 of} —SO ₂ OR ²⁴ is a hydrogen atom (that is, a sulfo group), the hydrogen atom may be dissociated or may be in a salt state.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 8 carbon atoms. The alkenyl group may be linear, branched or cyclic, and is preferably linear or branched.
The alkynyl group preferably has 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and still more preferably 2 to 25 carbon atoms. The alkynyl group may be linear, branched or cyclic, and is preferably linear or branched.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
The alkyl part of the aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group is the same as the above aryl group. The number of carbon atoms in the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and still more preferably 7 to 25.
The heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, and further preferably a single ring or a condensed ring having 2 to 4 condensations. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12.
The alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group and heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-described substituents.

Next, the group represented by Formula (2) represented by A ¹ and A ² will be described.

In the formula (2), R ² represents an alkyl group, an alkenyl group or an aralkyl group, and an alkyl group is preferable.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 12 carbon atoms.
The alkyl group and the alkenyl group may be linear, branched or cyclic, and are preferably linear or branched.
The aralkyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms.

In the formula (2), the nitrogen-containing heterocycle formed by Z ¹ is preferably a 5-membered ring or a 6-membered ring. The nitrogen-containing heterocycle is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having 2 to 8 condensations, more preferably a single ring or a condensed ring having 2 to 4 condensations, Is particularly preferably a fused ring of 2 or 3. The nitrogen-containing heterocyclic ring may contain a sulfur atom in addition to the nitrogen atom. Moreover, the nitrogen-containing heterocycle may have a substituent. Examples of the substituent include the above-described substituents. For example, a halogen atom, an alkyl group, a hydroxyl group, an amino group, and an acylamino group are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 12 carbon atoms. The alkyl group is preferably linear or branched.

The group represented by the formula (2) is preferably a group represented by the following formula (3) or the formula (4).

In formulas (3) and (4), R ¹¹ represents an alkyl group, an alkenyl group or an aralkyl group, R ¹² represents a substituent, and when m is 2 or more, R ¹² are linked to each other. A ring may form, X represents a nitrogen atom or CR ¹³ R ¹⁴ , R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a substituent, and m is an integer of 0 to 4 And a wavy line represents a connecting hand with the formula (1).

R ¹¹ in formulas (3) and (4) has the same meaning as R ² in formula (2), and the preferred range is also the same.
R ¹² in the formulas (3) and (4) represents a substituent. Examples of the substituent include the substituent described in the above formula (1). For example, a halogen atom, an alkyl group, a hydroxyl group, an amino group, and an acylamino group are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 12 carbon atoms. The alkyl group is preferably linear or branched.
When m is 2 or more, R ¹² may be linked to form a ring. Examples of the ring include an alicyclic ring (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring. The ring may be monocyclic or polycyclic. When the substituents are linked to form a ring, the linking group includes —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and a divalent unsaturated chain. Formula hydrocarbon groups and combinations thereof. For example, it is preferable that R ¹² are connected to each other to form a benzene ring.
X in Formula (3) represents a nitrogen atom or CR ¹³ R ¹⁴ , and R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent. Examples of the substituent include the substituent described in the above formula (1). For example, an alkyl group etc. are mentioned. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. The alkyl group is preferably linear or branched, and particularly preferably linear.
m represents an integer of 0 to 4, preferably 0 to 2.

In the formula (1), cations are delocalized and exist as follows.

The squarylium compound used as the near-infrared absorbing compound in the present invention is preferably a compound represented by the following formula (5).
Ring A and Ring B each independently represent an aromatic ring or a heteroaromatic ring,
X ^A and X ^B each independently represent a substituent,
G ^A and ^{G B} independently represents a substituent,
kA represents an integer of 0 to n _A , kB represents an integer of 0 to n _B ,
n _A and n _B each represent the largest integer that can be substituted for ring A or ring B;
X ^A and G ^A, X ^B and G ^B may combine with each other to form a ring, if G ^A and G ^B are present in plural may be bonded to form a ring structure .

G ^A and ^{G B} independently represents a substituent. Examples of the substituent include the substituent described in the above formula (1).

X ^A and X ^B each independently represent a substituent. Examples of the substituent include the substituent described in the above formula (1), and a group having active hydrogen is preferable. —OH, —SH, —COOH, —SO ₃ H, —NR ^X1 R ^X2 , —NHCOR ^X1 , —CONR ^X1 R ^X2 , —NHCONR ^X1 R ^X2 , —NHCOOR ^X1 , —NHSO ₂ R ^X1 , —B (OH) ₂ and —PO (OH) ₂ are more preferable, —OH, —SH and —NR ^X1 R ^X2 is more preferable.
R ^X1 and R ^X1 each independently represent a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group, and an alkyl group is preferable. The alkyl group is preferably linear or branched. The details of the alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group are the same as those described in the above-mentioned substituent column.

Ring A and ring B each independently represent an aromatic ring or a heteroaromatic ring.
The aromatic ring and heteroaromatic ring may be a single ring or a condensed ring.
Specific examples of the aromatic ring and heteroaromatic ring include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, Naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran Ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, Antoren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and include phenazine ring, a benzene ring or a naphthalene ring is preferable.
The aromatic ring may be unsubstituted or may have a substituent. Examples of the substituent include the substituent described in the above formula (1).

X ^A and G ^A, X ^B and G ^B may combine with each other to form a ring, if G ^A and G ^B are present in plural may be bonded to each other to form a ring.
The ring is preferably a 5-membered ring or a 6-membered ring. The ring may be monocyclic or polycyclic.
X ^A and ^G A, ^{X B} and ^G B, when forming a ^{G A} or between ^{G B} are bonded to each other rings, may be they are attached directly to form a ring, an alkylene group, -CO-, A ring may be formed by bonding via a divalent linking group which is —O—, —NH—, —BR—, or a combination thereof. X ^A and ^G A, ^{X B} and ^G B, ^{G A} or between ^{G B} each other, it is preferable to form a ring via -BR-.
R represents a hydrogen atom or a substituent. Examples of the substituent include the substituent described in the above formula (1), and an alkyl group or an aryl group is preferable.

kA represents an integer of 0 to nA, kB represents an integer of 0 to nB, nA represents the largest integer that can be substituted on the A ring, and nB represents the largest integer that can be substituted on the B ring.
kA and kB are each independently preferably 0 to 4, more preferably 0 to 2, and particularly preferably 0 to 1.

One embodiment of the squarylium compound is a compound represented by the following formula (6). This compound is excellent in heat resistance.
Formula (6)

In the formula, R ¹ and R ² each independently represent a substituent,
R ³ and R ⁴ each independently represents a hydrogen atom or an alkyl group,
X ¹ and X ² each independently represent —O— or —N (R ⁵ ) —,
R ⁵ represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group,
Y ¹ to Y ⁴ each independently represent a substituent, Y ¹ and Y ² , and Y ³ and Y ⁴ may be bonded to each other to form a ring,
Y ¹ to Y ⁴ may be bonded to each other to form a ring when there are a plurality of Y ¹ to Y ⁴ .
p and s each independently represent an integer of 0 to 3,
q and r each independently represents an integer of 0 to 2.

Examples of the substituent represented by R ¹ , R ² , Y ¹ to Y ⁴ include the substituents described in the above-described formula (1).
R ³ and R ⁴ are each independently preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

X ¹ and X ² each independently represents —O— or —N (R ⁵ ) —. X ¹ and X ² may be the same or different, but are preferably the same.
R ⁵ represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
R ⁵ is preferably a hydrogen atom, an alkyl group or an aryl group. The alkyl group, aryl group and heteroaryl group represented by R ⁵ may be unsubstituted or may have a substituent. Examples of the substituent include the substituent described in the above formula (1).
The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, more preferably 1 to 4, and particularly preferably 1 to 2. The alkyl group may be linear or branched.
The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
The heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12.

Specific examples of the squarylium compound include the following compounds. Further, compounds described in paragraph numbers 0044 to 0049 of JP 2011-208101 A can be mentioned, the contents of which are incorporated herein.

(Cyanine compound)
In the present invention, the cyanine compound used as the near-infrared absorbing compound is preferably a compound represented by the following formula (C).
Formula (C)

In formula (C), Z ¹ and Z ² are each independently a nonmetallic atomic group that forms a 5-membered or 6-membered nitrogen-containing heterocycle that may be condensed,
R ¹⁰¹ and R ¹⁰² each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group,
L ¹ represents a methine chain having an odd number of methine groups,
a and b are each independently 0 or 1,
When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded by a single bond,
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents a number necessary for balancing the charge, and the site represented by Cy in the formula is an anion moiety. X ¹ represents a cation, c represents a number necessary to balance the charge, and when the charge of the site represented by Cy in the formula is neutralized in the molecule, c is 0.

In the formula (C), Z ¹ and Z ² each independently represent a nonmetallic atomic group that forms a 5-membered or 6-membered nitrogen-containing heterocyclic ring that may be condensed. The nitrogen-containing heterocycle may be condensed with another heterocycle, aromatic ring or aliphatic ring. The nitrogen-containing heterocycle is preferably a 5-membered ring. A structure in which a benzene ring or a naphthalene ring is condensed to a 5-membered nitrogen-containing heterocyclic ring is more preferable. Specific examples of the nitrogen-containing heterocycle include an oxazole ring, an isoxazole ring, a benzoxazole ring, a naphthoxazole ring, an oxazolocarbazole ring, an oxazodibenzobenzofuran ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, an indolenine ring, Examples include benzoindolenin ring, imidazole ring, benzimidazole ring, naphthimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, furopyrrole ring, indolizine ring, imidazoquinoxaline ring, quinoxaline ring, quinoline ring, indolenine ring Benzoindolenine ring, benzoxazole ring, benzothiazole ring and benzimidazole ring are preferable, and indolenine ring, benzothiazole ring and benzimidazole ring are particularly preferable. The nitrogen-containing heterocyclic ring and the ring condensed thereto may have a substituent. Examples of the substituent include the substituent described in Formula (1).

In the formula (C), R ¹⁰¹ and R ¹⁰² each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group.
The 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 alkyl group may be linear, branched or cyclic.
The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 8 carbon atoms. The alkenyl group may be linear, branched or cyclic.
The alkynyl group has preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 8 carbon atoms. The alkynyl group may be linear, branched or cyclic.
The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 10 carbon atoms. The aryl group may be unsubstituted or may have a substituent.
The alkyl part of the aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group is the same as the above aryl group. The number of carbon atoms in the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and still more preferably 7 to 25.
The alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, and an amino group. A carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may have a hydrogen atom dissociated or a salt state.

In the formula (C), L ¹ represents a methine chain having an odd number of methine groups. L ¹ is preferably a methine chain having 3, 5, or 7 methine groups.
The methine group may have a substituent. The methine group having a substituent is preferably a central (meso-position) methine group. Specific examples of the substituent include a substituent that the nitrogen-containing heterocycle of Z ¹ and Z ² may have, a group represented by the following formula (a), and the like. Further, two substituents of the methine chain may be bonded to form a 5- or 6-membered ring.

In the formula (a), * represents a linkage with a methine chain, and A ¹ represents —O—.

In the formula (C), a and b are each independently 0 or 1. When a is 0, the carbon atom and the nitrogen atom are bonded by a double bond, and when b is 0, the carbon atom and the nitrogen atom are bonded by a single bond. Both a and b are preferably 0. When a and b are both 0, the formula (C) is expressed as follows.

