JP7142740B2 - Curable composition, cured film, method for producing cured film, near-infrared cut filter, solid-state imaging device, image display device, and infrared sensor - Google Patents

Description

TECHNICAL FIELD 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 imaging device, an image display device, and an infrared sensor.

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

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

International publication WO2014/199937

In recent years, as one of the properties required for near-infrared cut filters, improved water-resistant adhesion to a support has been desired.

Further, according to the studies of the present inventors, it was 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 during film formation. In particular, when heat is applied during film formation, the near-infrared absorbing dye tends to agglomerate. When the size of aggregates derived from the near-infrared absorbing dye in the film increases, the spectral characteristics may vary and the smoothness of the film surface may decrease. Furthermore, when the size of the aggregates increases, the aggregates are likely to peel off from the film, and there is a risk that pores of the size of the aggregates may be generated where the aggregates were present.

SUMMARY OF THE INVENTION Accordingly, 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 aggregates 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 imaging device, an image display device, and an infrared sensor.

According to studies by the present inventors, a cured film obtained 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, The inventors have found that the water-resistant adhesiveness is good and the amount of aggregates derived from near-infrared absorbing dyes is small, leading to the completion of the present invention. Accordingly, the present invention provides the following.
<1> A curable composition comprising 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>, containing 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.
<5> The curable composition according to any one of <1> to <4>, containing 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 pinacol compounds and α-hydroxyacetophenone compounds.
<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 a monocyclic or condensed aromatic 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 pyrrolopyrrole compounds, squarylium compounds and cyanine compounds.
<9> A cured film obtained from the curable composition according to any one of <1> to <8>.
<10> applying the curable composition according to any one of <1> to <8> onto a support to form a curable composition layer;
and 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 copper-containing glass substrate.
<12> A near-infrared cut filter having the cured film according to <9>.
<13> The near-infrared cut filter according to <12>, having the cured film on the surface of a glass substrate containing copper.
<14> A solid-state imaging device having the cured film according to <9>.
<15> An image display device comprising the cured film according to <9>.
<16> An infrared sensor comprising 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 a near-infrared absorbing dye. In addition, the present invention can provide a cured film, a method for producing a cured film, a near-infrared cut filter, a solid-state imaging device, an image display device, and an infrared sensor.

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

The contents of the present invention will be described in detail below.
In this specification, a numerical range represented by "to" means a range including the numerical values before and after "to" as lower and upper limits.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, the term “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
In the present specification, "(meth)acrylate" represents both or either acrylate and methacrylate, "(meth)acryl" represents both or either acrylic and methacrylic, and "(meth) ) Allyl” represents both or either of allyl and methallyl, and “(meth)acryloyl” represents both or either of acryloyl and methacryloyl.
In this specification, the weight average molecular weight and number average molecular weight are defined as polystyrene equivalent values in gel permeation chromatography (GPC) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, using HLC-8220 (manufactured by Tosoh Corporation) and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6 .0 mm ID (inner diameter)×15.0 cm) and 10 mmol/L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
As used herein, near-infrared light refers to light with a wavelength of 700 to 2,500 nm.
As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent.
In this specification, the term "step" not only represents an independent step, but even if it cannot be clearly distinguished from other steps, if the intended action of the step is achieved, the term include.

<Curable composition>
The curable composition of the present invention is characterized by comprising 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-resistant adhesion and less aggregates derived from the near-infrared absorbing dye.
The reason why such an effect is obtained is presumed to be 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 generated from the thermal radical polymerization initiator generate radicals. The polymerization reaction of the polymerizable compound proceeds quickly, 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. In addition, a compound having a cyclic ether group has a slower curing rate than a radically polymerizable compound, but a compound having a cyclic ether group is considered to interact easily with the near-infrared absorbing dye. It is presumed that curing of the compound having a cyclic ether group proceeds at . Therefore, it is presumed that the curable composition of the present invention can effectively suppress the aggregation of the near-infrared absorbing dye during heating, and can produce a cured film with less aggregates derived from the near-infrared absorbing dye. be.
In addition, the cyclic ether group of the compound having a cyclic ether group readily reacts with a hydroxyl group on the support, and is presumed to provide excellent adhesion to the support. In addition, since a compound having a cyclic ether group is a compound that is resistant to curing shrinkage, it is speculated that a cured film that is resistant to curing shrinkage could be formed by including a compound having a cyclic ether group in the curable composition. be done. In addition, since a cured film having a high cross-linking density can be formed by the radically polymerizable compound, it is possible to effectively suppress the entry of water into the film. Thus, according to the present invention, a cured film having high adhesion to the support can be formed on the support while suppressing cure shrinkage. It is presumed that the infiltration of water into the interface between the support and the cured film could be effectively suppressed, and therefore excellent water-resistant adhesion was obtained. Each component of the curable composition of the present invention is described below.

<<Near-infrared absorption dye>>
The curable composition of the 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 together. When a near-infrared absorbing dye and a near-infrared absorbing pigment are used in combination, the mass ratio of the near-infrared absorbing dye and the near-infrared absorbing pigment is near-infrared absorbing dye:near-infrared absorbing pigment=99.9:0.1 to 0.1. It is preferably 1:99.9, more preferably 99.9:0.1 to 10:90, 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 2 g or more. It is more preferable that the amount is 5 g or more. Further, the near-infrared absorbing pigment preferably has a solubility of less than 1 g, more preferably 0.1 g or less, in 100 g of each solvent of cyclopentanone, cyclohexanone, and dipropylene glycol monomethyl ether at 23°C. 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 a monocyclic or condensed aromatic ring. Due to the interaction between the aromatic rings on the π-conjugated plane of the near-infrared absorbing dye, the J-aggregate of the near-infrared absorbing dye is easily formed during the production of the cured film, producing a cured film with excellent spectral characteristics in the near-infrared region. can. Moreover, it is easy to interact with compounds having a cyclic ether group, and is easy to form a cured film having superior water-resistant adhesion. In particular, when a compound having an aromatic ring is used as the compound having a cyclic ether group, it is likely to interact more strongly with the compound having a cyclic ether group, and water-resistant adhesion can be significantly 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. More preferably, the number is 30 or more, and particularly preferably 30 or more. The upper limit is, for example, preferably 80 or less, more preferably 50 or less.

The π-conjugated plane of the near-infrared absorbing dye preferably contains 2 or more monocyclic or condensed aromatic rings, more preferably 3 or more, more preferably 4 or more, and 5 or more. It is particularly preferred to include The upper limit is preferably 100 or less, more preferably 50 or less, even more preferably 30 or less. Examples of the above aromatic rings include benzene ring, naphthalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, quaterrylene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzoxazole ring, imidazoline ring, pyrazine ring, quinoxaline ring, pyrimidine ring, quinazoline ring, pyridazine ring, triazine ring, pyrrole ring, indole ring, isoindole ring, carbazole ring, and condensed rings 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, more preferably a compound having a maximum absorption wavelength in the wavelength range of 700 to 1,000 nm. In this specification, "having a maximum absorption wavelength in the wavelength range of 700 to 1,300 nm" means that, in the absorption spectrum of the near-infrared absorbing dye solution, the wavelength showing the maximum absorbance is the wavelength of 700 to It means that it is in the range of 1,300 nm. Chloroform, methanol, dimethylsulfoxide, ethyl acetate, and tetrahydrofuran are examples of measurement solvents used for measuring absorption spectra in solutions of near-infrared absorbing dyes. When the near-infrared absorbing dye is a compound that dissolves in chloroform, chloroform is used as the measurement solvent. Methanol is used for compounds that do not dissolve in chloroform. In addition, dimethylsulfoxide is used when it does not dissolve in either chloroform or methanol.

The near-infrared absorbing dye has a maximum absorption wavelength in the wavelength range of 700 to 1,000 nm, and the ratio A ¹ /A ² of the absorbance A ¹ at a wavelength of 500 nm to the absorbance A ² at the maximum absorption wavelength is 0.5. It is preferably 08 or less, 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 properties.

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 resulting cured film is broader than when one type of near-infrared absorbing dye is used, and near-infrared rays in a wide wavelength range can be shielded. When using at least two compounds with different maximum absorption wavelengths, the first near-infrared absorption dye having a maximum absorption wavelength in the wavelength range of 700 to 1,000 nm, and the first near-infrared absorption dye than the maximum absorption wavelength. It is on the short wavelength side and 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-infrared absorbing dye. The difference from the maximum absorption wavelength of the infrared absorbing dye is preferably 1 to 150 nm.

In the present invention, near-infrared absorbing dyes include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, diimmonium compounds, dithiol compounds, triarylmethane compounds, At least one selected from pyrromethene compounds, azomethine compounds, anthraquinone compounds and dibenzofuranone compounds is preferred, and at least one selected from pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds and quaterrylene compounds is more preferred, At least one selected from pyrrolopyrrole compounds, cyanine compounds and squarylium compounds is more preferred, and pyrrolopyrrole compounds are particularly preferred. Diimmonium compounds include, for example, compounds described in JP-A-2008-528706, the content of which is incorporated herein. Examples of the phthalocyanine compound include compounds described in paragraph number 0093 of JP-A-2012-77153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraph numbers 0013 to 0029 of JP-A-2013-195480. and vanadium phthalocyanines described in Japanese Patent No. 6081771, the contents of which are incorporated herein. Examples of naphthalocyanine compounds include compounds described in paragraph number 0093 of JP-A-2012-77153, the contents of which are incorporated herein. In addition, as the cyanine compound, phthalocyanine compound, naphthalocyanine compound, diimmonium compound and squarylium compound, compounds described in paragraphs 0010 to 0081 of JP-A-2010-111750 may be used, the contents of which are herein described. incorporated. In addition, the cyanine compound, for example, "Functional dyes, Makoto Okawara / Ken Matsuoka / Teijiro Kitao / Kosuke Hirashima, Kodansha Scientific" can be considered, the contents of which are incorporated herein. . Further, as the near-infrared absorbing dye, compounds described in JP-A-2016-146619 can also be used, the contents of which are incorporated herein. A compound having the following structure is also preferably used 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 formula (PP).

