JP2021101020A - Curable composition, cured film, method for producing cured film, near-infrared blocking filter, solid-state imaging element, image display device and infrared sensor - Google Patents

Abstract

To provide a curable composition which is capable of producing a cured film that exhibits good water-resistant adhesion, while being suppressed in the generation of aggregates derived from a near-infrared absorbing dye, and also provide: a cured film; a method for producing a cured film; a near-infrared blocking filter; a solid-state imaging element; an image display device; and an infrared sensor.SOLUTION: A curable composition contains a near-infrared absorbing dye, a compound having a cyclic ether group, a radically polymerizable compound and a thermal radical polymerization initiator. The content of the near-infrared absorbing dye is 3-35 mass% relative to the total solid content of the curable composition. The content of the radical-polymerizable compound is 20-300 pts.mass relative to 100 pts.mass of the near-infrared absorbing dye. The content of the compound having a cyclic ether group is 5-500 pts.mass relative to 100 pts.mass of the near-infrared absorbing dye. The curable composition is free of a colorant that blocks visible light.SELECTED DRAWING: None

Description

The present invention relates to a curable composition, a cured film, a method for producing a cured film, a near-infrared cut filter, a solid-state image sensor, an image display device, and an infrared sensor.

CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors), which are solid-state image sensors for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. These solid-state image sensors use silicon photodiodes that are sensitive to infrared rays in their light-receiving parts. For this reason, a near-infrared cut filter may be used to correct the luminosity factor.

The near-infrared cut filter is manufactured, for example, by using a curable composition containing a near-infrared absorbing dye (see Patent Document 1).

International Publication WO2014 / 199937

In recent years, as one of the characteristics required for a near-infrared cut filter, improvement of water resistance to a support has been desired.

Further, according to the study by the present inventor, it has been found that when a cured film is produced using a curable composition containing a near-infrared absorbing dye, the near-infrared absorbing dye tends to aggregate at the time of film formation. In particular, when heat is applied during film formation, the near-infrared absorbing dye tends to aggregate. When the size of the agglomerates derived from the near-infrared absorbing dye in the film becomes large, the spectral characteristics may vary and the smoothness of the film surface may decrease. Furthermore, as the size of the agglomerates increases, the agglomerates tend to peel off from the membrane, and there is a possibility that pores of the size of the agglomerates may be formed in the places where the agglomerates were present.

Therefore, an object of the present invention is to provide a curable composition capable of producing a cured film having good water-resistant adhesion and suppressing the generation of agglomerates derived from a near-infrared absorbing dye. Another object of the present invention is to provide a cured film, a method for producing a cured film, a near-infrared cut filter, a solid-state image sensor, an image display device, and an infrared sensor.

According to the study of the present inventor, a cured film obtained by using a curable composition containing a near-infrared absorbing dye, a compound having a cyclic ether group, a radically polymerizable compound, and a thermal radical polymerization initiator is available. We have found that the water resistance and adhesion are good and there are few aggregates derived from the near-infrared absorbing dye, and the present invention has been completed. Therefore, the present invention provides the following.
<1> A curable composition containing a near-infrared absorbing dye, a compound having a cyclic ether group, a radically polymerizable compound, and a thermal radical polymerization initiator.
<2> The curable composition according to <1>, wherein the cyclic ether group is an epoxy group.
<3> The curable composition according to <1> or <2>, wherein the compound having a cyclic ether group is a compound containing an aromatic ring.
<4> The curable composition according to any one of <1> to <3>, which contains 1 to 100 parts by mass of a radically polymerizable compound with respect to 100 parts by mass of the compound having a cyclic ether group.
<5> The curable composition according to any one of <1> to <4>, which contains 0.05 to 200 parts by mass of a thermal radical polymerization initiator with respect to 100 parts by mass of the radically polymerizable compound.
<6> The curable composition according to any one of <1> to <5>, wherein the thermal radical polymerization initiator is at least one selected from a pinacol compound and an α-hydroxyacetophenone compound.
<7> The curable composition according to any one of <1> to <6>, wherein the near-infrared absorbing dye is a compound having a π-conjugated plane containing an aromatic ring of a monocyclic ring or a condensed ring.
<8> The curable composition according to any one of <1> to <6>, wherein the near-infrared absorbing dye is at least one selected from a pyrrolopyrrole compound, a squarylium compound, and a cyanine compound.
<9> A cured film obtained from the curable composition according to any one of <1> to <8>.
<10> A step of applying the curable composition according to any one of <1> to <8> on the support to form a curable composition layer, and
A method for producing a cured film, which comprises a step of heat-curing the curable composition layer.
<11> The method for producing a cured film according to <10>, wherein the support is a glass base material containing copper.
<12> A near-infrared cut filter having the cured film according to <9>.
<13> The near-infrared cut filter according to <12>, which has the cured film on the surface of a glass substrate containing copper.
<14> A solid-state image sensor having the cured film according to <9>.
<15> An image display device having the cured film according to <9>.
<16> An infrared sensor having the cured film according to <9>.

According to the present invention, it is possible to provide a curable composition capable of producing a cured film having good water-resistant adhesion and suppressing the generation of aggregates derived from the near-infrared absorbing dye. The present invention can also provide a cured film, a method for producing a cured film, a near-infrared cut filter, a solid-state image sensor, an image display device, and an infrared 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, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either. ) Allyl ”represents both allyl and methacrylic, or either, and“ (meth) acryloyl ”represents both acryloyl and methacrylic acid, or either.
In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-equivalent values in gel permeation chromatography (GPC) measurements. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) is used as a column. It can be determined by using a 0.0 mm ID (inner diameter) x 15.0 cm) and using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
In the present specification, the near infrared ray means light having a wavelength of 700 to 2,500 nm.
In the present specification, the total solid content means the total mass of all the components of the composition excluding the solvent.
In the present specification, the term "process" not only refers to an independent process, but also refers to the term as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. include.

<Curable composition>
The curable composition of the present invention is characterized by containing a near-infrared absorbing dye, a compound having a cyclic ether group, a radically polymerizable compound, and a thermal radical polymerization initiator.
According to the curable composition of the present invention, it is possible to produce a cured film having good water resistance and adhesion and less agglomerates derived from the near-infrared absorbing dye.
It is presumed that the reason why such an effect is obtained is as follows. That is, since the curable composition of the present invention contains a radically polymerizable compound and a thermal radical polymerization initiator, by heating such a curable composition, radicals are generated by radicals generated from the thermal radical polymerization initiator. The polymerization reaction of the polymerizable compound proceeds rapidly, and the film can be cured quickly. Therefore, it is presumed that the near-infrared absorbing dye is rapidly incorporated into the crosslinked network in the film. Further, the compound having a cyclic ether group has a slower curing rate than the radical polymerizable compound, but the compound having a cyclic ether group is considered to easily interact with the near-infrared absorbing dye, and is in the vicinity of the near-infrared absorbing dye. It is presumed that the curing of the compound having a cyclic ether group proceeds. Therefore, it is presumed that the curable composition of the present invention could effectively suppress the aggregation of the near-infrared absorbing dye during heating, and could produce a cured film having less agglomerates derived from the near-infrared absorbing dye. To.
Further, it is presumed that the cyclic ether group of the compound having a cyclic ether group easily reacts with a hydroxyl group or the like on the support, whereby excellent adhesion to the support can be obtained. Further, since the compound having a cyclic ether group is a compound that is difficult to cure and shrink, it is presumed that by including the compound having a cyclic ether group in the curable composition, it was possible to form a cured film that is difficult to cure and shrink. Will be done. Further, since a cured film having a high crosslink density can be formed by the radically polymerizable compound, it is possible to effectively suppress the invasion of water into the film. As described above, according to the present invention, a cured film having high adhesion to the support can be formed on the support while suppressing curing shrinkage, so that even if such a cured film is immersed in water, it can be formed. It is presumed that water could be effectively suppressed from entering the interface between the support and the cured film, and therefore excellent water resistance and adhesion were obtained. Hereinafter, each component of the curable composition of the present invention will be described.

<< Near-infrared absorbing pigment >>
The curable composition of the present invention contains a near-infrared absorbing dye. The near-infrared absorbing dye may be a pigment (also referred to as a near-infrared absorbing pigment) or a dye (also referred to as a near-infrared absorbing dye). It is also preferable to use a near-infrared absorbing dye and a near-infrared absorbing pigment in combination. When the near-infrared absorbing dye and the near-infrared absorbing pigment are used in combination, the mass ratio of the near-infrared absorbing dye and the near-infrared absorbing pigment is as follows: near-infrared absorbing dye: near-infrared absorbing pigment = 99.9: 0.1 to 0. It is preferably 1: 99.9, more preferably 99.9: 0.1 to 10:90, and even more preferably 99.9: 0.1 to 20:80.

In the present invention, the near-infrared absorbing dye preferably has a solubility of 1 g or more in 100 g of at least one solvent selected from cyclopentanone, cyclohexanone, and dipropylene glycol monomethyl ether at 23 ° C., and is 2 g or more. More preferably, it is more preferably 5 g or more. Further, in the near-infrared absorbing pigment, the solubility of cyclopentanone, cyclohexanone, and dipropylene glycol monomethyl ether at 23 ° C. in 100 g of each solvent is preferably less than 1 g, more preferably 0.1 g or less. It is preferably 0.01 g or less, and more preferably 0.01 g or less.

The near-infrared absorbing dye is preferably a compound having a π-conjugated plane containing an aromatic ring of a monocyclic ring or a condensed ring. Due to the interaction between aromatic rings in the π-conjugated plane of the near-infrared absorbing dye, J-aggregates of the near-infrared absorbing dye are likely to be formed during the production of the cured film, and a cured film having excellent spectral characteristics in the near-infrared region is produced. it can. In addition, it easily interacts with a compound having a cyclic ether group, and easily forms a cured film having better water resistance and adhesion. In particular, when a compound having an aromatic ring is used as the compound having a cyclic ether group, it is more likely to interact more strongly with the compound having a cyclic ether group, and the water resistance adhesion can be remarkably improved.

The number of atoms other than hydrogen constituting the π-conjugated plane of the near-infrared absorbing dye is preferably 6 or more, more preferably 14 or more, further preferably 20 or more, and 25 or more. The above is more preferable, and 30 or more is particularly preferable. The upper limit is, for example, preferably 80 or less, and more preferably 50 or less.

The π-conjugated plane of the near-infrared absorbing dye preferably contains two or more aromatic rings of a monocyclic or condensed ring, more preferably three or more, further preferably four or more, and five 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. Examples of the above-mentioned aromatic rings include a benzene ring, a naphthalene ring, an inden ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentasen ring, a quaterylene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthalene ring, and a chrysene ring. Triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzoxazole ring, imidazoline ring, pyrazine Examples thereof include a ring, a quinoxaline ring, a pyrimidine ring, a quinazoline ring, a pyridazine ring, a triazine ring, a pyrrole ring, an indole ring, an isoindol ring, a carbazole ring, and a fused ring having these rings.

The near-infrared absorbing dye is preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1,300 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1,000 nm. In the present specification, "having a maximum absorption wavelength in the wavelength range of 700 to 1,300 nm" means that the wavelength showing the maximum absorbance in the absorption spectrum of the near-infrared absorbing dye in a solution has a wavelength of 700 to 700 to 1. It means that it is in the range of 1,300 nm. Examples of the measurement solvent used for measuring the absorption spectrum of the near-infrared absorbing dye in the solution include chloroform, methanol, dimethyl sulfoxide, ethyl acetate and tetrahydrofuran. When the near-infrared absorbing dye is a compound that dissolves in chloroform, chloroform is used as the measurement solvent. If the compound is insoluble in chloroform, methanol is used. If it is insoluble in either chloroform or methanol, dimethyl sulfoxide is used.

Near infrared absorbing dye has an absorption maximum wavelength in a wavelength range of 700～1,000Nm, and the ratio A ¹ / A ² between the absorbance A ² in the absorbance A ¹ and the maximum absorption wavelength in the wavelength 500 nm, 0. It is preferably 08 or less, and more preferably 0.04 or less. According to this aspect, it is easy to produce a cured film having excellent visible transparency and infrared shielding property.

In the present invention, it is also preferable to use at least two compounds having different maximum absorption wavelengths as the near-infrared absorbing dye. According to this aspect, the waveform of the absorption spectrum of the obtained cured film is wider than that when one kind of near-infrared absorbing dye is used, and near-infrared rays in a wide wavelength range can be shielded. When at least two compounds having different maximum absorption wavelengths are used, the first near-infrared absorbing dye having the maximum absorption wavelength in the wavelength range of 700 to 1,000 nm and the maximum absorption wavelength of the first near-infrared absorbing dye are higher than the maximum absorption wavelength. The short wavelength side includes at least a second near-infrared absorbing dye having a maximum absorption wavelength in the wavelength range of 700 to 1,000 nm, and the maximum absorption wavelength of the first near-infrared absorbing dye and the second near The difference from the maximum absorption wavelength of the infrared absorbing dye is preferably 1 to 150 nm.

In the present invention, the near-infrared absorbing dye is a pyrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, a quaterylene compound, a merocyanine compound, a croconium compound, an oxonor compound, a diimonium compound, a dithiol compound, a triarylmethane compound, At least one selected from pyromethene compounds, azomethine compounds, anthraquinone compounds and dibenzofuranone compounds is preferable, and at least one selected from pyrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds and quaterylene compounds is more preferable. At least one selected from the pyrolopyrrole compound, the cyanine compound and the squarylium compound is more preferable, and the pyrolopyrrole compound is particularly preferable. Examples of the diimonium compound include the compounds described in JP-A-2008-528706, the contents of which are incorporated in the present specification. Examples of the phthalocyanine compound include the compound described in paragraph No. 0093 of JP2012-77153, the oxytitanium phthalocyanine described in JP2006-343631, and paragraph numbers 0013 to 0029 of JP2013-195480. , And vanadium phthalocyanine described in Japanese Patent No. 6081771, the contents of which are incorporated herein by reference. Examples of the naphthalocyanine compound include the compound described in paragraph No. 0093 of JP2012-77153A, the contents of which are incorporated in the present specification. Further, as the cyanine compound, the phthalocyanine compound, the naphthalocyanine compound, the diimonium compound and the squarylium compound, the compounds described in paragraphs 0010 to 0081 of JP-A-2010-111750 may be used, and the contents thereof are described in the present specification. Be incorporated. Further, as the cyanine compound, for example, "functional dye, Shin Ogawara / Ken Matsuoka / Eijiro Kitao / Tsuneaki Hirashima, Kodansha Scientific" can be referred to, and this content is incorporated in the present specification. .. Further, as the near-infrared absorbing dye, a compound described in JP-A-2016-146619 can also be used, and the contents thereof are incorporated in the present specification. Further, it is also preferable to use a compound having the following structure as the near-infrared absorbing dye.