In the formula (C), when the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, and c represents a number necessary for balancing the charge. Examples of anions include halide ions (Cl ⁻ , Br ⁻ , I ^−, etc.), paratoluenesulfonic acid ions, ethyl sulfate ions, PF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , tris (halogenoalkylsulfonyl) methide anions ( For example, (CF ₃ SO ₂ ) ₃ C ⁻ ), di (halogenoalkylsulfonyl) imide anion (for example, (CF ₃ SO ₂ ) ₂ N ⁻ ), tetracyanoborate anion and the like can be mentioned.
In the formula (C), when the site represented by Cy in the formula is an anion portion, X ¹ represents a cation, and c represents a number necessary for balancing the charge. Examples of the cation include alkali metal ions (Li ⁺ , Na ⁺ , K ^+, etc.), alkaline earth metal ions (Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Sr ^2+, etc.), transition metal ions (Ag ⁺ , Fe ²⁺ , Co ⁺ ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ^2+, etc.), other metal ions (such as Al ³⁺ ), ammonium ions, triethylammonium ions, tributylammonium ions, pyridinium ions, tetrabutylammonium ions, guanidinium ions, tetramethylguanidini. Um ion, diazabicycloundecenium ion, and the like. Examples of the ^{^{^{^{cation, Na +, K +, Mg}}}} 2+, Ca 2+, Zn 2+, diazabicyclo undecenium ion.
In the formula (C), when the charge at the site represented by Cy in the formula is neutralized in the molecule, X ¹ does not exist. That is, c is 0.

The cyanine compound is also preferably a compound represented by the following formulas (C-1) to (C-3).

In the formula, R ^1A , R ^2A , R ^1B and R ^2B each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group,
L ^1A and L ^1B each independently represent a methine chain having an odd number of methine groups,
Y ¹ and Y ² each independently represent —S—, —O—, —NR ^X1 — or —CR ^X2 R ^X3 —
R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group,
V ^1A , V ^2A , V ^1B and V ^2B each independently represent a substituent,
m1 and m2 each independently represents 0 to 4;
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents a number necessary for balancing the charge,
When the site represented by Cy in the formula is an anion moiety, X ¹ represents a cation, c represents a number necessary for balancing electric charges,
When the charge at the site represented by Cy in the formula is neutralized in the molecule, X ¹ does not exist.

The groups represented by R ^1A , R ^2A , R ^1B and R ^2B are synonymous with the alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group described for R ¹⁰¹ and R ¹⁰² in formula (C), and are preferably in a preferred range. Is the same. These groups may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, and an amino group. A carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxyl group and the sulfo group may have a hydrogen atom dissociated or a salt state. When R ^1A , R ^2A , R ^1B and R ^2B represent an alkyl group, it is more preferably a linear alkyl group.

Y ¹ and ^{Y 2} are each independently, -S -, - O -, - NR X1 - or ^-CR X2 ^{R X3} - represents, ^{-NR X1} - is preferred. R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear. The alkyl group is particularly preferably a methyl group or an ethyl group.

L ^1A and L ^1B have the same meaning as L ^{1 in} formula (C), and the preferred range is also the same.
^{Examples of} the substituent represented by V ^1A , V ^2A , V ^1B, and V ^2B include the substituents described above, and the preferred ranges are also the same.
m1 and m2 each independently represents 0 to 4, preferably 0 to 2.
The anion and cation represented by X ¹ are synonymous with the range described for X ¹ in formula (C), and the preferred range is also the same.

Specific examples of the cyanine compound include the following compounds. Further, compounds described in JP-A-2015-172004 and JP-A-2015-172102 may be mentioned.

In the composition of the present invention, the content of the near-infrared absorbing compound is preferably 1 to 50% by mass with respect to the total solid content of the composition. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The near-infrared absorbing compound may be only one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.

<< Aggregation inhibitor >>
The composition of the present invention contains an aggregation inhibitor. In the present invention, as the aggregation inhibitor, a compound having at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring and having no absorption maximum wavelength in the wavelength range of 650 to 1,000 nm is used.

The aggregation inhibitor is preferably a compound that dissolves in a solvent. For example, the solubility in 100 g of at least one solvent selected from cyclopentanone, cyclohexanone, and propylene glycol monomethyl ether acetate at 23 ° C. is preferably 1 g or more, and more preferably 5 g or more.

The aromatic hydrocarbon ring and the heterocyclic ring possessed by the aggregation inhibitor may be a single ring or a condensed ring. The number of condensed rings is preferably 2 to 8, and more preferably 2 to 4.

The heterocycle possessed by the aggregation inhibitor is preferably a nitrogen-containing heterocycle. The heterocyclic ring is preferably an aromatic heterocyclic ring. The number of heteroatoms constituting the heterocyclic ring is preferably 1 to 3. Moreover, as a kind of hetero atom which comprises the ring of a heterocyclic ring, a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned. The heterocycle possessed by the aggregation inhibitor is preferably a nitrogen-containing heterocycle. Moreover, it is preferable that the heterocyclic ring which the aggregation inhibitor has is an aromatic heterocyclic ring.

In the present invention, the aggregation inhibitor preferably contains at least one ring selected from a benzene ring, a condensed ring containing a benzene ring, and a nitrogen-containing heterocycle, and includes a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, and an isoquinoline. Ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzoxazole ring, imidazoline ring, pyrazine ring, quinoxaline ring, pyrimidine ring, quinazoline ring, pyridazine ring , A triazine ring, a pyrrole ring, an indole ring, an isoindole ring, a fluorene ring, and a carbazole ring, and more preferably a pyridine ring, a quinoline ring, and an isoquinoline ring.

In addition, the ring of the aggregation inhibitor preferably has the same aromatic hydrocarbon ring or heterocyclic ring as the aromatic hydrocarbon ring or heterocyclic ring of the near-infrared absorbing compound. According to this aspect, the aggregation of the near-infrared absorbing compound can be effectively suppressed.

The reason why it is preferable to use a compound having the above ring as the aggregation inhibitor is as follows. In order to suppress aggregation of the near-infrared absorbing compound, it is necessary to suppress association of the near-infrared absorbing compound. By using a compound having at least one structure having a π-π interaction with the near infrared absorbing compound in the structure as an aggregation inhibitor, aggregation of the near infrared absorbing compound in the film can be suppressed, The aggregate size of the near-infrared absorbing compound can be reduced. As an example, the pyrrolopyrrole compound mentioned above as a specific example of the near-infrared absorbing compound has an aromatic hydrocarbon ring and / or a heterocyclic ring and a pyrrolopyrrole skeleton in the π plane. In order to interact with the pyrrolopyrrole compound, an aromatic hydrocarbon ring and / or a heterocyclic ring (preferably a nitrogen-containing heterocyclic ring) is required. For this reason, by using the above-mentioned compound having a ring as an aggregation inhibitor, the association of the near infrared absorbing compound can be effectively suppressed, and the aggregate size of the near infrared absorbing compound can be effectively suppressed.

In the present invention, the aggregation inhibitor is a compound represented by the following formula (b1-1), a compound having a partial structure represented by the following formula (b2-1), or a compound represented by the following formula (b3-1). It is preferably at least one selected from a compound having a partial structure and a compound having a partial structure represented by the following formula (b4-1).

B ^1- (R ^b1 ) _m1 (b1-1)
In the formula (b1-1), B ¹ represents an aromatic hydrocarbon ring or a heterocyclic ring, R ^b1 represents a substituent, m1 represents an integer of 0 to mA, and mA can be substituted with B ¹ Represents the maximum integer; when m1 is 2 or more, two or more R ^b1 may be the same or different.
* -B ^2- (R ^b2 ) _m2 (b2-1)
In formula (b2-1), * represents a bond with another atom or atomic group constituting the compound, B ² represents an aromatic hydrocarbon ring or a heterocyclic ring, and R ^b2 represents a substituent. , M2 represents an integer of 0 to mB, and mB represents the largest integer that can be substituted for B ² ; when m2 is 2 or more, two or more R ^b2s may be the same or different May be.

In the formula (b3-1), * represents a bond with another atom or atomic group constituting the compound,
B ³ and B ⁴ each independently represents an aromatic hydrocarbon ring or a heterocyclic ring,
R ^b3 and R ^b3 each independently represent a substituent,
L ¹ represents a single bond or a divalent linking group,
m3 represents an integer of 0 to mC, mC represents the largest integer that can be substituted for B ³ ;
m4 is 0 to an integer of mD, mD represents the largest integer that can be replaced with ^{B 4.}
When m3 is 2 or more, two or more R ^{b3 s} may be the same or different.
When m4 is 2 or more, two or more ^Rb4s may be the same or different.

In formula (b4-1), * ¹ and * ² represent a bond with another atom or atomic group constituting the compound,
B ⁵ and B ⁶ each independently represent an aromatic hydrocarbon ring or a heterocyclic ring,
R ^b5 and R ^b6 each independently represent a substituent,
L ¹ represents a single bond or a divalent linking group,
m5 represents an integer of 0 to mE, mE represents the largest integer that can be substituted for B ⁵ ;
m6 is 0 to an integer of mF, mF represents the largest integer that can be replaced by ^{B 6.}
When m5 is 2 or more, two or more R ^{b5 s} may be the same or different.
When m6 is 2 or more, two or more ^Rb6s may be the same or different.

The substituents represented by R ^b1 to R ^b6 are alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heteroaryls. Oxycarbonyl group, acyloxy group, amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heteroarylthio Group, alkylsulfonyl group, arylsulfonyl group, heteroarylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, heteroarylsulfinyl group, ureido group, phosphate phosphate Group, a mercapto group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, sulfino group, a hydrazino group, an imino group, a silyl group, a hydroxyl group, a halogen atom, a cyano group, an epoxy group. In the case where these groups are further substitutable groups, some or all of the hydrogen atoms may be substituted with substituents. For example, some or all of the hydrogen atoms in the alkyl group may be substituted with halogen atoms.

The aromatic hydrocarbon ring or heterocyclic ring represented by B ¹ to B ⁶ preferably includes at least one ring selected from a benzene ring, a condensed ring including a benzene ring, and a nitrogen-containing heterocyclic ring, and includes a benzene ring and a naphthalene ring. Pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzoxazole ring, imidazoline ring, pyrazine ring, quinoxaline ring, More preferably, it includes at least one ring selected from a pyrimidine ring, a quinazoline ring, a pyridazine ring, a triazine ring, a pyrrole ring, an indole ring, an isoindole ring, a fluorene ring, and a carbazole ring, a pyridine ring, a quinoline ring, and More isoquinoline ring Masui. B ³ to B ⁶ are more preferably a benzene ring. The aromatic hydrocarbon ring or heterocyclic ring represented by B ¹ to B ⁶ may be unsubstituted or may have a substituent. Examples of the substituent include the above-described substituents.

Examples of the divalent linking group represented by L ¹ include an alkylene group, —CO—, —O—, —NH—, —OCO—, —COO—, and a group consisting of a combination thereof.

In the formula (b1-1), m1 is preferably an integer of 1 or more. In the formula (b2-1), m1 is preferably an integer of 1 or more. In the formula (b3-1), m3 and m4 are preferably integers of 1 or more. In the formula (b4-1), m5 and m6 are preferably integers of 1 or more.

The compound having a partial structure represented by the formula (b2-1) includes (1) a compound in which a plurality of partial structures represented by the formula (b2-1) are bonded via a linking group; Examples thereof include compounds in which the partial structure represented by b2-1) is bonded to a repeating unit of the polymer through a single bond or a linking group.

When the compound having a partial structure represented by the formula (b2-1) is a compound in which a plurality of partial structures represented by the formula (b2-1) are bonded via a linking group, the linking group includes 1 And groups consisting of ˜100 carbon atoms, 0-10 nitrogen atoms, 0-50 oxygen atoms, 1-200 hydrogen atoms, and 0-20 sulfur atoms. For example, a group composed of a combination of two or more of the following structural units or the following structural units (which may form a ring structure) may be mentioned.

When the partial structure represented by the formula (b2-1) is a compound bonded to a polymer repeating unit via a single bond or a linking group (hereinafter, also referred to as a polymer compound), the polymer repeating unit includes: Examples thereof include a (meth) acrylic repeating unit and a vinylic repeating unit. The (meth) acrylic repeating unit means a repeating unit derived from a compound having a (meth) acryloyl group. The vinyl repeating unit means a repeating unit derived from a compound having a vinyl group.

Specific examples of the polymer compound include compounds having the following repeating units.

In the above formula, R ^b100 represents a hydrogen atom or an alkyl group. L ^b1 represents a single bond or a divalent linking group. B ² represents an aromatic hydrocarbon ring or a heterocyclic ring, R ^b2 represents a substituent, m ² represents an integer of 0 to mB, and m B represents the largest integer that can be substituted for B ² ; In the case of two or more, two or more R ^b2 may be the same or different.