In the formula, R ^1a and R ^1b each 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 are Each R ⁴ independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR ^4A R ^4B , or a metal atom, and R ⁴ is R It may be covalently or coordinately bonded to at least one selected from ^1a , R ^1b and R ³ , and R ^4A and R ^4B each independently represent a substituent. R ^4A and R ^4B may combine with each other to form a ring. For details of the formula (PP), paragraph numbers 0017 to 0047 of JP 2009-263614, paragraph numbers 0011 to 0036 of JP 2011-68731, paragraph numbers 0010 to 0024 of WO2015/166873 can be referred to, and the contents thereof are incorporated herein.

In formula (PP), R ^1a and R ^1b are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group. In addition, 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 substituent T.

(substituent T)
Alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms), alkenyl groups (preferably alkenyl groups having 2 to 30 carbon atoms), alkynyl groups (preferably alkynyl groups having 2 to 30 carbon atoms), aryl groups (preferably aryl group having 6 to 30 carbon atoms), amino group (preferably amino group having 0 to 30 carbon atoms), alkoxy group (preferably alkoxy group having 1 to 30 carbon atoms), aryloxy group (preferably 6 to 30 aryloxy group), heteroaryloxy group, acyl group (preferably an acyl group having 1 to 30 carbon atoms), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably 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), an alkoxycarbonylamino group (preferably alkoxycarbonylamino group having 2 to 30 carbon atoms), aryloxycarbonylamino group (preferably aryloxycarbonylamino group having 7 to 30 carbon atoms), sulfamoyl group (preferably sulfamoyl group having 0 to 30 carbon atoms), 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 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, imidic acid group, mercapto group, halogen atom, cyano group, alkylsulfino group, arylsulfino group, hydrazino group, imino group, a heteroaryl group (preferably having 1 to 30 carbon atoms); These groups may have further substituents if they are substitutable groups. Examples of the substituent include the groups described for the substituent T described above.

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, and an aryl group having an acyloxy group as a substituent.

In formula (PP), R ² and R ³ each independently represent a hydrogen atom or a substituent. Examples of the substituent include the substituent T described above. At least one of R ² and R ³ is preferably an electron-withdrawing group. A substituent having a positive Hammett's substituent constant σ value (sigma value) acts as an electron-withdrawing group. Here, there are a σp value and a σm value as substituent constants determined by Hammett's rule. These values can be found in many popular books. In the present invention, a substituent having a Hammett's substituent constant σ value of 0.2 or more can be exemplified as an electron-withdrawing group. The σ value is preferably 0.25 or more, more preferably 0.3 or more, and even more preferably 0.35 or more. Although the upper limit is not particularly limited, it is preferably 0.80 or less. Specific examples of the electron-withdrawing group include a cyano group (σp value = 0.66), a carboxyl group (-COOH: σp value = 0.45), an alkoxycarbonyl group (eg, -COOMe: σp value = 0.45). 45), an aryloxycarbonyl group (for example, —COOPh: σp value=0.44), a carbamoyl group (for example, —CONH ₂ : σp value=0.36), an alkylcarbonyl group (for example, —COMe: σp value= 0.50), arylcarbonyl groups (eg —COPh: σp value = 0.43), alkylsulfonyl groups (eg —SO ₂ Me: σp value = 0.72), arylsulfonyl groups (eg —SO ₂ Ph: σp value = 0.68), etc., and a cyano group is preferred. Here, Me represents a methyl group and Ph represents a phenyl group. Regarding Hammett's substituent constant σ value, for example, paragraphs 0017 to 0018 of JP-A-2011-68731 can be referred to, and the contents thereof are incorporated herein.

In formula (PP), R ² preferably represents an electron-withdrawing group (preferably a cyano group), and R ³ preferably represents a heteroaryl group. A heteroaryl group is preferably a 5- or 6-membered ring. The heteroaryl group is preferably a single ring or a condensed ring, preferably a single ring or a condensed ring with 2 to 8 condensed numbers, more preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers. The number of heteroatoms constituting the heteroaryl group is preferably 1-3, more preferably 1-2. Examples of heteroatoms include nitrogen atoms, oxygen atoms, and sulfur atoms. Heteroaryl groups preferably have one or more nitrogen atoms. Two R ² groups in formula (PP) may be the same or different. Two R ³ groups in formula (PP) may be the same or 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 , and is preferably a hydrogen atom, an alkyl group, an aryl group or -BR A group represented by ^4A R ^4B is more preferable, and a group represented by -BR ^4A R ^4B is even more preferable. The substituent represented by R ^4A and R ^4B is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and an aryl group. Especially preferred. These groups may further have a substituent. Two R ⁴ groups in formula (PP) may be the same or different. R ^4A and R ^4B may combine with each other to form a ring.

Specific examples of the compound represented by formula (PP) include the following compounds. In the following structural formulas, Ph represents a phenyl group. Further, as the pyrrolopyrrole compound, compounds described in paragraph numbers 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph numbers 0037-0052 of JP-A-2011-68731, International Publication WO2015/166873 Examples include compounds described in paragraphs 0010 to 0033 of the publication, the contents of which are incorporated herein.

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 each independently represent an aryl group, a heteroaryl group or a group represented by formula (A-1);

In formula (A-1), Z ¹ represents a nonmetallic atomic group forming a nitrogen-containing heterocyclic ring, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, A wavy line represents a link. For details of the formula (SQ), paragraph numbers 0020 to 0049 of JP-A-2011-208101, paragraph numbers 0043 to 0062 of Japanese Patent No. 6065169, and paragraph numbers 0024 to 0040 of WO2016/181987. , the contents of which are incorporated herein.

In formula (SQ), cations are present in a delocalized manner 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;
G ^A and G ^B each independently represent 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 each represent the maximum integer substitutable on ring A or ring B;
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, and when there are a plurality of each of G ^A and G ^B , they are bonded to each other to form a ring structure may form

Substituents represented by G ^A and G ^B include the substituent T described in formula (PP) above.

Substituents represented by X ^A and X ^B are preferably groups having active hydrogen, such as —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 ^X2 are more preferred. R ^X1 and R ^X1 each independently represent a hydrogen atom or a substituent. The substituent represented by X ^A and X ^B includes an alkyl group, an aryl group, or a heteroaryl group, preferably an alkyl group.

Ring A and ring B each independently represent an aromatic ring. The aromatic ring may be monocyclic or condensed. Specific examples of aromatic rings include benzene ring, naphthalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, and 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, indolizine ring, indole ring, benzofuran ring, benzothiophene ring , isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxy A satiine ring, a phenothiazine ring, and a phenazine ring can be mentioned, and a benzene ring or a naphthalene ring is preferred. The aromatic ring may be unsubstituted or may have a substituent. Substituents include the substituent T described in formula (PP) above.

X ^A and G ^A , X ^B and G ^B , and X ^A and X ^B may combine with each other to form a ring, and when there are a plurality of each of G ^A and G ^B , they combine with each other to form a ring. It may be formed. As the ring, a 5- or 6-membered ring is preferred. The ring may be monocyclic or condensed. When X ^A and G ^A , X ^B and G ^B , X ^A and X ^B , G ^A or G ^B are bonded to each other to form a ring, these may be directly bonded to form a ring, and alkylene A group, —CO—, —O—, —NH—, —BR—, and a divalent linking group consisting of a combination thereof may be used to form a ring. R represents a hydrogen atom or a substituent. Examples of the substituent include the substituent T described in formula (PP) above, and an alkyl group or an aryl group is preferable.

kA represents an integer of 0 to nA, kB represents an integer of 0 to nB, nA represents the maximum substitutable integer for ring _A , and nB represents the maximum substitutable integer for ring _B. show. kA and kB are each 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).
Formula (SQ-10)

Formula (SQ-11)

Formula (SQ-12)

In formulas (SQ-10) to (SQ-12), X is independently a formula in which one or more hydrogen atoms may be 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 formula (2).
-( _CH2 ) _n1- (1)
In formula (1), n1 is 2 or 3.
—(CH ₂ ) _n2 —O—(CH ₂ ) _n3 — (2)
In formula (2), n2 and n3 are each independently an integer of 0 to 2, and n2+n3 is 1 or 2.
R ¹ and R ² each independently represent an alkyl group or an aryl group. The alkyl group and aryl group may have a substituent or may be unsubstituted. Substituents include the substituent T described in formula (PP) above.
R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.
n is 2 or 3;

Examples of squarylium compounds include compounds having the following structures. In addition, compounds described in paragraph numbers 0044 to 0049 of JP-A-2011-208101, compounds described in paragraph numbers 0060 to 0061 of Japanese 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 JP-A-2014-126642, compounds described in JP-A-2016-146619, Compounds described in JP-A-2015-176046, compounds described in JP-A-2017-25311, compounds described in International Publication WO2016/154782, compounds described in Patent 5884953, in Patent 6036689 Compounds described, compounds described in Japanese Patent No. 5810604, compounds described in JP-A-2017-068120, and the like, the contents of which are incorporated herein.

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 Formula (C).
Formula (C)

wherein Z ¹ and Z ² are each independently a non-metal atomic group forming an optionally condensed 5- or 6-membered nitrogen-containing heterocyclic ring,
R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group;
L ¹ represents a methine chain with an odd number of methine groups,
a and b are each independently 0 or 1;
When a is 0, the carbon atom and the nitrogen atom are bonded with a double bond, and when b is 0, the carbon atom and the nitrogen atom are bonded with a single bond,
When the site represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents a number necessary to balance the charge, and the site represented by Cy in the formula is an anion moiety , X ¹ represents a cation, c represents a number necessary to balance the charge, and when the charge of the site represented by Cy in the formula is neutralized in the molecule, c is 0.

Specific examples of the cyanine compound include the compounds shown below. Further, as the cyanine compound, compounds described in paragraph numbers 0044 to 0045 of JP-A-2009-108267, compounds described in paragraph numbers 0026-0030 of JP-A-2002-194040, JP-A-2015-172004 Compounds described in, compounds described in JP-A-2015-172102, compounds described in JP-A-2008-88426, compounds described in JP-A-2017-031394, etc., the contents of which are the present incorporated into the specification.