式中、Ｒ^1aおよびＲ^1bは、各々独立にアルキル基、アリール基またはヘテロアリール基を表し、Ｒ²およびＲ³は、各々独立に水素原子または置換基を表し、Ｒ²およびＲ³は、互いに結合して環を形成してもよく、Ｒ⁴は、各々独立に、水素原子、アルキル基、アリール基、ヘテロアリール基、−ＢＲ^4AＲ^4B、または金属原子を表し、Ｒ⁴は、Ｒ^1a、Ｒ^1bおよびＲ³から選ばれる少なくとも一つと共有結合もしくは配位結合していてもよく、Ｒ^4AおよびＲ^4Bは、各々独立に置換基を表す。Ｒ^4AおよびＲ^4Bは互いに結合して環を形成していてもよい。式（ＰＰ）の詳細については、特開２００９−２６３６１４号公報の段落番号００１７〜００４７、特開２０１１−６８７３１号公報の段落番号００１１〜００３６、国際公開ＷＯ２０１５／１６６８７３号公報の段落番号００１０〜００２４の記載を参酌でき、これらの内容は本明細書に組み込まれる。 The pyrrolopyrrole compound is preferably a compound represented by the formula (PP).

In the formula, R ^1a and R ^1b independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ represent a hydrogen atom or a substituent, respectively. They may bond to each other to form a ring, where R ⁴ independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B , or a metal atom, where R ⁴ is R. ^It may be covalently or coordinated with at least one selected from 1a, R ^1b and R ^{3 , where R 4A} and R ^4B each independently represent a substituent. R ^4A and R ^4B may be combined with each other to form a ring. For details of the formula (PP), paragraph numbers 0017 to 0047 of JP2009-263614, paragraphs 0011 to 0036 of JP2011-68831, and paragraphs 0010 to 0024 of International Publication WO2015 / 166873. The description of the above can be taken into consideration, and these contents are incorporated in the present specification.

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

(Substituent T)
Alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), aryl group (preferably an aryl group having 2 to 30 carbon atoms). Aryl groups with 6 to 30 carbon atoms), amino groups (preferably amino groups with 0 to 30 carbon atoms), alkoxy groups (preferably alkoxy groups with 1 to 30 carbon atoms), aryloxy groups (preferably 6 to 30 carbon atoms). 30 aryloxy groups), heteroaryloxy groups, acyl groups (preferably acyl groups having 1 to 30 carbon atoms), alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 30 carbon atoms), aryloxycarbonyl groups (preferably aryloxycarbonyl groups). Is an aryloxycarbonyl group having 7 to 30 carbon atoms), an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), and an alkoxycarbonylamino group (preferably). An alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), a carbamoyl group. (Preferably a carbamoyl group having 1 to 30 carbon atoms), an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), a heteroarylthio group (preferably an arylthio group having 6 to 30 carbon atoms). 1 to 30 carbon atoms), alkylsulfonyl group (preferably 1 to 30 carbon atoms), arylsulfonyl group (preferably 6 to 30 carbon atoms), heteroarylsulfonyl group (preferably 1 to 30 carbon atoms), alkylsulfinyl group (Preferably 1 to 30 carbon atoms), arylsulfinyl group (preferably 6 to 30 carbon atoms), heteroarylsulfinyl group (preferably 1 to 30 carbon atoms), ureido group (preferably 1 to 30 carbon atoms), hydroxyl group , Carboxyl group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imide acid group, mercapto group, halogen atom, cyano group, alkylsulfino group, arylsulfino group, hydradino group, imino group, Heteroaryl group (preferably 1 to 30 carbon atoms). These groups may have additional substituents if they are further substitutable groups. Examples of the substituent include the group described in the above-mentioned Substituent T.

Specific examples of the groups represented by R ^1a and R ^1b include an aryl group having an alkoxy group as a substituent, an aryl group having a hydroxyl group as a substituent, an aryl group having an acyloxy group as a substituent, and the like.

In formula (PP), R ² and R ³ each independently represent a hydrogen atom or substituent. Examples of the substituent include the above-mentioned substituent T. At ^{least one of R 2} and R ³ is preferably an electron attracting group. Substituents with a positive Hammett substituent constant σ value (sigma value) act as electron-attracting groups. Here, the substituent constants obtained by Hammett's law include σp value and σm value. These values can be found in many common books. In the present invention, a substituent having a Hammett substituent constant σ value of 0.2 or more can be exemplified as an electron-attracting group. The σ value is preferably 0.25 or more, more preferably 0.3 or more, and even more preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80 or less. Specific examples of the electron-attracting group include a cyano group (σp value = 0.66), a carboxyl group (-COOH: σp value = 0.45), and an alkoxycarbonyl group (for example, -COOME: σp value = 0. 45), aryloxycarbonyl group (eg, -COOPh: σp value = 0.44), carbamoyl group (eg, -CONH ₂ : σp value = 0.36), alkylcarbonyl group (eg, -COMe: σp value =) 0.50), arylcarbonyl group (eg, -COPh: σp value = 0.43), alkylsulfonyl group (eg, -SO ₂ Me: σp value = 0.72), arylsulfonyl group (eg, -SO ₂₎ Ph: σp value = 0.68) and the like, and a cyano group is preferable. Here, Me represents a methyl group and Ph represents a phenyl group. Regarding the Hammett substituent constant σ value, for example, paragraphs 0017 to 0018 of JP2011-68831A can be referred to, and the contents thereof are incorporated in the present specification.

In formula (PP), R ² preferably represents an electron-attracting group (preferably a cyano group) and R ³ preferably represents a heteroaryl group. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group is preferably a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 8, and more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. The heteroaryl group preferably has one or more nitrogen atoms. Two R ² together in the formula (PP) may be the same or may be different. Also, two R ³ together in the formula (PP) may be the same or may be different.

In formula (PP), R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a group represented by ^{−BR 4A} R ^{4B, preferably a hydrogen atom, an alkyl group, an aryl group or −BR.} more preferably a group represented by ^4A R ^4B, and more preferably a group represented by -BR ^4A R ^4B. As the ^{substituent represented by R 4A} and R ^4B , a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group is preferable, an alkyl group, an aryl group, or a heteroaryl group is more preferable, and an aryl group is preferable. Especially preferable. These groups may further have substituents. Two R ⁴ together in the formula (PP) may be the same or may be different. R ^4A and R ^4B may be combined with each other to form a ring.

Specific examples of the compound represented by the formula (PP) include the following compounds. In the following structural formula, Ph represents a phenyl group. Examples of the pyrrolopyrrole compound include the compounds described in paragraphs 0016 to 0058 of JP2009-263614, the compounds described in paragraphs 0037 to 0052 of JP2011-68831, and WO2015 / 166873. Examples include the compounds described in paragraphs 0010 to 0033 of the publication, the contents of which are incorporated herein by reference.

式（ＳＱ）中、Ａ¹およびＡ²は、それぞれ独立に、アリール基、ヘテロアリール基または式（Ａ−１）で表される基を表す；

式（Ａ−１）中、Ｚ¹は、含窒素複素環を形成する非金属原子団を表し、Ｒ²は、アルキル基、アルケニル基またはアラルキル基を表し、ｄは、０または１を表し、波線は連結手を表す。式（ＳＱ）の詳細については、特開２０１１−２０８１０１号公報の段落番号００２０〜００４９、特許第６０６５１６９号公報の段落番号００４３〜００６２、国際公開ＷＯ２０１６／１８１９８７号公報の段落番号００２４〜００４０の記載を参酌でき、これらの内容は本明細書に組み込まれる。 As the squarylium compound, a compound represented by the following formula (SQ) is preferable.

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

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

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

環Ａおよび環Ｂは、それぞれ独立に芳香族環を表し、
Ｘ^AおよびＸ^Bはそれぞれ独立に置換基を表し、
Ｇ^AおよびＧ^Bはそれぞれ独立に置換基を表し、
ｋＡは０〜ｎ_Aの整数を表し、ｋＢは０〜ｎ_Bの整数を表し、
ｎ_Aおよびｎ_Bはそれぞれ環Ａまたは環Ｂに置換可能な最大の整数を表し、
Ｘ^AとＧ^A、Ｘ^BとＧ^B、Ｘ^AとＸ^Bは、互いに結合して環を形成しても良く、Ｇ^AおよびＧ^Bがそれぞれ複数存在する場合は、互いに結合して環構造を形成していても良い。 The squarylium compound is preferably a compound represented by the following formula (SQ-1).

Ring A and Ring B each independently represent an aromatic ring.
X ^A and X ^B each independently represent a substituent and
G ^A and G ^B independently represents a substituent,
kA _{represents an integer from 0 to n A} , kB represents an integer from 0 to n _B ,
n _A and n _B represent the largest integers that can be replaced with ring A or ring B, respectively.
X ^A and G ^A, X ^B and G ^B, X ^A and X ^B may be bonded to each other to form a ring, if G ^A and G ^B are present in plural can combine with each other to form a ring structure May be formed.

The substituent represented by G ^A and G ^B, include the substituent T described by the formula (PP) as described above.

As the ^{substituent represented by X A} and X ^B , a group having active hydrogen is preferable, and -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 preferred, and -OH, -SH and -NR ^X1 R ^X 2 are even more preferred. R ^X1 and R ^X1 independently represent a hydrogen atom or a substituent. Examples of the substituent represented by X ^A and X ^B include an alkyl group, an aryl group, and a heteroaryl group, and an alkyl group is preferable.

Ring A and Ring B each independently represent an aromatic ring. The aromatic ring may be a monocyclic ring or a condensed ring. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an inden ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthalene ring, a chrysen ring, and a triphenylene ring. , Fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring, indol ring, benzofuran ring, benzothiophene ring , Isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthalene ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, aclysine ring, phenanthrene ring, thianthrene ring, chromium ring, xanthene ring, phenoki Examples thereof include a satin ring, a phenothiazine ring, and a phenazine ring, and 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 T described in the above formula (PP).

X ^A and G ^A, X ^B and G ^B, X ^A and X ^B may be bonded to each other to form a ring, if G ^A and G ^B are present in plural, the rings bonded to each other It may be formed. As the ring, a 5-membered ring or a 6-membered ring is preferable. The ring may be a monocyclic ring or a condensed ring. X ^A and G ^A, X ^B and G ^B, X ^A and X ^B, if G ^A or between G ^B are bonded to each other to form a ring, may be they are attached directly to form a ring, alkylene Rings may be formed by bonding via a divalent linking group consisting of a group, -CO-, -O-, -NH-, -BR- and a combination thereof. R represents a hydrogen atom or a substituent. Examples of the substituent include the substituent T described in the above formula (PP), and an alkyl group or an aryl group is preferable.

kA represents an integer from 0 to nA, kB represents an integer from 0 to nB, n _A represents the largest integer substitutable for ring A, and n _B represents the largest integer substitutable for ring B. Represent. KA and kB are independently preferably 0 to 4, more preferably 0 to 2, and particularly preferably 0 to 1.

式（ＳＱ−１１）

式（ＳＱ−１２）

The squarylium compound is also preferably a compound represented by the following formula (SQ-10), formula (SQ-11) or formula (SQ-12).
Equation (SQ-10)

Equation (SQ-11)

Equation (SQ-12)

In formulas (SQ-10) to (SQ-12), X may independently have one or more hydrogen atoms substituted with a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group. It is a divalent organic group represented by (1) or the formula (2).
− (CH ₂ ) _n1 − ・ ・ ・ (1)
In formula (1), n1 is 2 or 3.
− (CH ₂ ) _n2 −O− (CH ₂ ) _n3 − ・ ・ ・ (2)
In the formula (2), n2 and n3 are independently integers of 0 to 2, and n2 + n3 is 1 or 2.
R ¹ and R ² independently represent an alkyl group or an aryl group, respectively. The alkyl group and the aryl group may have a substituent or may be unsubstituted. Examples of the substituent include the substituent T described in the above formula (PP).
R ^{3 to} R ⁶ independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.
n is 2 or 3.

Examples of the squarylium compound include compounds having the following structures. Further, the compounds described in paragraphs 0044 to 0049 of JP2011-208101A, the compounds described in paragraphs 0060 to 0061 of Patent No. 6065169, and paragraph numbers 0040 of International Publication WO2016 / 181987. Compounds, compounds described in International Publication WO2013 / 133099, compounds described in International Publication WO2014 / 088063, compounds described in JP2014-126642, compounds described in JP2016-146619, The compounds described in JP-A-2015-176046, the compounds described in JP-A-2017-25311, the compounds described in International Publication WO2016 / 154782, the compounds described in Patent No. 5884953, and JP-A-603669. Examples thereof include the compound described, the compound described in Japanese Patent Application Laid-Open No. 581604, and the compound described in JP-A-2017-068120, and the contents thereof are incorporated in the present specification.

式中、Ｚ¹およびＺ²は、それぞれ独立に、縮環してもよい５員または６員の含窒素複素環を形成する非金属原子団であり、
Ｒ¹⁰¹およびＲ¹⁰²は、それぞれ独立に、アルキル基、アルケニル基、アルキニル基、アラルキル基またはアリール基を表し、
Ｌ¹は、奇数個のメチン基を有するメチン鎖を表し、
ａおよびｂは、それぞれ独立に、０または１であり、
ａが０の場合は、炭素原子と窒素原子とが二重結合で結合し、ｂが０の場合は、炭素原子と窒素原子とが単結合で結合し、
式中のＣｙで表される部位がカチオン部である場合、Ｘ¹はアニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位がアニオン部である場合、Ｘ¹はカチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位の電荷が分子内で中和されている場合、ｃは０である。 The cyanine compound is preferably a compound represented by the formula (C).
Equation (C)

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

Specific examples of the cyanine compound include the following compounds. Examples of the cyanine compound include the compounds described in paragraphs 0044 to 0045 of JP2009-108267A, the compounds described in paragraphs 0026 to 0030 of JP2002-194040, and JP2015-172004. , The compound described in JP-A-2015-172102, the compound described in JP-A-2008-88426, the compound described in JP-A-2017-031394, and the like. Incorporated into the specification.