In the above formula, B ² , R ^b2 and m2 have the same meanings as B ² , R ^b2 and m2 in (b2-1).

The number of carbon atoms of the alkyl group represented by R ^b100 in the above formula is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1. In the above formula, R ^b100 is preferably a hydrogen atom or a methyl group.

As the divalent linking group represented by L ^b1 in the above formula, an alkylene group, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NR ¹⁰ — (R ¹⁰ Represents a hydrogen atom or an alkyl group, preferably a hydrogen atom), or a group consisting of a combination thereof. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be monocyclic or polycyclic.

When the aggregation inhibitor is a polymer compound, the aggregation inhibitor may further include other repeating units in addition to the repeating unit having the partial structure represented by the formula (b2-1). Examples of the other repeating unit include the repeating units described in the resin described later.

When the aggregation inhibitor is a polymer compound, the aggregation inhibitor preferably contains 5 to 100 mol% of repeating units having a partial structure represented by the formula (b2-1) based on the total repeating units of the polymer compound. More preferably, it is contained in an amount of ˜100 mol%, more preferably 30-100 mol%.

The compound having the partial structure represented by the formula (b3-1) includes (1) a compound in which a plurality of partial structures represented by the formula (b3-1) are bonded via a linking group; Examples thereof include compounds in which the partial structure represented by b3-1) is bonded to a repeating unit of the polymer through a single bond or a linking group. The linking group and the repeating unit of the polymer have the same meaning as described above.

The compound having a partial structure represented by the formula (b4-1) may have two or more partial structures represented by the formula (b4-1) in one molecule. That is, a compound having a structure in which a plurality of partial structures represented by the formula (b4-1) are bonded through a single bond or a linking group may be used. One of * ¹ and * ² may be bonded to the repeating unit of the polymer via a single bond or a linking group.

In the present invention, the aggregation inhibitor may be a compound having substantially no molecular weight distribution or a compound having a molecular weight distribution.

When a compound having substantially no molecular weight distribution is used as the aggregation inhibitor, the aggregation inhibitor tends to approach the near infrared absorbing compound, and the aggregation inhibitor and the near infrared absorbing compound interact effectively, Aggregation of the near infrared ray absorbing compound in the film can be effectively suppressed.
In addition, when a compound having a molecular weight distribution is used as an aggregation inhibitor, sublimation of the aggregation inhibitor from the film due to heating during film formation can be suppressed, and aggregation of near-infrared absorbing compounds in the film is more effective. Can be suppressed.

Here, the compound having a molecular weight distribution includes a compound having a repeating unit such as a polymer. Examples thereof include compounds having the repeating units represented by the above (b2-1-1) to (b2-1-3).
In the present invention, the compound having substantially no molecular weight distribution is preferably a compound having a dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.00 to 2.00. Are more preferable, compounds having a dispersity of 1.00 to 1.05 are more preferable, and compounds having a dispersity of 1.00 are particularly preferable. Further, the compound having substantially no molecular weight distribution is preferably a compound whose molecular weight can be calculated from the structural formula.

When the aggregation inhibitor is a compound having substantially no molecular weight distribution, the molecular weight of the aggregation inhibitor is preferably 100 to 500. The lower limit is more preferably 130 or more. The upper limit is more preferably 450 or less. If the molecular weight is in the above range, an effect of achieving both suppression of aggregation and suppression of sublimation by baking at high temperature can be expected.
In the case where the aggregation inhibitor is a compound having substantially no molecular weight distribution, it preferably has 1 to 10 rings in one molecule selected from aromatic hydrocarbon rings and heterocyclic rings. It is more preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 4.
The effect of the aggregation inhibitor is more prominent as the number of aromatic hydrocarbon rings and heterocyclic rings increases. Therefore, visible transparency may be reduced. The number of rings is preferably in the above range (particularly 1 to 4) from the viewpoint of visible transparency and aggregation suppression.

When the aggregation inhibitor is a compound having a molecular weight distribution, the weight average molecular weight of the aggregation inhibitor is preferably 3,000 to 50,000. The lower limit is more preferably 5,000 or more. The upper limit is more preferably 40,000 or less. If a weight average molecular weight is the said range, the effect that J association property and aggregation suppression can be made compatible can be anticipated.
When the aggregation inhibitor is a compound having a molecular weight distribution, the aggregation inhibitor is preferably a compound having a repeating unit. The repeating unit described above is preferably a repeating unit having at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring in the side chain, and has 1 to 10 rings in the side chain. It is more preferably a repeating unit, more preferably a repeating unit having 1 to 8 rings in the side chain, and particularly preferably a repeating unit having 1 to 6 rings in the side chain. The repeating unit having 1 to 4 rings in the side chain is most preferred.

In the present invention, the acid value of the aggregation inhibitor is preferably 100 mgKOH / g or less, more preferably 80 mgKOH / g or less, further preferably 50 mgKOH / g or less, and particularly preferably 10 mgKOH / g or less. According to this aspect, an effect of improving the developer resistance can be expected.

In the present invention, the aggregation inhibitor is preferably a compound having no carboxyl group. According to this aspect, it is possible to expect an effect that the developer resistance is improved.

In the present invention, the aggregation inhibitor is preferably a compound having no radical polymerizable group. According to this aspect, the effect that the further aggregation at the time of baking at high temperature after exposure is suppressed can be expected. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond, such as a vinyl group, a styryl group, a (meth) allyl group, and a (meth) acryloyl group.

In the present invention, the aggregation inhibitor may further have an antioxidant function and / or a polymerization inhibition function.

Specific examples of the aggregation inhibitor include the following compounds.

The content of the aggregation inhibitor is preferably 0.5 to 20% by mass with respect to the total solid content of the composition of the present invention. The upper limit is more preferably 10% by mass or less, and still more preferably 8% by mass or less. The lower limit is more preferably 1% by mass or more.
Further, 1 to 200 parts by mass of an aggregation inhibitor is included with respect to 100 parts by mass of the near-infrared absorbing compound (when two or more near-infrared absorbing compounds are included, the total of two or more near-infrared absorbing compounds is 100 parts by mass). It is preferable. The upper limit is more preferably 100 parts by mass or less, still more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, still more preferably 38 parts by mass or less, and particularly preferably 35 parts by mass or less. The lower limit is more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, still more preferably 4.5 parts by mass or more, still more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more.
If content of an aggregation inhibitor is more than said lower limit, aggregation of a near-infrared absorption compound can be suppressed effectively and coarsening of the aggregation size of a near-infrared absorption compound can be suppressed more effectively. Moreover, if content of an aggregation inhibitor is below said upper limit, a near-infrared absorptive compound can exist moderately aggregated in a film | membrane, and favorable light resistance and heat resistance are obtained.
The aggregation inhibitor may be only one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.

<< Chromatic colorant >>
The composition of the present invention can contain a chromatic colorant. In the present invention, the chromatic colorant means a colorant other than the white colorant and the black colorant. The chromatic colorant is preferably a colorant having absorption in a wavelength range of 400 nm or more and less than 650 nm. In the present invention, the chromatic colorant may be a pigment or a dye.

The pigment is preferably an organic pigment, and examples thereof include the following. However, the pigment that can be used in the present invention is not limited to these.
Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93 , 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129 , 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 etc. (above, yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Orange pigment)
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc. (above, red Pigment)
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigment),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (above, purple pigment),
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc. (above, blue pigment),
These organic pigments can be used alone or in various combinations.

The dye is not particularly limited, and a known dye can be used. The chemical structure includes pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene, phthalocyanine, benzopyran, indigo, and pyromethene dyes can be used. Moreover, you may use the multimer of these dyes. Further, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.

When the composition of the present invention contains a chromatic colorant, the content of the chromatic colorant is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total solid content of the composition, 15 A mass% or less is more preferable. For example, the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.
Moreover, the composition of this invention can also be made into the aspect which does not contain a chromatic color agent substantially. When the chromatic colorant is not substantially contained, the content of the chromatic colorant is preferably 0.005% by mass or less, and 0.001% by mass or less based on the total solid content of the composition of the present invention. More preferably, no chromatic colorant is contained.

<< Coloring material that transmits at least part of light in the near infrared region and shields light in the visible region (coloring material that blocks visible light) >>
The composition of the present invention may contain a colorant that transmits at least part of light in the near infrared region and shields light in the visible region (hereinafter also referred to as colorant that shields visible light). it can.

The colorant that blocks visible light preferably satisfies at least one of the following requirements (1) and (2), and more preferably satisfies the requirement (1).
(1): An embodiment containing two or more chromatic colorants.
(2): An embodiment containing an organic black colorant.

Examples of the chromatic colorant include the chromatic colorants described above. Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds and perylene compounds are preferable. Examples of the bisbenzofuranone compounds include compounds described in JP-T 2010-534726, JP-2012-515233, JP-2012-515234, and the like. An example is “Irgaphor Black” manufactured by BASF. Examples of perylene compounds include C.I. I. Pigment Black 31, 32 and the like. Examples of the azomethine compound include compounds described in JP-A-1-170601 and JP-A-2-34664, and examples thereof include “Chromofine Black A1103” manufactured by Dainichi Seika Kogyo Co., Ltd.

In the present invention, the colorant that blocks visible light is, for example, a ratio between the minimum absorbance A in the wavelength range of 450 nm to less than 650 nm and the minimum absorbance B in the wavelength range of 900 to 1,300 nm. / B is preferably 4.5 or more.
The above characteristics may be satisfied with one kind of material, or may be satisfied with a combination of a plurality of materials. For example, in the case of the above aspect (1), it is preferable that a plurality of chromatic colorants are combined to satisfy the spectral characteristics.

When two or more kinds of chromatic colorants are included as a colorant that blocks visible light, the chromatic colorants are red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants. It is preferable that it is a coloring agent chosen from these. Examples of combinations of chromatic colorants include the following.
(1) Embodiment containing yellow colorant, blue colorant, purple colorant and red colorant (2) Embodiment containing yellow colorant, blue colorant and red colorant (3) Yellow colorant, purple colorant And (4) an embodiment containing a yellow colorant and a purple colorant (5) an embodiment containing a green colorant, a blue colorant, a purple colorant and a red colorant (6) a purple colorant And an embodiment containing an orange colorant (7) an embodiment containing a green colorant, a purple colorant and a red colorant (8) an embodiment containing a green colorant and a red colorant.

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

When the composition of the present invention contains a colorant that blocks visible light, the content of the colorant that blocks visible light is preferably 30% by mass or less, and 20% by mass with respect to the total solid content of the composition. The following is more preferable, and 15% by mass or less is more preferable. For example, the lower limit may be 0.01% by mass or more, and may be 0.5% by mass or more.
Moreover, the composition of this invention can also be made into the aspect which does not contain the coloring material which shields visible light substantially. When the coloring material that blocks visible light is not substantially contained, the content of the coloring material that blocks visible light is preferably 0.005% by mass or less based on the total solid content of the composition of the present invention. 0.001 mass% or less is more preferable, and it is further more preferable not to contain the color material which shields visible light.

<< Pigment derivative >>
When the composition of this invention contains a pigment, it can contain a pigment derivative further. As the pigment derivative, a compound having a structure in which a part of the pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group is preferable. When the composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment contained in the composition. The lower limit is more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more. The upper limit is more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less. If content of a pigment derivative is the said range, the dispersibility of a pigment can be improved and aggregation of a pigment can be suppressed efficiently. Only one pigment derivative or two or more pigment derivatives may be used, and in the case of two or more pigment derivatives, the total amount is preferably within the above range.

<< Resin >>
The composition of the present invention preferably contains a resin. In addition, resin is components other than the aggregation inhibitor mentioned above. The resin is blended, for example, for the purpose of dispersing a pigment or the like in the composition and the purpose of a binder. A resin used mainly for dispersing pigments is also called a dispersant. However, such use of the resin is merely an example, and the resin can be used for other purposes.