In the present invention, a commercial product can also be used as the near-infrared absorbing dye. For example, SDO-C33 (manufactured by Arimoto Chemical Industry Co., Ltd.), eX Color IR-14, eX Color IR-10A, eX Color TX-EX-801B, eX Color TX-EX-805K (Co., Ltd. ) manufactured by Nippon Shokubai), ShigenoxNIA-8041, ShigenoxNIA-8042, ShigenoxNIA-814, ShigenoxNIA-820, ShigenoxNIA-839 (manufactured by Hakko Chemical Co., Ltd.), Epolite V-63, Epolish3801, Epolight V-63, Epolish3801, Epolight 3036 (manufactured by Fuji EP2L0L) Film Co., Ltd.), NK-3027, NK-5060 (Hayashibara Co., Ltd.), YKR-3070 (Mitsui Chemicals Co., Ltd.), and the like.

As for the near-infrared absorbing dye used in the present invention, the compounds used in the examples described later are also exemplified as preferred compounds.
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, more preferably 5% by mass or more. Only one type of near-infrared absorbing dye may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably 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 near-infrared absorbing dye described above. Other near-infrared absorbers include inorganic pigments (inorganic particles). The shape of the inorganic pigment is not particularly limited, and may be spherical, non-spherical, sheet-like, wire-like, or tube-like. As the inorganic pigment, metal oxide particles or metal particles are preferred. Examples of metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, fluorine-doped tin dioxide (F-doped SnO ₂ ) particles, niobium-doped titanium dioxide (Nb-doped TiO ₂ ) particles, and the like. Examples of metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, nickel (Ni) particles, and the like. A tungsten oxide compound can also be used as the inorganic pigment. The tungsten oxide compound is preferably cesium tungsten oxide. For details of the tungsten oxide-based compound, reference can be made to paragraph number 0080 of JP-A-2016-006476, the content of which is incorporated herein.

When the curable composition of the present invention contains other near-infrared absorbent, the content of the other near-infrared absorbent, relative to the total solid content of the curable composition of the present invention, 0.01 to 50 % by weight 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.
Further, the content of the other near-infrared absorbing agent in the total mass of the 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.
Moreover, it is also preferable that the curable composition of the present invention does not substantially contain other near-infrared absorbing agents. Substantially free of other near-infrared absorbing agents means that the content of other near-infrared absorbing agents in the total weight of the above-mentioned near-infrared absorbing dye and other near-infrared absorbing agents is 0.5% by mass or less. and more preferably 0.1% by mass or less, and further preferably contain no other near-infrared absorbing agent.

<<Radical polymerizable compound>>
The curable composition of the 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. A compound having 3 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, more preferably 6 or less. The group having an ethylenically unsaturated bond includes a vinyl group, a styryl group, a (meth)allyl group, a (meth)acryloyl group and the like, and a (meth)acryloyl group is preferred. The radically polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.

The radically polymerizable compound may be in the form of either a monomer or a polymer, but a monomer is preferred. 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. Also, the radically polymerizable compound is preferably a compound having substantially no molecular weight distribution. Here, the compound having substantially no molecular weight distribution is preferably a compound having a degree of dispersion (weight average molecular weight (Mw)/number average molecular weight (Mn)) of 1.0 to 1.5. 1.0 to 1.3 is more preferable.

Examples of the radically polymerizable compound can refer to paragraphs 0033 to 0034 of JP-A-2013-253224, the contents of which are incorporated herein. Examples of radically polymerizable compounds include ethyleneoxy-modified pentaerythritol tetraacrylate (as a commercial product, NK Ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (as a commercial product, KAYARAD D- 330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; Shin Nakamura Chemical Industry ( 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 preferred. These oligomeric types can also be used. In addition, the description of paragraphs 0034 to 0038 of Japanese Patent Laid-Open No. 2013-253224 can be taken into consideration, and the contents thereof are incorporated into this specification. In addition, the polymerizable monomers described in paragraph number 0477 of JP-A-2012-208494 (corresponding US Patent Application Publication No. 2012/0235099 paragraph number 0585), etc., are described herein. incorporated into. In addition, diglycerin EO (ethylene oxide)-modified (meth)acrylate (as a commercial product, M-460; manufactured by Toagosei), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT), 1,6 -Hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) is also preferred. These oligomeric types can also be used. Examples thereof include RP-1040 (manufactured by Nippon Kayaku Co., Ltd.).

The radically polymerizable compound may have an acid group such as a carboxyl group, a sulfo group and a phosphoric acid group. Examples of commercially available radically polymerizable compounds having an acid group include Aronix M-305, M-510 and M-520 (manufactured by Toagosei Co., Ltd.). The acid value of the radical polymerizable compound is preferably 0.1 to 40 mgKOH/g. More preferably, the lower limit is 5 mgKOH/g or more. The upper limit is more preferably 30 mgKOH/g or less.

A preferred embodiment of the radically polymerizable compound is a compound having a caprolactone structure. Radically polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. under the KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like. Regarding the radically polymerizable compound having a caprolactone structure, the description of paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, and the contents thereof are incorporated herein.

A compound having an alkyleneoxy group can also be used as the radically polymerizable compound. 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 has 4 to 20 ethyleneoxy groups. It is more preferable that it is a 3- to 6-functional (meth)acrylate compound having. Examples of commercially available radically polymerizable compounds having an alkyleneoxy group include SR-494, a tetrafunctional (meth)acrylate having four ethyleneoxy groups manufactured by Sartomer, and trifunctional (meth)acrylate having three isobutyleneoxy groups. ) KAYARAD TPA-330, which is an acrylate.

Examples of radically polymerizable compounds include urethane acrylates such as those described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. , JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are 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. . As the radically polymerizable compound, compounds described in JP-A-2017-48367, JP-A-6057891, and JP-A-6031807 can also be used. Commercially available urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.). It is also preferable to use 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemicals Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc., as the radically polymerizable compound.

The content of the radically polymerizable compound is preferably 0.1 to 40% by mass based on the total solid content of the curable composition. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less.
Also, 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, more preferably 10% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. If the ratio of the compound having a radically polymerizable compound and a cyclic ether group is within the above range, the water resistant adhesion is better, and the generation of aggregates derived from the near-infrared absorbing dye is more suppressed. It is easy to form a cured film. .
Also, 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 even more 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 even more preferably 60 parts by mass or more. If the ratio of the radically polymerizable compound and the near-infrared absorbing dye is within the above range, it is easy to form a cured film with better water-resistant adhesion and further suppressed generation of aggregates derived from the near-infrared absorbing dye.
The curable composition of the present invention may contain only one kind of radically polymerizable compound, or may contain two or more kinds thereof. When two or more radically polymerizable compounds are included, the total amount thereof is preferably within 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 initiates or promotes the polymerization reaction of a radically polymerizable compound by generating radicals with thermal energy. The thermal radical polymerization initiator may be a compound that generates radicals under the action of heat and light.

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

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

In formulas (T-1) to (T-3), Rt ¹ to Rt ⁴ each independently represent a substituent, and m1 to m4 each independently represent an integer of 0 to 4. When m1 is 2 to 4, m1 Rt ¹ may be the same or different. Also, two Rt ¹ of m1 Rt ¹ may be bonded to each other to form a ring. When m2 is 2 to 4, m2 Rt ² may be the same or different. In addition, two Rt ² out of m2 Rt ² may be bonded to each other to form a ring. When m3 is 2 to 4, m3 Rt ³ may be the same or different. In addition, two Rt ³ 's among m3 Rt ³ 's may be bonded to each other to form a ring. When m4 is 2 to 4, m4 Rt ⁴ may be the same or different. Also, two Rt ^4s among m4 Rt ^4s may be bonded to each other to form a ring. 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 , Rt ³ and Rt ⁴ may combine to form a ring.
In formula (T-1), Rt ⁵ and Rt ⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group, Ti(R ^M1 )(R ^M2 )(R ^M3 ), Zr(R ^M1 )(R ^M2 )(R ^M3 ), Si(R ^M1 )(R ^M2 )(R ^M3 ) or B(R ^M1 )(R ^M2 ), and R ^M1 to R ^M3 each independently represent a substituent.
In formula (T-2), M ¹ represents Ti(R ^M4 )(R ^M5 ), Zr(R ^M4 )(R ^M5 ), Si(R ^M4 )(R ^M5 ) or B(R ^M4 ); R ^M4 and R ^M5 each independently represent a substituent.
In formula (T-3), M ² represents Ti(R ^M6 ), Zr(R ^M6 ), Si(R ^M6 ) or B, ^RM6 represents a substituent, and L ¹ represents a divalent linking group. represents

Substituents represented by Rt ¹ to Rt ⁴ and R ^M1 to R ^M6 include alkyl groups, aryl groups, heterocyclic groups, nitro groups, cyano groups, halogen atoms, —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 etc. R ^X1 and R ^X2 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
The alkyl group as a substituent, the alkyl group represented by R ^X1 and R ^X2 , and the alkyl group represented by Rt ⁵ and Rt ⁶ in formula (T-1) preferably have 1 to 20 carbon atoms. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched.
The aryl group as a substituent, the aryl group represented by R ^X1 and R ^X2 , and the aryl group represented by Rt ⁵ and Rt ⁶ in formula (T-1) preferably have 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms. , 6 to 10 are more preferred. The aryl group may be monocyclic or condensed.
The heterocyclic group as a substituent and the heterocyclic group represented by R ^X1 and R ^X2 are preferably 5- or 6-membered rings. The heterocyclic group may be monocyclic or condensed. The number of carbon atoms constituting the heterocyclic group is preferably 3-30, more preferably 3-18, even more preferably 3-12. The number of heteroatoms constituting the heterocyclic group is preferably 1-3. A heteroatom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In addition, some or all of the hydrogen atoms in the heterocyclic group may be substituted with the above substituents.

Each of m1 to m4 independently represents an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, further preferably 0 or 1, and particularly preferably 0.

Examples of the divalent linking group represented by L ¹ include an alkylene group, an arylene group, and -NR'- (R' is a hydrogen atom, an optionally substituted alkyl group or a represents a good aryl group, preferably a hydrogen atom), --SO ₂ --, --CO--, --COO--, --OCO--, --O--, --S-- and groups formed by combining these.

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

Specific examples of pinacol compounds include benzopinacol and 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane. Further, with respect to the pinacol compound, the descriptions of JP-A-2014-521772, JP-A-2014-523939, and JP-A-2014-521772 can be referred to, and the contents thereof are incorporated herein.