In the present invention, a commercially available product can also be used as the near-infrared absorbing dye. For example, SDO-C33 (manufactured by Arimoto Chemicals Co., Ltd.), E-Excolor IR-14, E-Excolor IR-10A, E-Excolor TX-EX-801B, E-Excolor TX-EX-805K (Co., Ltd.) ) Nippon Catalyst), ShigenoxNIA-8041, ShigenoxNIA-8042, ShigenoxNIA-814, ShigenoxNIA-820, ShigenoxNIA-839 (manufactured by Hakko Chemicals), EpolyteV-63, EpoliteV-63, EpoliteV-63 Examples thereof include Film Co., Ltd., NK-3027, NK-5060 (manufactured by Hayashihara Co., Ltd.), and YKR-3070 (manufactured by Mitsui Chemicals, Inc.).

The near-infrared absorbing dye used in the present invention is also exemplified as a preferable compound by the compound used in Examples described later.
The content of the near-infrared absorbing dye is preferably 3 to 50% by mass with respect to the total solid content of the curable composition. The upper limit is preferably 40% by mass or less, more preferably 35% by mass or less. The lower limit is preferably 4% by mass or more, and more preferably 5% by mass or more. The near-infrared absorbing dye may be only one kind or two or more kinds. In the case of two or more types, it is preferable that the total amount thereof is within the above range.

<< Other near-infrared absorbers >>
The curable composition of the present invention may further contain a near-infrared absorbing agent (also referred to as another near-infrared absorbing agent) other than the above-mentioned near-infrared absorbing dye. Examples of other near-infrared absorbers include inorganic pigments (inorganic particles). The shape of the inorganic pigment is not particularly limited, and may be a sheet shape, a wire shape, or a tube shape regardless of whether it is spherical or non-spherical. As the inorganic pigment, metal oxide particles or metal particles are preferable. Examples of the metal oxide particles include indium tin oxide (ITO) particles, antimonthine oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, and fluorine-doped tin dioxide (F-doped). Examples _{thereof include SnO 2} ) particles and niob-doped titanium dioxide (Nb-doped TiO ₂ ) particles. Examples of the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, nickel (Ni) particles and the like. Further, a tungsten oxide-based compound can also be used as the inorganic pigment. The tungsten oxide-based compound is preferably cesium tungsten oxide. For details of the tungsten oxide-based compound, paragraph number 0080 of JP-A-2016-006476 can be referred to, and the content thereof is incorporated in the present specification.

When the curable composition of the present invention contains another near-infrared absorber, the content of the other near-infrared absorber is 0.01 to 50 with respect to the total solid content of the curable composition of the present invention. Mass% is preferred. The lower limit is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 15% by mass or less.
The content of the other near-infrared absorbing agent in the total mass of the above-mentioned near-infrared absorbing dye and the other near-infrared absorbing agent is preferably 1 to 99% by mass. The upper limit is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less.
It is also preferable that the curable composition of the present invention does not substantially contain other near-infrared absorbers. Substantially containing no other near-infrared absorber means that the content of the other near-infrared absorber in the total mass of the above-mentioned near-infrared absorbing dye and the other near-infrared absorbing agent is 0.5% by mass or less. It is more preferable that it is 0.1% by mass or less, and it is further preferable that it does not contain other near-infrared absorbers.

<< Radical Polymerizable Compound >>
The curable composition of the present invention contains a radically polymerizable compound. The radically 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 is ethylenically property. A compound having three or more groups having an unsaturated bond is more preferable. The upper limit of the number of groups having an ethylenically unsaturated bond in the radically polymerizable compound 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, a (meth) acryloyl group and the like, and a (meth) acryloyl group is preferable. The radically polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.

The radically polymerizable compound may be in the form of a monomer or a polymer, but a monomer is preferable. The monomer-type radically polymerizable compound preferably has a molecular weight of 100 to 3,000. The upper limit is more preferably 2,000 or less, and even more preferably 1,500 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more. Further, it is also preferable that the radically polymerizable compound is a compound having substantially no molecular weight distribution. Here, as the compound having substantially no molecular weight distribution, a compound having a dispersion degree (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the compound is preferably 1.0 to 1.5. More preferably 1.0 to 1.3.

As an example of the radically polymerizable compound, the description in paragraphs 0033 to 0034 of JP2013-253224A can be referred to, and the content thereof is incorporated in the present specification. Examples of the radically polymerizable compound include ethyleneoxy-modified pentaerythritol tetraacrylate (commercially available NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and dipentaerythritol triacrylate (commercially available KAYARAD D-). 330; Nippon Kayaku Co., Ltd.), Dipentaerythritol tetraacrylate (commercially available, KAYARAD D-320; Nihon Kayaku Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexa (meth) acrylate (commercially available, KAYARAD DPHA; manufactured by Nihon Kayaku Co., Ltd., A-DPH-12E; Shin-Nakamura Chemical Industry Co., Ltd. ( Co., Ltd.), and compounds having a structure in which these (meth) acryloyl groups are bonded via an ethylene glycol residue and / or a propylene glycol residue are preferable. Also, these oligomer types can be used. Further, the description of paragraphs 0034 to 0038 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. In addition, the polymerizable monomers described in paragraph No. 0477 of JP2012-208494A (paragraph No. 0585 of the corresponding US Patent Application Publication No. 2012/0235099) are mentioned, and the contents thereof are described in the present specification. Incorporated in. In addition, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available, M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-TMMT), 1,6 -Hexanediol diacrylate (KAYARAD HDDA, manufactured by Nippon Kayaku Co., Ltd.) is also preferable. These oligomer types can also be used. For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned.

The radically polymerizable compound may have an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group. Examples of commercially available products of radically polymerizable compounds having an acid group include Aronix M-305, M-510, and M-520 (all manufactured by Toagosei Co., Ltd.). The acid value of the radically polymerizable compound is preferably 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 radically polymerizable compound, a compound having a caprolactone structure is also a preferable embodiment. The radically polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120. Regarding the radically polymerizable compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification.

As the radically polymerizable compound, a compound having an alkyleneoxy group can also be used. The radically polymerizable compound having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and 4 to 20 ethyleneoxy groups. It is more preferably a 3- to hexafunctional (meth) acrylate compound having. Commercially available products of radically polymerizable compounds having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartmer, and trifunctional (meth) having three isobutyleneoxy groups. ) KAYARAD TPA-330 which is an acrylate and the like can be mentioned.

Examples of the radically polymerizable compound include urethane acrylates as described in JP-A-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. , A urethane compound having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 is also suitable. Further, it is also preferable to use a radically polymerizable compound 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. .. Further, as the radically polymerizable compound, the compounds described in Japanese Patent Application Laid-Open No. 2017-48637, Japanese Patent No. 6057891 and Japanese Patent No. 6031807 can also be used. Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and UA. -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned. Further, as the radically polymerizable compound, it is also preferable to use 8UH-1006, 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

The content of the radically polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the curable composition. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less.
The content of the radically polymerizable compound is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the compound having a cyclic ether group. The lower limit is preferably 3% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. When the ratio of the radically polymerizable compound to the compound having a cyclic ether group is in the above range, the water adhesion resistance is better, and it is easy to form a cured film in which the generation of aggregates derived from the near-infrared absorbing dye is further suppressed. ..
The content of the radically polymerizable compound is preferably 20 to 300 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye. The upper limit is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and further preferably 120 parts by mass or less. The lower limit is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and further preferably 60 parts by mass or more. When the ratio of the radically polymerizable compound to the near-infrared absorbing dye is in the above range, the water-resistant adhesion is better, and it is easy to form a cured film in which the generation of agglomerates derived from the near-infrared absorbing dye is further suppressed.
The curable composition of the present invention may contain only one type of radically polymerizable compound, or may contain two or more types of radically polymerizable compounds. When two or more radically polymerizable compounds are contained, the total amount thereof is preferably in the above range.

<< Thermal Radical Polymerization Initiator >>
The curable composition of the present invention contains a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a radically polymerizable compound. The thermal radical polymerization initiator may be a compound that generates radicals by the action of heat and light.

Examples of the thermal radical polymerization initiator include pinacol compounds, α-hydroxyacetophenone compounds, α-aminoacetophenone compounds, benzyldimethylketal compounds, organic peroxides, azo compounds and the like, and the effects of the present invention can be obtained more remarkably. A pinacol compound and an α-hydroxyacetophenone compound are preferable, and a pinacol compound is more preferable because it is easy to use. Further, in the present invention, it is also preferable to use a pinacol compound as a thermal radical polymerization initiator and a thermal radical polymerization initiator (another thermal radical polymerization initiator) other than the pinacol compound in combination. By using the pinacol compound in combination with another thermal radical polymerization initiator, the generation of aggregates derived from the near-infrared absorbing dye can be effectively suppressed. Furthermore, it is easy to obtain a cured film having excellent spectral characteristics. Examples of other thermal radical polymerization initiators to be used in combination with the pinacol compound include α-hydroxyacetophenone compound, α-aminoacetophenone compound, benzyldimethylketal compound, organic peroxide, azo compound and the like. preferable.

The pinacol compound is preferably a benzopinacol compound. Examples of the pinacol compound include compounds represented by the following formulas (T-1) to (T-3).

In formulas (T-1) to (T-3), Rt ^{1 to Rt 4} independently represent substituents, and m1 to m4 independently represent integers 0 to 4. When m1 is 2 to 4, m1 Rt ¹ may be the same or different. Also, m1 pieces two of the Rt ¹ of Rt ¹ each other may bond to each other to form a ring. When m2 is 2 to 4, m2 Rt ² may be the same or different. Further, m2 amino bonded to each other two Rt ² together of Rt ² may form a ring. If m3 is 2 to 4, m3 amino Rt ³ may each be the same or may be different. Also, m3 or two Rt ³ out of Rt ³ together may be bonded to each other to form a ring. If m4 is 2 to 4, m4 amino Rt ^4, respectively may be the same or may be different. Also, they may form a ring two Rt ⁴ are bonded to each other to each other among the m4 amino Rt ^4. Further, Rt ¹ and Rt ² , Rt ¹ and Rt ³ , Rt ¹ and Rt ⁴ , Rt ² and Rt ³ , Rt ² and Rt ⁴ , and Rt ³ and Rt ⁴ may be combined to form a ring.
In formula (T-1), Rt ⁵ and Rt ⁶ are independently hydrogen atom, alkyl group, aryl group, Ti ( ^RM1 ) ( ^RM2 ) ( ^RM3 ), Zr ( ^RM1 ) (R). ^M2) (R ^M3), represents a ^{Si (R M1) (R M2} ) (R M3) or ^{B (R M1) (R M2} ), R M1 ~R M3 represents a substituent independently.
In formula (T-2), M ¹ represents Ti ( ^RM4 ) ( ^RM5 ), Zr ( ^RM4 ) ( ^RM5 ), Si ( ^RM4 ) ( ^RM5 ) or B ( ^RM4 ). R ^M4 and R ^M5 each independently represent a substituent.
Wherein (T-3), M ^{2 is, Ti (R M6), Zr} (R M6), represents a Si (R ^M6) or B, R ^M6 represents a substituent, L ¹ is a divalent linking group Represents.

The substituent ^{Rt 1 ~Rt 4, R M1 ~R} M6 represents an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen ^{atom, -OR X1, -SR X1, -COR} X1, - COOR ^X1 , -OCOR ^X1 , -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -SO ₂ R ^X1 , -SO ₂ OR ^X1 , -NHSO ₂ R ^X1 And so on. R ^X1 and R ^X2 independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Alkyl group as a substituent, an alkyl group represented by R ^X1 and R ^X2, the carbon number of the alkyl group represented by Rt ⁵ and Rt ⁶ in formula (T-1) is 1 to 20 is preferred. The alkyl group may be linear, branched or cyclic, but linear or branched is preferred.
Aryl group as a substituent, an aryl group represented by R ^X1 and R ^X2, the number of carbon atoms of the aryl group represented by Rt ⁵ and Rt ⁶ in formula (T-1) is 6 to 20, more preferably 6 to 15 , 6-10 are more preferable. The aryl group may be a monocyclic ring or a condensed ring.
The heterocyclic group as a substituent and the heterocyclic group ^{represented by RX1} and ^RX2 are preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. Further, in the heterocyclic group, a part or all of hydrogen atoms may be substituted with the above-mentioned substituent.

m1 to m4 each independently represent an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, even more preferably 0 or 1, and particularly preferably 0.

The ^{divalent linking group represented by L 1} includes an alkylene group, an arylene group, and -NR'-(R'may have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. (Representing a good aryl group, preferably a hydrogen atom), -SO _2- , -CO-, -COO-, -OCO-, -O-, -S- and a group composed of a combination thereof can be mentioned.

In the formula (T-1), it is preferable that at least one of Rt ⁵ and Rt ⁶ is a hydrogen atom, and more preferably both Rt ⁵ and Rt ⁶ is a hydrogen atom.

Specific examples of the pinacol compound include benzopinacol, 1-hydroxy-2-trimethylsiloxy-1, 1, 2, 2-tetraphenylethane and the like. Further, regarding the pinacol compound, the descriptions in Japanese Patent Publication No. 2014-521772, Japanese Patent Publication No. 2014-523939, and Japanese Patent Publication No. 2014-521772 can be referred to, and the contents thereof are incorporated in the present specification.

式中Ｒｔ¹¹は、置換基を表し、Ｒｔ¹²およびＲｔ¹³は、それぞれ独立して、水素原子または置換基を表し、Ｒｔ¹²とＲｔ¹³が互いに結合して環を形成していてもよく、ｍは０〜４の整数を表す。 Examples of the α-hydroxyacetophenone compound include a compound represented by the following formula (T-11).
Equation (T-11)

In the formula, Rt ¹¹ represents a substituent, Rt ¹² and Rt ¹³ each independently represent a hydrogen atom or a substituent, and Rt ¹² and Rt ¹³ may be bonded to each other to form a ring. m represents an integer from 0 to 4.