The weight average molecular weight (Mw) of the resin is preferably 20,000 to 60,000. The lower limit is preferably 25,000 or more. The upper limit is preferably 55,000 or less.
The resin dispersity (Mw / Mn) is preferably 1.1 to 10.0. The lower limit is more preferably 1.3 or more, and further preferably 1.5 or more. The upper limit is more preferably 8.0 or less, and even more preferably 6.0 or less.

The glass transition temperature of the resin is preferably 0 to 100 ° C. The lower limit is more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher. The upper limit is more preferably 95 ° C. or less, and still more preferably 90 ° C. or less. In the present invention, the glass transition temperature of the resin is determined by weighing 5 mg of sample in a sample pan using a differential scanning calorimeter (Seiko Instruments, DSC1000) and in a nitrogen stream from 10 ° C / 200 ° C to -20 ° C to 200 ° C. It is the value measured by raising the temperature at a temperature elevation rate of minutes. The average value of the temperature at which the baseline begins to deviate and the temperature at which the baseline returns to the base line was taken as the glass transition temperature of the resin.

Types of resin include (meth) acrylic resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, Polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, and polysiloxane resin are exemplified, and (meth) acrylic resin is preferable. One kind selected from these resins may be used alone, or two or more kinds may be mixed and used.

Resin may have an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. These acid groups may be used alone or in combination of two or more. Resins having acid groups can also be used as alkali-soluble resins. Hereinafter, the resin having an acid group is also referred to as an alkali-soluble resin.

As the alkali-soluble resin, a polymer having a carboxyl group in the side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used. Examples include maleic acid copolymers, alkali-soluble phenol resins such as novolak resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers having a hydroxyl group added with an acid anhydride. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, Styrene macromonomer, polymethylmethacrylate macromonomer, and the like. As other monomers, N-substituted maleimide monomers described in JP-A-10-300922 such as N-phenylmaleimide and N-cyclohexylmaleimide can also be used. Only one kind of these other monomers copolymerizable with (meth) acrylic acid may be used, or two or more kinds may be used.

Examples of the alkali-soluble resin include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth) acrylate. A multi-component copolymer composed of / (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.

The alkali-soluble resin includes a monomer component including a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a polymer obtained by polymerization.

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

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

In the formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include methyl, ethyl, n- Linear or branched alkyl groups such as propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl, Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; benzyl and the like An alkyl group substituted with an aryl group of Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

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

The alkali-soluble resin may contain a repeating unit derived from the compound represented by the following formula (X).

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

In the above formula (X), the alkylene group of R ₂ preferably has 2 to 3 carbon atoms. The alkyl group of R ₃ has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R ₃ may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

Examples of alkali-soluble resins include paragraphs 0558 to 0571 in JP2012-208494A (paragraph numbers 0685 to 0700 in the corresponding US Patent Application Publication No. 2012/0235099), and JP2012-198408. The description of paragraph numbers 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated in the present specification. Specific examples of the alkali-soluble resin include the following resins. In the following structural formulas, Me represents a methyl group.

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

Resin (including alkali-soluble resin) may have a curable group. Examples of the curable group include a group having an ethylenically unsaturated bond, an epoxy group, a methylol group, and an alkoxysilyl group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, and a (meth) acryloyloxy group. Examples of the alkoxysilyl group include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group.

Examples of the repeating unit having a curable group include repeating units represented by the following formulas (A2-1) to (A2-4).

R ¹ represents a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1. R ¹ is preferably a hydrogen atom or a methyl group.

L ⁵¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, —O—, —S—, —CO—, —COO—, —OCO—, —SO ₂ —, —NR ¹⁰ — (R ¹⁰ represents a hydrogen atom Or a group consisting of a combination thereof, and a group consisting of at least one of an alkylene group, an arylene group and an alkylene group and —O— is preferable. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be monocyclic or polycyclic. The number of carbon atoms of the arylene group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10.

P ¹ represents a curable group. Examples of the curable group include a group having an ethylenically unsaturated bond, an epoxy group, a methylol group, and an alkoxysilyl group.

Examples of the resin containing a curable group and an acid group (an alkali-soluble resin having a curable group) include NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co., Ltd.). ), Biscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl 3800 (Daicel) UC Bee Co., Ltd.), ACRYCURE RD-F8 (manufactured by Nippon Shokubai Co., Ltd.), and the like.

The resin preferably also has a repeating unit represented by the following formulas (A3-1) to (A3-7).

In the formula, R ⁵ represents a hydrogen atom or an alkyl group, L ⁴ to L ⁷ each independently represents a single bond or a divalent linking group, and R ¹⁰ to R ¹³ each independently represents a hydrocarbon. Represents a group. R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom or a substituent.

R ⁵ has the same meaning as R ^{1 in} formulas (A2-1) to (A2-4), and the preferred range is also the same.
L ⁴ to L ⁷ have the same meaning as L ^{51 in} formulas (A2-1) to (A2-4), and the preferred ranges are also the same.

The hydrocarbon group represented by R ¹⁰ to R ¹³ is not particularly limited. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2 -Linear or branched alkyl groups such as ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl, etc. And an alicyclic hydrocarbon group; an alkyl group substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; an alkyl group substituted with an aryl group such as benzyl (aralkyl group); and the like.
The substituents represented by R ¹⁴ and R ¹⁵ are alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heteroaryls. Oxycarbonyl group, acyloxy group, amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heteroarylthio Group, alkylsulfonyl group, arylsulfonyl group, heteroarylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, heteroarylsulfinyl group, ureido group, phosphoric acid Bromide group, a mercapto group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, sulfino group, a hydrazino group, an imino group, a silyl group, a hydroxyl group, a halogen atom, and a cyano group. Among these, at least one of R ¹⁴ and R ¹⁵ preferably represents a cyano group or —COORa. Ra is preferably a hydrogen atom, an alkyl group or an aryl group.

In the present invention, the resin is a proof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (day Oil Co., Ltd., epoxy group-containing polymer), ARTON F4520 (manufactured by JSR Co., Ltd.), Acrybase FF-187 (Fujikura Kasei Co., Ltd.) and the like can also be used.

In the composition of the present invention, the resin content is preferably 1 to 80% by mass relative to the total solid content of the composition. The lower limit is more preferably 10% by mass or more, and further preferably 20% by mass or more. The upper limit is more preferably 70% by mass or less, and still more preferably 60% by mass or less.
In the present invention, the resin content is preferably 100 to 16000 parts by mass with respect to 100 parts by mass of the aggregation inhibitor described above. The upper limit is preferably 10,000 parts by mass or less, more preferably 7000 parts by mass or less, and still more preferably 6000 parts by mass or less. The lower limit is preferably 150 parts by mass or more, more preferably 200 parts by mass or more, and further preferably 300 parts by mass or more.

<< polymerizable compound >>
The composition of the present invention preferably contains a polymerizable compound. As the polymerizable compound, a compound that can be polymerized by the action of a radical is preferable. That is, the polymerizable compound is preferably a radical polymerizable compound. The polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more groups having an ethylenically unsaturated bond, and 3 groups having an ethylenically unsaturated bond. A compound having at least one is more preferable. The upper limit of the number of groups having an ethylenically unsaturated bond is, for example, preferably 15 or less, and more preferably 6 or less. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a styryl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.

The polymerizable compound may be in the form of either a monomer or a polymer, but is preferably a monomer. The monomer type polymerizable compound preferably has a molecular weight of 200 to 3,000. The upper limit of the molecular weight is more preferably 2,500 or less, and further preferably 2,000 or less. The lower limit of the molecular weight is more preferably 250 or more, and further preferably 300 or more.

As examples of the polymerizable compound, the description in paragraph numbers 0033 to 0034 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. Examples of the compound include ethyleneoxy-modified pentaerythritol tetraacrylate (commercially available product is NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available products are KAYARAD D-320; Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available products are KAYARAD D -310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available products are KAYARAD DPHA; Nippon Kayaku Co., Ltd., A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.) ), And these (meth) acryloyl groups are ethylene A structure in which they are bonded via a glycol glycol or propylene glycol residue is preferred. These oligomer types can also be used. In addition, the description of polymerizable compounds in paragraph numbers 0034 to 0038 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. In addition, polymerizable monomers described in paragraph No. 0477 of JP2012-208494A (paragraph No. 0585 of the corresponding US Patent Application Publication No. 2012/0235099) and the like are described in the present specification. Incorporated into.
Diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available product is 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 preferable. These oligomer types can also be used. Examples thereof include RP-1040 (manufactured by Nippon Kayaku Co., Ltd.).

The polymerizable compound may have an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group. A polymerizable compound having an acid group can be obtained by a method in which a part of hydroxyl groups of a polyfunctional alcohol is (meth) acrylated, and an acid anhydride is added to the remaining hydroxyl groups to form carboxyl groups. Further, an acid group may be introduced by reacting the above hydroxyl group with a non-aromatic carboxylic acid anhydride or the like. Specific examples of the non-aromatic carboxylic acid anhydride include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polymerizable compound to which a group is added is more preferable, and in the above-described ester, a compound in which the aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol is further preferable. Commercially available products include Aronix M-510, M-520 (manufactured by Toagosei Co., Ltd.), CBX-0, CBX-1 (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like. The acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH / g. The lower limit is more preferably 5 mgKOH / g or more. The upper limit is more preferably 30 mgKOH / g or less.

As the polymerizable compound, a polymerizable compound having a caprolactone structure is also a preferred embodiment. The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipenta Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone Can be mentioned. As the polymerizable compound having a caprolactone structure, a compound represented by the following formula (Z-1) is preferable.

In formula (Z-1), all six Rs are groups represented by formula (Z-2), or 1 to 5 of the six Rs are represented by formula (Z-2). And the remainder is a group represented by the formula (Z-3).

In formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents 1 or 2, and “*” represents a bond.

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

Polymerizable compounds having a caprolactone structure are commercially available, for example, from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (Z-1) to (Z-3), Number of groups represented by (Z-2) = 2, a compound in which R ¹ is all hydrogen atoms), DPCA-30 (formula, m = 1, number of groups represented by formula (Z-2)) = 3, a compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, a compound in which R ¹ is all hydrogen atoms ), DPCA-120 (a compound in which m = 2 in the formula, the number of groups represented by formula (Z-2) = 6, and all R ¹ are hydrogen atoms).

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

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

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

The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in the formula (Z-5), a form in which all six Xs are acryloyl groups is preferable.

Among the compounds represented by the formula (Z-4) or the formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”). Among them, exemplary compounds (a), (f) b), (e) and (f) are preferred.

Examples of commercially available polymerizable compounds represented by the formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer Co., Ltd., Japan Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains, manufactured by Kayaku Co., Ltd.

The polymerizable compound is also preferably isocyanuric acid ethyleneoxy-modified (meth) acrylate. Examples of commercially available products include Aronix M-315, M-313 (manufactured by Toagosei Co., Ltd.), NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), SR368 (manufactured by Sartomer Co., Ltd.), and the like. . Also, the following compounds can be used.

Polymerizable compounds include urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Can do.
Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600, and light acrylate DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.).

In the composition of the present invention, the content of the polymerizable compound is preferably 0.01 to 50% 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 further preferably 0.5% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 15% by mass or less. When the composition of this invention contains 2 or more types of polymeric compounds, it is preferable that those total amount exists in the said range.

<< photopolymerization initiator >>
The composition of the present invention preferably contains a photopolymerization initiator. There is no restriction | limiting in particular as a photoinitiator, It can select suitably from well-known photoinitiators. For example, a compound having photosensitivity to light in the ultraviolet region to the visible region is preferable. The photopolymerization initiator is preferably a photoradical polymerization initiator. The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like. Examples of the halogenated hydrocarbon derivative having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in GB 1388492, a compound described in JP-A-53-133428, a compound described in DE 3337024, F . C. J. Schaefer Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, Examples include the compounds described in Japanese Patent No. 4221976.