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 α-hydroxyacetophenone compounds include compounds represented by the following formula (T-11).
Formula (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 combine to form a ring, m represents an integer of 0 to 4;

The substituent represented by Rt ¹¹ includes the substituents described above, and is preferably an alkyl group or an alkoxy group. Alkyl groups and alkoxy groups may be unsubstituted or may have a substituent. A hydroxy group etc. are mentioned as a substituent.

Rt ¹² and Rt ¹³ each independently represent a hydrogen atom or a substituent. Examples of the substituent include the substituents described above, and an alkyl group and an aryl group are preferable. Also, Rt ¹² and Rt ¹³ may combine with 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 α-hydroxyacetophenone compounds include 1-hydroxy-cyclohexyl-phenyl-ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1- On and the like. Commercially available α-hydroxyacetophenone compounds include IRGACURE-184 and IRGACURE-2959 (manufactured by BASF).

α-Aminoacetophenone compounds include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)- 1-butanone, 2-dimethylamino-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and the like. Commercially available α-aminoacetophenone compounds include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (manufactured by BASF).

Benzyl dimethyl ketal compounds include 2,2-dimethoxy-2-phenylacetophenone and the like. Commercially available products include IRGACURE-651 (manufactured by BASF).

Azo compounds include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-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 azo compounds include V-70, V-65, V-60, V-59, V-40, V-30, V-501, V-601, VE-073, VA-080, 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, Wako Jun manufactured by Yakukogyo Co., Ltd.) and the like.
Examples of organic peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methyl cyclohexanone 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-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide Peroxide, paramethane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumylperoxide 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, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert-butyl peroxyoctanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, 3,3'4,4'-tetra-(tert-butylperoxycarbonyl)benzophenone, 3,3' 4,4′-tetra-(t-amylperoxycarbonyl)benzophenone, 3,3′4,4′-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-butylperoxydihydrogendiphthalate), carbonyldi(tert-hexylperoxydihydrogendiphthalate) and the like. Commercially available organic peroxides include Perbutyl O, Perbutyl Z, and Perhexa 25B (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 ⁻¹ ·cm ⁻¹ or less is more preferable. If the thermal radical polymerization initiator has a molar extinction coefficient of 100 L·mol ⁻¹ ·cm ⁻¹ or less at a wavelength of 365 nm, the thermal radical polymerization initiator can effectively generate radicals during storage of the curable composition. and the storage stability of the curable composition is good.

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 absorption 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 and adjusting a 5 mol % solution (measurement solution) of the thermal radical polymerization initiator. was calculated by measuring the absorbance of the measurement solution. Specifically, the above-described measurement solution is placed in a glass cell with a width of 1 cm, and the absorbance is measured using a UV-Vis-NIR spectrometer (Cary 5000) manufactured by Agilent Technologies. The extinction coefficient (L·mol ⁻¹ ·cm ⁻¹ ) was calculated.

In the above formula, ε is the molar extinction coefficient (L·mol ⁻¹ ·cm ⁻¹ ), A is the absorbance, c is the concentration of the solution to be measured (mol/L), and l is the optical path length (cm).

In the measurement of the molar extinction coefficient of the thermal radical polymerization initiator, acetonitrile and chloroform can be used as the solvent for preparing the measurement solution. When the thermal radical polymerization initiator is a compound that dissolves in acetonitrile, acetonitrile is used to prepare the measurement solution. When the thermal radical polymerization initiator is a compound that does not dissolve in acetonitrile but dissolves in chloroform, chloroform is used to prepare a measurement solution. When the thermal radical polymerization initiator is a compound that is insoluble in acetonitrile and chloroform but is soluble in dimethylsulfoxide, a measurement solution is prepared using dimethylsulfoxide.

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. If 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 stored. Good stability. In addition, when the thermal decomposition temperature of the thermal radical polymerization initiator is 270° C. or less, 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 thermogravimetry/differential thermal analysis (TG-DTA).

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. If the weight 1% temperature of the thermal radical polymerization initiator is within 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 the temperature at which the weight of the initiator alone decreases by 1% when measured by TG-DTA measurement.

The content of the thermal radical polymerization initiator is preferably 0.1 to 10% by mass based on the total solid content of the curable composition. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is more preferably 5% by mass or less.
Also, 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, may be 50 parts by mass or more, may be 80 parts by mass or more, or may exceed 100 parts by mass. The upper limit is preferably 150 parts by mass or less, more preferably 120 parts by mass or less. If the ratio of the thermal radical polymerization initiator and the radically polymerizable compound is within the above range, it is easier to form a cured film with better water-resistant adhesion and more suppressed generation of aggregates derived from the near-infrared absorbing dye. .
Further, when a pinacol compound and an α-hydroxyacetophenone compound are used together 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 preferred, more preferably 3 to 60 parts by mass, and even more 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 thereof. When two or more thermal radical polymerization initiators are included, the total amount thereof is preferably within the above range.
Moreover, in this invention, it can also be set as the structure which does not contain a photoradical polymerization initiator substantially. The term "substantially free" means, for example, that the content of the radical photopolymerization initiator is 1% by mass or less of the content of the thermal radical polymerization initiator.

<<Compound Having a Cyclic Ether Group>>
The curable composition of the invention contains a compound having a cyclic ether group. The cyclic ether group includes an epoxy group and an oxetanyl group, and an epoxy group is preferred. A 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 even more preferably 5 or less.

The cyclic ether group equivalent weight 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 weight is preferably 100 g/mol or more, more preferably 150 g/mol or more. The upper limit is preferably 350 g/mol or less, more preferably 300 g/mol or less.
Further, 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. Preferably. The lower limit of the epoxy group equivalent weight is preferably 100 g/mol or more, more preferably 150 g/mol or more. The upper limit is preferably 350 g/mol or less, more preferably 300 g/mol or less.

The compound having a cyclic ether group may be a low-molecular-weight compound (e.g., molecular weight less than 1,000) or a macromolecule (e.g., molecular weight 1,000 or more, in the case of a polymer, a weight-average molecular weight of 1,000 or more). good too. The molecular weight of the compound having a cyclic ether group (weight average molecular weight in the case of polymer) is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the molecular weight (weight average molecular weight in the case of polymers) is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1500 or less.

The compound having a cyclic ether group used in the present invention is preferably a compound having repeating units. When the compound having a cyclic ether group is a compound having repeating units, the cyclic ether group may be present in the side chain of the repeating unit or may be present at the end of the main chain. Among them, a compound having a cyclic ether group in a side chain is preferable because it can be surface-adsorbed to a support and more excellent water-resistant 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, 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 superior water-resistant adhesion.

The aromatic ring is preferably an aromatic hydrocarbon ring. Moreover, 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, and the like. It is preferred that at least a naphthalene ring is included because compatibility with the near-infrared absorbing dye is enhanced and excellent water-resistant adhesion is likely to be obtained. .
When the compound having a cyclic ether group contains an aromatic ring, the number of aromatic rings is preferably 1 or more, which enhances compatibility with the near-infrared absorbing dye and provides excellent water-resistant adhesion. It is more preferable that the number is two or more because it is easy. The upper limit is preferably 5 or less, more preferably 4 or less. Further, when the compound having a cyclic ether group is a compound having repeating units, the number of aromatic rings in one repeating unit is preferably 1 to 10. The upper limit is preferably 7 or less, more preferably 5 or less. The lower limit is preferably two or more. The number of aromatic rings in a compound having a cyclic ether group is the sum of the number of monocyclic aromatic rings and the number of condensed rings. 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 compound having this cyclic ether group has two aromatic rings. In the case of a compound having a benzene ring and a naphthalene ring as aromatic rings in a compound having a cyclic ether group, the compound having this cyclic ether group has three aromatic rings.

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 attached to the aromatic ring and/or the aliphatic ring via a single bond or a linking group. Bonding is preferred. As the linking group, an alkylene group, an arylene group, -NR'- (R' represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, hydrogen atoms are preferred), --SO ₂ --, --CO--, --COO--, --OCO--, --O--, --S-- and combinations thereof.

Compounds having a cyclic ether group, paragraph numbers 0034 to 0036 of JP-A-2013-011869, paragraph numbers 0147-0156 of JP-A-2014-043556, paragraph numbers 0085-0092 of JP-A-2014-089408 It is also possible to use the compounds described. The contents of these are incorporated herein. Examples of commercially available compounds having a cyclic ether group include EPICLON HP5000 and EPICLON HP4032D (manufactured by DIC Corporation) as naphthalene-modified epoxy resins. Examples of alkyldiphenol-type epoxy resins include EPICLON 820 (manufactured by DIC Corporation). As bisphenol A type epoxy resins, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (and Co., Ltd.) and the like. As bisphenol F type epoxy resins, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (manufactured by DIC Corporation), LCE-21, RE-602S ( and Nippon Kayaku Co., Ltd.). Examples of phenolic novolac epoxy resins include jER152, jER154, jER157S70, jER157S65 (manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (manufactured by DIC Corporation) and the like. mentioned. EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (manufactured by DIC Corporation) as cresol novolac type epoxy resins , and EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.). Aliphatic epoxy resins include ADEKA RESIN EP-4080S, EP-4085S, and EP-4088S (manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, and EPOLEAD. PB 4700 (manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (manufactured by Nagase ChemteX Corporation) and the like. Further, as compounds having an oxetanyl group, OXT-101, OXT-121, OXT-212, OXT-221 (manufactured by Toagosei Co., Ltd.), OXE-10, OXE-30 (manufactured by Osaka Organic Chemical Industry ( Co., Ltd.) and the like.

The content of the compound having a cyclic ether group is preferably 1 to 45% by mass based on the total solid content of the curable composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
Also, 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 even more preferably 300 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 20 parts by mass or more. If the ratio of the compound having a cyclic ether group and the near-infrared absorbing dye is within the above range, a cured film having better water-resistant adhesion and more suppressed generation of aggregates derived from the near-infrared absorbing dye can be formed. easy.
The curable composition of the present invention may contain only one type of compound having a cyclic ether group, or may contain two or more types thereof. When two or more compounds having a cyclic ether group are included, the total amount thereof is preferably within the above range.