Examples of the ^{substituent represented by Rt 11} include the above-mentioned substituents, and alkyl groups and alkoxy groups are preferable. The alkyl group and the alkoxy group may be unsubstituted or have a substituent. Examples of the substituent include a hydroxy group and the like.

Rt ¹² and Rt ¹³ independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituents, and an alkyl group and an aryl group are preferable. Further, Rt ¹² and Rt ¹³ may be bonded to each other to form a ring (preferably a ring having 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms).

Specific examples of the α-hydroxyacetophenone compound include 1-hydroxy-cyclohexyl-phenyl-ketone and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-. For example, on. Examples of commercially available α-hydroxyacetophenone compounds include IRGACURE-184 and IRGACURE-2959 (all manufactured by BASF).

Examples of the α-aminoacetophenone compound include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)-. Examples thereof include 1-butanone and 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone. Examples of commercially available α-aminoacetophenone compounds include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all manufactured by BASF).

Examples of the benzyl dimethyl ketal compound include 2,2-dimethoxy-2-phenylacetophenone. Examples of commercially available products include IRGACURE-651 (manufactured by BASF).

Examples of the azo compound include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and dimethyl-2,2'-azobis (2,2'-azobis). 2-Methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [N- (2-) Propenyl) 2-methylpropionamide], 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide) and the like. Commercially available products of azo compounds include V-70, V-65, V-60, V-59, V-40, V-30, V-501, V-601, VE-073, VA-080, and VA-. 086, VF-096, VAm-110, VAm-111, VA-044, VA-046B, VA-060, VA-061, V-50, VA-057, VA-067, VR-110 (above, Jun Wako) (Made by Yakuhin Kogyo Co., Ltd.) and the like.
Examples of organic peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butylhydroperoxide, cumenehydroperoxide, diisopropylbenzenehydro Peroxide, parameteran hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, tert-butylcumyl peroxide, dicumylper Oxide, bis (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-xanoyl peroxide, succinic peroxide, benzoyl peroxide , 2,4-Dichlorobenzoyl peroxide, tert oil peroxide, diisopropyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, di-2-ethoxyethyl peroxy dicarbonate, dimethoxyisopropyl peroxy carbonate, Di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butylperoxyacetate, tert-butylperoxypivalate, tert-butylperoxyneodecanoate, tert-butylperoxyoctanoate, tert-Butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, 3,3'4,5'-tetra- (tert-butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,5'-tetra- (tert-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra-( tert-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, Carbo Nildi (tert-butyl peroxydihydrogen diphthalate), carbonyl di (tert-hexyl peroxy dihydrogen diphthalate) and the like can be mentioned. Examples of commercially available organic peroxide products include perbutyl O, perbutyl Z, and perhexa 25B (all manufactured by NOF CORPORATION).

The molar extinction coefficient of the thermal radical polymerization initiator at a wavelength of 365 nm is preferably 100 L · mol ^-1 · cm ^-1 or less, more preferably 50 L · mol ^-1 · cm ^-1 or less, and 10 L · mol. It is more preferably ^-1 · cm ^{-1 or less.} When the molar absorption coefficient of the thermal radical polymerization initiator at a wavelength of 365 nm is 100 L · mol ^-1 · cm ^-1 or less, it is effective to generate radicals from the thermal radical polymerization initiator during storage of the curable composition. The curable composition has good storage stability.

上記式においてεはモル吸光係数（Ｌ・ｍｏｌ^-1・ｃｍ^-1）、Ａは吸光度、ｃは測定溶液の濃度（ｍｏｌ／Ｌ）、ｌは光路長（ｃｍ）を表す。 In the present invention, the molar absorbance coefficient of the thermal radical polymerization initiator at a wavelength of 365 nm is determined by dissolving the thermal radical polymerization initiator in a solvent to prepare a 5 mol% solution (measurement solution) of the thermal radical polymerization initiator. It was calculated by measuring the absorbance of the measurement solution. Specifically, the above-mentioned measurement solution was placed in a glass cell having a width of 1 cm, the absorbance was measured using a UV-Vis-NIR spectrum meter (Cary5000) manufactured by Asian Technologies, and the molar extinction at a wavelength of 365 nm was applied to the following formula. The extinction coefficient (L · mol ^-1 · cm ^-1 ) was calculated.

In the above formula, ε represents the molar extinction coefficient (L · mol ^-1 · cm ^-1 ), A represents the absorbance, c represents the concentration of the measurement solution (mol / L), and l represents the optical path length (cm).

Examples of the solvent used for preparing the measurement solution in the measurement of the molar extinction coefficient of the thermal radical polymerization initiator include acetonitrile and chloroform. If the thermal radical polymerization initiator is a compound that dissolves in acetonitrile, use acetonitrile to prepare a measurement solution. If the thermal radical polymerization initiator is a compound that does not dissolve in acetonitrile but dissolves in chloroform, prepare a measurement solution using chloroform. If the thermal radical polymerization initiator is a compound that does not dissolve in acetonitrile and chloroform but dissolves in dimethyl sulfoxide, prepare a measurement solution using dimethyl sulfoxide.

The thermal decomposition temperature of the thermal radical polymerization initiator is preferably 120 to 270 ° C. The upper limit of the thermal decomposition temperature is preferably 250 ° C. or lower, more preferably 220 ° C. or lower, and even more preferably 190 ° C. or lower. The lower limit of the thermal decomposition temperature is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and even more preferably 170 ° C. or higher. When the thermal decomposition temperature of the thermal radical polymerization initiator is 120 ° C. or higher, the generation of radicals from the thermal radical polymerization initiator can be effectively suppressed during storage of the curable composition, and the curable composition can be preserved. Good stability. Further, when the thermal decomposition temperature of the thermal radical polymerization initiator is 270 ° C. or lower, radicals can be rapidly generated by heating, and the curability of the curable composition is good.

In the present invention, the thermal decomposition temperature of the thermal radical polymerization initiator is a value measured by thermogravimetric / differential thermal (TG-DTA) measurement.

The weight 1% temperature of the thermal radical polymerization initiator is preferably 90 to 220 ° C. The upper limit of the weight 1% temperature is preferably 215 ° C. or lower, more preferably 210 ° C. or lower, and even more preferably 200 ° C. or lower. The lower limit of the weight 1% temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and even more preferably 150 ° C. or higher. When the weight 1% temperature of the thermal radical polymerization initiator is in the above range, it is easy to achieve both low temperature curability and storage stability of the composition.

In the present invention, the 1% weight temperature of the thermal radical polymerization initiator is a temperature at which the weight of the initiator alone is reduced by 1% as measured by TG-DTA measurement.

The content of the thermal radical polymerization initiator is preferably 0.1 to 10% by mass with respect to the total solid content of the curable composition. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 5% by mass or less.
The content of the thermal radical polymerization initiator is preferably 0.05 to 200 parts by mass with respect to 100 parts by mass of the radically polymerizable compound. The lower limit is preferably 1 part by mass or more, more preferably 10 parts by mass or more, 50 parts by mass or more, 80 parts by mass or more, or 100 parts by mass or more. The upper limit is preferably 150 parts by mass or less, more preferably 120 parts by mass or less. When the ratio of the thermal radical polymerization initiator and the radically polymerizable compound is within the above range, the water adhesion resistance is better, and it is easy to form a cured film in which the generation of agglomerates derived from the near-infrared absorbing dye is further suppressed. ..
When a pinacol compound and an α-hydroxyacetophenone compound are used in combination as a thermal radical polymerization initiator, the content of the α-hydroxyacetophenone compound is 1 to 70 parts by mass with respect to 100 parts by mass of the pinacol compound. Is more preferable, and it is more preferably 3 to 60 parts by mass, and further preferably 5 to 50 parts by mass.
The curable composition of the present invention may contain only one type of thermal radical polymerization initiator, or may contain two or more types of thermal radical polymerization initiators. When two or more kinds of thermal radical polymerization initiators are contained, the total amount thereof is preferably in the above range.
Further, in the present invention, the structure may be substantially free of the photoradical polymerization initiator. Substantially not contained means, for example, that the content of the photoradical polymerization initiator is 1% by mass or less of the content of the thermal radical polymerization initiator.

<< Compound with cyclic ether group >>
The curable composition of the present invention contains a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, and an epoxy group is preferable. The compound having a cyclic ether group is preferably a compound having two or more cyclic ether groups in one molecule. The upper limit of the number of cyclic ether groups in the compound having a cyclic ether group is preferably 100 or less, more preferably 10 or less, and further preferably 5 or less.

The cyclic ether group equivalent of the compound having a cyclic ether group (molecular weight of the compound having a cyclic ether group / number of cyclic ether groups in the compound having a cyclic ether group) is preferably 50 to 400 g / mol. The lower limit of the cyclic ether group equivalent is preferably 100 g / mol or more, and more preferably 150 g / mol or more. The upper limit is preferably 350 g / mol or less, and more preferably 300 g / mol or less.
When the compound having a cyclic ether group is a compound having an epoxy group, the epoxy group equivalent (molecular weight of the compound having an epoxy group / the number of epoxy groups in the compound having an epoxy group) is 50 to 400 g / mol. It is preferable to have. The lower limit of the epoxy group equivalent is preferably 100 g / mol or more, and more preferably 150 g / mol or more. The upper limit is preferably 350 g / mol or less, and more preferably 300 g / mol or less.

The compound having a cyclic ether group may be a low molecular weight compound (for example, a molecular weight of less than 1000) or a polymer compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). May be good. The molecular weight of the compound having a cyclic ether group (in the case of a polymer, the weight average molecular weight) is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the molecular weight (in the case of a polymer, the weight average molecular weight) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1500 or less.

The compound having a cyclic ether group used in the present invention is preferably a compound having a repeating unit. When the compound having a cyclic ether group is a compound having a repeating unit, the cyclic ether group may be contained in the side chain of the repeating unit or at the end of the main chain. Of these, a compound having a cyclic ether group in the side chain is preferable because it is surface-adsorbed to the support and more excellent water resistance and adhesion can be easily obtained.

The compound having a cyclic ether group is preferably a compound having a structure having an aromatic ring and / or an aliphatic ring, and more preferably a compound having a structure having an aromatic ring. When a compound having an aromatic ring is used as the compound having a cyclic ether group, it easily interacts with the near-infrared absorbing dye and easily forms a cured film having better water adhesion.

The aromatic ring is preferably an aromatic hydrocarbon ring. Further, the aromatic ring may be a monocyclic ring or a condensed ring. Specific examples of the aromatic ring include a benzene ring and a naphthalene ring, and it is preferable to include at least a naphthalene ring because the compatibility with the near-infrared absorbing dye is enhanced and excellent water resistance and adhesion can be easily obtained. ..
When the compound having a cyclic ether group contains an aromatic ring, the number of aromatic rings is preferably one or more, the compatibility with the near-infrared absorbing dye is enhanced, and excellent water resistance and adhesion can be obtained. It is more preferable that the number is two or more because it is easy. The upper limit is preferably 5 or less, and more preferably 4 or less. When the compound having a cyclic ether group is a compound having a repeating unit, the number of aromatic rings in one repeating unit is preferably 1 to 10. The upper limit is preferably 7 or less, and more preferably 5 or less. The lower limit is preferably two or more. The number of aromatic rings in the compound having a cyclic ether group is the total value of the number of monocyclic aromatic rings and the number of rings constituting the fused ring. For example, in the case of a compound having a naphthalene ring as an aromatic ring in a compound having a cyclic ether group, the number of aromatic rings of the compound having this cyclic ether group is two. In the case of a compound having a benzene ring and a naphthalene ring as the aromatic ring in the compound having a cyclic ether group, the number of aromatic rings of the compound having the cyclic ether group is three.

When the compound having a cyclic ether group is a compound having a structure having an aromatic ring and / or an aliphatic ring, the cyclic ether group is formed into an aromatic ring and / or an aliphatic ring via a single bond or a linking group. It is preferable that they are bonded. Examples of the linking group include an alkylene group, an arylene group, and -NR'-(R'represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and hydrogen. Atomic preferred), -SO _2- , -CO-, -COO-, -OCO-, -O-, -S- and groups consisting of a combination thereof can be mentioned.

Compounds having a cyclic ether group can be found in paragraphs 0034 to 0036 of JP2013-011869, paragraphs 0147 to 0156 of JP2014-043556, and paragraph numbers 0085-0092 of JP2014-089408. The described compounds can also be used. These contents are incorporated herein by reference. Examples of commercially available compounds having a cyclic ether group include EPICLON HP5000 and EPICLON HP4032D (all manufactured by DIC Corporation) as naphthalene-modified epoxy resins. Examples of the alkyldiphenol type epoxy resin include EPICLON 820 (manufactured by DIC Corporation). As bisphenol A type epoxy resin, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051 (Manufactured by Co., Ltd.) and the like. As bisphenol F type epoxy resin, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, manufactured by DIC Corporation), LCE-21, RE-602S (above, manufactured by DIC Corporation). As mentioned above, Nippon Kayaku Co., Ltd.) and the like can be mentioned. Examples of the phenol novolac type epoxy resin include jER152, jER154, jER157S70, jER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation) and the like. Can be mentioned. As cresol novolac type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (all manufactured by DIC Corporation). , EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) and the like. As aliphatic epoxy resins, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA Corporation), celoxide 2021P, celoxide 2081, celoxide 2083, celoxide 2085, EHPE3150, EPOLEAD PB 3600, EPO 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 can be mentioned. In addition, as compounds having an oxetanyl group, OXT-101, OXT-121, OXT-212, OXT-221 (all manufactured by Toagosei Co., Ltd.), OXE-10, OXE-30 (all above, Osaka Organic Chemical Industry Co., Ltd.) Made by Co., Ltd.) and the like.

The content of the compound having a cyclic ether group is preferably 1 to 45% by mass with respect to the total solid content of the curable composition. The lower limit is preferably 2% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
The content of the compound having a cyclic ether group is preferably 5 to 500 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye. The upper limit is preferably 400 parts by mass or less, more preferably 350 parts by mass or less, and further preferably 300 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. When the ratio of the compound having a cyclic ether group to the near-infrared absorbing dye is in the above range, a cured film having better water resistance and more suppressed generation of aggregates derived from the near-infrared absorbing dye is formed. easy.
The curable composition of the present invention may contain only one compound having a cyclic ether group, or may contain two or more compounds. When two or more compounds having a cyclic ether group are contained, the total amount thereof is preferably in the above range.