As photopolymerization initiators, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, tria. A compound selected from the group consisting of a reel imidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound and a 3-aryl-substituted coumarin compound is preferred. Examples of α-aminoketone compounds include 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1- [4- (hexyl) phenyl] -2-morpholinopropane-1- ON, 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- And (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone. Examples of commercially available products of α-aminoketone compounds include IRGACURE907, IRGACURE369, and IRGACURE379 (trade names: all manufactured by BASF). Examples of commercially available α-hydroxyketone compounds include IRGACURE184, DAROCUR1173, IRGACURE500, IRGACURE2959, IRGACURE127 (trade names: all manufactured by BASF). Examples of commercially available acylphosphine compounds include IRGACURE 819 and IRGACURE TPO (trade names: both manufactured by BASF).

It is also preferable to use an oxime compound as the photopolymerization initiator. Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, compounds described in JP-A No. 2006-342166, and JP-A No. 2016-21012. The compounds described in the publication can be used.

Examples of oxime compounds that can be preferably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, -Acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2 -One, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660, J.A. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples thereof include compounds described in JP-A Nos. 202 to 232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797, and JP-A 2006-342166. As commercially available products, IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE03, IRGACURE OXE04 (manufactured by BASF) are also preferably used. Also, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-930 (manufactured by ADEKA Corporation), Adeka Optomer N-1919 (manufactured by ADEKA Corporation), JP 2012-14052 A Can be used.

Further, as oxime compounds other than those described above, compounds described in JP-T 2009-519904, in which an oxime is linked to the N-position of the carbazole ring, and those described in US Pat. Compounds, compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye site, ketoxime compounds described in International Publication WO2009 / 131189, triazine skeleton and oxime A compound described in US Pat. No. 7,556,910 containing a skeleton in the same molecule, a compound described in JP2009-221114A having an absorption maximum wavelength at 405 nm and good sensitivity to a g-ray light source Paragraph No. 00 of JP 2014-137466 A The like may be used compounds described in 6-0079.
Preferably, for example, paragraph numbers 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
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 oxime N—O bond is an (E) isomer, or the oxime N—O bond may be a (Z) oxime compound. Z) It may be a mixture with the body.

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In the formula (OX-1), the monovalent substituent represented by B 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 the substituent include the above-described substituents.
In the formula (OX-1), the divalent organic group represented by A 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 the substituent include the above-described substituents.

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

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

In the present invention, an oxime compound having a nitro group can be used as a 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 paragraph numbers 0031 to 0047 of JP2013-114249A, paragraph numbers 0008 to 0012 and 0070 to 0079 of JP2014-137466A, paragraph of JP4223071. No. 0007 to 0025, Adeka Arcles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.

In the present invention, an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples include OE-01 to OE-75 described in International Publication No. WO2015 / 036910.

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

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

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

The photopolymerization initiator preferably contains an oxime compound and an α-aminoketone compound. By using both in combination, the developability is improved and a pattern having excellent rectangularity can be easily formed. When the oxime compound and the α-aminoketone compound are used in combination, the α-aminoketone compound is preferably 50 to 600 parts by mass, more preferably 150 to 400 parts by mass with respect to 100 parts by mass of the oxime compound.

The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably based on the total solid content of the composition of the present invention. 1 to 20% by mass. Within this range, better sensitivity and pattern formability can be obtained. The composition of the present invention may contain only one kind of photopolymerization initiator, or may contain two or more kinds. When 2 or more types are included, the total amount thereof is preferably within the above range.

<< Chain transfer agent >>
The composition of the present invention preferably contains a chain transfer agent. According to this aspect, in exposure at the time of pattern formation, hardening of the film surface (pattern surface) by exposure can be promoted. For this reason, it can suppress that the thickness of a film | membrane reduces at the time of exposure, and it is easy to form the pattern excellent in the rectangularity.

Examples of chain transfer agents include N, N-dialkylaminobenzoic acid alkyl esters and thiol compounds, with thiol compounds being preferred. The thiol compound is preferably a compound having 2 or more (preferably 2 to 8, more preferably 3 to 6) thiol groups in the molecule. Specific examples of the thiol compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1 , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and other thiol compounds having a heterocyclic ring, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercapto) And aliphatic thiol compounds such as butyryloxy) butane. Moreover, it is also preferable to use the following compound. Commercially available chain transfer agents include PEMP (manufactured by Nagase Sangyo Co., Ltd., thiol compound), Sunseller M (manufactured by Sanshin Chemical Co., Ltd., thiol compound), Karenz MT BD1 (Showa Denko Co., Ltd.) And thiol compounds).

The content of the chain transfer agent is preferably 0.2 to 5.0% by mass, more preferably 0.4 to 3.0% by mass, based on the total solid content of the composition of the present invention.
In addition, the content of the chain transfer agent is preferably 1 to 40 parts by mass, and more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable compound.

<< Compound having epoxy group >>
The composition of this invention can also contain the compound which has an epoxy group. As for the compound which has an epoxy group, the compound which has 1 or more of epoxy groups in 1 molecule is mentioned, The compound which has 2 or more is preferable. It is preferable to have 2 to 100 epoxy groups in one molecule. The upper limit of the epoxy group can be, for example, 10 or less, or 5 or less.

The compound having an epoxy group preferably has an epoxy equivalent (= molecular weight of the compound having an epoxy group / number of epoxy groups) of 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, and 100 to 300 g. / Equivalent is more preferable.

The compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 1,000) or a high molecular weight compound (for example, a molecular weight of 1,000 or more, and in the case of a polymer, the weight average molecular weight is 1,000). Any of the above). The molecular weight of the compound having an epoxy group (weight average molecular weight in the case of a polymer) is preferably 200 to 100,000, and more preferably 500 to 50,000.

Compounds having an epoxy group are described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraph numbers 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014089408A. The prepared compounds can also be used. These contents are incorporated herein. As commercial products, for example, as bisphenol A type epoxy resin, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050 , EPICLON 1051, EPICLON 1055 (above, manufactured by DIC Corporation) and the like. Examples of the bisphenol F type epoxy resin include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, made by DIC Corporation), LCE-21, RE-602S. (Nippon Kayaku Co., Ltd.) and the like. As phenol novolac type epoxy resins, jER152, jER154, jER157S70, jER157S65 (Mitsubishi Chemical Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC Corporation), etc. Is mentioned. Cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) ), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), and the like. Aliphatic epoxy resins include ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), and the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation), OXT-221 (manufactured by Toagosei Co., Ltd.) and the like.

As the compound having an epoxy group, a compound described in paragraph No. 0045 of JP-A-2009-265518 can also be used.

The content of the compound having an epoxy group is preferably 0.5 to 20% by mass with respect to the total solid content of the composition of the present invention. The lower limit is more preferably 1% by mass or more, and further preferably 2% by mass or more. The upper limit is more preferably 15% by mass or less, and further preferably 10% by mass or less.

<< Solvent >>
The composition of the present invention can contain a solvent. Examples of the solvent include organic solvents. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the composition, but is preferably selected in consideration of the applicability and safety of the composition.

Examples of organic solvents include the following. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxyacetate ( For example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl esters of 3-alkoxypropionic acid (eg, Methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropio) 2-alkoxypropionic acid alkyl esters (for example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, 2- Ethyl methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate ( For example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Methyl, - ethyl oxobutanoate, and the like. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol Examples thereof include monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of aromatic hydrocarbons include toluene and xylene. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may be better reduced for environmental reasons (for example, 50 ppm by weight per part of organic solvent). (million) or less, or 10 mass ppm or less, or 1 mass ppm or less).

Organic solvents may be used alone or in combination of two or more. When two or more organic solvents are used in combination, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone A mixed solution composed of two or more selected from ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.

In the present invention, it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably 10 mass ppb (parts per billion) or less, for example. If necessary, a solvent having a mass ppt (parts per trillation) level may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015). .

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

The solvent may contain isomers (compounds having the same number of atoms and different structures). Moreover, only 1 type may be included and the isomer may be included multiple types.

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

The content of the solvent is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 25 to 75% by mass with respect to the total amount of the composition of the present invention. .

<< Silane coupling agent >>
The composition of the present invention can further contain a silane coupling agent. In the present invention, the silane coupling agent is a component different from the polymerizable compound described above. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Further, as the functional group other than the hydrolyzable group, a group that exhibits an affinity by forming an interaction or bond with the resin is preferable. Examples thereof include a vinyl group, a styryl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, and an isocyanate group, and a (meth) acryloyl group and an epoxy group are preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group and at least one of a (meth) acryloyl group and an epoxy group.

Specific examples of the silane coupling agent include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycol. Sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, parastyryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldi Toxisilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl- Butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris- (trimethoxysilylpropyl) isocyanurate , 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc. . In addition to the above, alkoxy oligomers can be used. Also, the following compounds can be used.

Commercially available products include Shin-Etsu Silicone's KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM-3063, KBM-3066, KBM-3086, KBE-3063, KBE-3083, KBM-3103, KBM-7103, SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE- 402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, BE-585, KBM-802, KBM-803, KBE-846, KBE-9007, X-40-1053, X-41-1059A, X-41-1056, X-41-1805, X-41-1818, X-41-1810, X-40-2651, X-40-2655A, KR-513, KC-89S, KR-500, X-40-9225, X-40-9246, X-40-9250, KR- 401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213, X-40-2308, X-40-9238, and the like. Examples of the silane coupling agent include compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703, and compounds described in paragraph numbers 0056 to 0066 of JP-A-2009-242604. Incorporated herein.

The content of the silane coupling agent is preferably 0.01 to 15.0 mass%, more preferably 0.05 to 10.0 mass%, based on the total solid content of the composition of the present invention. The silane coupling agent may be only one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.

<< Surfactant >>
The composition of the present invention may contain various surfactants from the viewpoint of further improving applicability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

By including a fluorosurfactant in the above composition, the liquid properties (particularly fluidity) when prepared as a coating liquid can be further improved, and the uniformity of coating thickness and liquid saving can be further improved. it can. That is, when a film is formed using a coating liquid to which a composition containing a fluorosurfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is reduced. Is improved, and the coating property to the coated surface is improved. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

The fluorine 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 fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.

Specific examples of the fluorosurfactant include surfactants described in JP 2014-41318 A, paragraphs 0060 to 0064 (paragraph numbers 0060 to 0064 of the corresponding international publication WO 2014/17669), and the like. Examples include surfactants described in paragraphs 0117 to 0132 of JP2011-132503A, 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, F780 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, the product made by OMNOVA) etc. are mentioned.

In addition, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which the fluorine atom is volatilized by cleavage of the functional group containing the fluorine atom when heated is suitably used. Can be used. Examples of such a fluorosurfactant include Megafac DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016). -21, which can be used.

As the fluorosurfactant, a block polymer can be used. Examples thereof include compounds described in JP2011-89090A. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as the fluorosurfactant used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. % Which shows the ratio of a repeating unit in said compound is the mass%.

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

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF ), Tetronic 304, 701, 704, 901, 904, 150R1 (B SF), Solsperse 20000 (Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.), Pionein D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Olphine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.

Examples of cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

Examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.

Examples of silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.

Only one surfactant may be used, or two or more surfactants may be combined.
The content of the surfactant is preferably from 0.001 to 2.0% by mass, more preferably from 0.005 to 1.0% by mass, based on the total solid content of the composition of the present invention.

<< UV absorber >>
It is preferable that the composition of this invention contains a ultraviolet absorber.
Examples of the ultraviolet absorber include conjugated diene compounds and diketone compounds, and conjugated diene compounds are preferable. The conjugated diene compound is more preferably a compound represented by the following formula (UV-1).

In the formula (UV-1), R ¹ and R ² 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 ¹ and R ² May be the same as or different from each other, but do not represent a hydrogen atom at the same time.
R ¹ and R ² may form a cyclic amino group together with the nitrogen atom to which R ¹ and R ² are bonded. Examples of the cyclic amino group include piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group and the like.
R ¹ and R ² 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 ³ and R ⁴ represent an electron withdrawing group. R ³ and R ⁴ are preferably acyl, carbamoyl, alkyloxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfonyl, arylsulfonyl, sulfonyloxy, sulfamoyl, acyl, carbamoyl Group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, sulfamoyl group are preferred. R ³ and R ⁴ may be bonded to each other to form a cyclic electron withdrawing group. Examples of the cyclic electron withdrawing group formed by combining R ³ and R ⁴ with each other include a 6-membered ring containing two carbonyl groups.
At least one of the above R ¹ , R ² , R ³ , and R ⁴ 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 another monomer.