<<Photo radical polymerization initiator>>
The curable composition of the invention may further contain a radical photopolymerization initiator. As the radical photopolymerization initiator, a compound that generates radicals with respect to light in the ultraviolet region to the visible region is preferable.

Photoradical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, α-aminoacetophenone compounds, α-hydroxyacetophenone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium. compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds.

The radical photopolymerization initiator is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. Moreover, the radical photopolymerization 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 15 L·mol ⁻¹ . ·cm ⁻¹ is more preferable, more preferably more than 50 L·mol ⁻¹ ·cm ⁻¹ is more preferably more than 100 L·mol ⁻¹ ·cm ⁻¹ is particularly preferable.

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, more preferably 15% by mass, based on the total solid content of the curable composition. Preferably, 10% by mass is more preferable. The lower limit is, for example, preferably 0.5% by mass or more, more preferably 1% by mass or more. The radical photopolymerization 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 within the above range.

<<Resin>>
The curable composition of the present invention can contain a resin as a component other than the compound having a cyclic ether group and the radically polymerizable compound described above. The resin is blended, for example, for the purpose of dispersing particles such as pigment in the composition and for the purpose of binder. A resin that is mainly used to disperse particles such as pigments is also called a dispersant. However, such uses of the resin are only examples, and the resin can be used for purposes other than such uses.

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, more preferably 5,000 or more.

Resins include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, and polyamideimide resins. , polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and the like. One of these resins may be used alone, or two or more may be mixed and used. As the cyclic olefin resin, norbornene resin can be preferably used from the viewpoint of improving heat resistance. Commercially available norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (for example, ARTON F4520). Further, the resin is the resin described in the examples of International Publication WO2016/088645, the resin described in JP-A-2017-57265, the resin described in JP-A-2017-32685, JP-A-2017. The resin described in JP-A-075248 and the resin described in JP-A-2017-066240 can also be used, the contents of which are incorporated herein.

The resin used in the present invention may have an acid group. The acid group includes, for example, a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferred. Only one kind of these acid groups may be used, or two or more kinds thereof may be used. A resin having an acid group can also be used as an alkali-soluble resin.

As a resin having an acid group, a polymer having a carboxyl group in a side chain is preferable. Specific examples include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and alkali-soluble polymers such as novolak resins. Phenolic resins, acidic cellulose derivatives having carboxyl groups in side chains, and resins obtained by adding acid anhydrides to polymers having hydroxyl groups can be mentioned. In particular, copolymers of (meth)acrylic acid and other monomers copolymerizable therewith are suitable as the alkali-soluble resin. Other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylates, aryl (meth)acrylates, vinyl compounds, and the like. Alkyl (meth)acrylates and aryl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer and the like. Other monomers that can be used include N-substituted maleimide monomers described in JP-A-10-300922, such as N-phenylmaleimide and N-cyclohexylmaleimide. In addition, these other monomers copolymerizable with (meth)acrylic acid may be of only one type, or may be of two or more types.

The acid group-containing resin may further have a polymerizable group. Polymerizable groups include (meth)allyl groups, (meth)acryloyl groups, and the like. Commercially available products include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Viscoat R-264, KS Resist 106 (both of which are Osaka organic Kagaku Kogyo Co., Ltd.), Cychromer P series (for example, ACA230AA), Plaxel CF200 series (both manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), Acrycure RD-F8 (Ltd. Nippon Shokubai Co., Ltd.) and the like.

Acid group-containing resins include benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth)acrylate copolymer, benzyl (meth) A multicomponent copolymer consisting of acrylate/(meth)acrylic acid/other monomers can be preferably used. Also, a copolymer of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer described in JP-A-7-140654, 2 -Hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene A macromonomer/benzyl methacrylate/methacrylic acid copolymer 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"). Polymers containing repeating units derived from components are also preferred.

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 hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.

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 in JP-A-2010-168539 can be referred to.

Specific examples of the ether dimer, for example, paragraph number 0317 of JP-A-2013-29760 can be referred to, the contents of which are incorporated herein. Only one kind of ether dimer may be used, or two or more kinds thereof may be used.

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 acid group-containing resin may contain a repeating unit derived from a compound represented by formula (X) below.

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, R ₃ represents a hydrogen atom or a C 1 to 20 group which may contain a benzene ring. represents an alkyl group of n represents an integer of 1-15.

For the resin having an acid group, JP 2012-208494, paragraph numbers 0558 to 0571 (corresponding US Patent Application Publication No. 2012/0235099, paragraph numbers 0685 to 0700), JP 2012-198408 The descriptions in paragraphs 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated herein. Moreover, resin which has an acid group can also use a commercial item. For example, Acrybase FF-426 (manufactured by Fujikura Kasei Co., Ltd.) can be used.

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

Resins having an acid group include, for example, resins having the following structures. In the following structural formulas, 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。 The curable composition of the present invention preferably uses a resin having repeating units represented by 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 a substituent.

^R5 represents a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group is preferably 1-5, more preferably 1-3, and particularly preferably 1. ^R5 is preferably a hydrogen atom or a methyl group.

Each of L ⁴ to L ⁷ independently represents 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 -, and -NR ¹⁰ - (R ¹⁰ is a hydrogen atom or represents an alkyl group, preferably a hydrogen atom), or a group consisting of a combination thereof. The number of carbon atoms in the alkylene group is preferably 1-30, more preferably 1-15, even more preferably 1-10. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be linear, branched or cyclic. Moreover, the cyclic alkylene group may be monocyclic or polycyclic. The arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms.

The alkyl groups represented by R ¹⁰ to R ¹³ may be linear, branched or cyclic, preferably cyclic. The alkyl group may have a substituent or may be unsubstituted. The number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-20, even more preferably 1-10. 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 still more preferably 6 carbon atoms. 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.

Substituents represented by ^R14 and ^R15 are halogen atoms, cyano groups, nitro groups, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, aralkyl groups, alkoxy groups, aryloxy groups, and heteroaryloxy groups. , an alkylthio group, an arylthio group, a heteroarylthio group, -NR ^a1 R ^a2 , -COR ^a3 , -COOR ^a4 , -OCOR ^a5 , -NHCOR ^a6 , -CONR ^a7 R ^a8 , -NHCONR ^a9 R ^a10 , -NHCOOR ^a11 , -SO ₂ R ^a12 , -SO ₂ OR ^a13 , -NHSO ₂ R ^a14 or -SO ₂ NR ^a15 R ^a16 . R ^a1 to R ^a16 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. 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.

Commercially available resins having a repeating unit represented by formula (A3-7) include ARTON F4520 (manufactured by JSR Corporation). In addition, for details of the resin having a repeating unit represented by formula (A3-7), the descriptions of paragraphs 0053 to 0075 and 0127 to 0130 of JP-A-2011-100084 can be referred to, and the contents thereof are the present specification. incorporated into the book.

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

The resin used as the dispersant preferably contains a repeating unit having an acid group. When 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 pixels during pattern formation by photolithography.

It is also preferable that the resin used as the dispersant is a graft copolymer. The graft copolymer has affinity with the solvent due to the graft chain, and is therefore excellent in pigment dispersibility and dispersion stability over time. Details of the graft copolymer can be referred to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein. Further, specific examples of the graft copolymer include the following resins. The following resins are also resins having acid groups (alkali-soluble resins). Further, examples of graft copolymers include resins described in paragraphs 0072 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.

In the present invention, the resin (dispersant) is also preferably an oligoimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The oligoimine-based dispersant has a structural unit having a partial structure X having a functional group with a pKa of 14 or less, and a side chain containing a side chain Y having an atomic number of 40 to 10,000. Resins having at least one basic nitrogen atom are preferred. 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 of paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein. Specific examples of the oligoimine-based dispersant include the following. The following resins are also resins having acid groups (alkali-soluble resins). Further, as the oligoimine-based dispersant, resins described in paragraphs 0168 to 0174 of JP-A-2012-255128 can be used.

Dispersants are also commercially available, and specific examples thereof include Disperbyk-111 (manufactured by BYK Chemie) and Solsperse 76500 (manufactured by Nippon Lubrizol Co., Ltd.). Also, the pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can be used, the contents of which are incorporated herein. Moreover, the above-mentioned resin having an acid group can also be used as a dispersant.

In the curable composition of the present invention, the resin content is preferably 1 to 60% by mass based on 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.

Moreover, when a dispersant is contained as the resin, the content of the dispersant is preferably 0.1 to 40% by mass based on the total solid content of the curable composition. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. Also, 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, more preferably 60 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, more preferably 5 parts by mass or more.

<<Chromatic coloring agent>>
The curable composition of the invention can contain a chromatic colorant. In the present invention, a chromatic colorant means a colorant other than a white colorant and a black colorant. The chromatic colorant is preferably a colorant that absorbs in a wavelength range of 400 nm or more and less than 650 nm.

A chromatic colorant may be a pigment or a dye. The pigment is preferably an organic pigment. Examples of organic pigments include those shown below.
Color Index (C.I.) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. (above, yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (above, orange pigment),
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, 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. (the above are purple pigments),
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 singly or in various combinations.

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

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 based on 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. Also, the total amount of the chromatic colorant and the near-infrared absorbing dye is preferably 1 to 80% by mass based on 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 chromatic colorants, the total amount thereof is preferably within the above range.
Moreover, it is preferable that the curable composition of the present invention does not substantially contain a chromatic colorant. “Containing substantially no 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. It is more preferable that it is the following, and it is further preferable that it does not contain a chromatic colorant.

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

The chromatic colorants include those described above. Examples of organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. The bisbenzofuranone compounds are described in JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, International Publication WO2014/208348, JP-A-2015-525260, and the like. compound, for example, available as "Irgaphor Black" manufactured by BASF. As a perylene compound, C.I. I. Pigment Black 31, 32 and the like. Examples of the azomethine compound include compounds described in JP-A-1-170601 and JP-A-2-34664, and can be obtained, for example, as "Chromofine Black A1103" manufactured by Dainichiseika Co., Ltd.