<< Photoradical Polymerization Initiator >>
The curable composition of the present invention can further contain a photoradical polymerization initiator. As the photoradical polymerization initiator, a compound that generates radicals with respect to light rays in the ultraviolet region to the visible region is preferable.

Examples of the photoradical polymerization initiator include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-aminoacetophenone compounds, α-hydroxyacetophenone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium. Examples thereof include compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxaziazole compounds and 3-aryl substituted coumarin compounds.

The photoradical polymerization initiator is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. Further, the photoradical polymerization initiator is preferably a compound having high absorbance at 365 nm and 405 nm. The molar extinction coefficient of the photoradical polymerization initiator at a wavelength of 365 nm ^{preferably exceeds 5 L · mol -1} · cm ^-1 , more preferably exceeds 10 L · mol ^-1 · cm ^-1, and more preferably 15 L · mol ^-1. - more preferably of greater than cm ^-1, even more preferably greater than 50L · mol ^-1 · cm ^-1, and particularly preferably more than 100L · mol ^-1 · cm ^-1.

When the curable composition of the present invention contains a photoradical polymerization initiator, the content of the photoradical polymerization initiator is preferably 20% by mass or less, preferably 15% by mass, based on the total solid content of the curable composition. It is preferable, and 10% by mass is more preferable. The lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more. The photoradical polymerization initiator may be used alone or in combination of two or more. When two or more photoradical polymerization initiators are used in combination, the total amount is preferably in the above range.

<< Resin >>
The curable composition of the present invention may contain a resin as a component other than the above-mentioned compound having a cyclic ether group and the radically polymerizable compound. The resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition and for the purpose of a binder. A resin mainly used for dispersing particles such as pigments is also referred to as a dispersant. However, such an application of the resin is an example, and the resin can be used for a purpose other than such an application.

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

Examples of the resin include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, and polyamideimide resin. , Polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and the like. One of these resins may be used alone, or two or more of these resins may be mixed and used. As the cyclic olefin resin, a norbornene resin can be preferably used from the viewpoint of improving heat resistance. Examples of commercially available norbornene resins include the ARTON series manufactured by JSR Corporation (for example, ARTON F4520). The resins include the resin described in Examples of International Publication WO2016 / 088645, the resin described in JP-A-2017-57265, the resin described in JP-A-2017-32685, and JP-A-2017. The resin described in Japanese Patent Application Laid-Open No. -075248 and the resin described in JP-A-2017-066240 can also be used, and the contents thereof are incorporated in the present specification.

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

As the resin having an acid group, a polymer having a carboxyl group in the side chain is preferable. Specific examples include alkali-soluble methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolak resins. Examples thereof include a phenol resin, an acidic cellulose derivative having a carboxyl group in the side chain, and a resin in which an acid anhydride is added to a polymer having a hydroxy group. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like. Examples of alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth) acrylate. Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, trill (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Examples thereof include α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethylmethacrylate macromonomer and the like. As the other monomer, N-substituted maleimide monomers described in JP-A-10-300922, for example, N-phenylmaleimide, N-cyclohexylmaleimide and the like can also be used. The other monomers copolymerizable with these (meth) acrylic acids may be only one kind or two or more kinds.

The resin having an acid group may further have a polymerizable group. Examples of the polymerizable group include a (meth) allyl group and a (meth) acryloyl group. Commercially available products include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, Diamond Shamlock Co., Ltd.), Viscort R-264, and KS resist 106 (all of which are Osaka Organics). Chemical Industry Co., Ltd., Cyclomer P series (for example, ACA230AA), Praxel CF200 series (all manufactured by Daicel Co., Ltd.), Ebecryl3800 (manufactured by Daicel UCB Co., Ltd.), Acrycure RD-F8 Co., Ltd. (Made by Nippon Catalyst) and the like.

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

The resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferable that the polymer contains a repeating unit derived from the component.

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

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

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

式（Ｘ）において、Ｒ₁は、水素原子またはメチル基を表し、Ｒ₂は炭素数２〜１０のアルキレン基を表し、Ｒ₃は、水素原子またはベンゼン環を含んでもよい炭素数１〜２０のアルキル基を表す。ｎは１〜１５の整数を表す。 The resin having an acid group may contain a repeating unit derived from the compound represented by the following formula (X).

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

Regarding the resin having an acid group, the description in paragraph Nos. 0558 to 0571 of JP2012-208494A (paragraph number 0685-0700 of the corresponding US Patent Application Publication No. 2012/0235099), JP2012-198408 The description of paragraphs 0076 to 09999 of the publication can be taken into consideration, and these contents are incorporated in the present specification. Further, as the resin having an acid group, a commercially available product can also be used. For example, Acrybase FF-426 (manufactured by Fujikura Kasei Co., Ltd.) and the like can be mentioned.

The acid value of the resin having an acid group is preferably 30 to 200 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more. The upper limit is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less.

Examples of the resin having an acid group include a resin having the following structure. In the following structural formula, Me represents a methyl group.

式中、Ｒ⁵は水素原子またはアルキル基を表し、Ｌ⁴〜Ｌ⁷は各々独立に単結合または２価の連結基を表し、Ｒ¹⁰〜Ｒ¹³は各々独立にアルキル基またはアリール基を表す。Ｒ¹⁴およびＲ¹⁵は、各々独立に水素原子または置換基を表す。 In the curable composition of the present invention, it is also preferable to use as the resin a resin having a repeating unit represented by the 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 represent a single bond or a divalent linking group, and R ^{10 to} R ¹³ each independently represent an alkyl group or an aryl group. .. R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or substituent.

R ⁵ represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. R ⁵ is preferably a hydrogen atom or a methyl group.

L ^{4 to} L ⁷ each independently represent a single bond or a divalent linking group. The divalent linking group includes an alkylene group, an arylene group, -O-, -S-, -CO-, -COO-, -OCO-, -SO _2- , -NR ^10- (R ¹⁰ is a hydrogen atom or (Representing an alkyl group, preferably a hydrogen atom), or a group consisting of a combination thereof can be mentioned. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms. The 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 either monocyclic or polycyclic. The arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms.

The ^{alkyl group represented by R 10 to} R ¹³ may be linear, branched or cyclic, and cyclic is preferable. The alkyl group may have a substituent or may be unsubstituted. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The ^{aryl group represented by R 10 to} R ¹³ preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6. R ¹⁰ is preferably a cyclic alkyl group or aryl group. R ¹¹ and R ¹² are preferably linear or branched alkyl groups. R ¹³ is preferably a linear alkyl group, a branched alkyl group, or an aryl group.

The ^{substituents represented by R 14} and R ¹⁵ are halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aralkyl group, alkoxy group, aryloxy group and heteroaryloxy group. , Alkylthio group, arylthio group, heteroarylthio group, -NR ^a1 R ^a2 , -COR ^a3 , -COOR ^a4 , -OCOR ^{a5 , -NHCOR a6} , -CONR ^a7 R ^a8 , -NHCONR ^a9 R ^a10 , -NHCOOR ^a11 , ^Examples thereof include −SO ₂ R ^a12 , −SO ₂ OR a13, −NHSO ₂ R ^a14 or −SO ₂ NR ^a15 R ^a16 . R ^{a1 to} R ^a16 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. Among them, ^{at least one of R 14} and R ¹⁵ preferably represents a cyano group or −COOR ^a4. R ^a4 preferably represents a hydrogen atom, an alkyl group or an aryl group.

Examples of commercially available resins having a repeating unit represented by the formula (A3-7) include ARTON F4520 (manufactured by JSR Corporation). Further, for details of the resin having a repeating unit represented by the formula (A3-7), the description in paragraphs 0053 to 0075 and 0127 to 0130 of JP2011-100084A can be referred to, and the contents thereof are described in the present specification. Incorporated into the book.

The curable composition of the present invention may also contain a resin as a dispersant. In particular, when a pigment is used, it is preferable to include a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and is substantially an acid. A resin consisting only of groups is more preferable. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and even more preferably 60 to 105 mgKOH / g. Further, the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. The basic group contained in the basic dispersant is preferably an amino group.

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

The resin used as the dispersant is also preferably a graft copolymer. Since the graft copolymer has an affinity with a solvent due to the graft chain, it is excellent in the dispersibility of the pigment and the dispersion stability after aging. For details of the graft copolymer, the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the content thereof is incorporated in the present specification. Specific examples of the graft copolymer include the following resins. The following resins are also resins having an acid group (alkali-soluble resin). Further, examples of the graft copolymer include the resins described in paragraphs 0072 to 0094 of JP-A-2012-255128, the contents of which are incorporated in the present specification.

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

The dispersant is also available as a commercially available product, and specific examples thereof include Disperbyk-111 (manufactured by BYK Chemie) and Solspers 76500 (manufactured by Nippon Lubrizol Co., Ltd.). Further, the pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, and the contents thereof are incorporated in the present specification. Further, the above-mentioned resin having an acid group or the like can also be used as a dispersant.

In the curable composition of the present invention, the content of the resin is preferably 1 to 60% by mass with respect to the total solid content of the curable composition of the present invention. The lower limit is preferably 5% by mass or more, more preferably 7% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 30% by mass or less.

When the dispersant is contained as the resin, the content of the dispersant is preferably 0.1 to 40% by mass with respect to the total solid content of the curable composition. The upper limit is preferably 20% by mass or less, and more preferably 10% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The content of the dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the pigment. 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 2.5 parts by mass or more, and more preferably 5 parts by mass or more.

<< Coloring agent >>
The curable 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.

The chromatic colorant may be a pigment or a dye. The pigment is preferably an organic pigment. Examples of the organic pigment include those shown below.
Color Index (CI) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34, 35,35: 1,36,36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86, 93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128, 129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 etc. (above, yellow pigment),
C. I. Pigment Orange 2,5,13,16,17: 1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73, etc. (The above is orange pigment),
C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48: 1,48: 2,48: 3,48: 4, 49,49: 1,49: 2,52: 1,52: 2,53: 1,57: 1,60: 1,63: 1,66,67,81: 1,81: 2,81: 3, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279 etc. 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 known dyes can be used. The chemical structures include pyrazole azo, anilino azo, triarylmethane, anthraquinone, anthrapylidene, benzylidene, oxonol, pyrazorotriazole azo, pyridone azo, cyanine, phenothiazine, and pyrrolopyrazole azomethine. Dyes such as xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based, and pyromethene-based 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 curable composition of the present invention contains a chromatic colorant, the content of the chromatic colorant is preferably 0.1 to 70% by mass with respect to the total solid content of the curable composition of the present invention. .. The lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less. The total amount of the chromatic colorant and the near-infrared absorbing dye is preferably 1 to 80% by mass with respect to the total solid content of the curable composition of the present invention. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less. When the curable composition of the present invention contains two or more kinds of chromatic colorants, the total amount thereof is preferably within the above range.
It is also preferable that the curable composition of the present invention does not substantially contain a chromatic colorant. The term "substantially free of chromatic colorant" means that the content of the chromatic colorant is preferably 0.05% by mass or less, preferably 0.01% by mass, based on the total solid content of the curable composition. The following is more preferable, and it is further preferable that the chromatic colorant is not contained.

<< Coloring material that transmits infrared rays and blocks visible light >>
The curable composition of the present invention may also contain a coloring material that transmits infrared rays to block visible light (hereinafter, also referred to as a coloring material that blocks visible light).
In the present invention, the color material that blocks visible light is preferably a color material that absorbs light in the wavelength region of purple to red. Further, in the present invention, the coloring material that blocks visible light is preferably a coloring material that blocks light in the wavelength region of 450 to 650 nm. Further, the color material that blocks visible light is preferably a color material that transmits light having a wavelength of 900 to 1300 nm.
In the present invention, the coloring material that blocks visible light preferably satisfies at least one of the following requirements (A) and (B).
(A): Contains two or more kinds of chromatic colorants, and forms black with a combination of two or more kinds of chromatic colorants.
(B): Contains an organic black colorant.

Examples of the chromatic colorant include those 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 compound are described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234, International Publication No. WO2014 / 208348, Japanese Patent Publication No. 2015-525260 and the like. Compounds are mentioned and are available, for example, as "Irgaphor Black" manufactured by BASF. Examples of the perylene compound include C.I. I. Pigment Black 31, 32 and the like can be mentioned. Examples of the azomethine compound include compounds described in JP-A-1-170601 and JP-A-2-34664, and are available as, for example, "Chromofine Black A1103" manufactured by Dainichiseika.

Examples of the combination of chromatic colorants when black is formed by the combination of two or more kinds of chromatic colorants include the following.
(1) An embodiment containing a yellow colorant, a blue colorant, a purple colorant, and a red colorant.
(2) An embodiment containing a yellow colorant, a blue colorant, and a red colorant.
(3) An embodiment containing a yellow colorant, a purple colorant, and a red colorant.
(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) An embodiment containing a purple colorant and 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.

When the curable composition of the present invention contains a coloring material that blocks visible light, the content of the coloring material that blocks visible light is preferably 60% by mass or less based on the total solid content of the curable composition. , 50% by mass or less is more preferable, 30% by mass or less is further preferable, 20% by mass or less is further preferable, and 15% by mass or less is particularly preferable. The lower limit can be, for example, 0.1% by mass or more, or 0.5% by mass or more.
It is also preferable that the curable composition of the present invention does not substantially contain a coloring material that blocks visible light. The fact that the color material that blocks visible light is substantially not contained means that the content of the color material that blocks visible light is preferably 0.05% by mass or less based on the total solid content of the curable composition. , 0.01% by mass or less, and more preferably no coloring material that blocks visible light.

<< Pigment derivative >>
The curable composition of the present invention can further contain a pigment derivative. Examples of the pigment derivative include compounds in which at least one group selected from an acid group and a basic group is bonded to the pigment skeleton. As the pigment derivative, a compound represented by the formula (B1) is preferable.