Specific examples of the ultraviolet absorber represented by the formula (UV-1) include the following compounds. The description of the substituent of the ultraviolet absorber represented by the formula (UV-1) is given in paragraph numbers 0024 to 0033 of the international publication WO2009 / 123109 (paragraph number 0040 of the corresponding US Patent Application Publication No. 2011/0039195). To 0059), the contents of which are incorporated herein. Preferable specific examples of the compound represented by the formula (UV-1) include those described in paragraph Nos. 0034 to 0037 (paragraph number 0060 of the corresponding US Patent Application Publication No. 2011/0039195) of International Publication No. WO2009 / 123109. Descriptions of exemplary compounds (1) to (14) can be taken into account, and the contents thereof are incorporated herein. Examples of commercially available ultraviolet absorbers represented by the formula (UV-1) include UV503 (manufactured by Daito Chemical Co., Ltd.).

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

In the formula (UV-2), R ¹⁰¹ and R ¹⁰² each independently represent a substituent, and m1 and m2 each independently represent 0 to 4. Substituents are 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, heteroarylsulfonyl, alkylsulfinyl, arylsulfinyl, heteroarylsulfinyl, ureido, phosphate amide, mercapto, E group, a carboxyl group, a nitro group, a hydroxamic acid group, sulfino group, a hydrazino group, an imino group, a silyl group, a hydroxyl group, a halogen atom, or a cyano group, an alkyl group and alkoxy group are preferred.
The alkyl group preferably has 1 to 20 carbon atoms. Examples of the alkyl group include linear, branched, and cyclic, and linear or branched is preferable, and branched is more preferable.
The number of carbon atoms of the alkoxy group is preferably 1-20. Examples of the alkoxy group include straight chain, branched, and cyclic, and straight chain or branched is preferable, and branched is more preferable.
A combination in which one of R ¹⁰¹ and R ¹⁰² is an alkyl group and the other is an alkoxy group is preferable.
m1 and m2 each independently represents 0-4. m1 and m2 are each independently preferably 0 to 2, more preferably 0 to 1, and particularly preferably 1.

Examples of the compound represented by the formula (UV-2) include the following compounds.

As the UV absorber, Yubinal A (manufactured by BASF) can be used. As the ultraviolet absorber, an ultraviolet absorber such as an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a triazine compound, or the like can be used. Specific examples include the compounds described in JP2013-68814A. Is mentioned. As the benzotriazole compound, MYUA series (Chemical Industry Daily, February 1, 2016) manufactured by Miyoshi Oil & Fats Co., Ltd. may be used.

The content of the ultraviolet absorber is preferably from 0.01 to 10% by mass, more preferably from 0.01 to 5% by mass, based on the total solid content of the composition of the present invention.
The ultraviolet absorber is preferably contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the polymerizable compound. The upper limit is preferably 80 parts by mass or less, and more preferably 60 parts by mass or less. The lower limit is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more.

<< Polymerization inhibitor >>
The composition of the present invention may contain a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition. Examples of polymerization inhibitors include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium compounds , Cationic dyes, sulfide group-containing compounds, nitro group-containing compounds, phosphorus compounds, lactone compounds, transition metal compounds (FeCl ₃ , CuCl ₂ etc.). In addition, these compounds may be composite compounds in which a plurality of structures that exhibit a polymerization inhibiting function such as a phenol skeleton and a phosphorus-containing skeleton are present in the same molecule. For example, the compounds described in JP-A-10-46035 are also preferably used. Specific examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine salts (ammonium salt, primary cerium salt, etc.) can be mentioned. Of these, paramethoxyphenol is preferred.
The content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the composition of the present invention.
The polymerization inhibitor is preferably contained in an amount of 0.001 to 1 part by mass with respect to 100 parts by mass of the polymerizable compound. The upper limit is preferably 0.5 parts by mass or less, and more preferably 0.2 parts by mass or less. The lower limit is preferably 0.01 parts by mass or more, and more preferably 0.03 parts by mass or more.

<< Antioxidant >>
The composition of the present invention preferably contains an antioxidant. Examples of the antioxidant include a phenol compound, a phosphite compound, a thioether compound, a hindered amine compound, and the like, and a phenol compound and a hindered amine compound are preferable. The molecular weight of the antioxidant is preferably 500 or more.

As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferable phenolic compounds include hindered phenolic compounds. In particular, a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable, and a methyl group, an ethyl group, a propionyl group, an isopropionyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group. Group, t-pentyl group, hexyl group, octyl group, isooctyl group and 2-ethylhexyl group are more preferable. A compound having a phenol group and a phosphite group in the same molecule is also preferred.

The phenol compound is preferably a polysubstituted phenol compound. Multi-substituted phenolic compounds are roughly classified into three types (substitution position and structure below) (following formula (A) hindered type, following formula (B) semi-hindered type, and following formula (C) less hindered type). is there.

In the formulas (A) to (C), R represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, amino group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylamino group, arylamino group, alkylsulfonyl group, and arylsulfonyl group. The amino group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylamino group, arylamino group, alkylsulfonyl group, and arylsulfonyl group may further have a substituent.

The phenol compound is preferably a compound in which a plurality of structures represented by the formulas (A) to (C) are present in the same molecule, and the structure represented by the formulas (A) to (C) is 2 in the same molecule. More preferred are compounds having ˜4.

Examples of the phenol compound include p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, 4,4-thiobis (3-methyl-6-tert-butylphenol), 2,2′- Examples thereof include compounds selected from the group consisting of methylenebis (4-methyl-6-tert-butylphenol), phenol resins, and cresol resins.
Representative examples that can be obtained as a commercially available product include Sumitizer BHT (manufactured by Sumitomo Chemical Co., Ltd.), Irganox 1010, 1222 (manufactured by BASF), Adekastab AO-20, AO-50, AO-50F, AO-60, AO-60G, AO-330 (manufactured by ADEKA Co., Ltd.) and the like. As the compound of the above formula (B), Sumilizer BBM-S (manufactured by Sumitomo Chemical Co., Ltd.), Irganox H.245 (manufactured by BASF), Adeka Stub AO-80 (manufactured by ADEKA Co., Ltd.) and the like, and examples of the compound of the above formula (C) include Adeka Stub AO-30 and AO-40 (manufactured by ADEKA).

Examples of the hindered amine compound include compounds having one or more partial structures represented by the following formula (HA) in one molecule.
Formula (HA)

In the formula (HA), a wavy line represents a bond with another atom or atomic group constituting the hindered amine compound. R ¹ to R ⁴ each independently represents a hydrogen atom or an alkyl group, and R ⁵ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group.
The hindered amine compound is preferably a compound having two or more partial structures represented by the above formula (HA) in one molecule. The upper limit is preferably 100 or less, more preferably 50 or less, further preferably 20 or less, and particularly preferably 10 or less.
Examples of hindered amine compounds include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, and LA-87 (ADEKA CORPORATION). Manufactured).

As the phosphite compound, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine- 6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2- Yl) oxy] ethyl] amine and at least one compound selected from the group consisting of ethyl bis (2,4-di-tert-butyl-6-methylphenyl) phosphite.

As the antioxidant, in addition to those described above, ADK STAB PEP-36A, ADK STAB AO-412S (manufactured by ADEKA Corporation), and the like can also be used.

The content of the antioxidant is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass, based on the total solid content of the composition of the present invention. Only one type of antioxidant may be used, or two or more types may be used. In the case of two or more types, the total amount is preferably within the above range.

<< Other ingredients >>
The composition of the present invention may contain a sensitizer, a curing accelerator, a filler, a thermal curing accelerator, a thermal polymerization inhibitor, a plasticizer, and other auxiliary agents (for example, conductive particles, fillers, An antifoaming agent, a flame retardant, a leveling agent, a peeling accelerator, a fragrance, a surface tension adjusting agent, etc.). By appropriately containing these components, it is possible to adjust the properties such as the stability and film properties of the target optical filter such as a near-infrared cut filter. These components are described in, for example, paragraph No. 0183 of JP2012-003225A (corresponding to paragraph No. 0237 of US Patent Application Publication No. 2013/0034812), paragraph No. of JP2008-250074A Descriptions such as 0101-0104, 0107-0109, and the like can be taken into consideration, and the contents thereof are incorporated in the present specification.

<Method for preparing composition>
The composition of the present invention can be prepared by mixing the aforementioned components.
In preparing the composition, the components may be mixed together, or may be sequentially mixed after each component is dissolved or dispersed in a solvent. In addition, there are no particular restrictions on the input order and work conditions when mixing. For example, the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time, and if necessary, each component is suitably used as two or more solutions or dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
Moreover, when the composition of this invention contains particles, such as a pigment, it is preferable to include the process of disperse | distributing particles. In the process of dispersing the particles, the mechanical force used for dispersing the particles includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of the disperser of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high-speed impeller, a sand grinder, a flow jet mixer, a high-pressure wet atomization, and an ultrasonic dispersion. In the pulverization of particles in a sand mill (bead mill), it is preferable to use a bead having a small diameter, or to increase the pulverization efficiency by increasing the filling rate of beads. Further, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. Also, the process and disperser for dispersing particles are described in “Dispersion Technology Taizen, Issued by Information Technology Corporation, July 15, 2005” and “Dispersion technology and industrial application centering on suspension (solid / liquid dispersion system)”. The process and disperser described in Paragraph No. 0022 of Japanese Unexamined Patent Publication No. 2015-157893 can be suitably used. In the process of dispersing the particles, the particles may be refined in the salt milling process. As materials, equipment, processing conditions and the like used in the salt milling process, for example, those described in JP-A-2015-194521 and JP-A-2012-046629 can be used.

In preparing the composition, it is preferable to filter the composition with a filter for the purpose of removing foreign substances or reducing defects. The material of the filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluorine resin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (for example, nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, super high And a filter using a molecular weight polyolefin resin). Among these materials, polypropylene (including high density and ultra high molecular weight polypropylene) and nylon are preferable.
The filter has a pore size of about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm. By setting it as this range, it becomes possible to remove a fine foreign material reliably. It is also preferable to use a fiber-shaped filter medium. Examples of the fiber-shaped filter medium include polypropylene fiber, nylon fiber, glass fiber, and the like, specifically, SBP type series (SBP008 etc.), TPR type series (TPR002, TPR005 etc.), SHPX type manufactured by Loki Techno Co., Ltd. Series (such as SHPX003) 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 twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, select from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. can do.
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtration with the first filter may be performed only with the dispersion, and the second filtration may be performed after mixing the other components.

The viscosity (at 23 ° C.) of the composition of the present invention is preferably 1 to 100 mPa · s. The lower limit is more preferably 2 mPa · s or more, and further preferably 3 mPa · s or more. The upper limit is more preferably 50 mPa · s or less, further preferably 30 mPa · s or less, and particularly preferably 15 mPa · s or less.
Although the total solid content of the composition of the present invention varies depending on the application method, it is preferably, for example, 1 to 50% by mass. The lower limit is more preferably 10% by mass or more. The upper limit is more preferably 30% by mass or less.

The composition of the present invention can be preferably used for forming a near-infrared cut filter or an infrared transmission filter.

<Membrane>
The film of the present invention is formed using the above-described composition of the present invention. The film of the present invention can be preferably used as a near-infrared cut filter or an infrared transmission filter. The film of the present invention may have a pattern, or may be a film without a pattern (flat film). Moreover, the film of the present invention may be used in a state of being laminated on a support, or the film of the present invention may be used after being peeled from the support.

When the film of the present invention is used as an infrared transmission filter, it is a filter using a composition containing the above-mentioned near-infrared absorbing compound and a colorant that blocks visible light, or a layer containing the above-mentioned near-infrared absorbing compound. In addition, it is preferable that the filter includes a layer containing a color material that blocks visible light. When using the film | membrane of this invention as an infrared rays permeable filter, the near-infrared absorption compound mentioned above has a role which limits the light (near-infrared rays) which permeate | transmit to a longer wavelength side.

The thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness 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 film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

The film of the present invention can also be used in combination with a color filter containing a chromatic colorant. A color filter can be manufactured using the coloring composition containing a chromatic colorant. Examples of the chromatic colorant include the chromatic colorant described in the composition of the present invention. The coloring composition can further contain a resin, a polymerizable compound, a photopolymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber, and the like. About these details, the material demonstrated by the composition of this invention is mentioned, These can be used. Moreover, it is good also as a filter provided with the function as a near-infrared cut filter and a color filter by making the film | membrane of this invention contain a chromatic colorant.

In the present invention, the near-infrared cut filter means a filter that transmits light having a wavelength in the visible region (visible light) and shields at least part of light having a wavelength in the near-infrared region (near infrared light). . The near-infrared cut filter may transmit all light having a wavelength in the visible region, and transmits light having a specific wavelength out of light having a wavelength in the visible region and shields light having a specific wavelength. It may be. In the present invention, the color filter means a filter that allows light having a specific wavelength to pass through and blocks light having a specific wavelength among light having a wavelength in the visible region. The infrared transmission filter means a filter that blocks light having a wavelength in the visible region and transmits at least part of light having a wavelength in the near infrared region (near infrared).

When the film of the present invention is used as a near infrared cut filter or an infrared transmission filter, a near infrared cut filter and an infrared transmission filter can be used in combination. By using a combination of a near-infrared cut filter and an infrared transmission filter, it can be preferably used for an infrared sensor that detects infrared rays having a specific wavelength. When both filters are used in combination, both the near-infrared cut filter and the infrared transmission filter can be formed using the composition of the present invention, and only one of them is formed using the composition of the present invention. You can also.

The film of the present invention can be used for various devices such as a solid-state imaging device such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal Oxide Semiconductor), an infrared sensor, and an image display device. Further, the film of the present invention includes a lens having a function of absorbing or cutting near infrared rays (a lens for a camera such as a digital camera, a mobile phone, an in-vehicle camera, an optical lens such as an f-θ lens, a pickup lens) and a semiconductor light receiving element. Optical filters, agricultural coatings for selective use of sunlight, recording media using near infrared absorption heat, near infrared filters for electronic devices and photographs, protective glasses, sunglasses, heat ray blocking filters Used for optical character reading and recording, confidential document copy prevention, electrophotographic photosensitive member, laser welding, and the like. It is also useful as a noise cut filter for CCD cameras and a filter for CMOS image sensors.

<Pattern formation method>
Next, the pattern forming method will be described. The pattern forming method includes a step of forming a composition layer on a support using the composition, and a pattern is formed on the composition layer by a photolithography method or a dry etching method. Forming.

The pattern forming method by the photolithography method includes a step of forming a composition layer on a support using the composition, a step of exposing the composition layer in a pattern, and developing and removing unexposed portions to form a pattern. Preferably including the step of forming. If necessary, a step of baking the composition layer (pre-bake step) and a step of baking the developed pattern (post-bake step) may be provided.
Further, the pattern forming method by the dry etching method includes a step of forming a composition layer on a support using the composition, a step of curing the composition layer to form a cured product layer, A step of forming a photoresist layer on the substrate, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of forming a pattern by dry etching the cured product layer using the resist pattern as an etching mask. It is preferable to contain. Hereinafter, each step will be described.

<< Step of Forming Composition Layer >>
In the step of forming the composition layer, the composition layer is formed on the support using the composition.

Examples of the support include a support made of a material such as glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. Further, a support for a solid-state imaging element in which a solid-state imaging element (light receiving element) such as a CCD or CMOS is provided on the support can be used.
The pattern may be formed on the solid-state image sensor formation surface side (front surface) of the solid-state image sensor substrate, or may be formed on the solid-state image sensor non-formation surface side (back surface). If necessary, the support may be provided with an undercoat layer for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the substrate surface.

As a method for applying the composition to the support, a known method can be used. For example, dropping method (drop casting); slit coating method; spray method; roll coating method; spin coating method (spin coating); casting coating method; slit and spin method; prewet method (for example, JP 2009-145395 A) Method described in the publication); inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Various printing methods; transfer method using a mold or the like; nanoimprint method. The application method in the ink jet is not particularly limited. For example, the method described in the patent publication shown in “Expanding and usable ink jet: unlimited possibilities seen in patents, issued in February 2005, Sumibe Techno Research”. (Particularly, pages 115 to 133), JP2003-262716A, JP2003-185831A, JP2003-261627A, JP2012-126830A, JP2006-169325A, and the like. The method described is mentioned.

The composition layer formed on the support may be dried (prebaked). When a pattern is formed by a low temperature process, pre-baking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower. For example, the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher. The pre-bake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Drying can be performed with a hot plate, oven, or the like.

(When forming a pattern by photolithography)
<< Exposure process >>
Next, the composition layer is exposed in a pattern (exposure process). For example, pattern exposure can be performed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
The radiation (light) that can be used for the exposure is preferably ultraviolet rays such as g-line and i-line, and particularly preferably i-line. Irradiation dose (exposure dose), for example, preferably 0.03 ~ 2.5J / cm ^2, more preferably 0.05 ~ 1.0J / cm ^2, most preferably 0.08 ~ 0.5J / cm ² .
The oxygen concentration at the time of exposure can be appropriately selected. In addition to being performed in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (preferably 15% by volume or less, more preferably 5% by volume or less, Preferably, the exposure may be performed in a substantially oxygen-free manner, and in a high oxygen atmosphere where the oxygen concentration exceeds 21% by volume (preferably 22% by volume or more, more preferably 30% by volume or more, further preferably 50% by volume or more). ) For exposure. The exposure illuminance can be appropriately set, and is usually 1,000 W / m ² to 100,000 W / m ² (preferably 5,000 W / m ² or more, more preferably 15,000 W / m ² or more, More preferably, it can be selected from the range of 35,000 W / m ² or more. Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10,000 W / ^{m 2} at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20,000W / ^{m 2.}

<< Development process >>
Next, the unexposed portion is developed and removed to form a pattern. The development removal of the unexposed portion can be performed using a developer. Thereby, the composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains.
The developer is preferably an alkaline developer that does not damage the underlying solid-state imaging device or circuit.
The temperature of the developer is preferably 20 to 30 ° C., for example. The development time is preferably 20 to 180 seconds. Moreover, in order to improve residue removability, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Organic alkalinity such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene Compounds. 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 to 10% by mass, and more preferably 0.01 to 1% by mass. Moreover, you may use an inorganic alkaline compound as an alkali agent of a developing solution. Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like. Further, a surfactant may be used for the developer. Examples of the surfactant include the surfactant described in the above-described composition, and a nonionic surfactant is preferable. In addition, when using the developing solution which consists of such alkaline aqueous solution, it is preferable to wash | clean (rinse) with a pure water after image development.

Developed, dried and then heat-treated (post-baked). Post-baking is a heat treatment after development for complete film curing. In the case of performing post-baking, the post-baking temperature is preferably 100 to 240 ° C., for example. From the viewpoint of film curing, 200 to 230 ° C. is more preferable. In addition, 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 lower, more preferably 120 ° C. or lower. Preferably, it is 100 ° C. or lower, and more preferably 90 ° C. or lower. The lower limit can be, for example, 50 ° C. or higher. Post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc., so that the film after development is in the above-mentioned condition. .

(When pattern is formed by dry etching method)
The pattern formation by the dry etching method is performed by curing the composition layer formed on the support to form a cured product layer, and then using the patterned photoresist layer as a mask to etch the obtained cured product layer. Can be used. In the formation of the photoresist layer, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming a photoresist, a mode in which heat treatment after exposure and heat treatment after development (post-bake treatment) are desirable. Regarding pattern formation by the dry etching method, the description of paragraph numbers 0010 to 0067 of JP2013-064993A can be referred to, and the contents thereof are incorporated in the present specification.

<Optical filter>
Next, the optical filter of the present invention will be described. The optical filter of the present invention has the film of the present invention. The optical filter can be preferably used as a near-infrared cut filter or an infrared transmission filter.

In addition to the film of the present invention, the optical filter of the present invention may further have a layer containing copper, a dielectric multilayer film, an ultraviolet absorbing layer, and the like.
For example, when the optical filter of the present invention is used as a near-infrared cut filter, in addition to the film of the present invention, it has a copper-containing layer and a dielectric multilayer film, so that the viewing angle is wide and the infrared shielding property is achieved. An excellent near-infrared cut filter can be obtained. In addition to the film of the present invention, a near-infrared cut filter having excellent ultraviolet shielding properties can be obtained by further comprising an ultraviolet absorbing layer. As an ultraviolet absorber contained in an ultraviolet absorption layer, the ultraviolet absorber demonstrated with the composition of this invention is mentioned. In addition, as the ultraviolet absorbing layer, for example, the description of paragraph numbers 0040 to 0070 and 0119 to 0145 of International Publication No. WO2015 / 099060 can be referred to, and the contents thereof are incorporated herein. As the dielectric multilayer film, the description of paragraph numbers 0255 to 0259 of JP 2014-41318 A can be referred to, and the contents thereof are incorporated in the present specification. As a layer containing copper, the glass substrate (copper containing glass substrate) comprised with the glass containing copper and the layer (copper complex containing layer) containing a copper complex are mentioned. Examples of the copper-containing glass substrate include a phosphate glass containing copper and a fluorophosphate glass containing copper. Commercially available products of copper-containing glass include NF-50 (manufactured by AGC Techno Glass Co., Ltd., product name), BG-60, BG-61 (manufactured by Schott Co., Ltd., product name), and CD5000 (manufactured by HOYA Corp.). , Product name) and the like. As a copper complex containing layer, the layer formed using the copper complex containing composition containing a copper complex is mentioned. The copper complex is preferably a compound having a maximum absorption wavelength in a wavelength region of 700 to 1,200 nm. The maximum absorption wavelength of the copper complex is more preferably in the wavelength region of 720 to 1,200 nm, and further preferably in the wavelength region of 800 to 1,100 nm.

In addition, it is preferable that the optical filter of the present invention has a pixel of the film of the present invention and a pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless.

<Laminate>
The laminate of the present invention has the film of the present invention and a color filter containing a chromatic colorant. In the laminate of the present invention, the film of the present invention and the color filter may or may not be adjacent in the thickness direction. When the film of the present invention and the color filter are not adjacent in the thickness direction, the film of the present invention may be formed on a support different from the support on which the color filter is formed. Between the film and the color filter, other members (for example, a microlens, a flattening layer, etc.) constituting the solid-state imaging device may be interposed.

<Solid-state imaging device>
The solid-state imaging device of the present invention has the above-described film of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a configuration having the film of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

On the support, there are a plurality of photodiodes that constitute the light receiving area of the solid-state imaging device, and transfer electrodes made of polysilicon, etc., and light shielding made of tungsten or the like that opens only the light receiving part of the photodiodes on the photodiodes and transfer electrodes. A structure having a film, having 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 portion, and having the cured film of the present invention on the device protective film It is.
Furthermore, on the device protective film, the structure having a light collecting means (for example, a microlens, etc., the same shall apply hereinafter) under the cured film of the present invention (side closer to the support), or on the cured film of the present invention. The structure etc. which have a condensing means may be sufficient.
Further, in the solid-state imaging device, the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape. The partition in this case preferably has a low refractive index for each color pixel. Examples of the image pickup apparatus having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.

<Image display device>
The film of the present invention can also be used for image display devices such as liquid crystal display devices and organic electroluminescence (organic EL) display devices. For example, when used with each colored pixel (for example, red, green, blue), the infrared light contained in the backlight of the display device (for example, white light emitting diode (white LED)) is blocked, and malfunction of peripheral devices is prevented. It can be used for the purpose of forming an infrared pixel in addition to each colored pixel.

For the definition of the image display device and details of the image display device, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, Issued 1990)”, “Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd.) ), Issued in 1989). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The image display device may have a white organic EL element. The white organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, JP 2003-45676 A, supervised by Akiyoshi Mikami, “Frontier of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection”, Technical Information Association, 326-328 pages, 2008, etc. The spectrum of white light emitted from the organic EL element preferably has a strong maximum emission peak in the blue region (430 to 485 nm), the green region (530 to 580 nm) and the yellow region (580 to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 to 700 nm) are more preferable.