When two or more chromatic colorants are combined to form a black color, examples of combinations 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 with respect to the total solid content of the curable composition. , 50% by mass or less is more preferable, 30% by mass or less is more preferable, 20% by mass or less is even more preferable, and 15% by mass or less is particularly preferable. The lower limit can be, for example, 0.1% by mass or more, and can also be 0.5% by mass or more.
Moreover, it is preferable that the curable composition of the present invention does not substantially contain a coloring material that blocks visible light. The content of the colorant that blocks visible light is preferably 0.05% by mass or less with respect to the total solid content of the curable composition. , 0.01% by mass or less, and more preferably does not contain a coloring material that blocks visible light.

<<Pigment derivative>>
The curable composition of the invention can further contain a pigment derivative. Pigment derivatives include compounds in which at least one group selected from an acid group and a basic group is bonded to a pigment skeleton. As the pigment derivative, a compound represented by 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. When m is 2 or more, a plurality of L's and X's may be different from each other, and when n is 2 or more, a plurality of X's may be different from each other.

The dye skeleton represented by P includes a pyrrolopyrrole dye skeleton, diketopyrrolopyrrole dye skeleton, quinacridone dye skeleton, anthraquinone dye skeleton, dianthraquinone dye skeleton, benzoisoindole dye skeleton, thiazineindigo dye skeleton, azo dye skeleton, and quinophthalone. At least one selected from a dye skeleton, a phthalocyanine dye skeleton, a naphthalocyanine dye skeleton, a dioxazine dye skeleton, a perylene dye skeleton, a perinone dye skeleton, a benzimidazolone dye skeleton, a benzothiazole dye skeleton, a benzimidazole dye skeleton, and a benzoxazole dye skeleton is preferred, at least one selected from a pyrrolopyrrole dye skeleton, a diketopyrrolopyrrole dye skeleton, a quinacridone dye skeleton and a benzimidazolone dye skeleton is more preferred, and a pyrrolopyrrole dye skeleton is particularly preferred.

The linking group represented by L includes a hydrocarbon group, a heterocyclic group, --NR--, --SO ₂ --, --S--, --O--, --CO-- or a combination thereof. R represents a hydrogen atom, an alkyl group or an aryl group.

The acid group represented by X includes a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, an imidic acid group, and the like. As the carboxylic acid amide group, a group represented by —NHCOR ^X1 is preferred. As the sulfonic acid amide group, a group represented by —NHSO ₂ R ^X2 is preferred. The imidic acid group is preferably a group represented by -SO ₂ ^NHSO ₂ R x3 , ^-CONHSO ₂ R x4 , ^-CONHCOR x5 or -SO ₂ ^NHCOR x6. R ^X1 to R ^X6 each independently represent a hydrocarbon group or a heterocyclic group. The hydrocarbon groups and heterocyclic groups represented by R ^X1 to R ^X6 may further have substituents. Further substituents include the substituent T described in formula (PP) above, preferably a halogen atom, more preferably a fluorine atom. Basic groups represented by X include an amino group. The salt structure represented by X includes salts of the above-described acid group or basic group.

Pigment derivatives include compounds having the following structures. In addition, JP-A-56-118462, JP-A-63-264674, JP-A-1-217077, JP-A-3-9961, JP-A-3-26767, JP-A-3-153780 Publications, JP-A-3-45662, JP-A-4-285669, JP-A-6-145546, JP-A-6-212088, JP-A-6-240158, JP-A-10-30063, JP-A-10-195326, paragraph numbers 0086 to 0098 of International Publication WO2011/024896, compounds described in paragraph numbers 0063 to 0094 of International Publication WO2012/102399, etc., compounds described in Patent No. 5299151 can also be used, the contents of which are incorporated herein.

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, 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. If the content of the pigment derivative is within the above range, the dispersibility of the pigment can be enhanced and aggregation of the pigment can be efficiently suppressed. Only one kind of pigment derivative may be used, or two or more kinds thereof may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Solvent>>
The curable composition of the invention preferably contains a solvent. An organic solvent is mentioned as a solvent. 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 esters, ethers, ketones, aromatic hydrocarbons, and the like. For these details, reference can be made to paragraph number 0223 of International Publication WO2015/166779, the content of which is incorporated herein. Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, Cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like. 3-Methoxy-N,N-dimethylpropanamide and 3-butoxy-N,N-dimethylpropanamide are also preferred from the viewpoint of improving solubility. In the present invention, one type of organic solvent may be used alone, or two or more types may be used in combination. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as solvents may be better reduced for environmental reasons (e.g., 50 mass ppm (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less).

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

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

The solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one isomer may be contained, or a plurality of isomers 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 contains substantially no peroxide.

The solvent content is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, even more preferably 25 to 75% by mass, based on the total amount of the curable composition. When two or more solvents are used, the total amount thereof is preferably within the above range. For environmental reasons, it is sometimes preferable that the curable composition does not contain aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as solvents.

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, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and 70% by mass. It is particularly preferable that it is above. The upper limit is preferably 96% by mass or less, more preferably 95% by mass or less.

<<polymerization inhibitor>>
The curable composition of the invention may contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred. 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 invention can contain a silane coupling agent. In the present invention, a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. Further, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction. Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Functional groups other than hydrolyzable groups include, for example, vinyl groups, styryl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups. etc., and (meth)acryloyl groups and epoxy groups are preferred. The silane coupling agent includes compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703, and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. 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. Only one kind of silane coupling agent may be used, or two or more kinds thereof may be used. When two or more types are used, the total amount is preferably within the above range.

<<Surfactant>>
The curable composition of the invention can contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants can be used. For surfactants, reference can be made to paragraphs 0238 to 0245 of International Publication WO2015/166779, the contents of which are incorporated herein.

In the present invention, the surfactant is preferably a fluorosurfactant. By incorporating a fluorosurfactant into the curable composition of the present invention, liquid properties (particularly, fluidity) can be further improved, and liquid saving can be further improved. In addition, it is also possible to form a film with less unevenness in thickness.

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

Specific examples of fluorine-based surfactants include surfactants described in paragraph numbers 0060 to 0064 of JP-A-2014-41318 (corresponding paragraph numbers 0060 to 0064 of WO 2014/17669), particularly Examples include surfactants described in paragraphs 0117-0132 of JP2011-132503, the contents of which are incorporated herein. Commercially available fluorosurfactants include, for example, MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS -330 (manufactured by DIC Corporation), Florard FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like. .

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

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

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

In the present invention, 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) as the fluorosurfactant. By using such a surfactant, the heat resistance of the obtained film can be further improved. Furthermore, excellent solvent resistance can be obtained. The reason why excellent solvent resistance can be obtained by using a fluorine-containing curable compound is presumed to be as follows. Since the fluorine-containing curable compound has a low surface free energy, for example, in a coating film formed by coating a composition on a support such as a substrate, a fluorine-containing The curable compound tends to be unevenly distributed. By curing the curable composition of the present invention in such a state that the fluorine-containing curable compound is unevenly distributed, a region having a high proportion of the cured product of the fluorine-containing curable compound is formed on the surface farther from the substrate. . Due to the presence of such a region, the near-infrared absorbing dye hardly oozes from the film surface even when the film is immersed in a solvent, and excellent solvent resistance can be obtained.

The curable group possessed by the fluorine-containing curable compound includes a (meth)acryloyloxy group, an epoxy group and an oxetanyl group, with a (meth)acryloyloxy group being preferred.

The fluorine-containing curable compound preferably has at least one selected from the group consisting of a fluorine atom-substituted alkylene group, a fluorine atom-substituted alkyl group, and a fluorine atom-substituted aryl group. .
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, the aryl group is preferably 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 a fluorine atom. As specific examples thereof, paragraphs 0266 to 0272 of Japanese Patent Application Laid-Open No. 2011-100089 can be referred to, the contents of which are incorporated herein.

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

The fluorine-containing curable compound may be a monomer or a polymer, 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, the polymer preferably has a repeating unit represented by the following formula (B1) and at least one of a repeating unit represented by the following formula (B2) and a 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 each independently represent a hydrogen atom, an alkyl group, or a halogen atom. L ¹ to L ⁴ each 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 a fluorine atom-substituted alkyl group or a fluorine atom-substituted aryl group, and X ³ represents the formula (X) Represents a group represented by

In formulas (B1) to (B3), R ¹ to R ¹¹ are each independently preferably a hydrogen atom or an alkyl group. When R ¹ to R ¹¹ represent alkyl groups, alkyl groups having 1 to 3 carbon atoms are preferred. When R ¹ to R ¹¹ represent halogen atoms, fluorine atoms are preferred.
In formulas (B1) to (B3), when L ¹ to L ⁴ represent a divalent linking group, the divalent linking group may be an alkylene group optionally substituted with a halogen atom, or an alkylene group optionally substituted with a halogen atom. an arylene group, -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ -, -SO ₂ NR ¹² -, -O-, -S-, -SO ₂ -, or any of these A combination is mentioned. Among them, at least one selected from the group consisting of an alkylene group optionally substituted by a halogen atom having 2 to 10 carbon atoms and an arylene group optionally substituted by a halogen atom having 6 to 12 carbon atoms, or , from the group consisting of these groups and -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ -, -SO ₂ NR ¹² -, -O-, -S- and -SO ₂ - alkylene groups optionally substituted with halogen atoms having 2 to 10 carbon atoms, -CO ₂ -, -O-, -CO-, -CONR ¹² - , or a group consisting of a combination of these groups is more preferred. Here, R ¹² above 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%, more preferably 45 to 90 mol%, based on the total repeating units in the fluorine-containing curable compound. more preferred.
The total content of the repeating units represented by the formula (B2) and the repeating units represented by the formula (B3) is 5 to 70 mol% with respect to all repeating units in the fluorine-containing curable compound. is preferred, and 10 to 60 mol % is more preferred. When the repeating unit represented by formula (B2) is not included and the repeating unit represented by formula (B3) is included, the content of the repeating unit represented by formula (B2) is assumed to be 0 mol%. , the content of the repeating unit represented by the formula (B3) is preferably within the above range.

In addition, the fluorine-containing curable compound may have repeating units other than the repeating units represented by the above formulas (B1) to (B3). The content of other repeating units is preferably 10 mol % or less, more preferably 1 mol % or less, relative to the total repeating units in the fluorine-containing curable compound.