式（Ｂ１）中、Ｐは色素骨格を表し、Ｌは単結合または連結基を表し、Ｘは酸基または塩基性基を表し、ｍは１以上の整数を表し、ｎは１以上の整数を表し、ｍが２以上の場合は複数のＬおよびＸは互いに異なっていてもよく、ｎが２以上の場合は複数のＸは互いに異なっていてもよい。

In formula (B1), P represents a dye skeleton, L represents a single bond or a linking group, X represents an acid group or a basic group, m represents an integer of 1 or more, and n represents an integer of 1 or more. Represented, when m is 2 or more, the plurality of Ls and Xs may be different from each other, and when n is 2 or more, the plurality of Xs may be different from each other.

The pigment skeleton represented by P includes pyrrolopyrrolop pigment skeleton, diketopyrrolopyrrole pigment skeleton, quinacridone pigment skeleton, anthraquinone pigment skeleton, dianthraquinone pigment skeleton, benzoisoindole pigment skeleton, thiazineindigo pigment skeleton, azo pigment skeleton, and quinophthalone. At least one selected from pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, dioxazine pigment skeleton, perylene pigment skeleton, perinone pigment skeleton, benzoimidazolone pigment skeleton, benzothiazole pigment skeleton, benzoimidazole pigment skeleton and benzoxazole pigment skeleton. Is preferable, at least one selected from the pyrolopyrrolop pigment skeleton, the diketopyrrolopyrrole pigment skeleton, the quinacridone pigment skeleton and the benzoimidazolone pigment skeleton is more preferable, and the pyrolopyrrolop pigment skeleton is particularly preferable.

Examples of the linking group represented by L include a hydrocarbon group, a heterocyclic group, -NR-, -SO _2- , -S-, -O-, -CO-, or a group consisting of a combination thereof. R represents a hydrogen atom, an alkyl group or an aryl group.

Examples of the acid group represented by X include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, and an imic acid group. As the carboxylic acid amide group, a group represented by ^{-NHCOR X1 is preferable.} As the sulfonic acid amide group, a group represented by _{−NHSO 2} R ^{X 2 is preferable.} As the imidic acid group, a group represented by -SO ₂ NHSO ₂ R ^X3 , -CONHSO ₂ R ^X4 , -CONHCOR ^X5 or -SO ₂ ^{NHCOR X6} is preferable. R ^{X1 to} R ^X6 independently represent a hydrocarbon group or a heterocyclic group. The hydrocarbon group and the heterocyclic group represented by ^{R X1 to} R ^{X6 may further have a substituent.} Examples of the further substituent include the substituent T described in the above formula (PP), which is preferably a halogen atom and more preferably a fluorine atom. Examples of the basic group represented by X include an amino group. Examples of the salt structure represented by X include the above-mentioned salts of acid groups or basic groups.

Examples of the pigment derivative include compounds having the following structures. In addition, Japanese Patent Application Laid-Open No. 56-118462, Japanese Patent Application Laid-Open No. 63-264674, Japanese Patent Application Laid-Open No. 1-2170777, Japanese Patent Application Laid-Open No. 3-9961, Japanese Patent Application Laid-Open No. 3-26767, Japanese Patent Application Laid-Open No. 3-153780. Japanese Patent Application Laid-Open No. 3-455662, Japanese Patent Application Laid-Open No. 4-285669, Japanese Patent Application Laid-Open No. 6-145546, Japanese Patent Application Laid-Open No. 6-21208, Japanese Patent Application Laid-Open No. 6-24158, Japanese Patent Application Laid-Open No. 10-30063, Compounds described in Japanese Patent Application Laid-Open No. 10-195326, paragraph numbers 0083 to 098 of International Publication WO2011 / 024896, paragraphs 0063 to 0094 of International Publication WO2012 / 102399, and compounds described in Japanese Patent No. 5299151. Can also be used and these contents are incorporated herein by reference.

When the curable 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. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. When the content of the pigment derivative is within the above range, the dispersibility of the pigment can be enhanced and the aggregation of the pigment can be efficiently suppressed. Only one kind of pigment derivative may be used, or two or more kinds may be used. When two or more types are used, the total amount is preferably in the above range.

<< Solvent >>
The curable composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. The type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition. Examples of organic solvents include, for example, esters, ethers, ketones, aromatic hydrocarbons and the like. For these details, paragraph number 0223 of WO2015 / 166779 can be referred to, the contents of which are incorporated herein by reference. Further, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, and the like. Examples thereof include cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. Further, 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are also preferable from the viewpoint of improving solubility. In the present invention, the organic solvent may be used alone or in combination of two or more. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may need to be reduced for environmental reasons (for example, 50 mass ppm (parts per) with respect to the total amount of the organic solvent. Million) or less, 10 mass ppm or less, or 1 mass ppm or less).

In the present invention, it is preferable to use a solvent having a low metal content. The metal content of the solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, a solvent at the mass ppt (parts per tension) level may be used, and such a high-purity solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical 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 diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon.

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

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

The content of the solvent is preferably 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 curable composition. When two or more kinds of solvents are used, the total amount thereof is preferably in the above range. Further, for environmental reasons, it may be preferable that the curable composition does not contain aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent.

The content of the solvent is preferably 10 to 97% by mass with respect to the total amount of the curable composition. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and 70% by mass. The above is particularly preferable. The upper limit is preferably 96% by mass or less, and more preferably 95% by mass or less.

<< Polymerization inhibitor >>
The curable composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, primary cerium salt, etc.). Of these, p-methoxyphenol is preferable. The content of the polymerization inhibitor is preferably 0.001 to 5% by mass with respect to the total solid content of the curable composition.

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

The content of the silane coupling agent is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass, based on the total solid content of the curable composition. 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 in the above range.

<< Surfactant >>
The curable composition of the present invention can contain a surfactant. 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. For surfactants, paragraph numbers 0238 to 0245 of WO2015 / 166779 can be referred to, the contents of which are incorporated herein by reference.

In the present invention, the surfactant is preferably a fluorine-based surfactant. By containing a fluorine-based surfactant in the curable composition of the present invention, the liquid properties (particularly, fluidity) can be further improved, and the liquid saving property can be further improved. It is also possible to form a film having a small thickness unevenness.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and 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 property, and has good solubility in the composition.

Specific examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Application Laid-Open No. 2014-41318 (paragraphs 0060 to 0064 of the corresponding international publication 2014/17669) and the like. The surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 2011-132503 are mentioned, and their contents are incorporated in the present specification. Commercially available products of fluorine-based surfactants include, for example, Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS. -330 (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA) and the like. ..

Further, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied is also suitable. Can be used. Examples of such fluorine-based surfactants include Megafuck DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafuck DS. -21 can be mentioned.

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

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

In the present invention, as the fluorine-based surfactant, it is preferable to use a compound having a fluorine atom and a curable group (hereinafter, also referred to as a fluorine-containing curable compound). By using such a surfactant, the heat resistance of the obtained film can be further improved. Further, excellent solvent resistance can be obtained. It is presumed that the reason why excellent solvent resistance can be obtained by using the fluorine-containing curable compound is as follows. Since the fluorine-containing curable compound has a low surface free energy, for example, in a coating film formed by applying the composition on a support such as a substrate, the fluorine-containing curable compound is in the vicinity of the coating film surface on the opposite side of the support. Curable compounds tend to be unevenly distributed. By curing the curable composition of the present invention in a state where the fluorine-containing curable compound is unevenly distributed in this way, a region having a large proportion of the cured product of the fluorine-containing curable compound is formed on the surface on the side far from the substrate. .. Due to the presence of such a region, even if the film is immersed in a solvent, the near-infrared absorbing dye is less likely to seep out from the film surface, and excellent solvent resistance can be obtained.

Examples of the curable group contained in the fluorine-containing curable compound include a (meth) acryloyloxy group, an epoxy group and an oxetanyl group, and a (meth) acryloyloxy group is preferable.

The fluorine-containing curable compound preferably has at least one selected from the group consisting of an alkylene group substituted with a fluorine atom, an alkyl group substituted with a fluorine atom, and an aryl group substituted with a fluorine atom. ..
The alkylene group substituted with a fluorine atom is preferably a linear, branched or cyclic alkylene group in which at least one hydrogen atom is substituted with a fluorine atom.
The alkyl group substituted with a fluorine atom is preferably a linear, branched or cyclic alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
The number of carbon atoms in the alkylene group substituted with a fluorine atom and the alkyl group substituted with a fluorine atom is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 5. preferable.
As for the aryl group substituted with a fluorine atom, it is preferable that the aryl group is directly substituted with a fluorine atom or substituted with a trifluoromethyl group.
The alkylene group substituted with a fluorine atom, the alkyl group substituted with a fluorine atom, and the aryl group substituted with a fluorine atom may further have a substituent other than the fluorine atom. As specific examples of these, for example, paragraphs 0266 to 0272 of JP2011-100089A can be referred to, and the contents thereof are incorporated in the present specification.

The fluorine-containing curable compound is preferably a compound containing a fluoroether group and a curable group. Examples of the fluoroether group include a group X (a group represented by the formula (X)) in which an alkylene group substituted with a fluorine atom and an oxygen atom are linked. The fluoroether group is preferably a perfluoroalkylene ether group. Note that the perfluoroalkylene ether groups, which means that L _A in formula (X) is a perfluoroalkylene group. The perfluoroalkylene group means a group in which all hydrogen atoms in the alkylene group are substituted with fluorine atoms.
Formula _{(X) - (L A -O} ) n-
The L _A represents an alkylene group substituted with a fluorine atom. The carbon number of the alkylene group substituted with the fluorine atom is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkylene group substituted with a fluorine atom may be linear or branched. n represents an integer of 1 or more, preferably 1 to 50, more preferably 1 to 20. When n is 2 or more, a plurality of _{- (L A -O) - L} A medium may be the same or different.

The fluorine-containing curable compound may be a monomer or a polymer, but is preferably a polymer.

When the fluorine-containing curable compound is a polymer, the polymer is preferably a polymer having a repeating unit having a fluoroether group and a repeating unit having a curable group. Further, it is preferable that the polymer has at least one of the repeating unit represented by the following formula (B1), the repeating unit represented by the following formula (B2) and the repeating unit represented by the formula (B3). A polymer having a repeating unit represented by the following formula (B1) and a repeating unit represented by the following formula (B3) is more preferable.

In formulas (B1) to (B3), R ^{1 to} R ¹¹ independently represent a hydrogen atom, an alkyl group, or a halogen atom. L ^{1 to} L ⁴ independently represent a single bond or a divalent linking group. X ¹ represents a (meth) acryloyloxy group, an epoxy group, or an oxetanyl group, X ² represents an alkyl group substituted with a fluorine atom or an aryl group substituted with a fluorine atom, and X ³ represents the formula (X). Represents a group represented by.

In formulas (B1) to (B3), R ^{1 to} R ¹¹ are preferably hydrogen atoms or alkyl groups, respectively. When R ^{1 to} R ¹¹ represent an alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable. When R ^{1 to} R ¹¹ represent a halogen atom, a fluorine atom is preferable.
In the formulas (B1) to (B3), when L ^{1 to} L ⁴ represent a divalent linking group, the divalent linking group is substituted with an alkylene group or a halogen atom which may be substituted with a halogen atom. which may be an arylene ^{group, -NR 12 -, - CONR 12} -, - CO -, - CO 2 -, - SO 2 NR 12 -, - O -, - S -, - SO 2 -, or, of Combinations can be mentioned. Among them, at least one selected from the group consisting of an alkylene group optionally substituted with a halogen atom having 2 to 10 carbon atoms and an arylene group optionally substituted with a halogen atom having 6 to 12 carbon atoms, or at least one selected from the group. these groups and ^{-NR 12 -, - CONR 12 -} , - CO -, - CO 2 -, - SO 2 NR 12 -, - O -, - S-, and -SO ₂ - is selected from the group consisting of that at least one group is preferably a combination of a group, an alkylene group optionally substituted with a halogen atom having 2 to 10 carbon _{atoms, -CO 2 -, - O -} , - CO -, - CONR 12 - , Or a group consisting of a combination of these groups is more preferable. Here, R ¹² represents a hydrogen atom or a methyl group.

The content of the repeating unit represented by the above formula (B1) is preferably 30 to 95 mol%, preferably 45 to 90 mol%, based on all the repeating units in the fluorine-containing curable compound. More preferred.
The total content of the repeating unit represented by the above formula (B2) and the repeating unit represented by the formula (B3) shall be 5 to 70 mol% with respect to all the repeating units in the fluorine-containing curable compound. Is preferable, and 10 to 60 mol% is more preferable. When the repeating unit represented by the formula (B2) is not included and the repeating unit represented by the formula (B3) is included, the content of the repeating unit represented by the formula (B2) is 0 mol%. , The content of the repeating unit represented by the formula (B3) is preferably in the above range.

Further, the fluorine-containing curable compound may have a repeating unit other than the repeating units represented by the above formulas (B1) to (B3). The content of the other repeating units is preferably 10 mol% or less, more preferably 1 mol% or less, based on all the repeating units in the fluorine-containing curable compound.

When the fluorine-containing curable compound is a polymer, the weight average molecular weight is preferably 5,000 to 100,000, more preferably 7,000 to 50,000. The degree of dispersion (weight average molecular weight / number average molecular weight) is preferably 1.80 to 3.00, and more preferably 2.00 to 2.90.

Commercially available products of the fluorine-containing curable compound include, for example, Megafvck RS-72-K, Megafvck RS-75, Megafvck RS-76-E, Megafvck RS-76-NS, and Megafvck RS manufactured by DIC Corporation. -77 etc. can be used. The fluorine-containing curable compound includes the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, and the compounds described in paragraphs 0015 to 0158 of JP2015-117327. It can also be used. Further, as the fluorine-containing curable compound, a polymer having a repeating unit represented by (B1-1) and a repeating unit represented by the formula (B3-1) can also be used. In formula (B3-1), X represents a fluoromethylene group or a fluoroethylene group, and r represents the number of repeating units.

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

The content of the surfactant is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005 to 3.0% by mass, based on the total solid content of the curable composition of the present invention. The surfactant may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably in the above range.