<Infrared sensor>
The infrared sensor of the present invention has the above-described film of the present invention. The configuration of the infrared sensor is not particularly limited as long as it is a configuration having the film of the present invention and functions as an infrared sensor.

Hereinafter, an embodiment of an infrared sensor of the present invention will be described with reference to the drawings.
In FIG. 1, reference numeral 110 denotes a solid-state image sensor. The imaging region provided on the solid-state imaging device 110 includes a near infrared cut filter 111 and an infrared transmission filter 114. A color filter 112 is laminated on the near infrared cut filter 111. A micro lens 115 is disposed on the incident light hν side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed so as to cover the microlens 115.

The characteristics of the near infrared cut filter 111 are selected according to the emission wavelength of an infrared light emitting diode (infrared LED) described later. For example, visible light (for example, light having a wavelength of 450 nm or more and less than 650 nm) is transmitted, and at least a part of the light having a wavelength of 650 nm or more (preferably at least a part of light having a wavelength of 650 to 1,000 nm, more preferably a wavelength of 700 to A filter that shields at least a part of light of 1,000 nm) is preferable. The near-infrared cut filter 111 can be formed using, for example, the composition of the present invention.

The color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible region are formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed can be used. For example, the description of paragraph numbers 0214 to 0263 in Japanese Patent Application Laid-Open No. 2014-043556 can be referred to, and the contents thereof are incorporated in the present specification.

The characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of an infrared LED described later. For example, when the emission wavelength of the infrared LED is 850 nm, the infrared transmission filter 114 preferably has a maximum value of 30% or less of the light transmittance in the film thickness direction in the wavelength range of 450 nm to less than 650 nm. 20% or less, more preferably 10% or less, and particularly preferably 0.1% or less. This transmittance preferably satisfies the above-described conditions over the entire wavelength range of 450 nm or more and less than 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 to 1,300 nm) is preferably 70% or more, and 80% or more. Is more preferable, and it is still more preferable that it is 90% or more. This transmittance preferably satisfies the above condition in a part of the wavelength range of 800 nm or more, and preferably satisfies the above condition 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, further preferably 5 μm or less, and particularly preferably 1 μm or less. The lower limit is preferably 0.1 μm. A method for measuring the spectral characteristics, film thickness, etc. of the infrared transmission filter 114 is shown below.
The film thickness was measured using a stylus type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC) on the dried support having the film. The spectral characteristic of the film is a value obtained by measuring transmittance in a wavelength range of 300 to 1,300 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation).

The infrared transmission filter 114 having the spectral characteristics described above can be formed using a composition containing a colorant that blocks visible light. The details of the colorant that blocks visible light are the same as those described in the above-described composition of the present invention.

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

The infrared transmission filter 114 having the spectral characteristics described above can be formed using a composition containing a colorant that blocks visible light and a near infrared absorber. The details of the colorant that blocks visible light are the same as those described in the above-described composition of the present invention. As a near-infrared absorber, the near-infrared absorption compound demonstrated with the composition of this invention mentioned above etc. are mentioned.

Hereinafter, the present invention will be specifically described with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “%” and “parts” are based on mass. In the following structural formulas, Me represents a methyl group, Bu represents a butyl group, and Ph represents a phenyl group.

<Measurement of weight average molecular weight>
The weight average molecular weight of the resin was measured by using HPC-8220GPC (manufactured by Tosoh Corp.) as a measuring device, TSKguardcolumn SuperHZ-L as a guard column, TSKgel SuperHZM-M as a column, TSKgel SuperHZ4000, TSKgel SuperTSZHZ3000, and TSKgel Super TS The column temperature was set to 40 ° C., 10 μL of a tetrahydrofuran solution having a sample concentration of 0.1% by mass was injected into the column, and tetrahydrofuran as an elution solvent was allowed to flow at a flow rate of 0.35 mL / min. RI (differential refractive index) The sample peak was detected by a detection device, and calculation was performed using a calibration curve prepared using standard polystyrene.

<Preparation of composition>
The raw materials shown in the following table were mixed and stirred at the ratio shown in the following table, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a composition. The numerical values described in the table are parts by mass.

The raw materials described in the above table are as follows.
(Near-infrared absorbing compound)
pp-1, pp-2, pp-3, pp-4, pp-5, sq-1, cy-1: the following compounds. The following compounds have a solubility of 2 g or more in 100 g of cyclopentanone at 23 ° C., 100 g of cyclohexanone at 23 ° C., and 100 g of propylene glycol monomethyl ether acetate at 23 ° C.

Resin 1: Cyclohexanone 30% by mass solution of a resin having the following structure (weight average molecular weight 41,400, glass transition temperature 53 ° C., the numerical value added to the repeating unit of the main chain is a molar ratio)

Resin 2: A cyclopentanone 30% by mass solution of a resin having the following structure (weight average molecular weight 41,400, glass transition temperature 53 ° C., the numerical value added to the repeating unit of the main chain is a molar ratio)

Resin 3: 40% by mass solution of propylene glycol monomethyl ether acetate in a resin having the following structure (weight average molecular weight 10,000, glass transition temperature 46 ° C., the numerical value added to the repeating unit of the main chain is a molar ratio)

Organic solvent 1: Cyclohexanone Organic solvent 2: Cyclopentanone Polymerizable compound 1: Mixture of the following compounds (Mix ratio of left compound to right compound is 7: 3)

Polymerizable compound 2: the following compound

Polymerizable compound 3: the following compound

Polymerizable compound 4: the following compound

Photopolymerization initiator 1: IRGACURE OXE01 (manufactured by BASF)
Photopolymerization initiator 2: the following compound

Surfactant: Megafac RS-72-K (manufactured by DIC Corporation, 30% by mass solution of propylene glycol monomethyl ether acetate)
Aggregation inhibitors 1 to 7: Compounds having the following structures (compounds 1 to 4, 6, and 7 are manufactured by TCI).
Aggregation inhibitor 1: 2-aminobenzimidazole Aggregation inhibitor 2: Flubendazole Aggregation inhibitor 3: 2-Methyl-8-quinolinol Aggregation inhibitor 4: Diethyldithiocarbamate-2-benzothiazolyl Aggregation inhibitor 6: 2,7- Dibromo-9-dodecylcarbazole aggregation inhibitor 7: 2,2-bis (4-hydroxy-3-methylphenyl) propane Aggregation inhibitor 5 has a weight average molecular weight of 110,000.

Polymerization inhibitor: p-hydroxyphenol

<Manufacture of membrane>
Each composition was spin-coated on a glass substrate or an 8-inch (1 inch = 2.54 cm) silicon wafer so that the film thickness after film formation was 1.0 μm, and an i-line stepper exposure apparatus FPA-3000i5 + Using Canon (manufactured by Canon Inc.), the entire surface was exposed at 1,000 mJ / cm ² . Subsequently, it heated at 220 degreeC for 5 minute (s) using the hotplate, and the film | membrane was manufactured.

<Evaluation of aggregate size (perforated size of membrane cross section)>
The silicon wafer on which the above film was formed was immersed in acetone at 23 ° C. for 5 minutes, and then using an ultra-high resolution scanning electron microscope (manufactured by Hitachi High-Technologies Corporation), an acceleration voltage of 2.0 kV and an observation magnification of 50 The cross section of the film was observed at a magnification of 1,000, and the length in the major axis direction of any three perforated shapes was measured, and the average value was calculated as the perforated size.
The near-infrared absorbing compounds pp-1, pp-2, pp-3, pp-4, pp-5, sq-1, and cy-1 described above are compounds that are soluble in acetone at 23 ° C. Therefore, the agglomerated size of the near-infrared absorbing compound corresponds to the perforated size in the film, and the smaller the perforated size, the smaller the agglomerated size of the near-infrared absorbing compound.

<Evaluation of light shielding property (light shielding property) in near infrared region>
With respect to the glass substrate on which the above film was formed, transmittance was measured in the wavelength range of 400 to 1,300 nm using an ultraviolet-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). . The minimum value (T) of transmittance in the wavelength range of 700 to 1,000 nm was determined according to the following criteria.
3: T <1%
2: 1% ≦ T <5%
1: 5% ≦ T

<Evaluation of light resistance>
With respect to the glass substrate on which the above film was formed, transmittance was measured in the wavelength range of 400 to 1,300 nm using an ultraviolet-visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). .
Next, the glass substrate on which the above film was formed was irradiated with a xenon lamp at 100,000 lux for 20 hours (equivalent to 2 million lux · h), and the transmittance of the film after irradiation with the xenon lamp was measured.
The transmittance change (ΔT) was measured in the wavelength range of 400 to 1,300 nm before and after irradiation with the xenon lamp. The light resistance was evaluated according to the following criteria based on the value with the largest transmittance change (ΔT) in the entire measurement wavelength range. The smaller the value of ΔT, the better the light resistance.
Transmittance change (ΔT) = | Transmittance of film before xenon lamp irradiation−Transmittance of film after xenon lamp irradiation |
3: ΔT <3%
2: 3 ≦ ΔT <5%
1: 5 ≦ ΔT%

From the above results, the films of the examples were excellent in the shielding property of light in the near infrared region (near infrared), and the aggregate size of the near infrared absorbing compound was small. Further, the films of the examples were excellent in light resistance.
On the other hand, the film of the comparative example could not achieve both the light shielding property in the near infrared region (near infrared) and the suppression of aggregation of the near infrared absorbing compound.

In Examples, an infrared transmission filter excellent in spectral variability can be obtained by further blending a colorant that blocks visible light.

In the example, even when the antioxidant and / or silane coupling agent described in the present specification is further included, the same effect as in the example can be obtained.

110: Solid-state imaging device, 111: Near-infrared cut filter, 112: Color filter, 114: Infrared transmission filter, 115: Micro lens, 116: Flattening layer

Claims

A near-infrared absorbing compound having a π-conjugated plane containing a single ring or a condensed aromatic ring and having an absorption maximum wavelength in the wavelength range of 650 to 1,000 nm;
A composition comprising an aggregation inhibitor having at least one ring selected from an aromatic hydrocarbon ring and a heterocyclic ring and having no absorption maximum wavelength in the wavelength range of 650 to 1,000 nm.
The composition according to claim 1, wherein the aggregation inhibitor includes at least one ring selected from a benzene ring, a condensed ring including a benzene ring, and a nitrogen-containing heterocyclic ring.
The aggregation inhibitor is benzene ring, naphthalene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzoxazole. Including at least one ring selected from a ring, an imidazoline ring, a pyrazine ring, a quinoxaline ring, a pyrimidine ring, a quinazoline ring, a pyridazine ring, a triazine ring, a pyrrole ring, an indole ring, an isoindole ring, a fluorene ring, and a carbazole ring. Item 3. The composition according to Item 1 or 2.
The composition according to any one of claims 1 to 3, wherein the π-conjugated plane of the near-infrared absorbing compound contains two or more monocyclic or condensed aromatic rings.
The composition according to any one of claims 1 to 4, wherein the near-infrared absorbing compound is at least one selected from a pyrrolopyrrole compound, a cyanine compound, and a squarylium compound.
The composition according to any one of claims 1 to 5, further comprising a resin.
The composition according to any one of claims 1 to 6, further comprising a polymerizable compound and a photopolymerization initiator.
The composition according to any one of claims 1 to 7, further comprising a colorant that transmits at least part of light in the near infrared region and shields light in the visible region.
A film using the composition according to any one of claims 1 to 8.
An optical filter having the film according to claim 9.
The optical filter according to claim 10, wherein the optical filter is a near-infrared cut filter or an infrared transmission filter.
A film pixel according to claim 9;
The optical filter according to claim 10 or 11, comprising at least one pixel selected from red, green, blue, magenta, yellow, cyan, black, and colorless.
A laminate comprising the film according to claim 9 and a color filter containing a chromatic colorant.
A solid-state imaging device having the film according to claim 9.
An image display device having the film according to claim 9.
An infrared sensor having the film according to claim 9.