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

Commercially available fluorine-containing curable compounds include Megafac RS-72-K, Megafac RS-75, Megafac RS-76-E, Megafac RS-76-NS, and Megafac RS manufactured by DIC. -77 etc. can be used. The fluorine-containing curable compound includes compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, and compounds described in paragraph numbers 0015-0158 of JP-A-2015-117327. can also be used. A polymer having a repeating unit represented by (B1-1) and a repeating unit represented by formula (B3-1) can also be used as the fluorine-containing curable compound. 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 (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.) Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Takemoto Oil Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.) etc.

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

<<Ultraviolet absorber>>
The curable composition of the invention can contain an 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 as the ultraviolet absorber. For details of these, paragraph numbers 0052 to 0072 of JP-A-2012-208374 and paragraph numbers 0317-0334 of JP-A-2013-68814 can be referred to, and the contents thereof are incorporated herein. Examples of commercially available conjugated diene compounds include UV-503 (manufactured by Daito Kagaku Co., Ltd.). As the benzotriazole compound, the MYUA series manufactured by Miyoshi Oil (Kagaku Kogyo Nippo, February 1, 2016) may also 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 ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<Other Ingredients>>
The curable composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermal polymerization inhibitors, plasticizers, adhesion promoters and other auxiliary agents (e.g., conductive particles, fillers, , antifoaming agents, flame retardants, leveling agents, release accelerators, antioxidants, latent antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.). These components can be referred to paragraph numbers 0101 to 0104, 0107 to 0109, etc. of JP-A-2008-250074, the contents of which are incorporated herein. In addition, antioxidants include phenol compounds, phosphite ester compounds, thioether compounds, and the like. As the antioxidant, a phenol compound having a molecular weight of 500 or more, a phosphite 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 combination of two or more. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group is particularly preferred. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Phosphorus-based antioxidants can also be suitably used as antioxidants. As a phosphorus antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, and at least one compound selected from the group consisting of ethylbis(2,4-di-tert-butyl-6-methylphenyl)phosphite. These are commercially available. 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. As the antioxidant, polyfunctional hindered amine antioxidants described in International Publication WO17/006600 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. When two or more types are used, the total amount is preferably within the above range.
A latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst. Therefore, it is preferable that the compound functions as an antioxidant after the protective group is eliminated. Examples of latent antioxidants include compounds described in International Publication WO2014/021023, International Publication WO2017/030005, and JP-A-2017-008219. Commercially available products include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).

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

The storage container for the curable composition of the present invention is not particularly limited, and known storage containers can be used. In addition, as a storage container, a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resin and a bottle with a 7-layer structure of 6 types of resin are used for the purpose of suppressing the contamination of raw materials and compositions with impurities. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351.

Applications of the curable composition of the present invention are not particularly limited. For example, it can be preferably used for forming a near-infrared cut filter. In addition, the curable composition of the present invention may further contain a coloring material that blocks visible light, thereby forming an infrared transmission filter capable of transmitting only near-infrared rays having a specific wavelength or longer.

<Method for preparing curable composition>
The curable compositions of the present invention can be prepared by mixing the aforementioned ingredients. In preparing the curable composition, all components may be simultaneously dissolved or dispersed in a solvent to prepare the curable composition, or if necessary, two or more solutions or A curable composition may be prepared by preparing dispersion liquids in advance and mixing them at the time of use (at the time of application).

Moreover, when the curable composition of the present invention contains particles such as pigments, it preferably includes a process of dispersing the particles. In the process of dispersing particles, mechanical forces used for dispersing particles include compression, squeezing, impact, shearing, cavitation, and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like. Further, in the pulverization of particles in a sand mill (bead mill), it is preferable to use small-diameter beads or to increase the packing rate of beads so as to increase the pulverization efficiency. Moreover, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. In addition, the process and dispersing machine for dispersing particles are described in "Dispersion Technology Encyclopedia, Information Organization Co., Ltd., July 15, 2005" and "Dispersion Technology Centered on Suspension (Solid/Liquid Dispersion System) and Industrial Application The process and disperser described in paragraph number 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used. In the process of dispersing the particles, the particles may be refined in the salt milling step. Materials, equipment, processing conditions, etc. used in the salt milling process can be referred to, for example, Japanese Patent Application Laid-Open Nos. 2015-194521 and 2012-046629.

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, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyethylene, polyolefin resins such as polypropylene (PP) (high density, ultra high molecular weight including polyolefin resin). Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.
The pore size of the filter is suitably about 0.01-7.0 μm, preferably about 0.01-3.0 μm, more preferably about 0.05-0.5 μm. If the pore diameter of the filter is within the above range, fine foreign matter can be reliably removed. It is also preferable to use a fiber-like filter medium. Examples of fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers. Specifically, 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. can be mentioned.

When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more.
Also, filters with different pore sizes within the range described above may be combined. The pore size here can refer to the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by Nippon Pall Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can do.
The second filter can be made of the same material or the like as the first filter.
Alternatively, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed.

<Cured film>
The cured film of the invention is obtained from the curable composition of the 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 transmitting filter. The cured film of the present invention may be used by being laminated on a support, or may be used by peeling from the support. 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 depending on the 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. and particularly preferably 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 conditions (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, even more preferably 85% or more, and particularly preferably 90% or more.
(2) The transmittance at a wavelength of 500 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, and particularly preferably 95% or more.
(3) The transmittance at a wavelength of 600 nm is preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, and particularly preferably 95% or more.
(4) The transmittance at a wavelength of 650 nm is preferably 70% or more, more preferably 80% or more, still more 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. A color filter can be produced using a coloring composition containing a chromatic colorant. Chromatic colorants include the chromatic colorants listed as those that may be included 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 the functions of a near-infrared cut filter and a color filter.

When the cured film of the invention is used in combination with a color filter, the color filter is preferably arranged on the optical path of the cured film of the invention. For example, the cured film of the present invention and a color filter can be laminated and used as a laminate. In the laminate, the cured film of the present invention and the color filter may or may not be adjacent in the thickness direction. When the cured film of the present invention and the color filter are not adjacent in the thickness direction, the cured film of the present invention may be formed on a support other than the support on which the color filter is formed. Between the cured film of the invention and the color filter, other members (for example, microlenses, flattening layers, etc.) constituting the solid-state imaging device may be interposed.

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

Since the cured film of the present invention is excellent in adhesiveness and water-resistant adhesiveness to glass containing copper, it is preferably used by being laminated on glass containing copper. Glass containing copper includes phosphate glass containing copper, fluorophosphate glass containing copper, and the like. 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 preferred.

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

Specific examples of glass containing copper include the following.
(1) P ₂ O ₅ 46-70%, AlF ₃ 0.2-20%, ΣRF (R=Li, Na, K) 0-25%, ΣR'F ₂ (R'=Mg, Ca, Sr, Ba, Pb) 1 to 50%, 0.5 to 32% F, 26 to 54% O for 100 parts by mass of the base glass, and 0.5 to 7 parts by mass of CuO in external display containing glass.
(2) 25-60% P ₂ O ₅ , 1-13% Al ₂ O ₃ , 1-10% MgO, 1-16% CaO, 1-26% BaO, 0-16% SrO, 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 up to 39% molar amount of O ^2- ions are replaced by F).
(3) P ₂ O ₅ 5-45%, AlF ₃ 1-35%, ΣRF (R=Li, Na, K) 0-40%, 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 is a number corresponding to the valence of R″) 0 to 15 % (although up to 70% of the total amount of fluoride can be replaced by oxide), and 0.2-15% CuO.
(4) In terms of cation %, 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" cations (R" = La, Y, Gd, Si, B, Zr, Ta) 0-8%, and Cu ²⁺ 0.5-13%. and further containing 17 to 80% F ⁻ in % anions.
(5) P ^{5+ 23-41} %, Al ^{3+ 4-16} %, Li ⁺ 11-40%, Na ⁺ 3-13%, ΣR cations (R=Mg, Ca, Sr, Ba, Zn) 12-53%, and Cu ²⁺ 2.6-4.7%, and further containing anion % F ^- 25-48% and O ^2- 52-75%.
(6) 70-85% P ₂ O ₅ , 8-17% Al ₂ O ₃ , 1-10% B ₂ O ₃ , 0-3% Li ₂ O, 0-5% Na ₂ O, in weight percent; K ₂ O 0-5%, provided that ΣR ₂ O (R=Li, Na, K) 0.1-5%, and SiO ₂ 0-3%. Glass containing 0.1 to 5 parts by mass.

A commercially available glass containing copper can also be used. Commercially available glass containing copper includes NF-50 (manufactured by AGC Techno Glass Co., Ltd.).

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

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

In the method for producing a cured film, the curable composition is preferably applied onto a support. Examples of the support include substrates composed of materials such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, glass substrates containing copper, and the like. An organic film, an inorganic film, or the like may be formed on these substrates. Materials for the organic film include, for example, the resins described above. Further, as the support, a substrate made of the resin described above can also be used. Moreover, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support. In some cases, the support also has a black matrix that isolates each pixel. If necessary, the support may be provided with an undercoat layer for improving adhesion to the upper layer, preventing diffusion of substances, or planarizing the surface of the substrate. In the present invention, it is preferable to use a glass substrate containing copper as the support. Conventionally, it was difficult to form a cured film with good adhesion to glass substrates containing copper, but the cured film of the present invention has adhesion to glass substrates containing copper. is excellent, and the water-resistant adhesion is also excellent, so the effect of the present invention is more remarkable.

A known method can be used as a method for applying the curable composition to the support. For example, drop method (drop cast); slit coating method; spray method; roll coating method; spin coating method (spin coating); methods described in publications); inkjet (e.g., on-demand method, piezo method, thermal method), discharge system printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Examples include various printing methods; transfer methods using molds and the like; nanoimprinting methods and the like. The application method for inkjet is not particularly limited. 133 page), and methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. mentioned. In addition, regarding the application method of the curable composition, the descriptions in International Publication WO2017/030174 and International Publication WO2017/018419 can be referred to, and the contents thereof are incorporated herein.

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

In the step of heat curing the curable composition layer, the heating temperature is preferably 100 to 240° C., for example. From the viewpoint of film hardening, 180 to 230° C. is more preferable. The heating time is preferably 2 to 10 minutes, more preferably 4 to 8 minutes. The heat curing treatment can be performed using 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 forming a pattern by photolithography, it is preferable to heat-harden the curable composition layer after forming the pattern. Moreover, when forming a pattern by a dry etching method, it is preferable to form a pattern after heat-hardening a curable composition layer. When the cured film of the present invention is used as a flat film, the step of forming a pattern may be omitted. The process of forming the pattern will be described in detail below.