<< UV absorber >>
The curable composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminobutadiene compound, a methyldibenzoyl compound, a coumarin compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound and the like can be used. For details thereof, the description of paragraphs 0052 to 0072 of JP2012-208374A and paragraphs 0317 to 0334 of JP2013-68814 can be referred to, and these contents are incorporated in the present specification. Examples of commercially available conjugated diene compounds include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Further, as the benzotriazole compound, the MYUA series manufactured by Miyoshi Oil & Fat Co., Ltd. (The Chemical Daily, February 1, 2016) may be used.
The content of the ultraviolet absorber is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the curable composition. In the present invention, only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

<< Other ingredients >>
The curable composition of the present invention can be used as a sensitizer, a curing accelerator, a filler, a thermal polymerization inhibitor, a plasticizer, an adhesion accelerator and other auxiliaries (for example, conductive particles, a filler), if necessary. , Antifoaming agent, flame retardant, leveling agent, peeling accelerator, antioxidant, latent antioxidant, fragrance, surface tension modifier, chain transfer agent, etc.) may be contained. For these components, the description of paragraph numbers 0101 to 0104, 0107 to 0109, etc. of JP-A-2008-250074 can be taken into consideration, and the contents thereof are incorporated in the present specification. Further, examples of the antioxidant include a phenol compound, a phosphite ester compound, a thioether compound and the like. As the antioxidant, a phenol compound having a molecular weight of 500 or more, a phosphite ester compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is more preferable. These may be used in mixture of 2 or more types. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred 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. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As a phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl] ) Oxy] ethyl] amines and ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) include at least one compound selected from the group. These are available as commercial products. For example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 Co., Ltd. ADEKA) and the like. Further, as the antioxidant, a polyfunctional hindered amine antioxidant described in WO17 / 004000 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 curable composition. 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 in the above range.
A latent antioxidant is a compound whose site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. Therefore, it is preferable that the compound has a protective group desorbed and functions as an antioxidant. Examples of the latent antioxidant include compounds described in International Publications WO2014 / 021023, International Publications WO2017 / 030005, and JP-A-2017-008219. Examples of commercially available products include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like.

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

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

The use of the curable composition of the present invention is not particularly limited. For example, it can be preferably used for forming a near-infrared cut filter or the like. Further, in the curable composition of the present invention, by further containing a coloring material that blocks visible light, it is possible to form an infrared transmission filter capable of transmitting only near infrared rays having a specific wavelength or higher.

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

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

In preparing the curable composition, it is preferable to filter the curable composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultrahigh molecular weight). A filter using a material such as (including the polyolefin resin of) is mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
The pore size of the filter is preferably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. If the pore size of the filter is within the above range, fine foreign matter can be reliably removed. It is also preferable to use a fibrous filter medium. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Specific examples thereof include filter cartridges of SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Roki Techno Co., Ltd.

When using filters, different filters (eg, first filter and second filter, etc.) may be combined. At that time, the filtration with each filter may be performed only once or twice or more.
Further, filters having different pore diameters may be combined within the above-mentioned range. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As a commercially available filter, for example, select from various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc. can do.
As the second filter, one formed of the same material as the first filter can be used.
Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration with the second filter may be performed.

<Cured film>
The cured film of the present invention is obtained from the curable composition of the present invention described above. The cured film of the present invention can be preferably used as a near-infrared cut filter. It can also be used as a heat ray shielding filter or an infrared ray transmitting filter. The cured film of the present invention may be used by being laminated on a support, or may be peeled off from the support and used. The cured film of the present invention may have a pattern or may be a film having no pattern (flat film).

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

The cured film of the present invention preferably has a maximum absorption wavelength in the wavelength range of 700 to 1300 nm, more preferably has a maximum absorption wavelength in the wavelength range of 700 to 1000 nm, and has a maximum absorption wavelength in the wavelength range of 720 to 980 nm. It is more preferable to have a maximum absorption wavelength in the wavelength range of 740 to 960 nm.

When the cured film of the present invention is used as a near-infrared cut filter, the cured film of the present invention preferably satisfies at least one of the following (1) to (4), and (1) to (4). It is more preferable to satisfy all the conditions of.
(1) The transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 80% or more, further preferably 85% or more, and particularly preferably 90% or more.
(2) The transmittance at a wavelength of 500 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.
(3) The transmittance at a wavelength of 600 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.
(4) The transmittance at a wavelength of 650 nm is preferably 70% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.

The cured film of the present invention can also be used in combination with a color filter containing a chromatic colorant. The color filter can be produced by using a coloring composition containing a chromatic colorant. Examples of the chromatic colorant include the chromatic colorants mentioned as those which may be contained in the curable composition of the present invention. Further, the cured film of the present invention may contain a chromatic colorant to form a filter having a function as a near-infrared cut filter and a color filter.

When the cured film of the present invention is used in combination with a color filter, it is preferable that the color filter is arranged on the optical path of the cured film of the present invention. For example, the cured film of the present invention and a color filter can be laminated and used as a laminated body. In the laminated body, the cured film of the present invention and the color filter may or may not be adjacent to each other in the thickness direction. When the cured film of the present invention and the color filter are not adjacent to each other in the thickness direction, the cured film of the present invention may be formed on a support different from the support on which the color filter is formed. Other members (for example, a microlens, a flattening layer, etc.) constituting the solid-state image sensor may be interposed between the cured film of the present invention and the color filter.

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 blocks at least a part of light having a wavelength in the near-infrared region (near infrared light). .. The near-infrared cut filter may transmit all the light having a wavelength in the visible region, and among the light having a wavelength in the visible region, it transmits the light in a specific wavelength region and blocks the light in the specific wavelength region. It may be something to do. Further, in the present invention, the color filter means a filter that transmits light in a specific wavelength region and blocks light in a specific wavelength region among light having a wavelength in the visible region. Further, in the present invention, the infrared transmission filter means a filter that blocks visible light and transmits at least a part of near infrared rays.

Since the cured film of the present invention is excellent in adhesion to glass containing copper and water resistance, it is preferable to use it by laminating it on glass containing copper. Examples of the copper-containing glass include copper-containing phosphate glass and copper-containing fluoride glass. The copper content in the copper-containing glass is preferably 0.1 to 20% by mass, more preferably 0.3 to 17% by mass, and 0.5 to 15% by mass. Is more preferable.

The copper-containing glass preferably has a maximum absorption wavelength in the wavelength range of 700 to 1100 nm. The lower limit is preferably 800 nm or more, and more preferably 900 nm or more. The upper limit is preferably 1050 nm or less, and more preferably 1000 nm or less.

Specific examples of the glass containing copper include the following.
(1) In mass%, P ₂ O ₅ 46 to 70%, AlF ₃ 0.2 to 20%, ΣRF (R = Li, Na, K) 0 to 25%, Σ R'F ₂ (R'= Mg, Ca, Sr, Ba, Pb) 1 to 50%, CuO 0.5 to 7 parts by mass on the outside, with respect to 100 parts by mass of the base glass containing F 0.5 to 32% and O 26 to 54%. Including glass.
(2) By mass%, P ₂ O ₅ 25-60%, Al ₂ O ₃ 1-13%, MgO 1-10%, CaO 1-16%, BaO 1-26%, SrO 0-16%, ZnO _{0~16%, Li 2 O 0~13%} , Na 2 O 0~10%, K 2 O 0~11%, CuO 1~7%, ΣRO (R = Mg, Ca, Sr, Ba) 15~40 _{%, ΣR '2 O (R} ' = Li, Na, K) 3~18% ( provided that 39% molar amount to the O ^2- ions are substituted by F) glass consisting of.
(3) By mass%, P ₂ O ₅ 5 to 45%, AlF _{3 1 to} 35%, ΣRF (R = Li, Na, K) 0 to 40%, ΣR'F ₂ (R'= Mg, Ca, Sr, Ba, Pb, Zn) 10 to 75%, R "F _m (R" = La, Y, Cd, Si, B, Zr, Ta, m are numbers corresponding to the valence of R ") 0 to 15 % (However, up to 70% of the total fluoride meter can be replaced with oxide), and glass containing 0.2 to 15% CuO.
(4) In% of cations, P ⁵⁺ 11-43%, Al ³⁺ 1-29%, ΣR cations (R = Mg, Ca, Sr, Ba, Pb, Zn) 14-50%, ΣR'cations (R) '= Li, Na, K) 0-43%, ΣR "cation (R" = La, Y, Gd, Si, B, Zr, Ta) 0-8%, and Cu ²⁺ 0.5-13% A glass containing, and further ^{containing 17-80% F-17 in% anion.}
(5) Cation%, P ⁵⁺ 23-41%, Al ³⁺ 4-16%, Li ⁺ 11-40%, Na ⁺ 3-13%, ΣR cation (R = Mg, Ca, Sr, Ba, Zn) twelve to fifty-three%, and comprises Cu ²⁺ 2.6 to 4.7%, ^F further anionic% - 25-48%, and O ^2-52-75% glass containing.
(6) By mass%, P ₂ O ₅ 70 to 85%, Al ₂ O ₃ 8 to 17%, B ₂ O ₃ 1 to 10%, Li ₂ O 0 to 3%, Na ₂ O 0 to 5%, K ₂ O 0 to 5%, but CuO is added to 100 parts by mass of the base glass consisting of _{ΣR 2} O (R = Li, Na, K) 0.1 to 5% and SiO _{20 to 3%.} Glass containing 0.1 to 5 parts by mass.

As the glass containing copper, a commercially available product can also be used. Examples of commercially available copper-containing glass include NF-50 (manufactured by AGC Techno Glass Co., Ltd.) and the like.

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

<Manufacturing method of cured film>
Next, the method for producing the cured film of the present invention will be described. The method for producing a cured film of the present invention includes a step of applying the curable composition of the present invention described above to form a curable composition layer, and a step of heat-curing the curable composition layer.

In the method for producing a cured film, the curable composition is preferably applied on a support. Examples of the support include a base material made of a material such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, and quartz glass, and a glass base material containing copper. An organic film, an inorganic film, or the like may be formed on these substrates. Examples of the material of the organic film include the above-mentioned resin. Further, as the support, a base material made of the above-mentioned resin can also be used. Further, the support may be formed with a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like. Further, the support may be formed with a black matrix that isolates each pixel. Further, if necessary, the support may be provided with an undercoat layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the substrate. In the present invention, it is preferable to use a glass base material containing copper as a support. Conventionally, it has been difficult to form a cured film having good adhesion to a glass substrate containing copper, but the cured film of the present invention also has adhesion to a glass substrate containing copper. The effect of the present invention is more remarkable because it is excellent in water resistance and adhesion.

As a method of applying the curable composition to the support, a known method can be used. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, Japanese Patent Application Laid-Open No. 2009-145395). Methods described in the publication); Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Various printing methods; transfer method using a mold or the like; nano-imprint method and the like can be mentioned. The application method for inkjet is not particularly limited, and for example, the method shown in "Expandable / Usable Inkjet-Infinite Possibilities Seen in Patents-, Published in February 2005, Sumi Betechno Research" (especially from page 115). (Page 133), and the methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned. Further, regarding the method of applying the curable composition, the description of International Publication WO2017 / 0307174 and International Publication WO2017 / 018419 can be referred to, and the contents thereof are incorporated in the present specification.

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

In the step of heat-curing the curable composition layer, the heating temperature is preferably, for example, 100 to 240 ° C. From the viewpoint of film curing, 180 to 230 ° C. is more preferable. The heating time is preferably 2 to 10 minutes, more preferably 4 to 8 minutes. The heat hardening treatment can be performed on a hot plate, an oven, or the like.

The method for producing a cured film of the present invention may further include a step of forming a pattern. Examples of the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method. When a pattern is formed by a photolithography method, it is preferable to heat-cure the curable composition layer after forming the pattern. When forming a pattern by a dry etching method, it is preferable to form the pattern after heat-curing the curable composition layer. When the cured film of the present invention is used as a flat film, it is not necessary to perform the step of forming the pattern. Hereinafter, the process of forming the pattern will be described in detail.

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

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

<Near infrared cut filter>
Next, the near-infrared cut filter of the present invention will be described. The near-infrared cut filter of the present invention includes the cured film of the present invention. The near-infrared cut filter of the present invention preferably has the cured film of the present invention on the support. Examples of the support include a base material made of a material such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, and quartz glass, and a glass base material containing copper, and glass containing copper. The base material is preferable.

In addition to the cured film of the present invention, the near-infrared cut filter of the present invention may further have a dielectric multilayer film, an ultraviolet absorbing layer, and the like. Since the near-infrared cut filter further has a dielectric multilayer film, it is easy to obtain a near-infrared cut filter having a wide viewing angle and excellent infrared shielding property. Further, since the near-infrared cut filter further has an ultraviolet absorbing layer, it can be a near-infrared cut filter having excellent ultraviolet shielding properties. As the ultraviolet absorbing layer, for example, the absorbing layer described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication WO2015 / 09960 can be referred to, and the contents thereof are incorporated in the present specification. As the dielectric multilayer film, the description in paragraphs 025 to 0259 of JP2014-413118A can be referred to, and the contents thereof are incorporated in the present specification.

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

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

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

<Image display device>
The image display device of the present invention includes the cured film of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device. For details and definitions of image display devices, see, for example, "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., 1990)", "Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd., 1989)" ) ”And so on. The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology". The image display device may have a white organic EL element. The white organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, Japanese Patent Application Laid-Open No. 2003-45676, supervised by Akiyoshi Mikami, "Frontiers of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association, It is described on pages 326-328, 2008 and the like. The spectrum of white light emitted by the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm-485 nm), the green region (530 nm-580 nm), and the yellow region (580 nm-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm-700 nm) are more preferable.

<Infrared sensor>
The infrared sensor of the present invention includes the cured film of the present invention described above. The configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. Hereinafter, an embodiment of the infrared sensor of the present invention will be described with reference to the drawings.

In FIG. 1, reference numeral 110 is a solid-state image sensor. The imaging region provided on the solid-state image sensor 110 includes a near-infrared cut filter 111 and an infrared transmission filter 114. Further, a color filter 112 is laminated on the near infrared cut filter 111. A microlens 115 is arranged on the incident light hν side of the color filter 112 and the infrared transmission filter 114. The flattening layer 116 is formed so as to cover the microlens 115.