(When patterning by photolithography)
The pattern formation method by photolithography includes a step of patternwise exposing the curable composition layer formed by applying the curable composition of the present invention (exposure step), and the unexposed portion of the curable composition. and a step of developing to form a pattern by removing the layer (developing step). If necessary, a step of baking the developed pattern (post-baking step) may be provided.

(When patterning by dry etching method)
Pattern formation by the dry etching method includes heating and curing the curable composition layer to form a cured product layer, then forming a patterned photoresist layer on the cured product layer, and then forming a patterned photoresist layer. It can be carried out by a method such as dry etching using an etching gas with respect to the cured product layer using the resist layer as a mask. Regarding pattern formation by a dry etching method, descriptions in paragraphs 0010 to 0067 of JP-A-2013-064993 can be referred to, and the contents thereof are incorporated into this 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 contains 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 a support. Examples of the support include substrates made of materials such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, glass substrates containing copper, and glass containing copper. Substrates are preferred.

The near-infrared cut filter of the present invention may further have a dielectric multilayer film, an ultraviolet absorbing layer, etc., in addition to the cured film of the present invention. Since the near-infrared cut filter further has a dielectric multilayer film, it is easy to obtain a near-infrared cut filter with a wide viewing angle and excellent infrared shielding properties. In addition, the near-infrared cut filter can be a near-infrared cut filter with excellent ultraviolet shielding properties by further having an ultraviolet absorption layer. As the ultraviolet absorbing layer, for example, the absorbing layers described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication WO2015/099060 can be considered, the contents of which are incorporated herein. As for the dielectric multilayer film, the description in paragraphs 0255 to 0259 of JP-A-2014-41318 can be referred to, and the contents thereof are incorporated herein.

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

<Solid-state image sensor>
The solid-state imaging device of the present invention has the cured film of the present invention described above. The configuration of the solid-state imaging device 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 imaging device. For example, the following configuration can be mentioned.

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

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

<Infrared sensor>
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. An embodiment of the infrared sensor of the present invention will be described below with reference to the drawings.

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

The near-infrared cut filter 111 can be formed 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 formed with pixels that transmit and absorb light of a specific wavelength in the visible region, and is not particularly limited, and conventionally known color filters for forming pixels can be used. For example, a color filter having red (R), green (G), and blue (B) pixels is used. For example, paragraph numbers 0214 to 0263 of JP-A-2014-043556 can be referred to, and the contents thereof are incorporated herein.

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 planarization layer 116 . Other near-infrared cut filters include those having copper-containing layers and/or dielectric multilayer films. These details are given above. A dual bandpass filter may be used as another near-infrared cut filter. Moreover, 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. Another layer may be arranged between the solid-state imaging device 110 and the near-infrared cut filter 111 and/or between the solid-state imaging device 110 and the infrared transmission filter 114 . Other layers include an organic layer formed using a composition containing a polymerizable compound, a resin, and a photopolymerization initiator. A planarization layer may be formed over the color filters 112 .

EXAMPLES The present invention will be described more specifically with reference to examples below. The materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified. In the structural formulas, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

<Preparation of composition>
After mixing and stirring the raw materials shown in the table below in the proportions (parts by mass) shown in the table below, each composition was filtered through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.). prepared.

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

(Near-infrared absorbing dye)
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 30% by mass solution of cyclopentanone of a resin having the following structure (weight average molecular weight: 41,400; the numerical value attached to the repeating unit is the number of moles).

Resin 2: A 30% by mass solution of cyclopentanone of a resin having the following structure (weight average molecular weight: 33,100; the numerical value attached 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 having a cyclic ether group: EPICLON HP5000 (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)
- Cyclic ether group-containing compound 3: EPICLON HP820 (manufactured by DIC Corporation, alkyldiphenol type epoxy resin, number of aromatic rings in one repeating unit = 2, epoxy group value = 200 to 250 g/mol)
· Compound 4 having a cyclic ether group: EPOLEAD PB 4700 (manufactured by Daicel Corporation, butadiene type epoxy resin, number of aromatic rings = 0, epoxy group value = 152 to 178 g / mol)
- Cyclic ether group-containing compound 5: EPICLON N-695 (manufactured by DIC Corporation, cresol novolac type epoxy resin, number of aromatic rings in one repeating unit = 1, epoxy group value = 209 to 219 g/mol)
· Compound 6 having a cyclic ether group: EH3150 (manufactured by Daicel Corporation, cyclohexanone type resin, number of aromatic rings = 0, epoxy group value = 170 to 190 g / mol)

(Radical polymerizable compound)
Radically polymerizable compound 1: a mixture of the following compounds (a mixture in which the molar ratio of the left compound and the right compound is 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） Radically polymerizable compound 2: a mixture of the following compounds (height ratio in high performance liquid chromatography: 46.15: 49.39: : 4.46)

Radically polymerizable compound 3: the following compound

Radically polymerizable compound 4: the following compound

(initiator)
· Initiator 1: IRGACURE-184 (manufactured by BASF, α-hydroxyacetophenone compound, molar absorption coefficient at wavelength 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, thermal decomposition temperature = 182°C, thermal radical polymerization initiator)

· Initiator 3: Perbutyl O (manufactured by NOF Corporation, organic peroxide, molar absorption coefficient at wavelength 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 wavelength 365 nm = 6 L mol ^-1 cm ^-1 or less, thermal decomposition temperature = 90 ° C., thermal radical polymerization initiation agent)
· Initiator 5: IRGACURE-OXE01 (manufactured by 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)) in propylene glycol monomethyl ether acetate (PGMEA) at 30% by mass. In the following formula (B3-1), X represents any one of -CF ₂ -CF ₂ -, -CF ₂ - and -CH ₂ -CF ₂ -, and r represents the number of repeating units. Regarding X, the ratio of the numbers of -CF ₂ -CF ₂ -, -CF ₂ - and -CH ₂ -CF ₂ - 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 1)
A raw material having the following composition is dispersed in a bead mill (high-pressure disperser NANO-3000-10 with decompression mechanism (manufactured by Nippon BEE Co., Ltd.)) for 2 hours using zirconia beads with a diameter of 0.3 mm. Liquid 1 was prepared.
- Composition of Dispersion 1 -
・Near-infrared absorbing dye having the following structure (average primary particle size: 200 nm): 11.6 parts by mass

・Pigment derivative having the following structure: 3.5 parts by mass

Dispersing agent (resin having the following structure, weight average molecular weight: 22,900, the number attached to the repeating unit of the main chain is the number of moles, and the number attached to the repeating unit of the side chain indicates the number of repeating units ) ... 7.2 parts by mass

· Cyclohexanone ... 77.77 parts by mass

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

<Evaluation of waterproof adhesion>
Each curable composition was placed on a fluorophosphate glass substrate (product name: NF-50, manufactured by AGC Techno Glass Co., Ltd., size 50 mm × 50 mm, thickness 0.05 mm, glass substrate containing copper). Then, the film is spin-coated with a Mikasa coater so that the film thickness after film formation is 2.5 μm, dried at 100 ° C. for 120 seconds using a hot plate, and then heated at 220 ° C. for 5 minutes to form a cured film. manufactured.
The fluorophosphate glass base material with the cured film formed thereon was immersed in water at 95° C. for 1 hour, then cross-cut into 100 squares of 1 mm×1 mm, and wrapped with plant-based Sellotape (registered trademark) No. 1 manufactured by Nichiban. A tape peeling test was performed using No. 405, and water resistant adhesion was 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 10. 30 1: The number of peeled squares is 31 or more

<Evaluation of aggregation size>
Each curable composition was placed on a fluorophosphate glass substrate (product name: NF-50, manufactured by AGC Techno Glass Co., Ltd., size 50 mm × 50 mm, thickness 0.05 mm, glass substrate containing copper). Then, the film was spin-coated 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 form a cured 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 examined using an ultra-high resolution scanning electron microscope (manufactured by Hitachi High-Technologies Corporation) at an acceleration voltage of 2.0 kV. , the cross section of the film was observed at an observation magnification of 50000 times, the lengths in the long axis direction of the perforated shape at arbitrary three locations were measured, and the average value was calculated as the aggregation size.

As shown in the table above, all of the examples had good water-resistant adhesion and produced cured films with small aggregation sizes.
In addition, in Example 1, even if the initiator of Example 17 described in JP-A-2014-521772 was used instead of Initiator 2, the same effect as in Example 1 was obtained.

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

Claims (17)

A curable composition comprising a near-infrared absorbing dye, a compound having a cyclic ether group, a radically polymerizable compound, and a thermal radical polymerization initiator,
The thermal radical polymerization initiator is at least one selected from pinacol compounds and α-hydroxyacetophenone compounds, and the thermal radical polymerization initiator has a molar absorption coefficient of 100 L·mol ⁻¹ ·cm ⁻¹ at a wavelength of 365 nm. and
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. 2. The curable composition of 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, comprising 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, comprising 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 based on the total solid content of the curable composition. The curable composition according to any one of claims 1 to 6 , 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 7 , wherein the near-infrared absorbing dye is a compound having a π-conjugated plane containing a monocyclic or condensed aromatic ring. The curable composition according to any one of claims 1 to 8 , wherein the near-infrared absorbing dye is at least one selected from pyrrolopyrrole compounds, squarylium compounds and cyanine compounds. A cured film obtained from the curable composition according to any one of claims 1 to 9 . applying the curable composition according to any one of claims 1 to 9 on a support to form a curable composition layer;
A method for producing a cured film, comprising the step of heat-curing the curable composition layer. 12. The method for producing a cured film according to claim 11 , wherein the support is a glass substrate containing copper. A near-infrared cut filter comprising the cured film according to claim 10 . The near-infrared cut filter according to claim 13 , having the cured film on the surface of a glass substrate containing copper. A solid-state imaging device comprising the cured film according to claim 10 . An image display device comprising the cured film according to claim 10 . An infrared sensor comprising the cured film according to claim 10 .

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