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

The color filter 112 is a color filter on which pixels that transmit and absorb light of a specific wavelength in the visible region are formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used. For example, the description in paragraphs 0214 to 0263 of JP2014-043556 can be referred to, and 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 the infrared LED used.

In the infrared sensor shown in FIG. 1, a near-infrared cut filter (another near-infrared cut filter) different from the near-infrared cut filter 111 may be further arranged on the flattening layer 116. Other near-infrared cut filters include those having a copper-containing layer and / or a dielectric multilayer film. These details include those mentioned above. Further, as another near-infrared cut filter, a dual bandpass filter may be used. Further, in the infrared sensor shown in FIG. 1, the positions of the near infrared cut filter 111 and the color filter 112 may be interchanged. Further, another layer may be arranged between the solid-state image sensor 110 and the near-infrared cut filter 111 and / or between the solid-state image sensor 110 and the infrared transmission filter 114. Examples of the other layer include an organic layer formed by using a composition containing a polymerizable compound, a resin and a photopolymerization initiator. Further, a flattening layer may be formed on the color filter 112.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed 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, "parts" and "%" are based on mass. In the structural formula, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

<Preparation of composition>
The raw materials shown in the table below are mixed and stirred at the ratios (parts by mass) shown in the table below, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to obtain each composition. Prepared.

The raw materials listed in the above table are as follows.

(Near infrared absorbing pigment)
A1 to A18, A20 to A22: Compounds having the following structures.
A19: NK-5060 (manufactured by Hayashibara Co., Ltd., cyanine compound)

・樹脂２：下記構造の樹脂（重量平均分子量３３１００、繰り返し単位に付記した数値はモル数である）のシクロペンタノン３０質量％溶液。

(resin)
-Resin 1: A cyclopentanone 30% by mass solution of a resin having the following structure (weight average molecular weight 41,400, the numerical value added to the repeating unit is the number of moles).

-Resin 2: A cyclopentanone 30% by mass solution of a resin having the following structure (weight average molecular weight 33100, the numerical value added to the repeating unit is the number of moles).

(Organic solvent)
-Organic solvent 1: Cyclopentanone-Organic solvent 2: 3-Methoxy-N, N-dimethylpropanamide-Organic solvent 3: 3-Butoxy-N, N-dimethylpropanamide

(Compound having a cyclic ether group)
Compound 1: EPICLON HP5000 having a cyclic ether group (manufactured by DIC Corporation, naphthalene-modified epoxy resin, number of aromatic rings in one repeating unit = 3, epoxy group value = 245 to 260 g / mol)
-Compound 2: having a cyclic ether group: EPICLON HP4032D (manufactured by DIC Corporation, naphthalene-modified epoxy resin, number of aromatic rings in one repeating unit = 2, epoxy group value = 136 to 148 g / mol)
-Compound 3: having a cyclic ether group: EPICLON HP820 (manufactured by DIC Corporation, alkyldiphenol type epoxy resin, number of aromatic rings in one repeating unit = 2, epoxy base value = 200 to 250 g / mol)
Compound 4: having a cyclic ether group: EPOLEAD PB 4700 (manufactured by Daicel Co., Ltd., butadiene type epoxy resin, number of aromatic rings = 0, epoxy group value = 152-178 g / mol)
Compound 5 having a cyclic ether group: EPICLON N-695 (manufactured by DIC Corporation, cresol novolac type epoxy resin, number of aromatic rings in one repeating unit = 1, epoxy base value = 209 to 219 g / mol)
-Compound 6: having a cyclic ether group: EH3150 (manufactured by Daicel Co., Ltd., cyclohexanone type resin, number of aromatic rings = 0, epoxy group value = 170 to 190 g / mol)

(Radical polymerizable compound)
Radical Polymerizable Compound 1: Mixture of the following compounds (mixture of left side compound and right side compound with a molar ratio of 7: 3)

ラジカル重合性化合物３：下記化合物

ラジカル重合性化合物４：下記化合物

（開始剤）
・開始剤１：ＩＲＧＡＣＵＲＥ−１８４（ＢＡＳＦ社製、α−ヒドロキシアセトフェノン化合物、波長３６５ｎｍにおけるモル吸光係数＝１９．５Ｌ・ｍｏｌ^-1・ｃｍ^-1、熱分解温度＝１５１℃、熱ラジカル重合開始剤）
・開始剤２：下記構造の化合物（ピナコール化合物、波長３６５ｎｍにおけるモル吸光係数＝１０Ｌ・ｍｏｌ^-1・ｃｍ^-1以下、熱分解温度＝１８２℃、熱ラジカル重合開始剤）

・開始剤３：パーブチルＯ（日油（株）製、有機過酸化物、波長３６５ｎｍにおけるモル吸光係数＝５Ｌ・ｍｏｌ^-1・ｃｍ^-1以下、熱分解温度＝１０５℃、熱ラジカル重合開始剤）
・開始剤４：Ｖ−６０１（和光純薬工業（株）製、アゾ化合物、波長３６５ｎｍにおけるモル吸光係数＝６Ｌ・ｍｏｌ^-1・ｃｍ^-1以下、熱分解温度＝９０℃、熱ラジカル重合開始剤）
・開始剤５：ＩＲＧＡＣＵＲＥ−ＯＸＥ０１（ＢＡＳＦ社製、オキシム化合物、光ラジカル重合開始剤） Radical Polymerizable Compound 2: Mixture of the following compounds (height ratio by high performance liquid chromatography: 46.15: 49.39 :: 4.46)

Radical Polymerizable Compound 3: The following compounds

Radical Polymerizable Compound 4: The following compounds

(Initiator)
Initiator 1: IRGACURE-184 (BASF, α-hydroxyacetophenone compound, molar extinction coefficient at a wavelength of 365 nm = 19.5 L · mol ^-1 · cm ^-1 , thermal decomposition temperature = 151 ° C., thermal radical polymerization initiator )
Initiator 2: A compound having the following structure (pinacol compound, molar extinction coefficient at a wavelength of 365 nm = 10 L · mol ^-1 · cm ^-1 or less, pyrolysis temperature = 182 ° C., thermal radical polymerization initiator)

Initiator 3: Perbutyl O (manufactured by Nichiyu Co., Ltd., organic peroxide, molar absorption coefficient at a wavelength of 365 nm = 5 L · mol ^-1 · cm ^-1 or less, thermal decomposition temperature = 105 ° C., thermal radical polymerization initiator )
-Initiator 4: V-601 (manufactured by Wako Pure Chemical Industries, Ltd., azo compound, molar absorption coefficient at a wavelength of 365 nm = 6 L · mol ^-1 · cm ^-1 or less, thermal decomposition temperature = 90 ° C., thermal radical polymerization initiation Agent)
Initiator 5: IRGACURE-OXE01 (BASF, oxime compound, photoradical polymerization initiator)

-Silane coupling agent: ureidopropyltrimethoxysilane

Surfactant: A polymer having a repeating unit represented by the following formula (B1-1) and a repeating unit represented by the following formula (B3-1) (weight average molecular weight = 7,400 g / mol, B1- 1: B3-1 = 92.5: 7.5 (molar ratio)) propylene glycol monomethyl ether acetate (PGMEA) 30% by mass solution. In the following formula (B3-1), X represents any of −CF ₂ −CF ₂ −, _{−CF 2} −, and −CH ₂ −CF ₂ −, and r represents the number of repeating units. For X, -CF ₂ -CF ₂ - and, -CF ₂ - and, -CH ₂ -CF ₂ - ratio of the number of _{is, -CF 2 -CF 2 -: -} CF 2 -: - CH 2 - CF _2- = 4.2: 1.9: 1.0.

-Polymerization inhibitor 1: p-methoxyphenol

・下記構造の顔料誘導体・・・・３．５質量部

・分散剤（下記構造の樹脂、重量平均分子量２２，９００、主鎖の繰り返し単位に付記した数値はモル数であり、側鎖の繰り返し単位に併記される数値は、繰り返し単位の繰り返し数を示す。）・・・７．２質量部

・シクロヘキサノン ・・・７７．７７質量部 (Dispersion liquid 1)
The raw material having the following composition is dispersed and dispersed over 2 hours with a bead mill (high pressure disperser NANO-3000-10 with decompression mechanism (manufactured by Nippon BEE Co., Ltd.)) using zirconia beads having a diameter of 0.3 mm. Liquid 1 was prepared.
-Composition of dispersion 1-
-Near-infrared absorbing dye with the following structure (average primary particle size 200 nm): 11.6 parts by mass

-Pigment derivative with the following structure ... 3.5 parts by mass

Dispersant (resin having the following structure, weight average molecular weight 22,900, the numerical value added to the repeating unit of the main chain is the number of moles, and the numerical value added to the repeating unit of the side chain indicates the number of repeating units of the repeating unit. .) ・ ・ ・ 7.2 parts by weight

-Cyclohexanone: 77.77 parts by mass

(Dispersion liquid 2)
C. I. 60 parts by mass of Pigment Black 32, C.I. I. Pigment Blue 15: 6, 20 parts by mass, C.I. I. 20 parts by mass of Pigment Yellow 139, 80 parts by mass of Solsperse 76500 (manufactured by Nippon Lubrizol Co., Ltd., solid content concentration 50% by mass), and 700 parts by mass of propylene glycol monomethyl ether acetate are mixed and 8 by mass using a paint shaker. After time dispersion, dispersion liquid 2 was obtained.

<Evaluation of water resistance>
Each curable composition is applied onto a fluorophosphate glass substrate (product name: NF-50, manufactured by AGC Techno Glass, 50 mm × 50 mm in size, 0.05 mm in thickness, and a glass substrate containing copper). Then, spin coat was applied with a Mikasa coater so that the film thickness after film formation was 2.5 μm, dried at 100 ° C. for 120 seconds using a hot plate, and then heated at 220 ° C. for 5 minutes to cure the film. Manufactured.
The fluorophosphate glass substrate on which the cured film was formed was immersed in water at 95 ° C. for 1 hour, cross-cut into 100 squares of 1 mm × 1 mm, and Nichiban's plant-based cellophane tape (registered trademark) No. A tape peeling test was conducted using 405, and the water resistance and adhesion were evaluated according to the following criteria.
5: The number of peeled squares is 0 4: The number of peeled squares is 1 to 5 3: The number of peeled squares is 6 to 10 2: The number of peeled squares is 11 to 1 30 pieces 1: The number of peeled squares is 31 or more

<Evaluation of aggregation size>
Each curable composition is applied onto a fluorophosphate glass substrate (product name: NF-50, manufactured by AGC Techno Glass, 50 mm × 50 mm in size, 0.05 mm in thickness, and a glass substrate containing copper). Then, spin coat was applied with a Mikasa coater so that the film thickness after film formation was 2.5 μm, dried at 100 ° C. for 120 seconds using a hot plate, and then heated at 220 ° C. for 5 minutes to cure the film. Manufactured.
The fluorophosphate glass substrate on which the cured film was formed was immersed in acetone at 23 ° C. for 5 minutes, and then an acceleration voltage of 2.0 kV was used using an ultra-high resolution scanning electron microscope (manufactured by Hitachi High-Technologies Corporation). The cross section of the membrane was observed at an observation magnification of 50,000 times, the lengths of the perforated shapes at arbitrary three locations in the major axis direction were measured, and the average value was calculated as the aggregation size.

As shown in the above table, all of the examples had good water resistance and adhesion, and a cured film having a small aggregation size could be produced.
In Example 1, even if the initiator of Example 17 shown in Special Table 2014-521772 was used instead of the initiator 2, the same effect as that of Example 1 was obtained.

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

Claims (19)

A curable composition containing a near-infrared absorbing dye, a compound having a cyclic ether group, a radically polymerizable compound, and a thermal radical polymerization initiator.
The content of the near-infrared absorbing dye is 3 to 35% by mass with respect to the total solid content of the curable composition.
The content of the radically polymerizable compound is 20 to 300 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye.
The content of the compound having a cyclic ether group is 5 to 500 parts by mass with respect to 100 parts by mass of the near-infrared absorbing dye.
The curable composition does not contain a coloring material that blocks visible light.
Curable composition. The curable composition according to claim 1, wherein the cyclic ether group is an epoxy group. The curable composition according to claim 1 or 2, wherein the compound having a cyclic ether group is a compound containing an aromatic ring. The curable composition according to any one of claims 1 to 3, which contains 1 to 100 parts by mass of the radically polymerizable compound with respect to 100 parts by mass of the compound having a cyclic ether group. The curable composition according to any one of claims 1 to 4, which contains 0.05 to 200 parts by mass of the thermal radical polymerization initiator with respect to 100 parts by mass of the radically polymerizable compound. The curable composition according to any one of claims 1 to 5, wherein the content of the thermal radical polymerization initiator is 0.1 to 10% by mass with respect to the total solid content of the curable composition. The curable composition according to any one of claims 1 to 6, wherein the molar extinction coefficient of the thermal radical polymerization initiator at a wavelength of 365 nm is 100 L · mol ^-1 · cm ^{-1 or less.} The curable composition according to any one of claims 1 to 7, wherein the thermal decomposition temperature of the thermal radical polymerization initiator is 120 to 270 ° C. The curable composition according to any one of claims 1 to 8, wherein the thermal radical polymerization initiator is at least one selected from a pinacol compound and an α-hydroxyacetophenone compound. The curable composition according to any one of claims 1 to 9, wherein the near-infrared absorbing dye is a compound having a π-conjugated plane containing an aromatic ring of a monocyclic ring or a condensed ring. The curable composition according to any one of claims 1 to 10, wherein the near-infrared absorbing dye is at least one selected from a pyrrolopyrrole compound, a squarylium compound, and a cyanine compound. A cured film obtained from the curable composition according to any one of claims 1 to 11. A step of applying the curable composition according to any one of claims 1 to 11 on a support to form a curable composition layer, and a step of forming the curable composition layer.
A method for producing a cured film, which comprises a step of heat-curing the curable composition layer. The method for producing a cured film according to claim 13, wherein the support is a glass base material containing copper. A near-infrared cut filter having the cured film according to claim 12. The near-infrared cut filter according to claim 15, which has the cured film on the surface of a glass substrate containing copper. The solid-state image sensor having the cured film according to claim 12. An image display device having the cured film according to claim 12. The infrared sensor having the cured film according to claim 12.

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